Porphyrazine colorant, ink composition containing thereof and coloured product

FIELD: chemistry.

SUBSTANCE: invention can be used for inkjet printing. A porphyrazine colorant or its salt is represented by formula (1), where rings A-D each independently represents a benzene ring or a 6-membered nitrogen-containing heteroaromatic ring. E represents alkylene, X represents sulfo-substituted group aniline or the like, which can additionally have a substituent, R1 represents C1-C6 alkyl group, b equals to 0.00 or more and less than 3.90, as the average value, c equals to 0.10 or more and less than 4, as the average value, and the sum of b and c equals to 1.00 or more and less than 4.00, as the average value. The composition of colorant for inkjet printing, which contains the porphyrazine colorant or its salt.

EFFECT: invention makes it possible to obtain the composition of a colorant, which has good shade, possesses excellent properties of various types of resistance, in particular, ozone resistance, provides a possibility of high density of printing, possesses properties which almost do not produce a bronze tint effect.

21 cl, 5 tbl, 17 ex

 

The technical FIELD

The present invention relates to a new porfirinova kasashima substance or its salt, the composition of the ink (ink)containing a substance, to inkjet recording method using this composition of the paint and the painted product.

PRIOR art

Accepted for registration of images using a variety of materials. In particular, in recent years the main direction are recording materials for forming a color image. As the registration system of the color image are actively using an inkjet system, a system of stamping, electrophotographic system, a system copy using photosensitive materials, printing system, a system that uses writing tools such as a pen, and the like, and as a material for forming a color image using various colorants (dyes or pigments). In addition, in respect of the displays in the LCD (liquid crystal displays) or PP (plasma panels) and in the case of photographic equipment in electronic devices, such as CCD (charge coupled device), use a color filter. And just to reproduce a full color image on the display by using these color filters or with a view the completion of registration of the color image, reproduced on the display, use the coloring matter (dye and pigment) for the 3 main colors of the so-called paint additive synthesis and colors of subtractive synthesis. However, in reality there is no coloring matter, which has absorption characteristics that provide the desired size of the color reproduction, and which can withstand various conditions, so their improvement is imperative.

Inkjet recording method quickly became widespread and additionally developed due to low material costs, the ability to quickly write less noise when recording, ease of registering color and the like. Inkjet recording method includes a continuous system of continuously spraying drops of ink and a system without waiting spray of ink droplets in response to an information signal of an image. In addition, the system ejection system includes ejection of drops of ink by applying pressure of piezoelectric elements; a system of ejection of droplets of ink by generating bubbles in the ink by heating; system using ultrasonic waves; a system of injection and ejection of drops of ink by electrostatic forces; or the like. Examples of the ink (ink), suitable for such inkjet recording include water-based paints, paint oil-based, solid (melting) paint and the like.

Characteristics required for the coloring matter used in the ink for inkjet recording, include the good solubility or dispersibility in solvents; the ability to print high density, good color brightness; good resistance to light, heat and active gases (oxidizing gases such as NOxand ozone, and, in addition, SOxand the like) in the environment; excellent resistance to water and chemicals; good fixation to foster material recording, resulting in the absence of spreading; excellent storage stability in the form of paint; non-toxicity, and low cost, and the like. In particular, it is highly desirable blue coloring matter with a nice blue tint, giving the possibility of obtaining the recorded materials with a high print density, without causing the effect of a bronze tint, and having excellent resistance of the recorded image, for example, light fastness (resistance to light), ozone resistance (resistance to ozone gas) and water resistance (resistance to high humidity).

The effect of a bronze tint means the effect, where the dye on the surface of the receiving material for the record is in the state of the metal is centred fragments and shines due to the binding of a dye stuff, bad ink or the like. When she meets this effect, all the properties of gloss, the recording quality, and the print density violated. In particular, when the coloring substance use paint based on phthalocyanine metal, the effect of a bronze tint often seen as "the effect of red spreading on the part where we are recording high concentrations. When the effect of the bronze sheen, the color balance of the entire image is nonuniform, and the image quality is reduced, and it is therefore necessary coloring matter, an effect of bronze shimmer. In addition, as a material for recording recently used by many glossy paper with a texture similar to the texture of the photographs, and on the surface of the recorded material are formed variations of gloss, and texture image much is lost if the images recorded on glossy paper, is the effect of bronze shimmer. From this point of view also in high need of coloring matter, an effect of bronze shimmer.

As a water-soluble blue dye substances used for cyan ink for inkjet recording, it is characteristic of the dye based on phthalocyanine and dye-based t is ivermectina. Typical dye-based phthalocyanine described and used in a very wide range, include phthalocyanine derivatives classified in the following derive from a to H.

And: Famous dye-based phthalocyanine having the number of QI (color index), such as direct blue 86, direct blue 87, direct blue 199, acid blue 249, reactive blue 71 or the like.

In: Dye-based phthalocyanine described in patent documents 1-3, and the like,

[for example, a mixture of cu-PC-(SO3PA)m(SO2NH2)n; m+n=1-4] (Cu-Pc - represents the residue of copper phthalocyanine, -(SO3PA)mand (SO2NH2)nare his deputies, and m and n each represents a number of alternates. Later in this paper, such a description has the same value].

From: Dye-based phthalocyanine described in patent document 4, and the like,

[for example, Cu-Pc-(CO2H)m(CONR1R2)n; m+n = a number from 0 to 4]

(R1R2in this case represent a Deputy, such as alkyl. Later in this paper, such a description has the same meaning.)

D: Dye-based phthalocyanine described in patent document 5, and the like,

[for example, Cu-Pc-(SO3H) m(SO2NR1R2)n; m+n = a number from 0 to 4, and m≠0].

E: Dye-based phthalocyanine described in patent document 6, and the like,

[for example, Cu-Pc-(SO3H)l(SO2NH2)m(SO2NR1R2)n; l+m+n = a number from 0 to 4].

F: Dye-based phthalocyanine described in patent document 7, and the like,

[for example, Cu-Pc-(SO2NR1R2)nn = a number from 1 to 5].

G: Dye-based phthalocyanine described in patent documents 8, 9 and 12, and the like,

[connection phthalocyanine, in which the position of substitution of the substituent is regulated, the coloring matter on the basis of phthalocyanine in which the Deputy is introduced into the beta-position].

N: Dye-based benzamidopiperidine having a 6-membered nitrogen-containing heteroaromatic ring such as a pyridine ring and the benzene ring, are described in patent documents 10, 13-17, and the like.

Dye based on phthalocyanine, characterized by QI direct blue 86 or QI direct blue 199, which is usually widely used at the present time, has excellent light fastness as compared with the Magenta coloring substances and yellow coloring substances, which are well known. However, the dye on the Snov, phthalocyanine has a greenish shade in acidic conditions, consequently it is highly preferred as the blue paint. Therefore, it is preferable that these dyes are used in conditions of neutral to alkaline when they are used as a blue dye. However, although the paint you want to use has the reaction from neutral to alkaline, it is possible that the hue of the recorded material changes significantly when used to receiving the recording medium is an acidic paper.

In addition, when the dye-based phthalocyanine is used as a cyan ink, the hue of the recorded material becomes colorless to greenish, and fading due to oxidizing gases, such as gaseous nitrogen dioxide and ozone, which are often considered at present as a problem for the environment, whereby at the same time reduces the print density.

On the other hand, dye-based triphenylmethane has a good tone, but very low light fastness, resistance to ozone and moisture resistance.

Since that time, as the scope of inkjet recording began to expand and inkjet recording became widely used in products for exhibitions and advertising, and the like, there is more likelihood of exposure to dye and paint light and Islamic gases in the environment. In this regard, an increasingly greater need to dye for ink-jet recording had a good shade, was inexpensive and, in addition, had a particularly distinctive qualities of different resistance, as described above. However, it is considered difficult to produce a blue dye pigments (for example, the coloring matter on the basis of the phthalocyanine) and blue paint, meet these requirements at a high level. Also in the past colorants based on phthalocyanine or dyes on the basis of benzamidopiperidine engineered resistance to ozone gases are disclosed in patent documents 3, 8-12 and 14-17. However, the blue dye, which satisfies all the qualities such as hue, print density, light fastness, resistance to ozone gas, moisture resistance and the like, and does not cause the effect of a bronze tint and, in addition, is inexpensive to manufacture, still need to get. Thus, the needs of the market is not satisfied.

Related patent literature

Patent literature

[Patent document 1] patent Laid publication Japan JP S62-190273 And

[Patent document 2] Laid patent publication Japan JP H7-138511 And

[Patent document 3] Laid patent publication Japan JP 2002-105349 And

[atentry document 4] Laid patent publication Japan JP H5-171085 And

[Patent document 5] Laid patent publication Japan JP NUDE-140063 AND

[Patent document 6] national publication of international patent application No. NO-515048 AND

[Patent document 7] Laid patent publication Japan JP S59-22967

[Patent document 8] Laid patent publication Japan JP 2000-303009 And

[Patent document 9] Laid patent publication Japan JP 2002-249677 And

[Patent document 10] Laid patent publication Japan JP 2003-34758 And

[Patent document 11] patent Laid publication Japan JP 2002-80762 And

[Patent document 12] the Publication of the international application WO 2004/087815

[Patent document 13] the Publication of the international application WO 2002/034844

[Patent document 14] Laid patent publication Japan JP 2004-75986 And

[Patent document 15] publication of the international application WO 2007/091631

[Patent document 16] publication of the international application WO 2007/116933

[Patent document 17] publication of the international application WO 2008/111635

The INVENTION

Objectives of the invention

The present invention is to develop porphyrinogen coloring substance or its salt, which has a good hue as a cyan ink, has excellent ozone resistance and moisture resistance, regardless of the level of concentration of the coloring matter, is acti does not cause the effect of a bronze tint and in addition, suitable for inkjet recording, which can be obtained with a high print density; and the composition of the paints containing this substance.

Means of solving the problem

The authors of the present invention conducted a study for the development of a coloring matter having a good hue, high print density and excellent light fastness and resistance to ozone and does not cause the effect of a bronze tint, and found that certain porphyrazine coloring matter represented by the following formula (1)may allow to solve the above problems, and have established the present invention.

Thus, the present invention relates to:

1) Porfirinova kasashima substance or its salt represented by the following formula (1)

where

rings A-D, are represented by broken lines, each independently represents a benzene ring or 6-membered nitrogen-containing heteroaromatic ring fused with piperazinonyl ring, where the number of nitrogen-containing heteroaromatic rings is in the range of 0.00 and of 3.00 or less as an average value, and the rest are benzene rings,

E represents a C2-C12alkylen,

X represents a group of sulfonanilide, group carboxyaniline, gr is the foam of phosphonomycin, group alphanaphthylamine, group carboxymethylamino or group of postdonation and may optionally have a substituent at least one group selected from the group consisting of sulfopropyl, carboxypropyl, phosphono group, sulfamoyl group, carbamoyl group, a hydroxy-group, C1-C6alkoxygroup, amino, mono-C1-C4alkylamino, di-C1-C4alkylamino, monoarylamino, diarylamino,1-C3alkylcarboxylic, ureides group, C1-C6alkyl groups, nitro, ceanography, halogen atom, a C1-C6alkylsulfonyl group and C1-C6allylthiourea,

R1represents a C1-C6alkyl group,

b is, as the average value is 0.00 or more and less 3,90,

with care as the average value of 0.10 or more and less than 4,00, and

the sum of b and C are equal, as the average value of 1.00 or more and less than 4,00,

2) Porfirinova kasashima substance or its salt according to the above 1), where 6-membered nitrogen-containing heteroaromatic ring represented by the rings A to D is a pyridine ring or pyrazinone ring,

3) Porfirinova kasashima substance or its salt according to the above 1) or 2), which originates put the m interaction connection porphyrazine, represented by the following formula (2), with an organic amine represented by the following formula (3), in the presence of ammonia

in the formula (2) rings A-D have the same meanings as described above in 1), and n is 1.00 or more and less than 4,00

in the formula (3) E, X and R1have the same meanings as described above in 1),

4) Porfirinova kasashima substance or its salt according to the above 1) or 2), where

E represents a C2-C4alkylen,

R1represents a C1-C3alkyl group, and

X represents a group of sulfonanilide, group carboxyaniline, group postroeniya, group alphanaphthylamine, group carboxymethylamino or group of postdonation and additionally has as substituents from 0 to 3 groups of at least one species selected from the group consisting of sulfopropyl, carboxypropyl, phosphono group, a hydroxy-group, C1-C6alkoxygroup,1-C3alkylcarboxylic, ureides group, nitro group and a chlorine atom,

5) Porfirinova kasashima substance or its salt according to the above 4), where

E represents remotemachine2-C4alkylen, and

X represents a group of sulfonanilide or g is the SCP, carboxyaniline and additionally has as substituents from 0 to 2 groups, at least one species, selected from the group consisting of sulfopropyl, carboxypropyl, hydroxy-group, C1-C6alkoxygroup, nitro and chlorine atom,

6) Porfirinova kasashima substance or its salt according to the above 1) or 2), where

nitrogen-containing heteroaromatic ring for the rings A to D each independently represents a pyridine ring fused at the 2 - and 3-position or at the 3 - and 4-position; or pyrazinone ring fused at the 2-and 3-position

E represents ethylene or propylene, and

X represents a group of sulfonanilide or group of carboxyaniline and additionally has as substituents from 0 to 2 groups, at least one species selected from the group consisting of sulfopropyl, carboxypropyl, hydroxy-group, C1-C6alkoxygroup, nitro and chlorine atom,

7) Porfirinova kasashima substance or its salt according to the above 1), where

nitrogen-containing heteroaromatic ring for the rings A to D each independently represents a pyridine ring fused at the 2 - and 3-position or at the 3 - and 4-position

E represents ethylene or propylene, and

X represents a group of sulfonanilide or group of alphanaphthylamine where the group of sulfonanilide additionally has as Deputy from 0 to 2 groups selected the s group, consisting of sulfopropyl, carboxypropyl, hydroxy-group, C1-C6alkoxygroup, amino, mono-C1-C4alkylamino, di-C1-C4alkylamino,1-C3alkylcarboxylic,1-C6alkyl group, nitro group, chlorine atom, C1-C6alkylsulfonyl group and C1-C6ancilliary and group alphanaphthylamine additionally has as a substituent, 1 or 2 groups selected from the group consisting of sulfopropyl, hydroxy-group and nitro group,

8) Porfirinova kasashima substance or its salt according to the above 1), where

nitrogen-containing heteroaromatic ring for the rings A to D each independently represents a pyridine ring fused at the 2 - and 3-position or at the 3 - and 4-position, where their number, as the average value is in the range from 0.00 to 3.00 or less, and the remaining number of benzene rings is, as the average value of 1.00 or more and less than 4,00,

E represents ethylene,

X represents a group of desultorily or group of alphanaphthylamine where the group of alphanaphthylamine additionally has as a substituent, 1 or 2 groups of one or two kinds selected from the group consisting of sulfopropyl and hydroxy-group,

R1represents a C1- 4alkyl group,

b is, as the average value is 0.00 or more and less 3,90,

with care as the average value of 0.10 or more and less than 4,00, and

the sum of b and C are equal, as the average value of 1.00 or more and less than 4,00,

9) the Composition of the paints containing porphyrazine dye or its salt according to any one of above 1) to 8) as the coloring matter,

10) of the paint Composition according to the above 9, which further comprises an organic solvent,

11) the Composition of the paint in accordance with the above 10)which is for inkjet recording,

12) the Inkjet recording method where recording is carried out on the receiving material for recording by ejection of droplets of ink comprising the composition of paints containing porphyrazine dye or its salt according to any one of above 1) to 8), in response to the print signal,

13) the Inkjet recording method according to the above 12), where the receiving material for the record is a reference sheet

14) the Inkjet recording method according to the above 13), where the reference sheet is a sheet subjected to surface treatment, and this sheet is a sheet having a receiving layer for ink containing particles of the white inorganic pigmentation treatment the NTA on the substrate,

15) the Container containing the composition of the paints containing porphyrazine dye or its salt according to any one of above 1) to 8),

16) Inkjet printer that contains the container in accordance with the above 15),

17) Colored product colored paint composition containing porphyrazine dye or its salt according to any one of above 1) to 8),

18) Porfirinova kasashima substance or its salt according to any one of above 1) to 8), where X is a group of desultorily or group of desulfonation, which may be substituted by a hydroxy-group,

19) Porfirinova kasashima substance or its salt according to the above 18), where X is a group of desultorily,

20) the Composition of the paints containing porphyrazine dye or its salt according to the above 1)or porphyrazine dye or its salt according to the above 1) or the above 19), where X is a group of desultorily or group of desulfonation, which may be substituted by a hydroxy-group, water and an organic solvent.

The effect of the invention

The composition of the ink containing the coloring matter of the present invention or its salt, has a good tone in kachestvennoi paint. In addition, the recorded image obtained by the composition of the inks according to the present invention, has excellent ozone resistance and good resistance regardless of the level of concentration of the coloring matter in the recorded image, and almost does not cause the effect of a bronze tint, making use of the paint composition of the present invention can be obtained a recorded image excellent in balance of properties, durability and quality.

In addition, the coloring matter of the present invention has a high print density and reduces the concentration of the printed image, which results in cost reduction when printing.

So porphyrazine coloring matter of the present invention or its salt and the composition of the cyan ink containing it is extremely useful as inks for different types of records, in particular for ink-jet recording.

The method of carrying out the invention

The present invention is hereinafter explained in more detail. The coloring matter of the present invention or its salt represented by the above formula (1) and exhibits a blue color, so it can be used as a coloring matter for the blue paint.

Piperazinone ring with ring A to D in the above formula (1), provide the focus of tetrabenzoporphyrin (usually referred to as phthalocyanine), in which from 0 to 3 or less, as the average value of the four benzo (benzene) rings substituted nitrogen-containing heteroaromatic ring.

In this regard, in the present description "porphyrazine coloring matter of the present invention or its salt" hereinafter for simplicity is described as "porphyrazine coloring matter of the present invention or for convenience, the coloring matter of the present invention".

In the above formula (1) nitrogen-containing heteroaromatic ring for the rings A-D (four rings a, b, C and D), represented by broken lines, include, for example, nitrogen-containing heteroaromatic ring containing 1 or 2 nitrogen atom, such as pyridine ring, pyrazinone ring, pyrimidine ring and pyridazinone ring. This nitrogen-containing heteroaromatic ring each independently preferably represents a pyridine ring or a pyridine ring fused at the 2 - and 3-position or at the 3 - and 4-position) or pyrazinone ring (pyrazinone ring condensed at the 2 - and 3-position) and more preferably a pyridine ring, a pyridine ring fused at the 2 - and 3-position or at the 3 - and 4-position). In some cases, the nitrogen-containing heteroaromatic ring, more preferably a represents a pyridine ring fused at the 3-position, especially with regard to shade, properties, durability and the like.

In this regard, in the present description, the provisions in "pyridine ring or pyrazinone ring condensed at the 2 - and 3-position" and the like represent the position of condensation, where the nitrogen atom of the pyridine ring or pirazinamida rings consider the 1-position.

Increasing the number of nitrogen-containing heteroaromatic rings ozone resistance is improved, but, as a rule, there is a tendency to the appearance of bronze shimmer. The number of nitrogen-containing heteroaromatic rings can accordingly be adjusted taking into account the ozone resistance and bronze shimmer to choose a good equilibrium value.

The number of nitrogen-containing heteroaromatic rings depends on the type of heterocyclic rings and it is difficult to specify precisely, but it is in the interval as an average value, usually from more than 0.0 to 3.0 or less, preferably 0.2 or more and 2.0 or less, more preferably 0.5 or more and 1.75 or less (where the interval is 0.5 or more and 1.5 or less is more preferable), and even more preferably of 0.75 or more and 1.5 or less. The rest of the rings A to D are benzene rings. The benzene ring for the rings A to D, therefore, usually are number of, as the average value of 1.0 or balaei lower than 4.0, preferably 2.0 or more and 3.8 or less, more preferably 2.25 or more and 3.5 or less (where the interval of 2.5 or more and 3.5 or less is more preferable), and even more preferably 2.5 or more and 3.25 or less. In this respect porphyrazine coloring matter of the present invention is a mixture of dyes from a variety of pigments with different numbers of nitrogen-containing heteroaromatic rings, as can be seen from the fact that the number of nitrogen-containing heteroaromatic ring for the rings A to D are shown as average values. It is difficult to separate this mixture of dyes, each dye, and there are no problems even when considering the mixture as a single connection, as shown in this average value, resulting in the mixture of the present invention is interpreted as a single connection, shown using the mean value.

In this regard, in the present description, the number of nitrogen-containing heteroaromatic rings is described in the form of digits before the first or second decimal place by rounding the second or third decimal place, unless specifically provided otherwise. However, for example, when the number of nitrogen-containing heteroaromatic rings is 1,375, and the number of benzene rings is 2,625, the first is equal to 1.38, and the second is 2,63 after rounding both numbers, which results in ktomu, that the sum of the two numbers exceeds 4,00 total number of rings A-D. In this case, for convenience of description, the third digit after the decimal point to the number of nitrogen-containing heteroaromatic rings is lowered, and the third digit after the decimal point to the number of benzene rings are rounded, so the first is equal to 1.37, and the second is 2,63, resulting in the sum of the two numbers is 4.

In addition, b and C in the formula (1) described as to the first or second decimal place by rounding the second or third decimal place, as necessary, as described above, although in the same case as above, the second or third decimal place b is lowered, and the second or third decimal place to round in such a way as to bring it into line with the number of benzene rings.

In the above formula (1) C2-C12alkylen for E includes remotemachine, branched or cyclic alkylene, preferably remotemachine or cyclic and preferably remotemachine. The range of carbon atoms typically includes C2-C12preferably C2-C6more preferably2-C4and even more preferably2-C3.

Concrete examples of C2-C12alkylene for E include remotemachine C2-C12alkylene, such as ethylene, propylene, butylene, pentile, gexi the Yong, septilin, octiles, Nonlin, deciles, undecided and modellen; branched C2-C12alkylene, such as 2-mutilation; cyclic C2-C12alkylene, such as cyclopropylethyl, 1,2 - or 1,3-cyclopentanediol and 1,2-, 1,3 - or 1,4-cyclohexanediol; and the like. Preferred specific examples of C2-C12alkylene for E is ethylene, propylene, butylene, pentile, hexylen, more preferably ethylene, propylene and butylene, more preferably ethylene and propylene, and particularly preferably ethylene.

In the above formula (1) X is a group of sulfonanilide, group carboxyaniline, group postroeniya, group alphanaphthylamine, group carboxymethylamino or phosphonoamidate, and may additionally have a Deputy, as described above. In this regard, in the present invention, when just mention the group sulfonanilide, group carboxyaniline, group postroeniya, group alphanaphthylamine, group carboxymethylamino or group of postdonation, this means that each group has as a substituent sulfo, carboxy or phosphono group on the phenyl group or naftilos group, unless specifically noted otherwise. For example, X includes a group of sulfonanilide, such as 2-sulfonanilide, 3 sulfonanilide and 4 sulfonanilide; group carbon is anilino, such as 2-carboxyaniline, 3 carboxyaniline and 4 carboxyaniline; group postroeniya, such as 2-postroeniya, 3 postroeniya and 4 postroeniya; group alphanaphthylamine, such as 3-sulfo-1 naphthylamine, 6-sulfo-1 naphthylamine, 6-sulfo-1 naphthylamine, 1 sulfo-2-naphthylamine, 3 sulfo-2-naphthylamine, 4-sulfo-2-naphthylamine, 5-sulfo-2-naphthylamine, 6-sulfo-2-naphthylamine, 7 sulfo-2-naphthylamine and 8 sulfo-2-naphthylamine; group carboxymethylamino, such as 3-carboxy-1-naphthylamine, 6-carboxy-1-naphthylamine, 1-carboxy-2-naphthylamine and 6-carboxy-2-naphthylamine; group postdonation, such as 6-phosphono-1 naphthylamine; and the like, preferably a group of sulfonanilide, group carboxyaniline, group postroeniya or group of alphanaphthylamine, more preferably a group sulfonanilide or group of alphanaphthylamine and particularly preferably a group of sulfonanilide.

In this regard, the term "phosphono" means phosphate group [-P(O)(OH)2].

The above group sulfonanilide, carboxyaniline, phosphonomycin, alphanaphthylamine, carboxymethylamino or group phosphonoglycine in X can optionally have a substituent group selected from the group (hereinafter in this work, this group is called "group of twenty entries Deputy"), consisting of (1) sulfopropyl; (2) the carb is syrupy; (3) phosphono group; (4) sulfamoyl group; (5) carbamoyl group; (6) hydroxy-group; (7) C1-C6alkoxygroup; (8) amino; (9) mono-C1-C4alkylamino; (10) di-C1-C4alkylamino; (11) monoarylamino; (12) diarylamino; (13) C1-C3alkylcarboxylic; (14) ureides group; (15) C1-C6alkyl group; (16) nitro; (17) ceanography; (18) of the halogen atom; (19)1-C6alkylsulfonyl group; and (20) C1-C6allylthiourea (hereinafter referred to in this paper also briefly referred to as additional substituents).

The number of substitution groups (additional substituents), selected from the group consisting of the above-described twenty kinds of substituents, X is usually from 0 to 4, preferably from 0 to 3, more preferably from 0 to 2 and more preferably 0 or 1. When the above number substitution is other than 0, the number of additional substituents can be from one to four species in accordance with the number of additional substituents on 1 to 4 of the same group type. Preferably it is one or two species. More preferably it is one kind, when X represents a group of aniline, such as the above group sulfonanilide, and one or two species, when X is the Wallpaper group naphthylamine, such as the above group alphanaphthylamine where alphagraph preferred for the first and the hydroxy-group or/and alphagraph preferred for the second, and where alphagraph preferred in the case of a single species, and the hydroxy-group and alphagraph preferred in the case of two types.

The position of substitution for the additional substituent is not specifically limited.

C1-C6alkoxygroup for additional substituent includes remotemachine, branched or cyclic With1-C6alkoxy, preferably remotemachine or branched C1-C6alkoxy and more preferably remotemachine1-C6alkoxy. The range of carbon atoms of alkoxygroup usually includes With1-C6preferably1-C4and more preferably1-C3.

Concrete examples of C1-C6alkoxygroup include remotemachine C1-C6alkoxy, such as methoxy, ethoxy, n-propoxy, n-butoxy, n-pentox and n-hexyloxy; branched C1-C6alkoxy, such as isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, isopentylamine, etexilate; cyclic C1-C6alkoxy, such as cyclopropane, cyclopentane, cyclohexyloxy; and the like. Among them, methoxy, ethoxy of predpochtitel the us, and methoxy is particularly preferred.

Mono-C1-C4alkylamino for additional substituent includes remotemachine or branched C1-C4alkylamino, and the range of number of carbon atoms is usually C1-C4and preferably1-C3.

Specific examples

Mono-C1-C4alkylamino include remotemachine C1-C4alkylamino, such as methylamino, ethylamino, n-propylamino and n-butylamino; branched C1-C4alkylamino, such as Isopropylamine, isobutylamine, sec-butylamino and tert-butylamino; and the like. Among them, preferred group methylamino.

Di-C1-C4alkylamino for additional substituent includes dialkylamino, regardless of having two groups remotemachine or branched C1-C4the alkyl listed for above monoalkylamines, preferably remotemachine or branched C1-C3alkyl. Specific examples of di-C1-C4alkylamino include dimethylamino, diethylamino, methylethylamine and the like. Among them, preferred dimethylamino group.

Monoarylamino for additional substituent includes mono-C6-C10aromatic amino group, predpochtitel is about a group of phenylamino or group of naphtylamine and more preferably a group phenylamino.

Diarylamino for additional substituent includes diarylamino, having two independently With6-C10aromatic groups listed for above monoarylamino, preferably phenyl or naphthyl, and preferably phenyl. Diarylamino includes amino groups, preferably having two of the same arrow and more preferably two of the same phenyl groups. Specific examples of diarylamino include diphenylamino.

C1-C3alkylcarboxylic for additional substituent includes a group of carbylamine, substituted remotemachine or branched C1-C3the alkyl, preferably a group of carbylamine, substituted remotemachine1-C3the alkyl. Its specific examples include a group of carbylamine, substituted remotemachine1-C3the alkyl, such as methylcobalamin (acetylamino)ethylcarbodiimide and n-propylnitrosamine; and group carbylamine, substituted branched C1-C3the alkyl, such as isopropylcarbodiimide. Among them, preferred acetylamino group.

C1-C6the alkyl group for additional substituent includes remotemachine, branched or cyclic C1-C6preferably C1-C4and bol is e preferably C 1-C3alkyl group. Among them, preferred pravarasena or branched alkyl group, and more preferred pravarasena alkyl group. Its specific examples include remotemachine C1-C6alkyl, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl and n-hexyl; a branched C1-C3alkyl, such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl and isohexyl; cyclic C1-C6alkyl, such as cyclopropyl, cyclopentyl and cyclohexyl; and the like. Among them, preferred methyl.

The halogen atom for additional substituent include a fluorine atom, a chlorine atom and a bromine atom, preferably a fluorine atom or a chlorine atom, and more preferably a chlorine atom.

C1-C6alkylsulfonyl group for additional substituent includes remotemachine or branched C1-C6alkylsulfonyl group, preferably remotemachine or branched C1-C4alkylsulfonyl group, and more preferably remotemachine or branched C1-C3alkylsulfonyl group. Among them, preferred pravarasena1-C3alkylsulfonyl group. Its specific examples include remotemachine C1-C6alkylsulfonyl, such as methanesulfonyl (methyl who sulfonyl), econsultancy (ethylsulfonyl), n-propanesulfonyl (n-propylsulfonyl), n-butylsulfonyl, n-intercultural and n-hexylsilane; branched C1-C6alkylsulfonyl, such as isopropylalcohol and isobutylphenyl; and the like.

C1-C6allylthiourea for additional substituent includes remotemachine or branched C1-C6allylthiourea, preferably remotemachine or branched C1-C4allylthiourea and more preferably remotemachine or branched C1-C3allylthiourea. Among them, preferred pravarasena1-C3allylthiourea. Its specific examples include remotemachine C1-C6alkylthio, such as methylthio, ethylthio, n-propylthio, n-butylthio, n-pentylthio and n-hexylthio; branched C1-C6alkylthio, such as isopropylthio, isobutyric, tert-butylthio, isopentyl, isohexyl; and the like.

As an additional Deputy preferred alphagraph, carboxypropyl, phosphono group, a hydroxy-group, C1-C6alkoxygroup, C1-C3alkylcarboxylic, uraidla group, the nitro-group and the chlorine atom, and more preferred alphagraph, carboxypropyl, the hydroxy-group, C1-C6alkoxygroup, the nitro-group and the volume of chlorine. The number of substitution additional Deputy is usually from 0 to 4, preferably from 0 to 3, more preferably from 0 to 2 and more preferably 0 or 1.

As an additional Deputy preferred alphagraph. In particular, additional Deputy most preferably represents one alphagroup when additional Deputy substituted on the phenyl nucleus, except as stated otherwise, and the number of substitutions is 1 or 2, when additional Deputy substituted on naftalina the nucleus, where alphagraph most preferred when the number of substitution is equal to one, and the most preferred one alphagraph and one hydroxy-group, when the number of substitution equal to 2.

As an additional substituent in the case where X is a group of sulfonanilide, preferred alphagraph, carboxypropyl, the hydroxy-group, With1-C6alkoxygroup, amino group, mono-C1-C4alkylamino, di-C1-C6alkylamino, C1-C3alkylcarboxylic,1-C6alkyl group, a nitrogroup, a chlorine atom, a C1-C6alkylsulfonyl group and allylthiourea, more preferred alphagraph, carboxypropyl, the hydroxy-group, C1-C6alkoxygroup, the nitro-group and ATO is chlorine, especially preferred alphagraph.

As an additional substituent in the case where X is a group of carboxyaniline, preferred carboxypropyl, the hydroxy-group, With1-C6alkoxygroup, the nitro-group and the chlorine atom, and in some cases preferred carboxypropyl, alfamarine group and the hydroxy-group.

In the case where X is a group of phosphonomycin preferred group postroeniya, no additional Deputy.

As an additional substituent in the case where X is a group of alphanaphthylamine, preferred alphagraph, the hydroxy-group and the nitro-group, where preferred group having 1 or 2 groups selected from the group consisting of sulfopropyl and hydroxy-group, still more preferred having one alphagroup or with both groups, one alphagroup and one hydroxy-group, and the last is most preferable.

As an additional substituent in the case where X is a group of carboxymethylamino, preferred carboxypropyl and the hydroxy-group.

As an additional substituent in the case where X is a group of postdonation preferred group postdonation, no additional Deputy.

Concrete is reamers in case where X in the above formula (1) is a group of sulfonanilide, which has an additional Deputy, include:

group sulfonanilide, additionally having 0 or 1 alphagroup as a substituent, such as 2-sulfonanilide, 3 sulfonanilide, 4-sulfonanilide, 2,4-desultorily and 2.5-desultorily;

group sulfonanilide, optionally having one carboxypropyl as a substituent, such as 2-carboxy-4-sulfonanilide and 2-carboxy-5-sulfonanilide (in other words, the group carboxyaniline with one alphagroup as Deputy);

group sulfonanilide, optionally having at least one C1-C6alkoxygroup as a substituent, such as 4-methoxy-2-sulfonanilide, 4-ethoxy-2-sulfonanilide and 4 ethoxy-6-sulfonanilide;

group sulfonanilide, optionally having one amino group as a substituent, such as 3-amino-4-sulfonanilide;

group sulfonanilide, optionally having at least one mono-C1-C4alkylamino as a substituent, such as 4-methylamino-6-sulfonanilide;

group sulfonanilide, optionally having at least one di-C1-C4alkylamino as a substituent, such as 4-dimethylamino-5-sulfonanilide;

group sulfonanilide, optionally having at least one C1-C6the alkyl group as the substituent, such as 2-methyl-5-sulfonanilide and 3-methyl-6-sulfonanilide;

group sulfonanilide, optionally having at least one mono - or diarylamino as a substituent, such as 4-aniline-3-sulfonanilide;

group sulfonanilide, optionally having one With1-C3alkylcarboxylic as a substituent, such as 4-acetylamino-2-sulfonanilide;

group sulfonanilide, optionally having 1 or 2 halogen atom, preferably chlorine atom as a substituent, such as 2-chloro-5-sulfonanilide and 3,5-dichloro-4-sulfonanilide;

group sulfonanilide, optionally having at least one C1-C6alkylsulfonyl group as a substituent, such as 4-methylsulphonyl-5-sulfonanilide and 4-hexylsilane-2-sulfonanilide;

group sulfonanilide, optionally having one With1-C6allylthiourea as a substituent, such as 4-methylthio-2-sulfonanilide and 4-hexylthio-2-sulfonanilide;

group sulfonanilide with each of the two types of groups selected from the above optional substituents, such as 3-carboxy-4-hydroxy-5-sulfonanilide, 2-hydroxy-6-nitro-3-sulfonanilide, 2-methoxy-4-nitro-5-sulfonanilide, 3-methyl-6-methoxy-4-sulfonanilide and 2-hydroxy-N-acetylamino-5-sulfonanilide;

and the like.

Among the above groups of more than predpochtite the flax group sulfonanilide, such as 2,4-desultorily and 2.5-desultorily, and most preferred is 2,5-desultorily.

Specific examples in the case where X in the above formula (1) is a group of carboxyaniline, which may have the above-described additional Deputy, include:

group carboxyaniline, additionally having 0 or 1 carboxypropyl as a substituent, such as 2-carboxyaniline, 3 carboxyaniline, 4-carboxyaniline and 3.5-dicarbocyanine;

group carboxyaniline, optionally having one sulfamoyl group as a substituent, such as 4-aminosulfonyl-2-carboxyaniline;

group carboxyaniline, optionally having one hydroxy-group as a substituent, such as 3-carboxy-4-hydroxyanisole;

group carboxyaniline, advanced with each of the two species groups listed above as an additional substituent, such as 4-hydroxy-3-sulfo-5-carboxyaniline;

and the like.

Specific examples of the group postroeniya in the case where X in the above formula (1) is a group of phosphonomycin, which may have the above-mentioned additional Deputy, include a group of phosphonomycin, such as 2-postroeniya, 3 postroeniya and 4 postroeniya, and the like.

Specific examples in the case where the above formula (1) is a group of alphanaphthylamine, which may have the above-mentioned additional Deputy, include:

group alphanaphthylamine (group di - or trisulfonated), with 1 or 2 sulfopropyl as an additional substituent, such as 3,6-disulfo-1 naphthylamine, 1.5-disulfo-2-naphthylamine, 3,8-disulfo-1 naphthylamine, 4,8-disulfo-2-naphthylamine, 5,7-disulfo-2-naphthylamine, 6,8-disulfo-2-naphthylamine, 3,6,8-Triunfo-1 naphthylamine and 3,6,8-Triunfo-2-naphthylamine;

group alphanaphthylamine, optionally having one hydroxy-group as a substituent, such as 5-hydroxy-7-sulfo-2-naphthylamine;

group alphanaphthylamine with each of the two types of groups selected from the optional substituents, such as 3,6-disulfo-8-hydroxy-1-naphthylamine, 8-chloro-3,6-disulfonato-1 ylamine and 6-nitro-4,8-disulfo-2-naphthylamine;

and the like.

Among the above groups group alphanaphthylamine, which may have an additional Deputy, more preferably represents a group of desulfonation or group of hydroxydesloratadine, and even more preferably a group hydroxydesloratadine.

Specific examples in the case where X in the above formula (1) is a group of carboxymethylamino, which may have an additional Deputy, include:

group carboxylation is but additionally, having one carboxypropyl as a substituent, such as 1,6-dicarboxy-2-naphthylamine;

group carboxymethylamino, optionally having one hydroxy-group as a substituent such as 8-hydroxy-6-carboxy-1-naphthylamine;

group carboxymethylamino, advanced with each of the two types of groups selected from the group consisting of the above-described twenty species of deputies, as a substituent, such as 8-hydroxy-3,6-dicarboxy-1 naphthylamine;

and the like.

Preferred X is a group sulfonanilide, which may have an additional Deputy, a group of carboxyaniline, which may have an additional Deputy, or group of alphanaphthylamine, which may have additional Deputy.

Described the first group of sulfonanilide, which may have a Deputy, can have as the preferred additional Deputy 1 or 2 of at least one kind of groups selected from the group consisting of sulfopropyl, carboxypropyl, hydroxy-group, C1-C6alkoxygroup, amino, mono-C1-C4alkylamino, di-C1-C4alkylamino, C1-C3alkylcarboxylic, C1-C6alkyl group, nitro group, chlorine atom, With1-C6alkylsulfonyl and ancilliary, and among them, more preferred alphagraph, carboxypropyl, the hydroxy-group, C1-C6alkoxygroup, the nitro-group and the chlorine atom. Group sulfonanilide, which may have an additional Deputy, still more preferably represents a group of desultorily and most preferably 2.5 desultorily.

Describe the second group carboxyaniline, which may have an additional Deputy, preferably can have as additional Deputy 1 or 2 of at least one kind of groups selected from the group consisting of sulfopropyl, carboxypropyl, hydroxy-group, C1-C6alkoxygroup, nitro and chlorine atom.

Described the last group alphanaphthylamine, which may have an additional Deputy, can have as the preferred additional Deputy 1 or 2 of at least one kind of groups selected from the group consisting of sulfopropyl, hydroxy-group and nitro group. Group alphanaphthylamine, which may have an additional Deputy, more preferably represents the above group desulfonation or hydroxydesloratadine, and most preferably a group of hydroxydesloratadine.

More preferably X is a group of sulfonanilide, the cat heaven may have additional Deputy, or group of alphanaphthylamine, which may have an additional Deputy, and the preferred, more preferred and most preferred groups among these groups are as described above.

More specifically, even more preferred X may include a group of sulfonanilide, which may have one alphagroup as an additional substituent, more preferably a group sulfonanilide (group desultorily)having one alphagroup as an additional substituent; a group of alphanaphthylamine (group desulfonation or group of hydroxydesloratadine), having as additional Deputy 1 or 2 of the two types of groups selected from sulfopropyl and hydroxy-group, preferably one alphagroup or one alphagroup and one hydroxy-group, respectively, and more preferably a group hydroxydesloratadine.

The most preferable group as X is a group desultorily.

Among the above specific examples of X are preferred 3,8-disulfo-1 naphthylamine, 4,8-disulfo-2-naphthylamine, 6,8-disulfo-2-naphthylamine, 3,6-disulfo-8-hydroxy-1-naphthylamine and 2.5-desultorily preferred 3,6-disulfo-8-hydroxy-1-naphthylamine and 2.5-desultorily, and especially preferred group of 2,5-dial is foreline.

In the above formula (1) C1-C6the alkyl group for R1includes remotemachine, branched or cyclic C1-C6alkyl, preferably remotemachine or branched C1-C6alkyl and more preferably remotemachine1-C6alkyl. Interval number of carbon atoms is usually C1-C6preferably1-C4and more preferably C1-C3. Concrete examples of C1-C6alkyl groups for R1include remotemachine C1-C6alkyl, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl and n-hexyl; a branched C1-C6alkyl, such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl and isohexyl; cyclic C1-C6alkyl, such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; and the like.

Among them, preferred methyl, ethyl or isopropyl, more preferred methyl or ethyl, and even more preferred methyl.

In the present description any numeric values, described as b, and the sum of b and C in the above formula (1)is the average value in the above porfirinova Crusades the substance of the present invention. Also, as described for the number of nitrogen-containing heteroaromatic rings or benzene rings to the rings of A-, porphyrazine coloring matter represented by the above formula (1), according to the present invention is a mixture of many dyes having different values of b and C. it is Difficult to separate this mixture on each component, and have no problems, if you treat it as a compound with the same number of alternates, as their average value, and this method is convenient, resulting in the present invention the mixture is interpreted as a compound with the same number of deputies, in the form of its average value. Therefore, any of the numbers, like b, C, the number of nitrogen-containing heteroaromatic rings and benzene rings, described below, represents the average value, unless specifically noted otherwise.

In porfirinova Crusades the substance represented by the above formula (1), according to the present invention b is 0.0 or more and less than 3,9, is 0.1 or more and lower than 4.0, and the sum of b and C is 1.0 or more and lower than 4.0. In this case, the number of nitrogen-containing heteroaromatic ring for the rings A to D is above 0.0 and 3.0 or less, and in this way the number of benzene rings is 1.0 or more and lower than 4.0.

Preferably the number of nitrogen-containing heteroaromatic ring for the rings A to D is 0.2 or more and 2.0 or less, the number of benzene rings is 2.0 or more and 3.8 or less, b is 0.0 or Bo is her and 3.3 or less, C is 0.5 or more and 2.0 or less, and the sum of b and C is equal to 2.0 or more and 3.8 or less.

More preferably, the number of nitrogen-containing heteroaromatic ring for the rings A to D is 0.5 or more and 1.75 or less, the number of benzene rings is 2.25 or more and 3.5 or less, b is equal to 0.45 or more and 3.0 or less, C is 0.5 or more and 1.8 or less, and the sum of b and C is equal to 2.25 or more and 3.5 or less.

Even more preferably, the number of nitrogen-containing heteroaromatic ring for the rings A to D is equal to 0.75 or more and 1.5 or less, the number of benzene rings is 2.5 or more and 3.25 or less, b is equal to 0.9 or more and to 2.55 or less, is 0.7 or more and 1.6 or less, and the sum of b and C is equal to 2.5 or more and 3.25 or less.

With increasing b, the ozone resistance tend to improve, but is inclined to see the effect of a bronze tint, so the numbers b and C can be appropriately adjusted taking into account the ozone resistance and the effect of a bronze tint to choose a good equilibrium value.

In this regard, each of b and C represents the number of substitution groups, enclosed in parentheses, where any of these groups, enclosed in parentheses (unsubstituted Altamarena group and substituted Altamarena group), is a group substituted on the benzene ring, but not at 6-membered nitrogen-containing heteroaromatic ring, causing her presence is there on the benzene ring of rings A-D, but not at 6-membered nitrogen-containing heteroaromatic ring for the rings A-D.

In this regard, in the present description any of b, C and the sum of b and C is described as the digit before the first or second decimal place by rounding the second or third decimal place, in accordance with need.

Preferably the dye, having a preferred value of A is D, E, X, R1, b and C, described above, more preferably the dye, where the preferred values are combined, and even more preferably the dye, where the preferred values are combined. The same is true for the combination even more preferred values the preferred combination of values and preferred values, and the like.

Preferred porphyrazine coloring matter of the present invention may include piperazinone dyes or their salts in accordance with(2)-(8), (18) and (19), described in paragraph "a Means of solving the problem", and, in addition, the following piperazinone dyes or their salts can be included as the preferred porphyrinogen the coloring matter of the present invention.

(i) Porphyrazine dye or its salt according to any one of above 1)to 3), where in the above formula (1)

X is the Wallpaper group desultorily or group of desulfonation, which may be substituted by a hydroxy-group,

E represents a C2-C4alkylen, and

R1represents a C1-C3alkyl group.

(ii) Porphyrazine dye or its salt according to any one of above 1)to 8), 18) and 19) and the above-described (i)where in the above formula (1). the number of nitrogen-containing heteroaromatic ring for the rings a to D is 0.2 or more and 2.0 or less, and the number of benzene rings to the rings A to D is 2.0 or more and 3.8 or less, b is 0.0 or more and 3.3 or less, C is 0.5 or more and 2.0 or less, and the sum of b and C equal to 2.0 or more and 3.8 or less.

(iii) Porphyrazine dye or its salt according to any one of above 1)to 8), 18) and 19) and the above-described (i) and (ii)where in the above formula (1). the number of nitrogen-containing heteroaromatic ring for the rings A to D is 0.5 or more and 1.75 or less, the number of benzene rings is 2.25 or more and 3.5 or less, b is equal to 0.45 or more and 3.0 or less, C is 0.5 or more and 1.8 or less, and the sum of b and C is equal to 2.25 or more and 3.5 or less.

(iv) Porphyrazine dye or its salt according to any one of above 1)to 8), 18) and 19) and the above-described (i)to(iii)where in the above formula (1). the number of nitrogen-containing heteroaromatic ring for the rings A to D is 0.5 or more and 1.5 or less, and the number of benzene rings equally is 2.5 or more and 3.5 or less.

(v) Porphyrazine dye or its salt according to the above (iv), where b is equal to 0.45 or more and 3.0 or less, C is 0.5 or more and 3 or less, and the sum of b and C is equal to 2.5 or more and 3.5 or less.

(vi) Porphyrazine dye or its salt according to any one of above 1)to 8), 18) and 19) and the above-described (i)to(v), where in the above formula (1) nitrogen-containing heteroaromatic ring for the rings A to D each independently represents a pyridine ring fused at the 2 - and 3-position or at the 3 - and 4-position.

(vii) Porphyrazine dye or its salt according to the above (vi), where the nitrogen-containing heteroaromatic ring for the rings a to D is a pyridine ring fused at the 2 - and 3-position, b is 1 or more and 3.0 or less, C is 0.5 or more and 2 or less, and the sum of b and C is equal to 2.5 or more and 3.5 or less.

(viii) Porphyrazine dye or its salt according to the above (vii), where b is 1.5 or more and 2.5 or less, C is 0.5 or more and 1 or less, and the sum of b and C is equal to 2.5 or more and 3.5 or less.

(ix) Porphyrazine dye or its salt according to any one of above 1)to 8), 18) and 19) and the above-described (i)to(viii)where in the above formula (1) R1represents methyl or ethyl, more preferably methyl./p>

(x) Porphyrazine dye or its salt according to any one of above 1)to 8), 18) and 19) and the above-described (i)to(ix), where in the above formula (1) X is a 2.5-desultorily.

Porphyrazine coloring matter of the present invention represented by the above formula (1)may form a salt by using sulfopropyl, carboxypropyl, phosphono group and the like, it has inside a molecule. In the formation of salts, it is preferable to form a salt with protivoatomnom inorganic metal, ammonia or organic bases, or the like.

Inorganic metal include alkali metal and alkaline earth metal. Examples of the alkali metal include lithium, sodium, potassium and the like. Alkaline earth metal includes, for example, calcium, magnesium and the like.

The organic base include organic amines, in particular, for example, With1-C3alkylamine, such as methylamine and ethylamine, mono-, di - or tri-C1-C4alkanolamine, such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine.

Among the salts, using the above proteotion, preferably includes a salt of an alkali metal such as sodium, potassium and lithium; salts with mono-, di - Il is three 1-C4alkanolamines, such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine; and ammonium salt. In General, the alkali metal salt is more preferable.

In addition, there are also several cases where salt porphyrinogen the coloring matter of the present invention is changed in physical properties such as solubility and the like, or the quality of the paint when used as a paint, in particular, the quality and the like related to the properties of resistance, depending on the type of salt. In this regard, in some cases it is preferable to choose the type of salt in accordance with the implied quality paints and the like.

Specific examples of rings A-D, E, X and R1and average values of the numbers b and C in porfirinova Crusades the substance of the present invention represented by the above formula (1)shown in table 1.

The following examples show typical dyes with the specific purpose of explaining the coloring matter of the present invention, and the coloring matter of the present invention is not limited to the following examples.

In addition, for example, when nitrogen-containing heterocyclic ring in the rings A to D is a pyridine ring,a positional isomers are present in relation to the position of substitution of the nitrogen-containing heteroaromatic rings and the position of substitution of the nitrogen atom in the nitrogen-containing heteroaromatic ring, as described below, which, when synthesized dye of the present invention, the coloring matter, which is to be obtained, is a mixture of these isomers. In addition, it is a mixture of compounds with different numbers pyridine rings with different numbers b and C, as described above. It is difficult to distinguish each of these compounds, as described above, and it is also difficult to identify the isomers with the analysis. In connection with this mixture as it is usually interpreted as each individual connection, but with an average value of the number of nitrogen-containing heteroaromatic rings and the average values of the numbers b and C, as described above. In the present description, when the coloring matter of the present invention shows a structural formula, ring A-D for convenience, indicated by broken lines, and in the following table is a typical structure of rings A-D described in columns A-D.

The number of b and C in the table below are described by rounding the first decimal place in order to avoid complications. In this regard, "2,3-pyrido or 3,4-pyrido in table 1 respectively indicate the pyridine ring condensed with piperazinonyl ring in 2 - and 3-positions or the 3 - and 4-positions, and "gasoline" means a benzene ring condensed with piperazinonyl ring, respectively.

Table 1
No.AndInDEXR1b
12,3-PyridoBenzoBenzoBenzoEthylene2.5 DesultorilyMethyl21
22,3-PyridoBenzoBenzoBenzoEthylene2,4-DesultorilyMethyl21
32,3-PyridoBenzoBenzoBenzoEthylene2 SulfonanilideMethyl 21
42,3-PyridoBenzoBenzoBenzoEthylene3 SulfonanilideMethyl21
52,3-PyridoBenzoBenzoBenzoEthylene4 SulfonanilideMethyl21
62,3-PyridoBenzoBenzoBenzoEthylene2.5 DesultorilyEthyl21
72,3-PyridoBenzoBenzoBenzoEthylene2.5 DesultorilyIsopr who drank 21
82,3-PyridoBenzoBenzoBenzoEthylene4,8-Disulfo-2-naphthylamineButyl21
92,3-PyridoBenzoBenzoBenzoEthylene1.5-Disulfo-2-naphthylaminePencil21
102,3-PyridoBenzoBenzoBenzoEthylene3,6-Disulfo-1 naphthylamineHexyl21
112,3-PyridoBenzo2,3-PyridoBenzoEthylene 3,6,8-Triunfo-1 naphthylamineMethyl11
12Benzo2,3-Pyrido2,3-Pyrido2,3-PyridoEthylene2.5 DesultorilyMethyl01
13Benzo2,3-Pyrido2,3-PyridoBenzoEthylene2.5 DesultorilyMethyl11
142,3-PyridoBenzoBenzoBenzoPropylene2.5 DesultorilyMethyl21
152,3-PyridoBenzo2,3-PyridoBenzo Propylene2.5 DesultorilyMethyl11
162,3-PyridoBenzo2,3-Pyrido2,3-PyridoPropylene2.5 DesultorilyMethyl01
172,3-PyridoBenzoBenzoBenzoEthylene3,6-Disulfo-8-hydroxy-1-Methyl21
182,3-PyridoBenzoBenzoBenzoEthylene4-Methoxy-2-sulfonanilideMethyl21
192,3-PyridoBenzo BenzoBenzoEthylene4-Nitro-2-sulfonanilideMethyl21
202,3-PyridoBenzoBenzoBenzoEthylene2-Chloro-5-sulfonanilideMethyl21
212,3-PyridoBenzoBenzoBenzoEthylene3-Methyl-6-sulfonanilideIsopropyl21
222,3-PyridoBenzoBenzoBenzoEthylene2-Carboxy-4-sulfonanilideEthyl21

No.AndInDEXR1b
232,3-PyridoBenzoBenzoBenzoEthylene2.5 DicarbocyanineIsopropyl21
242,3-PyridoBenzoBenzoBenzoEthylene3 PostroeniyaIsopropyl21
252,3-PyridoBenzoBenzoBenzoEthylene2-Hydroxy-3-acetylamino-5-sulfonanilideIsopropyl21
262,3-PyridoBenzoBenzoBenzoEthylene4 Ethoxy-6-sulfonanilideIsopropyl21
272,3-PyridoBenzoBenzoBenzoEthylene3,6,8-Triunfo-2-naphthylamineMethyl11
282,3-PyridoBenzoBenzoBenzoEthylene6-Nitro-4,8-disulfo-2-Methyl01
292,3-PyridoBenzoBenzoBenzoEthylene5,7-Disulfo-2-naphthylamineMethyl/td> 11
302,3-PyridoBenzoBenzoBenzoEthylene6,8-Disulfo-2-naphthylamineMethyl21
312,3-PyridoBenzoBenzoBenzoEthylene3-carboxy-4-hydroxy-5-sulfonanilideIsopropyl11
322,3-PyridoBenzoBenzoBenzoEthylene3-Methyl-6-methoxy-4-sulfonanilideIsopropyl01
332,3-PyridoBenzoBenzoBenzoThe ethyl is 4-Methylsulphonyl-2-sulfonanilideMethyl21
342,3-PyridoBenzoBenzoBenzoEthylene4-Methylthio-2-sulfonanilideMethyl21
352,3-PyridoBenzoBenzoBenzoEthylene3-Amino-4-sulfonanilideMethyl21
362,3-PyridoBenzoBenzoBenzoEthylene4-Methylamino-5-sulfonanilideMethyl21
372,3-PyridoBenzoBen what about the BenzoEthylene4-Dimethylamino-5-sulfonanilideMethyl21
382,3-PyridoBenzoBenzoBenzoEthylene4-Aminosulfonyl-2-carboxyanilineMethyl21
392,3-PyridoBenzoBenzoBenzoEthylene4-Hexylthio-2-sulfonanilideIsopropyl21
402,3-PyridoBenzoBenzoBenzoEthylene4-Hexylsilane-2-sulfonanilideIsopropyl21
41 3,4-PyridoBenzoBenzoBenzoEthylene2.5 DesultorilyMethyl21
423,4-PyridoBenzoBenzoBenzoEthylene2,4-DesultorilyMethyl21
433,4-PyridoBenzoBenzoBenzoEthylene2 SulfonanilideMethyl21

Benzo
No.AndInDEXR1bc
443,4-PyridoBenzoBenzoBenzoEthylene3 SulfonanilideMethyl21
453,4-PyridoBenzoBenzoBenzoEthylene4 SulfonanilideMethyl21
463,4-PyridoBenzoBenzoBenzoEthylene2.5 DesultorilyEthyl21
473,4-PyridoBenzoBenzoBenzoEthylene2.5 DesultorilyIsopropyl2
483,4-PyridoBenzoBenzoBenzoEthylene4,8-Disulfo-2-naphthylamineButyl21
493,4-PyridoBenzoBenzoBenzoEthylene1.5-Disulfo-2-naphthylaminePencil21
503,4-PyridoBenzoBenzoBenzoEthylene3,6-Disulfo-1 naphthylamineHexyl21
513,4-PyridoBenzo3,4-PyridoBenzoEthylene3,6,8-Triunfo-1 naphthylamine Methyl11
52Benzo3,4-Pyrido3,4-Pyrido3,4-PyridoEthylene2.5 DesultorilyMethyl01
53Benzo3,4-Pyrido3,4-PyridoBenzoEthylene2.5 DesultorilyMethyl11
543,4-PyridoBenzoBenzoBenzoPropylene2.5 DesultorilyMethyl21
553,4-PyridoBenzo3,4-PyridoBenzoPropylene 2.5 DesultorilyMethyl11
563,4-PyridoBenzo3,4-Pyrido3,4-PyridoPropylene2.5 DesultorilyMethyl01
573,4-PyridoBenzoBenzoBenzoEthylene3,6-Disulfo-8-hydroxy-1-naphthylamineMethyl21
583,4-PyridoBenzoBenzoBenzoEthylene4-Methoxy-2-sulfonanilideMethyl21
593,4-PyridoBenzoBenzoEthylene4-Nitro-2-sulfonanilideMethyl21
603,4-PyridoBenzoBenzoBenzoEthylene2-Chloro-5-sulfonanilideMethyl21
613,4-PyridoBenzoBenzoBenzoEthylene3-Methyl-6-sulfonanilideIsopropyl
623,4-PyridoBenzoBenzoBenzoEthylene2-Carboxy-4-sulfonanilideEthyl21
633,4-PyridoBenzoBenzoEthylene2.5 DicarbocyanineIsopropyl21
643,4-PyridoBenzoBenzoBenzoEthylene3 PostroeniyaIsopropyl21

No.AndInDEXR1bc
653,4-PyridoBenzoBenzoBenzoEthylene2-Hydroxy-3-acetylamino-5-sulfonanilideIsopropyl21
66 3,4-PyridoBenzoBenzoBenzoEthylene4 Ethoxy-6-sulfonanilideIsopropyl21
673,4-PyridoBenzoBenzoBenzoEthylene3,6,8-Triunfo-2-naphthylamineMethyl11
683,4-PyridoBenzoBenzoBenzoEthylene6-Nitro-4,8-disulfo-2-Methyl01
693,4-PyridoBenzoBenzoBenzoEthylene5,7-Disulfo-2-naphthylamineMethyl11/td>
703,4-PyridoBenzoBenzoBenzoEthylene6,8-Disulfo-2-naphthylamineMethyl21
713,4-PyridoBenzoBenzoBenzoEthylene3-carboxy-4-hydroxy-5-sulfonanilideIsopropyl11
723,4-PyridoBenzoBenzoBenzoEthylene3-Methyl-6-methoxy-4-sulfonanilideIsopropyl01
733,4-PyridoBenzoBenzoBenzoEthylene4-Methylsulphonyl-2-Sultani the Ino Methyl21
743,4-PyridoBenzoBenzoBenzoEthylene4-Methylthio-2-sulfonanilideMethyl21
753,4-PyridoBenzoBenzoBenzoEthylene3-Amino-4-sulfonanilideMethyl21
763,4-PyridoBenzoBenzoBenzoEthylene4-Methylamino-5-sulfonanilideMethyl21
773,4-PyridoBenzoBenzoBenzo Ethylene4-Dimethylamino-5-sulfonanilideMethyl21
783,4-PyridoBenzoBenzoBenzoEthylene4-Aminosulfonyl-2-carboxyanilineMethyl21
793,4-PyridoBenzoBenzoBenzoEthylene4-Hexylthio-2-sulfonanilideIsopropyl21
803,4-PyridoBenzoBenzoBenzoEthylene4-Hexylsilane-2-sulfonanilideIsopropyl21

Porphyrazine coloring matter of the present invention can usually use the AMB without mixing with another dye, but in some cases, known as blue dye, and porphyrazine coloring matter of the present invention can be mixed for use in a range not impairing the effects of the present invention.

In the case where the mix both substances, known as blue dye, and porphyrazine coloring matter of the present invention, as a coloring matter for mixing you can use dye-based triphenylmethane or dye based on phthalocyanine, which given the number of QI, and among them, preferably phthalocyanine dye with the number of QI.

Next explained is a method of obtaining porphyrinogen the coloring matter of the present invention represented by the above formula (1).

The coloring matter represented by the above formula (1)may be obtained by reacting compounds of porphyrazine represented by the above formula (2), with an organic amine represented by the above formula (3), in the presence of ammonia.

Connection piperazine represented by the above formula (2)may be obtained by synthesis of the compound (porphyrinogen ring)represented by the following formula (4), and then chlorosulfonylisocyanate this connection is known from the special or method in accordance with this operation.

That is, the compound represented by the following formula (4), can be synthesized by the method in accordance with a known method disclosed, for example, in published international application WO 2007/091631 and publication of the international application WO 2007/116933. In these known literary sources not revealed any ways to get the connection, where the number of nitrogen-containing heterocyclic rings, which rings A to D is less than 1. However, by changing the mixing ratio decarbonisation derived nitrogen-containing heteroaromatic ring, which is used as raw material for interaction, and a derivative of phthalic acid in the synthesis of known nitrile way or method of Wyler is also possible to synthesize the compound represented by formula (4), where the number of nitrogen-containing heteroaromatic ring for the rings A to D is less than 1.

In this respect, as described in the above well-known literary sources, the obtained compound represented by the formula (4)will be a mixture of positional isomers in relation to the position of substitution of the nitrogen-containing heteroaromatic ring for the rings A to D and the position of substitution of the nitrogen atom in the nitrogen-containing heteroaromatic ring.

where the rings A to D are the same values that the La of the above formula (1).

The method of synthesis porphyrinogen compounds represented by formula (2)described in a publication of the international application, which describes a method for the synthesis of compounds represented by the above formula (4). By chlorosulfonylisocyanate compounds represented by formula (4), in accordance with a known method or a method in accordance with this work, can be obtained compound of the formula (2). Chlorosulfonyl group in the formula (2) to impose on the benzene ring for the rings A to D, and not on the nitrogen-containing heteroaromatic ring for the rings A to d is Usually one chlorosulfonyl group introduced on the benzene ring, so the number n in the formula (2) is within the number of benzene rings of rings A-D. Therefore, the number "n" chlorosulfonyl groups in the formula (2) is, in accordance with the number of benzene rings connection piperazine represented by the formula (2), 1.00 or more and less than 4,00, preferably 2.0 or more and 3.8 or less more preferably 2.25 or more and 3.5 or less and even more preferably 2.5 or more and 3.25 or less.

The method of synthesis of compounds of piperazine represented by the formula (2)includes other than the described above method, where the connection porphyrazine with alphagroup, synthesized by the cyclocondensation sulfophthalic acid decarbonisation derivative of the nitrogen-containing heteroa the case of rings, such as quinolinic acid (pyridine-2,3-dicarboxylic acid) and Tikhomirova acid (pyridine-3,4-dicarboxylic acid), followed by conversion of the specified sulfopropyl in chlorosulfonyl group using a suitable glorieuses agent such as thionyl chloride. In this case, by selecting sulfophthalic acid, where the position of substitution of sulfopropyl is a 3-position, and sulfophthalic acid, where the position of substitution of sulfopropyl is a 4-position, as raw material for the synthesis is possible to adjust the position of substitution of sulfopropyl placed on the connection of piperazine represented by the formula (2). That is, there can be obtained a compound of porphyrazine where alphagraph selectively substituted in the alpha-position in the formula below (5) when using 3-sulfophthalic acid or beta-position in the formula below (5) when using the 4-sulfophthalic acid, respectively. In this regard, in the present invention, the term "alpha-position porphyrinogen rings" or "beta-position porphyrinogen ring" means the relevant provision of the following formula (5), unless specifically stated otherwise

In addition, as described above, the connection with Deputy selectively to the alpha-is ogenyi or beta position, or a mixture of compounds having the substituent in the alpha-position, and compounds having a substituent in the beta-position, can be easily obtained separately using this method of synthesis. By selecting the position of Deputy or Vice versa, by obtaining a mixture of positional isomers of substituents in some cases receive the dye with a different balance of physical properties, color, properties, durability and the like.

Therefore preferably also carried out obtaining the coloring matter separately in accordance with the purpose.

On the other hand, the organic amine represented by the above formula (3)can also be obtained in a known manner.

For example, from 5 to 60 mol of the alcohol corresponding to R11 mol of 2,4,6-trichloro-8-triazine (cyanuric chloride, the acid chloride cyanuric acid) and from 0.8 to 1.2 mol of sodium bicarbonate are interaction terms from 5 to 70°C for 1 to 12 hours from the receipt of the first condensate. The first condensate can be separated by filtration allocation in the form of a wet sludge.

Then the reaction liquid or wet sediment above the first condensate is added to aqueous solution of from 0.9 to 1.5 mol of substituted aniline or substituted naphtylamine, corresponding to X, the reaction liquid was adjusted to a pH of from about 4 to 10 hydroxide selecing the metal, such as sodium hydroxide, and interact under conditions of reaction temperature from 5°to 80 ° C for from 0.5 to 12 hours to obtain a second condensate.

One mole of the received second condensate and from 1 to 50 mol alkylenediamine corresponding to E, is subjected to the interaction in the conditions of a pH of about 5 to 12 and the reaction temperature is from 5 to 90°C for from 0.5 to 12 hours to obtain an organic amine represented by the above formula (3).

To regulate the pH of each reaction condensation usually use an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide, a carbonate of an alkali metal such as sodium carbonate and potassium carbonate, or the like. In this regard, good to the order of condensation was appropriately decided in accordance with the reactivity of each type of connection to be condensed with the acid chloride cyanuric acid, and it is not limited to the above order.

The interaction of compounds piperazine represented by the above formula (2), with an organic amine represented by the above formula (3), carried out by reacting in the presence of ammonia in an aqueous solvent, under conditions of pH from about 8 to 10 and the reaction temperature is from 5 to 70°C for 1 to 20 hours. This reaction gives porphyry target the new coloring matter of the present invention, represented by formula (1).

As ammonia is used for the above reaction, it is possible to use an aqueous solution of ammonia and chemical substance called ammonia by neutralization or decomposition (both of these substances together called "aminimum agent"). Miniraise agent used in the above reaction includes, for example, the connection form by neutralizing ammonia, such as ammonium salt is ammonium chloride, ammonium sulfate and the like; a compound that forms ammonia by thermal decomposition, such as urea; ammonia gas or aqueous ammonia; and the like. However, it is not limited to this. Miniraise agent used in the above reaction is preferably an aqueous solution of ammonia. When used in the above reaction it is possible to use a concentrated solution of ammonia in water, available in a commercial product (usually commercially available as aqueous ammonia with a concentration of about 28%), or diluent, where it is diluted with water if necessary.

The amount used of the organic amine represented by the above formula (3), is usually the amount equivalent to or more excess compared with the number corresponding to theoretical value [vicis the military to the number of mol of an organic amine, represented by the above formula (3), which is required to obtain values in the target Crusades the substance represented by the above formula (1)], relative to 1 mol of compound of piperazine represented by the above formula (2). However, the amount used of the organic amine varies depending on the reactivity of the organic amine and the reaction conditions that you want to use, and is not limited to this number.

The amount used of the organic amine is usually approximately molar equivalent, corresponding to 1-3 times, preferably molar equivalent corresponding to 1 to 2 times above theoretical value. That is, the amount used of the organic amine is approximately 1-3 times the value, preferably 1-2-fold molar equivalent relative to 1 mol of compound of piperazine represented by the above formula (2).

In addition, porphyrazine coloring matter of the present invention represented by the above formula (1), synthesized from the compounds represented by the above formula (2) and formula (3), under the reaction conditions, does not require anhydrous conditions and preferably synthesized using an aqueous solvent. In this regard, in theory we can assume that soy is inania, where some of chlorosulfonyl groups in the formula (2) are subjected to hydrolysis with water, mixed in the reaction system, and converted into sulfonic acid, forming a by-product, and as a result, this by-product is mixed with the target dye represented by formula (1).

However, it is difficult to make a distinction between unsubstituted sulfamoyl group and sulfopropyl on mass spectrometry, and in the present invention all chlorosulfonyl group in the formula (2), which is not reacted with an organic amine represented by the formula (3), describe as converted into unsubstituted sulfamoyl group.

In addition, during the reaction is a very small amount of dimer (for example, Pz-L-Pz) or trimmer, where copper porphyrazine ring (Pz) are linked through a divalent linking group (L), and sometimes they are mixed in an admixture with the coloring matter represented by the above formula (1).

The above divalent linking group represented by L includes-SO2-, -SO2-NH-SO2and the like, and in the case of the trimer sometimes forms a by-product, containing two groups of L.

Porphyrazine coloring matter of the present invention, obtained as described above, it is possible to allocate in the form of solid substances is and by separation by filtration or similar methods for separating solids, precipitated by acid deposition, vysalivaniya or the like from the reaction liquid of the last steps in the synthesis reaction. Salting out is preferably carried out in the interval, for example, from acid to alkaline conditions, preferably pH 1 to 11. The salting out temperature is not specifically limited, but usually ranges from 40 to 80°C., preferably from 50 to 70°C. Specifically, the salting out is preferably carried out by heating the reaction liquid containing porphyrazine coloring matter of the present invention, to the above-described temperature followed by the addition of sodium chloride or the like to bring the pH to the above range.

Porphyrazine coloring matter of the present invention, synthesized as described above is obtained in the form of a free acid or a salt thereof. The way to select the coloring matter in the form of the free acid includes, for example, the deposition of acid. On the other hand, the allocation method in the form of salts can be done by vysalivaniya. If desired salt is obtained by vysalivaniya, target salt can be obtained, for example, in a known manner of exchange of salts or the like, such as method, where the resulting salt is converted into the free acid, and then add the desired organic or inorganic base.

Further on is the Isan composition of the ink (ink) of the present invention.

The paint composition of the present invention is characterized by the content porphyrinogen the coloring matter of the present invention represented by the above formula (1). The paint composition of the present invention can be obtained by dissolving or dispersing porphyrinogen the coloring matter of the present invention represented by the above formula (1), in a solvent. Thus, the paint composition of the present invention contains porphyrazine coloring matter of the present invention and a solvent, and if necessary, it may further contain an additive, such as an agent for paint preparation. The solvent may be any organic solvent and water or a mixed solvent of both.

Porphyrazine dye of formula (1) in the present invention has a high solubility, so it is preferably dissolved in water to obtain the composition of water-based paints essentially in solution. Porphyrazine coloring matter of the present invention exhibits a bright blue color, so the composition of the paints containing this dye can be used as a blue dye. The composition of the paints containing porphyrazine dye on the present and the finding, can be used not only as a cyan ink having a high concentration of the coloring matter, but also a blue ink having a low concentration of the coloring matter (called light blue paint, photographic blue paint or the like)that can be used to gently play tint of the image or to reduce the phenomenon of grain hypochromic area. In addition, it can be used as a green dye by mixing with yellow dye and as purple or blue ink by mixing with purple dye. It is also possible to use it as each color from dark yellow, grey or black by additional mixing multiple colors to get the colors.

When the paint composition of the present invention is used as the ink (ink for inkjet recording, the preferred paint composition of the present invention, having a lower content of anions, such as CL-,and the like contained as impurities in porfirinova Crusades the substance of the present invention. As for the content of anions, only as a guide, the total content of CL-anda total mass of the coloring matter with the hat 5% wt./mass. or less, preferably 3 wt. -%/mass. or less and even more preferably 1% wt./mass. or less. In addition, it is preferable that the content of anions in this way was less in the composition of the ink, and the content of anions is preferably 1% wt./mass. or less relative to the total weight of the composition of the paint. The lower limit may be the detection limit or less of the apparatus for detection, specifically 0%, more preferably.

With the aim of obtaining porphyrinogen the coloring matter of the present invention, containing a smaller number of Cl-andyou can desalting treatment, for example, in the usual way, using the reverse osmosis membrane; a method where the dried form or wet sediment porphyrinogen the coloring matter of the present invention is suspended in an aqueous organic solvent, preferably in an aqueous alcohol, and stirred; or similar.

The alcohol used for the above-described aqueous alcohol, includes With1-C4alcohol, preferably1-C3alcohol, more preferably methanol, ethanol, n-propanol or 2-propanol. For desalting, you can also use the method, when using aqueous alcohol, a suspension, in which the suspended dye desirable to about what Scrivania, heated nearly to its boiling point and then cooled.

It is also possible to porphyrazine coloring matter of the present invention, subjected to desalting treatment in aqueous alcohol, can be dried after separation by filtration to obtain in the form of coloring matter in the dried state.

The content of CL-andin Crusader substance is measured, for example, by ion chromatography.

When the composition of the ink (ink) of the present invention is used for applying ink-jet recording, the content of impurities such as heavy metals, such as zinc and iron ions, such as calcium, silica and the like other than the above CL-andalso is preferably smaller.

However porphyrazine coloring matter of the present invention has a Central metal, linked by ionic bonding, coordination and the like, and forms a complex with copper, so that the Central metal not included in the admixture.

Only as guidance for the above impurity content, each of the heavy metals such as zinc and iron ions, such as calcium, silica and the like, dried and purified drug porphyrinogen the coloring matter is preferably PR is approximately 500‰ or less. The lower limit of the content of an impurity may be the detection limit or less analytical equipment, specifically 0‰.

The content of heavy metal ions and the like can be measured using ion chromatography, atomic desorption or emission spectrometry ICP (inductively coupled plasma).

The paint composition of the present invention contains from 0.1 to 8 wt. -%/mass., preferably from 0.3 to 6 wt. -%/mass. porphyrinogen the coloring matter of the present invention represented by the above formula (1), where else is a solvent for paint preparation. The paint composition of the present invention preferably is a composition of water-based paints containing water as a solvent for paint preparation. The water content in this case is from 92 to 99.9% wt./mass., preferably from 94 to 99.7% of mass./mass. relative to the total amount of the composition of the paint.

Composition of water-based paints of the present invention may further contain, if necessary, water-soluble organic solvent and the agent for paint preparation within the interval, not violating the effects of the invention. Usually the paint composition of the present invention more preferably contains them.

In some of the s cases, water-soluble organic solvent also has the function of dissolving the dye, prevent drying (moistening), modification of viscosity, increasing permeability, modification of the surface tension, defoaming and/or the like. The paint composition of the present invention more preferably contains a water-soluble organic solvent.

Agent for paint preparation includes, for example, an antiseptic and fungicide, a pH regulator, a chelating agent, a corrosion inhibitor, an agent absorbing UV light, a viscosity modifier agent, solvent dye, a fading inhibitor, emulsion stabilizer, a surface tension modifier, defoamer, dispersant, dispersion stabilizer and the like. They can be added to the paint composition of the present invention if necessary.

The paint composition of the present invention preferably further comprises a substance other than the dye of the present invention and water, from 0 to 60 wt. -%/mass., preferably from 10 to 50 wt%./mass. and more preferably from 10 to 30% wt./mass. the above water-soluble organic solvent and from 0 to 20 wt. -%/mass., preferably from 0 to 15% wt./mass. the above agent for paint preparation, respectively, relative to the total weight of the paint composition of the present invention. The rest, other than water-soluble organic the cue solvent, agent for paint preparation and porphyrazine coloring matter of the present invention, is water.

The coloring matter of the present invention, used in the paint composition of the present invention may be any dye included in the dye or its salt represented by the formula (1), and the most preferred paint, which is used porphyrazine dye or its salt according to any of the above 2)-8), 18), 19) and (i)to(x).

The above water-soluble organic solvent includes, for example, C1-C4alcohol, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, Isobutanol, secondary butanol or tertiary butanol; carboxylic acid amide, such as N,N-dimethylformamide or N,N-dimethylacetamide; heterocyclic ketone such as 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexylamine-2-he; ketone or cytosport, such as acetone, methyl ethyl ketone or 2-methyl-2-hydroxypentanal-4-one;

cyclic ether, such as tetrahydrofuran or dioxane; mono-, oligo - or polyalkyleneglycol or thioglycol with C2-C6alkylene link, such as ethylene glycol, 1,2 - or 1,3-propylene glycol, 1,2 - or 1,4-butyleneglycol, 1,6-hexyleneglycol, diethylene glycol, createlang the Col, tetraethylene glycol, dipropyleneglycol, thiodiglycol, polyethylene glycol or polypropyleneglycol; polyol (preferably a triol, such as glycerol or hexane-1,2,6-triol; C1-C4monoalkylated a polyhydric alcohol such as ethylene glycol onomatology ether, ethylene glycol monotropy ether, diethylene glycol onomatology ether, diethylene monotropy ether, diethylene glycol monobutyl ether (butylcarbamoyl), triethylene glycol onomatology ether or triethylene glycol monotropy ether; γ-butyrolactone; dimethylsulfoxide; and the like.

As the above water-soluble organic solvent is preferred isopropanol, glycerol, mono-, di - or triethylene glycol, dipropyleneglycol, 2-pyrrolidone, N-methyl-2-pyrrolidone and butylcarbamoyl, and more preferably isopropanol, glycerol, diethylene glycol, N-methyl-2-pyrrolidone, 2-pyrrolidone and butylcarbamoyl.

These water-soluble organic solvents are used individually or as a mixture.

Antiseptic and fungicide includes, for example, compounds in sulfur-based, nitrogen-containing organic base, on halogenorganics basis, on the basis of halogenosilanes, based iodopropargyl, based on N-halogenoacetyl, based on benzotriazole, based on the nitrile-based, pyridine-based 8-oxii the oline, based on isothiazoline, on the basis of a dithiol-based pyridinoline, on the basis of nitropropane, ORGANOTIN basis, on the basis of phenol, based on the Quaternary ammonium salt, based on the triazine-based thiadiazine, based on anilide, based on adamantane, based on dithiocarbamate, on the basis of the brominated indanone-based benzylbromide, on the basis of inorganic salts and the like.

The connection on halogenorganics the base includes, for example, pentachlorophenol sodium. Connection-based pyridinoline includes, for example, sodium 2-pyridinethiol-1-oxide. The connection on the basis of isothiazoline includes, for example, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride and the like.

Specific examples of the antiseptic and fungicide include sodium sorbate, sodium benzoate, sodium acetate and the like, and their commercial products include, for example, ProxelRTMGXL(S), ProxelRTMXL-2(S) (trade names) and the like, manufactured by Arch Chemicals, Inc.

In this regard, in the present description Superscript "RTM" is a registered trademark.

As the pH regulator can be used arbitrarily the substance, if it can adjust the pH of the ink in the range from 6.0 to 11.0 to improve stability during storage. For example, it includes alkanolamine, such as diethanolamine and triethanolamine; alkali metal hydroxide such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonium hydroxide (aqueous ammonia); carbonate of an alkali metal such as lithium carbonate, sodium carbonate and potassium carbonate; aminosulfonic acid such as taurine; or the like.

Chelating agent includes, for example, disodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium brazilianite and the like.

The corrosion inhibitor includes, for example, salt hydrosulfite, sodium thiosulfate, thioglycolate ammonium, Diisopropylamine nitrite, pentaerythritol TETRANITRATE, dicyclohexylammonium nitrite and the like.

Agent absorbing UV light, includes, for example, a connection based on benzophenone, connection-based benzotriazole, the connection on the basis of cinnamic acid, a compound based on triazine, a compound based on stilbene and the like. In addition, you can use the connection, absorbing ultraviolet rays and emitting fluorescence, typical representative of which is the connection on the Nove of benzoxazole, the so-called fluorescent whitening agent.

The viscosity modifier comprises a water-soluble polymer compound such as polyvinyl alcohol, a derivative of cellulose, polyamine, polyimid and the like.

Agent, a solvent dye includes, for example, urea, Epsilon-caprolactam, ethylene carbonate resulting and the like.

The fading inhibitor used to improve the stability during storage of images. As an inhibitor of fading, you can use various fading inhibitors based on organic and metal complexes. Organic fading inhibitor include hydrochinone, alkoxyphenyl, dialkoxybenzene, phenols, anilines, amines, indāni, chromane, alkoxysilane, heterocycles and the like. The metal complexes include Nickel complex, a complex of zinc and the like.

The surface tension modifier comprises a surfactant, for example, anionic surfactant, amphoteric surfactant, cationic surfactant, nonionic surfactant, and the like.

The anionic surfactant includes alkylcarboxylic, alpha reincorporate, polyoxyethylenesorbitan acetate, N-acylaminoacyl and its salt, salt N-arylmethylidene, alkylmethacrylamide sulfate, alkylchlorosilanes phosphate, soap rosin acid, sulfate, Castoro the CSOs oil, sulfate lauric alcohol, ether phosphate ALKYLPHENOLS type, ether alkyl phosphate type, alkylarylsulfonate, diethylsulfoxide, diethylhexylphthalate, dioctylsulfosuccinate and the like.

The cationic surfactant includes derivatives of 2-vinylpyridine) - derivatives, derivatives of poly(4-vinylpyridine) - derivatives), and the like.

The amphoteric surfactant includes lauryldimethylamine acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxymethylimidazole betaine, amide fatty acids of coconut oil, propyltrimethylammonium acid betaine, polyacrylonitrile and, in addition, imidazoline derivatives and the like.

The nonionic surfactant includes a surfactant on the basis of simple ether, such as polyoxyethyleneglycol ether, polyoxyethyleneglycol ether, polyoxyethyleneglycol ether, polyoxyethyleneglycol ether, polyoxyethyleneglycol ether and polyoxyethyleneglycol ether; surfactant-based complex ester such as an ester of polyoxyethylene, ester polyoxyethylenated, corbicular, servicemonitor, servicemanual, servicesecurity, polyoxyethylenated, polyoxyethylenated and the like; a surfactant based on the acetylene alcohol such as 2,4,7,9-tetramethyl-5-Decin-4,7-diol, 3,6-dimethyl-4-octyn-3,6-diol and 3,5-dimethyl-1-Gex is h-3-ol (for example, SurfynolRTM104, 82 and 465, OlfineRTMSTG and the like, produced Nissin Chemical Industry Co., Ltd.); and the like.

As antifoam you can use this highly oxidised compounds oil-based, connection-based esters of glycerol and fatty acids, on the basis of fluorine-based and silicone if necessary.

These agents for the preparation of paint used individually or as mixtures thereof. In this respect, the surface tension of the ink of the present invention typically ranges from 25 to 70 mn/m, preferably from 25 to 60 mn/m, the Viscosity of the ink of the present invention preferably modify up to 30 MPa·s or less, more preferably 20 MPa·s or less.

Upon receipt of a paint composition of the present invention, the order of dissolution of each component, which must be contained in it, is not specifically limited. Water for use in the preparation of the paint composition preferably is a water with a lower content of impurities such as metal ions and the like, such as ion exchange water, distilled water or the like. In addition, foreign substances can be removed by microfiltration using a membrane filter or the like if necessary, and when used as an ink (ink for ink jet recording is preferably avodat the microfiltration. The pore size of the filter for microfiltration is usually from 1 μm to 0.1 μm, preferably from 0.8 μm to 0.1 μm.

The paint composition of the present invention can be used not only for forming monochrome images, but also for forming a full color image. When forming a full color image, it is used to set the colors of the 3 primary colors with purple paint and yellow paint, and to set the colors of the 4 colors, where to this additionally added black color. In addition, for forming high-resolution images, it is also used for a set of colors by using light Magenta ink, blue ink, green ink, orange ink, dark yellow paint, gray paint, and the like in combination. Dye used for each color used in the paint sets by applying the paint composition of the present invention in combination, includes the known dye of each color.

Known yellow dye includes, for example, the coloring matter on azo-based, containing aryl and/or heteroaryl; dye-based Metin, such as benzylidene dye and monoaminoxidase dye; dye-based quinone, such as nattokinese dye and antrahinonove dye; dye-based chieftan; dye nitro-nitroso basis; dye on acridine-based; dye on acridinone basis; and the like.

Famous purple dye includes, for example, the coloring matter on azo-based, containing aryl and/or heteroaryl; dye-based h; dye-based Metin, such as arylidene dye steriline dye merocyanine dye, cyanine dye and oksanalove dye; dye-based Carbonia, such as diphenylmethane dye triphenylmethane dye and xanthene dye; dye-based quinone, such as naphthoquinone, anthraquinone and intraperitone; dye-based condensed political, such as dioxazine dye; and the like.

Famous black dye includes dye on azo-based, such as diazo, triazo or tetraaza; sulphur dye; the dispersion of carbon black; and the like.

The paint composition of the present invention can be used in various applications for printing, such as printing sheets, copying, marking, writing, drawing and stamping, and she CCA is i.i.d. suitable for inkjet recording.

Inkjet recording method of the present invention is a method, where the droplets of the ink composition of the ink of the present invention, for example a paint composition containing porphyrazine dye of formula (1) or its salt, preferably a paint composition, optionally containing water and a water-soluble organic solvent emitted in response to the print signal, and it is attached to the receiving material to record to record. The image formed by this method of recording has excellent hue, has excellent properties of resistance, in particular, such as ozone resistance, moisture resistance and the like, and does not cause the effect of bronze shimmer.

For ejection of drops of ink energy can be fed to the above-described composition of the ink in response to a print signal, and as the ejection of drops of ink can be applied to various systems described in the Prior art.

The above receiving the recording medium may include plain paper, paper, polymer-coated special paper for inkjet printers, glossy paper, glossy film, paper for Electrophotography, fiber/textiles, fabric (such as cellulose, nylon and wool), glass, metal, ceramics, leather or the like.

If which is the training image by ink jet recording method of the dispersion of polymer particles (also called polymer latex) can be used to make the image glossiness and water resistance, or improve pogodnosti. This polymer latex can be applied to the receiving material for the recording or pre-mix composition of the paint.

Periodization, when a polymer latex serves for receiving the recording medium, may be the previous, subsequent or simultaneous with the application of paint on the receiving material for the record.

Specifically, the recording can be done on the receiving material to record, containing pre-polymer latex paint composition of the present invention, or the recording can be done on the receiving material to write a paint composition of the present invention, containing pre-polymer latex. Otherwise, the receiving surface of the recording medium can be processed liquid polymer latex in the liquid state before or after fixation on the receiving material to write a paint composition according to the present invention.

The painted object of the present invention means a material, painted piperazinonyl dye of the present invention or the composition of the inks according to the present invention containing this substance. The material that should be painted, not specifically limited, but includes, for example, reference sheet, such as paper or film, fiber/textile and fabric (such as cellulose, nylon and wool), leather is, the substrate for a color filter and the like. The material that should be painted, preferably represents a reference sheet.

As described above, the reference sheet is the preferred sheet subjected to surface treatment, specifically the sheet, where the receiving layer for the coloring matter on the substrate, such as paper, synthetic paper, film or the like. The receiving layer for the coloring matter receive, for example, by the way, where cationic polymer impregnated or covered above the substrate; a method where the surface of the above substrate to cover the inorganic particles (inorganic particles of white pigment, can absorb the coloring matter in the ink, such as porous silica, alumetal and special ceramics, together with a hydrophilic polymer such as polyvinyl alcohol and polyvinylpyrrolidone, or the like.

Informational sheet provided with such a receiving layer for ink, usually referred to as paper (film) special purpose for inkjet recording, glossy paper (film) or the like.

Typical examples of the above special paper for inkjet recording, commercially available, are Glossy photo paper Pro Platinum Grade" and the photo paper Glossy Gold, izge tableviii firm Canon Inc.; photo CR1SP1A (high-gloss), photo paper (glossy and matte photo paper, manufactured by company Seiko Epson Corporation; Advance photo paper (glossy)manufactured by Hewlett Packard Japan, Ltd.; glossy Premium Plus photo paper, manufactured by company Brother Industries, Ltd.; and the like, where all of these names are trade names.

It should be note that the image recorded on paper for special purposes, such as to a surface of a substrate coated with the above-described inorganic particles, can easily withstand the harmful effects of gas having an oxidizing effect in the air, such as ozone gas. Porphyrazine coloring matter of the present invention or the composition of the ink of the present invention, containing, exhibits excellent ozone resistance, even when the recording is carried out on such a special paper for inkjet recording.

In addition, of course, the paint composition of the present invention can also be used for recording on plain paper. Simple paper, in particular, includes RV PAPER GF500, produced by company Canon Inc.; plain paper double-sided high quality, produced by company Seiko Epson Corporation; and the like.

The application of the paint composition of the present invention is not limited to account for these professional papers, about what that paper and the like.

For the purpose of recording on the above-described receiving the recording medium by an inkjet recording method of the present invention, for example, a container containing the above composition of the paint, can be placed in a predetermined position of an inkjet printer, and the recording can be done by the above described recording method.

An inkjet printer includes, for example, the printer piezosystem using mechanical vibration; printing with bubble jet system printing "Bubble Jet"RTCusing the foam formed by heating; and the like. However, the paint composition of the present invention is not limited in the application of these systems release, and it can be used in the printer of any system.

The paint composition of the present invention is free from precipitation or separation during storage. In addition, when the composition of the ink used for inkjet recording, it also does not cause blockage in the injector (head inkjet printer). The paint composition of the present invention there is also no change in physical properties when recording over a relatively long hours, and constant recirculation continuous inkjet printer; when the periodic recording by the printer without waiting; or the like.

Composition of paints containing porphyrazine dye for this is th invention, it has a bright blue color, has excellent hue as a cyan ink, and has no deposition of solids, no changes in physical properties, no color change or the like after storage for a long period of time, and thus it has good storage stability. The recorded image obtained by the composition of the ink of the present invention, has a high print density and makes it possible to reduce the concentration of the coloring matter in print, therefore, has an industrial advantage, such as cost reduction. In addition, it allows various properties of the resistance of the recorded image, such as light fastness, water resistance, ozone resistance, moisture resistance and the like, particularly ozone resistance and moisture resistance, and almost does not cause the effect of a bronze tint, providing, thus, a high-quality image.

In addition, the color tone in a wide visible region can be expressed by using each of its dark and light blue paint, and, in addition, in combination with paint yellow and/or Magenta, and optionally with other paint green, red, orange, blue, and/or the like.

So porphyrazine coloring prophetic the ETS according to the present invention and the composition of the paint, contains very useful as a blue coloring matter and blue ink for inkjet recording.

INFORMATION CONFIRMING the POSSIBILITY of carrying out the INVENTION

Examples

Further, the present invention is more specifically explained with reference to Examples. In this regard, "part(s)" and "%" in the context based on weight, unless otherwise indicated. In addition, each operation, such as interaction, crystallization, purification and the like, is conducted under stirring, unless specifically noted otherwise. "LEOCOLRTMTD-90", which is a trading name used in the synthesis reaction, is a surfactant, manufactured by the firm Lion Corporation.

In this respect, all the coloring matter represented by the above formula (1)synthesized in the Examples are mixtures containing isomers and the like, as described above. Therefore, in the structural formula in each Example, the Deputy on porfirinova ring specifically shown structural formula, and, unless specifically noted otherwise, the ring from the ring And the ring D porphyrinogen ring shown in broken lines, and the number of substituents on porfirinova ring, n, b, and C, as shown by these characters. In addition, a specific number of nitrogen-containing heterocyclic ring, the benzene rings b and C, described in each Example and each output description the n as one connection, with these numbers, including the isomers, and the like. In addition, unless specifically noted otherwise, the coloring matter of the present invention is a mixture, where unsubstituted Altamarena group and substituted Altamarena group each independently substituted in the alpha-position and β-position porphyrinogen ring in the ratio of b and C. the Dye of the present invention synthesized in each Example, consider as a mixture, containing nearly the same amount of product substitution in alpha-position and product substitution beta-position, with the exception of Examples 14 and 15.

The maximum absorption wavelength (λmaxeach porphyrinogen coloring substance for the present invention and for comparison obtained in the Examples described as the value measured in aqueous solution of pH 7-9. To bring the pH in this case, use an aqueous solution of sodium hydroxide.

The number of benzene rings and 6-membered nitrogen-containing heteroaromatic ring for the rings A to D and b and described in the form of numbers to the second decimal place by rounding to the third decimal place. These values of b and C can be determined by measuring the copper content using emission spectrometry ICP, using the target compound in the sample, measurement of water content using the method of the Karl Fischer and measurement of the content of inorganic impurities (ions, such as sodium, potassium and chlorine) using ion chromatography.

In this regard, any of the synthesized porphyrinoid dyes of the present invention showed an extremely high solubility of 10% wt./mass. or more relative to the total mass of the aqueous solution.

In each synthesis reaction, when the required quantity of each target compound or the like was not obtained for one synthesis, the same or similar operation is repeated to obtain the necessary number.

Example 1

(Stage 1)

The synthesis of compounds represented by the following formula (4), where 1.37 rings A to D are pyridine rings fused at the 2 - and 3-position, and the rest 2,63 represent a benzene ring

375 parts of sulfolane was added 29,16 parts of phthalic anhydride, 17,23 parts of quinolinic acid, 108 parts of urea, a 10.1 parts of copper chloride (II) and 1.5 parts of ammonium molybdate. The liquid temperature was raised to 200°C., and the reaction liquid was maintained at this temperature for 5 hours. After completion of the reaction, the reaction liquid was cooled to 65°C., thereto was added 50 parts of DMF (N,N-dimethylformamide), and the precipitated solid substance was separated by filtration. The obtained solid is washed with 50 parts of DMF to obtain 75,1 frequent the wet sludge. The obtained wet sediment was added to 450 parts of DMF, the liquid temperature was raised to 110°C and maintained at this temperature for one hour. A solid substance was separated by filtration, washed with 200 parts of water to obtain a wet sludge. The obtained wet sediment was added to 450 parts of 5% hydrochloric acid, and the liquid temperature was raised to 60°C. and maintained at this temperature for 1 hour. A solid substance was separated by filtration and washed with 200 parts of water to obtain a wet sludge. The obtained wet sediment was added to 450 parts of 5% aqueous ammonia solution, the liquid temperature was raised to 60°C. and maintained at this temperature for 1 hour. A solid substance was separated by filtration and washed with 200 parts of water with obtaining 78,6 part of the wet sludge. The obtained wet precipitate was dried at 80°C To produce 23,1 part of the above target compound in the form of a blue solid.

(Stage 2)

The synthesis of compounds represented by the following formula (2), where 1.37 rings A to D are pyridine rings fused at the 2 - and 3-position, and the rest 2,63 represent a benzene ring, and n is 2,63

To of 46.2 parts of chlorosulfonic acid was added to 5.8 parts of the compound of the above formula (4)obtained in Example 1 (Stud is I 1) so gradually, to ensure that the temperature did not exceed 60°C and then the reaction liquid was maintained at 140°C for 4 hours. After the reaction liquid was cooled to 70°C., was added dropwise to 17.9 parts of thionyl chloride for 30 minutes, and the reaction was conducted further at 70°C for 3 hours. The reaction liquid was cooled to 30°C or less and slowly poured into 800 parts of ice water. The precipitated solid was separated by filtration and washed with 200 parts of cold water to obtain 33.0 parts of wet sediment target compound represented by the above formula (2).

(Stage 3)

The synthesis of the organic amine represented by the following formula (6) [organic amine of the above formula (3), where E represents ethylene, X represents a 2.5 desultorily, and R1represents a methyl]

To 160 parts of methanol was added to 36.8 parts of the acid chloride cyanuric acid, 4 parts of LEOCOLRTMTD-90 (trade name) and 16.8 parts of sodium bicarbonate, and the reaction was carried out at 30°C or less within 1 hour, obtaining a reaction liquid containing the first condensate.

To 280 parts of water was added to 56.1 parts of 2,5-desultorily and additionally were added 32 parts of 25% aqueous sodium hydroxide solution to bring the pH of this fluid to 3-5. To this liquid gradually on balali liquid, containing the first condensate obtained as described above, and bringing the pH to 6-7 by addition of 25% aqueous sodium hydroxide solution the reaction was carried out overnight at room temperature with obtaining a reaction liquid containing a second condensate.

To the resulting reaction liquid was added to 360 parts of hydrochloric acid and 125 parts of ice, the reaction liquid was cooled to 0°C and added dropwise to 120 parts of ethylene diamine. When communicating to pH 5-6 by addition of 25% aqueous solution of sodium hydroxide to the resulting liquid reaction was carried out at 80°C for 2.5 hours with obtaining a reaction liquid containing a third condensate.

To this reaction liquid was added 55 parts of hydrochloric acid to bring the pH of the reaction liquid to 1.0. The volume of liquid at this time was 1000 parts. To the resulting liquid was added 200 parts of sodium chloride, and the liquid was stirred for 30 minutes with the deposition of solids. The precipitated solid was separated by filtration to obtain 183 parts of wet sediment. The obtained wet sediment was added to 1000 parts of water was added 25% aqueous solution of sodium hydroxide to reach a pH of 9.0. To this solution was added 55 parts of hydrochloric acid to reach a pH of 1.0. At this time, the volume of liquid was 1400 parts. To this liquid is added 280 parts of sodium chloride, and this liquid was stirred at room temperature for 30 minutes and then at 0°C for 30 minutes. The precipitated solid was separated by filtration to obtain 60 parts of wet sediment. To a mixed liquid of 224 parts of methanol and 56 parts of water was added to the obtained wet precipitate, and the liquid was stirred at 50°C for 1 hour. Then the solid substance was separated by filtration to obtain 51,3 part of the wet sludge. The obtained wet precipitate was dried to obtain 37,0 parts of white powder target organic amine represented by the above formula (6).

(Stage 4)

Synthesis porphyrinogen the coloring matter of the present invention represented by the following formula (7) [coloring matter of the above formula (1), where 1.37 rings A to D are pyridine rings fused at the 2 - and 3-position, the remaining 2,63 represent a benzene ring, E represents ethylene, X represents a 2.5 desultorily, R1represents methyl, b is equal to 1.83, and is 0.8]

To 120 parts of ice water was added 33,0 part of the wet sludge compounds represented by the above formula (2)obtained in Example 1 (stage 2), and the mixture was suspended by stirring at 5°C or less. Ten minutes later, support the living liquid at a temperature of 10°C or less, to this suspension was added to the solution, dissolving 3,3 part of the organic amine represented by the above formula (6), in a mixed liquid of 1 part of 28% aqueous ammonia solution and 40 parts of water. Then the reaction was carried out, maintaining the suspension at a pH of 9.0 28% aqueous ammonia solution. While maintaining the pH of the suspension liquid temperature was raised to 20°C for 1 hour, and the reaction was conducted further at this temperature for 8 hours. Liquid volume of the reaction liquid at this time was 200 parts. The temperature of the reaction liquid was raised to 50°C., was added thereto to 28.5 parts of sodium chloride, and the mixture was stirred for 30 minutes. Then added concentrated hydrochloric acid for 20 minutes to bring the pH of this reaction liquid to 1.0. The precipitated solid was separated by filtration and washed with 100 parts of 10% aqueous solution of sodium chloride with getting 62,3 part of the wet sludge.

The obtained wet sediment was added to 200 parts of water, and thereto was added 25% aqueous solution of sodium hydroxide to bring the pH to 9.0, resulting in the wet precipitate was dissolved. The volume of liquid at this time was 275 parts. The temperature of this solution was raised to 50°C., it was added to 22.5 parts of sodium chloride, and the solution was stirred for 30 minutes. Then added concentrated hydrochloric acid for 0 minutes to bring the pH of this reaction liquid to 1.0, and the precipitated solid substance was separated by filtration and washed with 100 parts of 10% aqueous solution of sodium chloride with getting 37,1 part of the wet sludge. The obtained wet sediment was added to a mixed liquid of 160 parts of ethanol and 40 parts of water, and this liquid was stirred at 50°C for 1 hour. Then the solid was separated by filtration to obtain 32.0 parts of wet sediment. The obtained wet precipitate was dried to obtain 10.0 parts of free acid, the coloring matter of the present invention represented by the above formula (7), in the form of a blue powder.

λmax: 600 nm.

Example 2

(Stage 1)

The synthesis of compounds represented by the above formula (4), where 1.00 rings A to D is a pyridine ring fused at the 2 - and 3-position, and the rest of 3.00 are benzene rings

375 parts of sulfolane was added 33,32 parts of phthalic anhydride, 10,08 parts of quinolinic acid, 108 parts of urea, a 10.1 parts of copper chloride (II) and 1.5 parts of ammonium molybdate. The liquid temperature was raised to 200°C., and the reaction liquid was maintained at this temperature for 5 hours. After completion of the reaction, the reaction liquid was cooled to 65°C., thereto was added 50 parts of DMF (N,N-dimethylformamide), and the precipitated solid substance was separated by filtration. The obtained solid is the second substance is washed with 50 parts of DMF to obtain a 75.1 parts of wet sediment. The obtained wet sediment was added to 450 parts of DMF, the liquid temperature was raised to 110°C., and the liquid was maintained at this temperature for one hour. A solid substance was separated by filtration and washed with 200 parts of water to obtain a wet sludge. The obtained wet sediment was added to 450 parts of 5% hydrochloric acid, and the liquid temperature was raised to 60°C. and maintained at this temperature for 1 hour. A solid substance was separated by filtration and washed with 200 parts of water to obtain a wet sludge. The obtained wet sediment was added to 450 parts of 5% aqueous ammonia solution, and the liquid temperature was raised to 60°C. and maintained at this temperature for 1 hour. A solid substance was separated by filtration and washed with 200 parts of water with obtaining 78,6 part of the wet sludge. The obtained wet precipitate was dried at 80°C To produce 25,2 part of the above target compound in the form of a blue solid.

(Stage 2)

The synthesis of compounds represented by the above formula (2), where 1.00 rings A to D is a pyridine ring fused at the 2 - and 3-position, the rest of 3.00 are benzene rings and n is equal to 3.00

To of 46.2 parts of chlorosulfonic acid was gradually added to 5.8 parts of the compound of formula (4)obtained in the above Example 1 (stage 1), so h is ordinary temperature did not exceed 60°C, and the reaction liquid was maintained at 140°C for 4 hours. Then the reaction liquid was cooled to 70°C., was added dropwise to 17.9 parts of thionyl chloride for 30 minutes, and the reaction is further carried out at 70°C for 3 hours. The reaction liquid was cooled to 30°C or less and slowly poured into 800 parts of ice water. The precipitated solid was separated by filtration and washed with 200 parts of cold water with the receipt of 31.5 parts of wet sediment target compound represented by the above formula (2).

(Stage 3)

Synthesis porphyrinogen the coloring matter of the present invention represented by the above formula (7) [coloring matter of the above formula (1), where 1.00 rings A to D is a pyridine ring fused at the 2 - and 3-position, the rest of 3.00 are benzene rings, E represents ethylene, X represents a 2.5 desultorily, R1represents methyl, b is 2,30, and is 0.7]

To 200 parts of ice water was added to 31.5 parts of wet sediment compounds represented by the above formula (2)obtained in Example 2 (stage 2), and the mixture was suspended by stirring at 5°C or less. Ten minutes later, while maintaining the liquid temperature at 10°C or less, to this suspension was added to the solution, the solvent of 2.9 parts of EOS is ancescao amine, represented by the above formula (6)obtained in Example 1 (stage 3), in a mixed liquid of 1 part of 28% aqueous ammonia solution and 40 parts of water. Then there was the reaction, maintaining the suspension at a pH of 9.0 28% aqueous ammonia solution. While maintaining the pH of the suspension liquid temperature was raised to 20°C for 1 hour, and the reaction was conducted further at this temperature for 8 hours. The volume of liquid at this time was 225 parts. The temperature of the reaction liquid was raised to 50°C., was added thereto and 33.8 parts of sodium chloride, and the mixture was stirred for 30 minutes. Then added concentrated hydrochloric acid for 20 minutes to bring the pH of this reaction liquid to 1.0. The precipitated solid was separated by filtration and washed with 100 parts of 10% aqueous solution of sodium chloride with getting 39,7 part of the wet sludge.

The obtained wet sediment was added to 170 parts of water, and thereto was added 25% aqueous solution of sodium hydroxide to bring the pH to 9.0, resulting in the wet precipitate was dissolved. The volume of liquid at this time was 225 parts, the temperature of this solution was raised to 50°C., it was added to 22.5 parts of sodium chloride, and the solution was stirred for 30 minutes. Then added concentrated hydrochloric acid for 20 minutes to bring the pH of this reaction liquid to 1.0, and OSA is built solid substance was separated by filtration and washed with 100 parts of 10% aqueous solution of sodium chloride with getting 41,2 part of the wet sludge. The obtained wet sediment was added to a mixed liquid of 160 parts of ethanol and 40 parts of water, and the liquid was stirred at 50°C for 1 hour. Then the precipitated solid was separated by filtration receipt of 29.3 parts of wet sediment. The obtained wet precipitate was dried to obtain 11.0 parts of free acid, the coloring matter of the present invention represented by the above formula (7), in the form of a blue powder.

λmax: 605 nm.

Example 3

(Stage 1)

The synthesis of compounds represented by the above formula (4), where 0.75 rings A to D is a pyridine ring fused at the 2 - and 3-position, and the rest of 3.25 represent a benzene ring

375 parts of sulfolane was added 36,1 parts of phthalic anhydride, and 9.4 parts of quinolinic acid, 108 parts of urea, a 10.1 parts of copper chloride (II) and 1.5 parts of ammonium molybdate. The liquid temperature was raised to 200°C., and the reaction liquid was maintained at this temperature for 5 hours.

After completion of the reaction, the reaction liquid was cooled to 65°C., thereto was added 50 parts of DMF (N,N-dimethylformamide), and the precipitated solid substance was separated by filtration. The obtained solid is washed with 50 parts of DMF to obtain a 75.1 parts of wet sediment. The obtained wet sediment was added to 450 parts of DMF, temperatureheat was raised to 110°C, and the mixture is maintained at this temperature for one hour. A solid substance was separated by filtration and washed with 200 parts of water to obtain a wet sludge. The obtained wet sediment was added to 450 parts of 5% hydrochloric acid, and the liquid temperature was raised to 60°C. and maintained at this temperature for 1 hour. A solid substance was separated by filtration and washed with 200 parts of water to obtain a wet sludge. The obtained wet sediment was added to 450 parts of 5% aqueous ammonia solution, the liquid temperature was raised to 60°C., and the mixture was maintained at this temperature for 1 hour. A solid substance was separated by filtration and washed with 200 parts of water with obtaining 78,6 part of the wet sludge. The obtained wet precipitate was dried at 80°C To produce a 32.6 parts of the above target compound in the form of a blue solid.

(Stage 2)

The synthesis of compounds represented by the above formula (2), where 0.75 rings A to D is a pyridine ring fused at the 2 - and 3-position, the rest of 3.25 represent a benzene ring, and n is equal to 3.25

To 46,1 parts of chlorosulfonic acid was gradually added to 5.7 parts of the compound of the above formula (4)obtained in the above Example 3 (stage 1), so that the temperature did not exceed 60°C and then the reaction liquid supports the whether at 145°C for 4 hours. Then the reaction liquid was cooled to 70°C., was added thereto dropwise with 17.8 parts of thionyl chloride for 30 minutes, and then the liquid temperature was raised to 80°C., and the reaction was conducted further at this temperature for 3 hours. The reaction liquid was cooled to 30°C or less and slowly poured into 800 parts of ice water. The precipitated solid was separated by filtration and washed with 100 parts of cold water with the receipt of 32.2 parts of wet sediment target compound represented by the above formula (2).

(Stage 3)

Synthesis porphyrinogen the coloring matter of the present invention represented by the above formula (7) [coloring matter of the above formula (1), where 0.75 rings A to D is a pyridine ring fused at the 2 - and 3-position, the rest of 3.25 represent a benzene ring, E represents ethylene, X represents a 2.5 desultorily, R1represents methyl, b is of 2.45, and is 0.8]

To 150 parts of ice water was added to 32.2 parts of the wet precipitate obtained in Example 3 (stage 2), and the mixture was suspended by stirring at 5°C or less. Ten minutes later, while maintaining the liquid temperature at 10°C or less, to this suspension was added to the solution, dissolving 3,3 part of the organic amine represented by the above what armoloy (6), in a mixed liquid of 1 part of 28% aqueous ammonia solution and 50 parts of water. The reaction was carried out, maintaining the suspension at a pH of 9.0 28% aqueous ammonia solution. While maintaining the pH of this suspension is the liquid temperature was raised to 20°C for 1 hour, and the reaction was conducted further at this temperature for 8 hours. The volume of liquid at this time was 250 parts. The temperature of the reaction liquid was raised to 50°C., it was added to 37.5 parts of sodium chloride, and the mixture was stirred for 30 minutes. Then added concentrated hydrochloric acid for 20 minutes to bring the pH of this reaction liquid to 1.0. The precipitated solid was separated by filtration and washed with 100 parts of 10% aqueous solution of sodium chloride with the receipt of 51.1 parts of wet sediment.

The obtained wet sediment was added to 200 parts of water, and by bringing the pH to 9.0 25% aqueous solution of sodium hydroxide was dissolved wet sediment. The volume of liquid at this time was 275 parts. The temperature of this solution was raised to 50°C, were added to 27.5 parts of sodium chloride, and the solution was stirred for 30 minutes. Then added concentrated hydrochloric acid for 20 minutes to bring the pH of this reaction liquid to 1.0, and the precipitated solid substance was separated by filtration and washed with 100 parts of 10% aqueous solution of sodium chloride with p is the receiving 47,3 part of the wet sludge. The obtained wet sediment was added to a mixed liquid of 160 parts of ethanol and 40 parts of water, and this liquid was stirred at 50°C for 1 hour. Then the solid was separated by filtration receipt of 16.3 parts of wet sediment. The obtained wet precipitate was dried to obtain 10.0 parts of free acid, the coloring matter of the present invention represented by the above formula (7), in the form of a blue powder.

λmax: 604 nm.

Example 4

(Stage 1)

The synthesis of the organic amine represented by the following formula (8) [organic amine of the above formula (3), where E represents ethylene, X represents a 2.5 desultorily, and R1represents ethyl]

To 80 parts of ethanol was added to 18.4 parts of cyanuric acid chloride acid, 2 parts of LEOCOLRTMTD-90 (trade name) and 8.4 parts of sodium bicarbonate, and the reaction was carried out at 30°C or less within 4 hours to obtain the reaction liquid containing the first condensate.

To 150 parts of water was added to 30.1 parts of 2,5-desultorily and additionally was added 17 parts of 25% aqueous sodium hydroxide solution to bring the pH of this fluid to 3-5. To this liquid was gradually added to the reaction liquid containing the first condensate obtained as described above, and so is bringing the pH to 6-7 additional addition of 25% aqueous sodium hydroxide solution the reaction was carried out at room temperature for 7 hours to obtain the reaction liquid, contains a second condensate.

To the resulting reaction liquid was further added dropwise 180 parts of hydrochloric acid and 63 parts of ice, the reaction liquid was cooled to 0°C. was further added dropwise 60,1 parts of ethylene diamine, and then the reaction was carried out at room temperature over night with obtaining a reaction liquid containing a third condensate.

To this solution was added 20 parts of hydrochloric acid to bring the pH of the reaction liquid to 1.0. The volume of liquid at this time was 700 parts. To this liquid was added 140 parts of sodium chloride, and the liquid was stirred for 30 minutes with the deposition of solids. The precipitated solid was separated by filtration to obtain 130,9 parts of wet sediment. The obtained wet sediment was added to 850 parts of water, and thereto was added 25% aqueous solution of sodium hydroxide to bring the pH to 9.0, resulting in the wet precipitate was dissolved. To this solution were added 64 parts of hydrochloric acid to bring the pH to 1.0. At this time, fluid volume was 900 parts. To this liquid was added 180 parts of sodium chloride, and the liquid was stirred at room temperature for 30 minutes and then at 0°C for 30 minutes. The precipitated solid was separated by filtration to obtain 39,6 part of the wet sludge. The obtained wet about what ADOC was added to a mixed liquid of 160 parts of methanol and 40 parts of water, and the liquid was stirred at 50°C for 1 hour. A solid substance was separated by filtration receipt of 15.4 parts of wet sediment. The obtained wet precipitate was dried to obtain 11,8 part of the white powder target organic amine represented by the above formula (8).

(Stage 2)

Synthesis porphyrinogen the coloring matter of the present invention represented by the following formula (9) [coloring matter of the following formula (9), where 1.00 rings A to D is a pyridine ring fused at the 2 - and 3-position, the rest of 3.00 are benzene rings, E represents ethylene, X represents a 2.5 desultorily, R1represents ethyl, b is 2.0, and with equal 1,0]

To 100 parts of ice water was added to 31.5 parts of wet sludge obtained in the same manner as in Example 2 (stage 1) (stage 2), and the mixture was suspended by stirring at 5°C or less. Ten minutes later, while maintaining the liquid temperature at 10°C or less, to this suspension was added to the solution, the solvent of 4.2 parts of the organic amine represented by the above formula (8), in the mixed liquid of 3 parts of 28% aqueous ammonia solution and 40 parts of water. The reaction was carried out, maintaining the suspension at a pH of 9.0 28% aqueous ammonia solution. If p is darjani pH of the suspension liquid temperature was raised to 20°C for 1 hour, and the reaction was conducted further at this temperature for 8 hours. The volume of liquid at this time was 225 parts. The temperature of the reaction liquid was raised to 50°C. thereto was added and 33.8 parts of sodium chloride, and the mixture was stirred for 30 minutes. Then added concentrated hydrochloric acid for 20 minutes to bring the pH of this reaction liquid to 1.0. The precipitated solid was separated by filtration and washed with 100 parts of 10% aqueous solution of sodium chloride with getting 59,9 part of the wet sludge.

The obtained wet sediment was added to 150 parts of water, and thereto was added 25% aqueous solution of sodium hydroxide to bring the pH to 9.0, resulting in the wet precipitate was dissolved. The volume of liquid at this time was 225 parts. The temperature of this solution was raised to 50°C., it was added to 22.5 parts of sodium chloride, and the mixture was stirred for 30 minutes. Then added concentrated hydrochloric acid for 20 minutes to bring the pH of this reaction liquid to 1.0, and the precipitated solid substance was separated by filtration and washed with 100 parts of 10% aqueous solution of sodium chloride with getting 55,1 part of the wet sludge. The obtained wet sediment was added to a mixed liquid of 240 parts of ethanol and 60 parts of water, and the liquid was stirred at 50°C for 1 hour. Then the solid was separated by filtration is a Finance with getting to 52.1 parts of wet sediment. The obtained wet precipitate was dried to obtain 9,2 part of the free acid, the coloring matter of the present invention represented by the above formula (9), in the form of a blue powder.

λmax: 603 nm.

Example 5

(Stage 1)

The synthesis of the organic amine represented by the following formula (10) [organic amine of the above formula (4), where E represents ethylene, X represents a 3.8-disulfo-1 naphthylamine, and R1represents a methyl]

To 80 parts of methanol and 20 parts of ice was added to 9.2 parts of cyanuric acid chloride acid, 1 part of LEOCOLRTMTD-90 (trade name) and 4.2 parts of sodium bicarbonate, and the reaction was carried out at 30°C or less within 1 hour, obtaining a reaction liquid containing the first condensate.

To 75 parts of water was added to 14.9 parts 3,8-disulfo-1-naphtylamine and additionally was added 5 parts of 25% aqueous sodium hydroxide solution to bring the pH of this fluid to 4-6. To this liquid was gradually added to the reaction liquid containing the above-described first condensate, and bringing the pH to 6-7 additional addition of 25% aqueous sodium hydroxide solution the reaction was carried out at room temperature over night with obtaining a reaction liquid containing a second condensate.

It received the Oh reaction liquid was added 90 parts of hydrochloric acid and 30 parts of ice, the reaction liquid was cooled to 0°C and was further added dropwise to 30.1 parts of ethylene diamine. Then, when bringing the pH to 5-6 by adding to the resulting liquid 25% aqueous sodium hydroxide solution, the reaction was carried out at room temperature over night with obtaining a reaction liquid containing a third condensate.

To this solution was added 20 parts of hydrochloric acid to bring the pH of the solution to 1.0. The volume of liquid at this time was 350 parts. To it was added 40 parts of sodium chloride, and the liquid was stirred for 30 minutes with the deposition of solids. The precipitated solid was separated by filtration to obtain 58,0 parts of wet sediment. The obtained wet sediment was placed in a beaker, were added 300 parts of water was further added 25% aqueous solution of sodium hydroxide to bring the pH to 9.0, the resulting solid substance was dissolved. To this solution was added 24 parts of hydrochloric acid to bring the pH to 1.0. At this time, the volume of liquid was 410 parts. To this liquid was added 80 parts of sodium chloride, and the liquid was stirred overnight at room temperature and additionally stirred at 0°C for 30 minutes with the deposition of solids. The precipitated solid was separated by filtration to obtain 1,3 part of the wet sludge. The obtained wet sediment was placed in a beaker, to it was added 48 parts of methanol and 12 parts of water, and the liquid was stirred at 50°C for 1 hour. Then the solid was separated by filtration to obtain 9,1 part of the wet sludge. The obtained wet precipitate was dried to obtain 8,3 part of the white powder target organic amine represented by the above formula (10).

(Stage 2)

Synthesis porphyrinogen the coloring matter of the present invention represented by the following formula (11) [coloring matter of the above formula (1), where 1.00 rings A to D is a pyridine ring fused at the 2 - and 3-position, the rest of 3.00 are benzene rings, E represents ethylene, X represents a 3.8-disulfo-1 naphthylamine, R1represents methyl, b is 2.0, with 1.0]

To 120 parts of ice water was added to 31.5 parts of wet sludge obtained in the same manner as in Example 2 (stage 1) (stage 2), and the mixture was suspended by stirring at 5°C or less. Ten minutes later, while maintaining the liquid temperature at 10°C or less, to this suspension was added to the solution, dissolving 4,7 part of the organic amine represented by the above formula (10), 1 part of 28% aqueous ammonia solution is 40 parts of water. By adding 28% aqueous ammonia solution was maintained pH at 9.0 of this suspension and the reaction was performed. While maintaining the pH of the suspension liquid temperature was raised to 20°C for 1 hour, and the reaction was conducted further at the same temperature for 8 hours. The volume of liquid at this time was 290 parts. The temperature of the reaction liquid was raised to 50°C. thereto was added 53 parts of sodium chloride, and the mixture was stirred for 30 minutes. Then added concentrated hydrochloric acid for 20 minutes to bring the pH of this reaction liquid to 1.0. The precipitated solid was separated by filtration and washed with 100 parts of 10% aqueous solution of sodium chloride to obtain a 41.3 parts of wet sediment.

The obtained wet sediment was added to 200 parts of water, and by bringing the pH to 9.0 25% aqueous solution of sodium hydroxide wet precipitate was dissolved. The volume of liquid at this time was 260 parts. The temperature of this solution was raised to 50°C., and thereto was added 45 parts of sodium chloride. The solution was stirred for 30 minutes and then was added concentrated hydrochloric acid for 20 minutes to bring the pH of the solution to 4.0. The precipitated solid was separated by filtration and washed with 100 parts of 20% aqueous solution of sodium chloride with the receipt of 23.9 parts of wet sediment. The obtained wet sediment was added to the mixture is nomu the solvent of 40 parts of water, 80 parts of methanol and 80 parts of isopropyl alcohol, and the liquid was stirred at 50°C for 1 hour. Then the solid was separated by filtration receipt of 21.6 parts of wet sediment. The obtained wet precipitate was dried to obtain 9,5 part of the free acid, the coloring matter of the present invention represented by the above formula (11), in the form of a blue powder.

λmax: 603 nm.

Example 6

(Stage 1)

The synthesis of the organic amine represented by the following formula (12) [organic amine of the above formula (3), where E represents ethylene, X represents a 4.8-disulfo-2-naphthylamine, and R1represents a methyl]

To 80 parts of methanol and 20 parts of ice was added to 18.4 parts of cyanuric acid chloride acid, 2 parts of LEOCOLRTMTD-90 (trade name) and 8.4 parts of sodium bicarbonate, and the reaction was carried out at 30°C or less within 1 hour, obtaining a reaction liquid containing the first condensate.

To 180 parts of water was added 30,4 part 2-amino-4,8-desulfonation and was further added 10 parts of 25% aqueous sodium hydroxide solution to bring the pH of this fluid to 4-6. To this liquid was gradually added to the reaction liquid containing the above-described first condensate, and bringing the pH to 6-7 additionally the m by addition of 25% aqueous sodium hydroxide solution the reaction was carried out at room temperature for 3 hours to obtain the reaction liquid, contains a second condensate.

To the resulting reaction liquid was added 180 parts of hydrochloric acid and 60 parts of ice, the reaction liquid was cooled to 0°C and was further added dropwise 60,1 parts of ethylene diamine. Then, when bringing the pH to 5-6 by addition of 25% aqueous sodium hydroxide solution, the reaction was carried out at room temperature over night with obtaining a reaction liquid containing a third condensate.

To this solution was added 40 parts of hydrochloric acid to bring the pH of the reaction liquid to 1.0. The volume of liquid at this time was 720 parts. To it was added 120 parts of sodium chloride, and the liquid was stirred for 30 minutes with the deposition of solids. The precipitated solid was separated by filtration to obtain 141,3 part of the wet sludge. The obtained wet sediment was placed in a beaker, were added 600 parts of water and additionally used a 25% aqueous solution of sodium hydroxide to bring the pH to 9.0, resulting in the wet precipitate was dissolved. To this solution was added 65 parts of hydrochloric acid to bring the pH to 1.0. At this time, fluid volume was 820 parts. To this liquid was added 190 parts of sodium chloride, and the liquid was stirred for 30 minutes at room temperature and then at 0°C for 30 minutes with precipitation of solid substances is TBA. The precipitated solid was separated by filtration to obtain 52,2 part of the wet sludge. The obtained wet sediment was placed in a beaker, to it was added 200 parts of methanol and 50 parts of water, and the mixture was stirred at 50°C for 1 hour. A solid substance was separated by filtration to obtain 58,6 part of the wet sludge. The obtained wet precipitate was dried to obtain 34,3 part of the white powder target organic amine represented by the above formula (12).

(Stage 2)

Synthesis porphyrinogen the coloring matter of the present invention represented by the following formula (13) [coloring matter of the above formula (1), where 1.00 rings A to D is a pyridine ring fused at the 2 - and 3-position, the rest of 3.00 are benzene rings, E represents ethylene, X represents a 4.8-disulfo-2-naphthylamine, R1represents methyl, b is 2.0, and with equal 1,0]

To 120 parts of ice water was added to 31.5 parts of wet sludge obtained in the same manner as in Example 2 (stage 1) (stage 2), and the mixture was suspended by stirring at 5°C or less. Ten minutes later, while maintaining the liquid temperature at 10°C or less, to this suspension was added to the solution, the solvent of 5.4 parts of organic AMI is a, represented by the above formula (12), 1 part of 28% aqueous ammonia solution and 40 parts of water. Adding to a suspension of 28% aqueous ammonia was supported pH 9.0 and carried out the reaction. While maintaining the pH of the suspension liquid temperature was raised to 20°C for 1 hour, and the reaction was conducted further at this temperature for 8 hours. The volume of liquid at this time was 230 parts. The temperature of the reaction liquid was raised to 50°C., it was added to 34.5 parts of sodium chloride, and the mixture was stirred for 30 minutes. Then added concentrated hydrochloric acid for 20 minutes to bring the pH of this reaction liquid to 1.0. The precipitated solid was separated by filtration and washed with 100 parts of 10% aqueous solution of sodium chloride with getting 51,5 part of the wet sludge.

The obtained wet sediment was added to 200 parts of water, and by bringing the pH to 9.0 25% aqueous solution of sodium hydroxide wet precipitate was dissolved. The volume of liquid at this time was 225 parts. The temperature of this solution was raised to 50°C., it was added to 22.5 parts of sodium chloride, and the solution was stirred for 30 minutes. Then added concentrated hydrochloric acid for 20 minutes to bring the pH to 4.0, and then the precipitated solid was separated by filtration and washed with 100 parts of 10% aqueous solution of chloride on the rija obtaining 53,9 part of the wet sludge. The obtained wet sediment was added to a mixed solvent of 160 parts of ethanol and 40 parts of water, and the liquid was stirred at 50°C for 1 hour. Then the solid was separated by filtration receipt of 22.2 parts of wet sediment. The obtained wet precipitate was dried to obtain 10.0 parts of free acid, the coloring matter of the present invention represented by the above formula (13), in the form of a blue powder.

λmax: 607 nm.

Example 7

(Stage 1)

The synthesis of the organic amine represented by the following formula (14) [organic amine of the above formula (4), where E represents ethylene, X represents 6,8-disulfo-2-naphthylamine, and R1represents a methyl]

To 80 parts of methanol and 20 parts of ice was added to 18.4 parts of cyanuric acid chloride acid, 2 parts of LEOCOLRTMTD-90 (trade name) and 8.4 parts of sodium bicarbonate, and the mixture was stirred at 30°C or less within 1 hour, obtaining a reaction liquid containing the first condensate. To this reaction liquid was added 60 parts of ice, and the reaction liquid was stirred at 0°C for 30 minutes with the deposition of solids. The precipitated solid was separated by filtration to obtain 17,7 part of the wet sludge of the first condensate.

K160 parts of water was added 33,1 part 2-amino-6,8-disulfonato and 0.2 parts of LEOCOL RTMTD-90 and was additionally added 6 parts of 25% aqueous sodium hydroxide solution to bring the pH to 3-5. With stirring, the liquid was gradually added to the wet precipitate containing the above-described first condensate, and then bringing the pH to 5-7 by the addition of 25% aqueous sodium hydroxide solution the reaction was carried out at room temperature for 2 hours with obtaining a reaction liquid containing a second condensate.

To the resulting reaction liquid was added 180 parts of hydrochloric acid and 60 parts of ice, the reaction liquid was cooled to 0°C and added dropwise to 54.1 parts of ethylene diamine. Then, when bringing the pH to 5-6 by adding to the resulting liquid 25% aqueous sodium hydroxide solution, the liquid was stirred at room temperature overnight with obtaining a reaction liquid containing a third condensate.

To this solution was added 40 parts of hydrochloric acid to bring the pH of the solution to 1.0. The volume of liquid at this time was 600 parts. To the resulting solution were added 60 parts of sodium chloride, and the solution was stirred for 30 minutes with the deposition of solids. The precipitated solid was separated by filtration to obtain 95,6 part of the wet sludge. The obtained wet sediment was placed in a beaker, were added 500 parts of water and is more used 25% aqueous solution of sodium hydroxide to bring the pH to 9.0, resulting wet precipitate was dissolved. To this solution was added 20 parts of hydrochloric acid to bring the pH to 1.0. At this time, the volume of liquid was 640 parts. To this solution was added 80 parts of sodium chloride, and the solution was stirred for 30 minutes at room temperature and additionally stirred at 0°C for 30 minutes with the deposition of solids. The precipitated solid was separated by filtration to obtain 121,7 part of the wet sludge. The obtained wet sediment was placed in a beaker, to it was added 480 parts of methanol and 120 parts of water, and the liquid was stirred at 50°C for 1 hour. Then the solid was separated by filtration to obtain 73,8 part of the wet sludge. The obtained wet precipitate was dried to obtain 33,1 part of the white powder target organic amine represented by the above formula (14).

(Stage 2)

The synthesis of the coloring matter of the present invention represented by the following formula (15) [coloring matter of the above formula (1), where 1.00 rings A to D is a pyridine ring fused at the 2 - and 3-position, the rest of 3.00 are benzene rings, E represents ethylene, X represents 6,8-disulfo-2-naphthylamine, R1represents methyl, b is 2.0, and with equal 1,0]

To 120 parts of ice water was added 33,0 part of the wet sludge obtained in the same manner as in Example 2 (stage 1) (stage 2), and the mixture was suspended by stirring at 5°C or less. Ten minutes later, while maintaining the liquid temperature at 10°C or less, to this suspension was added to the solution, dissolving 5,9 part of the organic amine represented by the above formula (14), 1 part of 28% aqueous ammonia solution and 40 parts of water. Adding 28% aqueous ammonia solution pH of the suspension was maintained at 9.0 and carried out the reaction. While maintaining the pH of the suspension liquid temperature was raised to 20°C for 1 hour, and the reaction was conducted further at this temperature for 8 hours. The volume of liquid at this time was 200 parts. The temperature of the reaction liquid was raised to 50°C. thereto was added 44 parts of sodium chloride, and the mixture was stirred for 30 minutes. Then added concentrated hydrochloric acid for 20 minutes to bring the pH of the reaction liquid to 1.0. The precipitated solid was separated by filtration and washed with 100 parts of 10% aqueous solution of sodium chloride to obtain 45.0 parts of wet sediment.

The obtained wet sediment was added to 200 parts of water, and by bringing the pH to 9.0 25% aqueous solution of sodium hydroxide was dissolved this wet precipitate. The volume of liquid at this time with Talal 250 pieces. The temperature of this solution was raised to 50°C., were added 80 parts of sodium chloride, and the solution was stirred for 30 minutes. Then added concentrated hydrochloric acid for 20 minutes to bring the pH to 7.0, and then the precipitated solid was separated by filtration and washed with 100 parts of 10% aqueous solution of sodium chloride to obtain 33.5 parts of wet sediment. The obtained wet sediment was added to a mixed solvent of 80 parts of methanol and 80 parts of isopropyl alcohol and 40 parts of water, and the liquid was stirred at 50°C for 1 hour. Then the solid was separated by filtration receipt of 27.2 parts of wet sediment. The obtained wet precipitate was dried to obtain 11,1 part of the free acid, the coloring matter of the present invention represented by the above formula (15), in the form of a blue powder.

λmax: 608 nm.

Example 8

(Stage 1)

The synthesis of the organic amine represented by the following formula (16) [organic amine of the above formula (3), where E represents ethylene, X represents a 8-hydroxy-3,6-disulfonato-1 ylamino, and R1represents a methyl]

To 80 parts of methanol was added 20 parts of ice, of 18.4 parts of cyanuric acid chloride acid, 2 parts of LEOCOLRTMTD-90 (trade name)and 16.8 parts of sodium bicarbonate, and the reaction was carried out at 30°C or less within 1 hour, obtaining a reaction liquid containing the first condensate.

To the liquid, where 38,7 part 8-hydroxy-3,6-disulfo-1-naphtylamine (commercial product having a purity of 82.5%) and 16 parts of 25% aqueous sodium hydroxide solution were added to 200 parts of water was gradually added to the reaction liquid containing the first condensate obtained as described above. When making this reaction liquid to pH 6-7 by addition of 25% aqueous sodium hydroxide solution this liquid was stirred at room temperature overnight with obtaining a reaction liquid containing a second condensate.

To the resulting reaction liquid was added 180 parts of hydrochloric acid and 60 parts of ice, the reaction liquid was cooled to 0°C and was further added thereto dropwise 60 parts of ethylene diamine. When bringing the pH of this fluid to 5-6 25% aqueous sodium hydroxide solution, the reaction liquid was stirred at 80°C for 2.5 hours with obtaining a reaction liquid containing a third condensate.

To this solution was added 55 parts of hydrochloric acid to bring the pH of the solution to 1.0. The volume of liquid at this time was 500 parts. To this liquid was added to 100 parts of sodium chloride, and the liquid was stirred for 30 minutes with the deposition of solids. Besieged the second solid substance was separated by filtration to obtain 77,1 part of the wet sludge. The obtained wet sediment was added to 300 parts of water, and thereto was added 25% aqueous solution of sodium hydroxide to bring the pH to 9.0, resulting in the wet precipitate was dissolved. To this solution was added 15.0 parts of hydrochloric acid to bring the pH of the solution to 1.0. The volume of liquid at this time was 420 parts.

To this liquid was added 84 parts of sodium chloride, and the liquid was stirred at room temperature for 30 minutes and then at 0°C for 30 minutes with the deposition of solids. The precipitated solid was separated by filtration to obtain 66,1 part of the wet sludge. To a mixed liquid of 120 parts of methanol, 120 parts of isopropanol and 60 parts of water, was added to the obtained wet precipitate, and the liquid was stirred at 50°C for 1 hour. Then the solid was separated by filtration to obtain 62,1 part of the wet sludge. The obtained wet precipitate was dried to obtain 23,5 part of the light purple powder target organic amine represented by the above formula (16).

(Stage 2)

Synthesis porphyrinogen the coloring matter of the present invention represented by the following formula (17) [coloring matter of the above formula (1), where 1.00 rings A to D is a pyridine ring fused at the 2 - and 3-position, the rest of 3.00 represent the ow of the benzene ring, E represents ethylene, X represents a 8-hydroxy-3,6-disulfonato-1 ylamino, R1represents methyl, b is 2.0, and with equal 1,0]

To 200 parts of ice water was added to 31.5 parts of wet sludge obtained in the same manner as in Example 2 (stage 1) (stage 2), and the mixture was suspended by stirring at 5°C or less. Ten minutes later, while maintaining the liquid temperature at 10°C or less, to this suspension was added to the solution, the solvent of 4.9 parts of the organic amine represented by the above formula (16), 1 part of 28% aqueous ammonia solution and 40 parts of water. Additionally, adding 28% aqueous ammonia solution, the pH of the suspension was maintained at 9.0 and carried out the reaction. While maintaining the pH of the suspension liquid temperature was raised to 20°C for 1 hour, and the reaction was conducted further at this temperature for 8 hours. The volume of liquid at this time was 250 parts. The temperature of the reaction liquid was raised to 50°C., was added thereto 50 parts of sodium chloride, and the reaction liquid was stirred for 30 minutes. Then added concentrated hydrochloric acid for 20 minutes to bring the pH of the reaction liquid to 5.0. The precipitated solid was separated by filtration and washed with 100 parts of 20% aqueous solution of sodium chloride with getting 42,1 frequent the wet sludge.

The obtained wet sediment was added to 170 parts of water, and thereto was added 25% aqueous solution of sodium hydroxide to bring the pH to 9.0, resulting in the wet precipitate was dissolved. The volume of liquid at this time was 250 parts. The temperature of this solution was raised to 50°C. thereto was added 25 parts of sodium chloride, and the solution was stirred for 30 minutes. Then added concentrated hydrochloric acid for 20 minutes to bring the pH to 2.0, and then the precipitated solid was separated by filtration and washed with 100 parts of 10% aqueous solution of sodium chloride with getting to 43.2 parts of wet sediment. The obtained wet sediment was added to a mixed solvent of 160 parts of ethanol and 40 parts of water, and the liquid was stirred at 50°C for 1 hour. Then the solid was separated by filtration receipt of 13.3 parts of wet sediment. The obtained wet precipitate was dried to obtain 9.8 part of the free acid, the coloring matter of the present invention represented by the above formula (17), in the form of a blue powder.

λmax: 607 nm.

[Synthesis of the coloring matter for comparison]

Later in this paper explains the method of synthesis of the coloring matter for comparison.

Example of synthesis 1

(Stage 1)

The synthesis of organic amine for comparison represented by the following formula (18)/p>

To 330 parts of ice water was added to 18.4 parts of cyanuric acid chloride acid and 0.2 parts of LEOCOLRTMTD-90 (trade name), and this liquid was stirred at 10°C. or less for 30 minutes. To this liquid was added to 17.4 parts of 4-sulfonanilide (commercial product having a purity of 99.3%), and bringing the pH of this fluid further addition of 10% aqueous sodium hydroxide solution the reaction was carried out at pH from 2.6 to 3.0 and a temperature of from 0 to 5°C for 1 hour and then at pH from 3.0 to 3.5 and 0-5°C for 1 hour, while maintaining the pH from 3.0 to 3.5 it carried further at a temperature of from 25 to 30°C for 1 hour. To the resulting reaction liquid was added to 12.6 parts of 2-sulfotyrosine, and bringing the pH to 7.0 to 8.0 additional by adding 10% aqueous sodium hydroxide solution the reaction was carried out at 25°C for 2 hours. To this reaction liquid was added 250 parts of ice, the reaction liquid was cooled to 0°C. thereto was further added dropwise 60 parts of ethylene diamine at 5°C or less, and the reaction was conducted at room temperature over night. Then, using concentrated hydrochloric acid, the pH of the reaction liquid was brought to 1.0. While bringing the pH of concentrated hydrochloric acid to the reaction liquid was added ice to suppress the exothermic heat, and temp is the temperature of the liquid was maintained at 10-15°C. At this time, the volume of liquid was 980 parts. To this liquid was added 190 parts of sodium chloride, the liquid was stirred for 30 minutes, and the precipitated solid substance was separated by filtration to obtain 70,6 part of the wet sludge.

The obtained wet sediment was added to 280 parts of water, and thereto was added a 10% aqueous solution of sodium hydroxide to bring the pH to 9.0, resulting in the wet precipitate was dissolved. At this time, fluid volume was 400 parts. This solution brought to a pH of 1.0 with concentrated hydrochloric acid was then added 80 parts of sodium chloride, and then the mixture was stirred for 30 minutes. The precipitated solid was separated by filtration to obtain 110,1 part of the wet sludge. The obtained wet sediment was added to a mixed liquid of 260 parts of methanol and 26 parts of water, the liquid was stirred at 50°C for 1 hour and then the solid substance was separated by filtration to obtain 89,1 part of the wet sludge. The obtained wet precipitate was dried to obtain 49,3 part of the white powder target organic amine for comparison represented by the above formula (18).

(Stage 2)

The synthesis of the coloring matter for comparison represented by the following formula (19) [coloring matter of the following formula (19), where 1.00 rings A to D is a pyridine Kohl is about, condensed at the 2 - and 3-position, the rest of 3.00 are benzene ring, b is 1,625, and with equal 1,0]

To 100 parts of ice water was added to 31.5 parts of wet sludge obtained in the same manner as in Example 2 (stage 1) (stage 2), the mixture was suspended by stirring at 5°C or less. Ten minutes later, while maintaining the liquid temperature at 10°C or less, to this suspension was added to the solution, dissolving the 4.3 organic amine for comparison represented by the above formula (18), 2 parts of 28% aqueous ammonia solution and 50 parts of water, and while maintaining the pH of the liquid at 9,0 28% aqueous ammonia solution were reaction. While maintaining the pH of the suspension liquid temperature was raised to 20°C for 1 hour, and the reaction was conducted further at this temperature for 8 hours. The volume of liquid at this time was 225 parts. The temperature of the reaction liquid was raised to 50°C. thereto was added 33,7 parts of sodium chloride, and the reaction liquid was stirred for 30 minutes. Then added concentrated hydrochloric acid for 20 minutes to bring the pH of the reaction liquid to 2.0. The precipitated solid was separated by filtration and washed with 100 parts of 10% aqueous solution of sodium chloride with getting 46,1 part of the wet sludge.

The humid OS the dock was added to 150 parts of water, and thereto was added 25% aqueous solution of sodium hydroxide to bring the pH to 9.0, resulting in the wet precipitate was dissolved. The volume of liquid at this time was 225 parts, the temperature of the resulting solution was raised to 50°C., it was added to 22.5 parts of sodium chloride, and the solution was stirred for 30 minutes. Then added concentrated hydrochloric acid for 20 minutes to bring the pH to 1.0, and the precipitated solid substance was separated by filtration and washed with 100 parts of 10% aqueous solution of sodium chloride to obtain a 44.2 parts of wet sediment. The obtained wet sediment was added to a mixed liquid of 255 parts of methanol and 45 parts of water, and the liquid was stirred at 50°C for 1 hour. Then the solid was separated by filtration receipt of 25.2 parts of wet sediment. The obtained wet precipitate was dried to obtain 9.8 part of the free acid target coloring substance for comparison represented by the above formula (19), in the form of a blue powder.

λmax: 604 nm.

Example of synthesis 2

(Stage 1)

The synthesis of organic amine for comparison represented by the following formula (20)

To 150 parts of ice water was added to 36.8 parts of the acid chloride cyanuric acid and 0.4 parts of LEOCOLRTMTD-90 (trade name), and this liquid premesis is whether under 10°C or less within 30 minutes. Then thereto was added 62,0 parts of aniline-2,5-disulfonic acid monosodium salt (commercial product having a purity of 90.5 per cent), and bringing the pH of this fluid to 2.5-3.0 additional by adding 10% aqueous sodium hydroxide solution the reaction was carried out at 0-10°C for 1 hour and 30 minutes, and then at 20-25°C for 1 hour and 30 minutes. When bringing the pH to 9.0 to 9.5 by adding 10% aqueous sodium hydroxide solution to the reaction liquid, the reaction was carried out at 45°C for 1 hour and then at like bringing the pH to 10.0 to 10.5 it was carried out at 45°C for 1 hour. To the resulting reaction liquid was added 250 parts of ice for cooling the reaction liquid to 0°C., and adjusting the temperature so that it does not exceed 5°C. to this reaction liquid was added dropwise to 120 parts of ethylene diamine. The resulting reaction liquid was stirred at room temperature overnight, and then brought the pH to 2.0 with concentrated hydrochloric acid. While adding concentrated hydrochloric acid was added ice to maintain the liquid temperature at 10-15°C. While maintaining the temperature of the resulting liquid at 50°C or less was added 411,0 part hydrochloric acid to bring the pH to 1.0. At this time, fluid volume was 1200 parts. To it was added 240 parts of sodium chloride and fluid re exively for 30 minutes with the deposition of solids. The precipitated solid was separated by filtration to obtain 60,6 part of the wet sludge.

The obtained wet sediment was added to 470 parts of water were added 10% aqueous solution of sodium hydroxide to bring the pH to 10.0, resulting in the wet precipitate was dissolved. To this solution was added 33,2 part hydrochloric acid to bring the pH to 1.0. At this time, fluid volume was 600 parts. To the resulting liquid was added 120 parts of sodium chloride, and the mixture was stirred for 30 minutes with the deposition of solids. The precipitated solid was separated by filtration receipt of 38.4 parts of wet sediment. The obtained wet sediment was added to a mixed liquid of 320 parts of methanol and 80 parts of water, the liquid was stirred at 50°C for 1 hour, and then the precipitated solid was separated by filtration to obtain 38,2 part of the wet sludge. The obtained wet precipitate was dried to obtain 34,0 part of the white powder target organic amine for comparison represented by the above formula (20).

(Stage 2)

The synthesis of the coloring matter for comparison represented by the following formula (21) [coloring matter of the following formula (21), where 1.37 rings A to D are pyridine rings fused at the 2 - and 3-position, the remaining 2,63 represent analnye ring, b is 2.0, and with equal 1,0]

To 100 parts of ice water was added 33,0 part of the wet sludge obtained in the same manner as in Example 1 (stage 1) (stage 2), and the mixture was suspended by stirring at 5°C or less. Ten minutes later, while maintaining the liquid temperature at 10°C or less, to this suspension was added to the solution, the solvent of 4.2 parts of the organic amine represented by the above formula (20), 2 parts of 28% aqueous ammonia solution and 30 parts of water. Maintaining the pH of the suspension of 9.0 28% aqueous ammonia solution, the reaction. While maintaining the pH of the suspension liquid temperature was raised to 20°C for 1 hour, and the reaction was conducted further at this temperature for 8 hours. The volume of liquid at this time was 225 parts. The temperature of the reaction liquid was raised to 50°C. thereto was added 33,7 parts of sodium chloride, and the reaction liquid was stirred for 30 minutes. Then pH of the reaction liquid was brought to 1.0 within 20 minutes of concentrated hydrochloric acid. The precipitated solid was separated by filtration and washed with 100 parts of 15% aqueous solution of sodium chloride with getting 126 parts of wet sediment.

The obtained wet sediment was added to 120 parts of water, and thereto was added 25% aqueous solution of sodium hydroxide to bring the pH to 9.0, result is what those wet precipitate was dissolved. The volume of liquid at this time was 275 parts. The temperature of the resulting solution was raised to 50°C, were added to 27.5 parts of sodium chloride, and the solution was stirred for 30 minutes. Then added concentrated hydrochloric acid for 20 minutes to bring the pH to 1.0, and then the precipitated solid was separated by filtration and washed with 100 parts of a 5% aqueous solution of sodium chloride with getting 141,2 part of the wet sludge. The obtained wet sediment was added to a mixed solvent of 250 parts of methanol and 50 parts of water, and the liquid was stirred at 50°C for 1 hour. Then the solid was separated by filtration to obtain 74,9 part of the wet sludge. The obtained wet precipitate was dried to obtain a 10.6 parts of free acid target coloring substance for comparison represented by the above formula (21), in the form of a blue powder.

λmax: 602 nm (in aqueous solution).

Examples 9-13

(A) Preparation of paints

The ingredients described in the following table 2, was dissolved by stirring and filtered using 0.45 μm membrane filter (manufactured by the firm Advantec Co. Ltd.), to get the paint for evaluation. As "water" in the preparation of paints used ion-exchange water. In addition, when making the pH of the ink to 8-10 aqueous solution of hydro is sid sodium water and an aqueous solution of sodium hydroxide was added so to the total ink amount was 100 parts. The preparation of paints using the coloring matter obtained in example 1 is an Example 9, and similarly preparations paints with pigments obtained in Examples 2-4 are Examples 10-12, respectively, and the preparation of paints using the coloring matter obtained in example 8, is an Example of 13.

In addition, paint for comparison was prepared in the same way as in Examples 9 to 13, except that the used dyes for comparison obtained in the Examples of synthesis, instead of coloring substances in the samples. These preparations paints represent Comparative Example 1 (using the coloring matter for comparison obtained in Example 1 and Comparative Example 2 (using the coloring matter for comparison obtained in Example 2), respectively.

In this respect, as a "surfactant", as described in the following table 2, were used SurfynolRTM104PG50 (trade name), manufactured by the company Nissin Chemical Industry Co., Ltd.

Table 2
Composition of paint to test
The coloring matter obtained in each example is e 5.0 parts
Glycerin5.0 parts
Urea5.0 parts
N-Methyl-2-pyrrolidone4,0 part
Isopropyl alcoholto 3.0 parts
Butylcarbamoyl2.0 part
Taurine0.3 part
Disodium ethylenediaminetetraacetate0.1 part
Surfactant0.1 part
Water + aqueous solution of sodium hydroxide75,5 part
Only100.0 parts

(B) an Inkjet recording

Using an inkjet printer (manufactured by company Canon Inc., trade name: PIXUSRTMip4100), inkjet recording was performed on the paper "Kassai Photo-finishing Pro", manufactured by the company, Fujifilm Corporation, as glossy paper.

The inkjet recording pattern image was created this way to get a six gradations of density 100%, 85%, 70%, 55%, 40% and 25%, and was obtained recorded material in the Aster image, which was used as the test sample. In the test ozone resistance measurement was carried out on parts of 70% and 55% grading to determine the residual ratio of the coloring matter.

In addition, the optical density in the reflected light was measured using a colorimetric system (SpectroEyeRTM, produced by the company X-rite). The color measurement was carried out under the conditions of DIN as a criterion for density, angle of 2° and a light source D65.

Testing method of the recorded image and the method of evaluation of the tests described below.

(C) Evaluation of the recorded image

1. Test ozone resistance (high concentration of coloring matter)

Using atmospheric ozone chamber (produced by the firm Suga Test Instruments Co., Ltd., model: OMS-H), each tested sample was left under the conditions of an ozone concentration of 10‰, temperature chamber 24°C and humidity 60% RH for 64 hours. After test L*, a* and b* of each test sample was measured using the above colorimetric system, and the color difference (ΔΕ) before and after the test was calculated by using the following calculation formula, and was evaluated on a 4-point scale.

ΔΕ=(Δ2+ & Delta; b2+ & Delta; b2)1/2

In this regard, the portion of 70% of the gradation of each of the test sample used in the measurement of color. the Central value of optical density in the reflected light Dc of each of the test samples before the test amounted to 1.4.

◎: ΔΕ less than 14.

○: ΔΕ is 14 or more and less than 16.

Δ: ΔΕ is 16 or more and less than 17.

X: ΔΕ is 18 or more.

A smaller value of ΔΕ means less color change and better ozone resistance. The results are presented in the following table 3.

2. Test ozone resistance (low concentration of the coloring matter)

Using atmospheric ozone chamber (produced by the firm Suga Test Instruments Co., Ltd., model: OMS-H), each tested sample was left under the conditions of an ozone concentration of 10‰, temperature chamber 24°C and humidity 60% RH for 64 hours. In the same way as in test ozone resistance on the above high concentration of the coloring matter, each color difference (ΔΕ) before and after the test was evaluated on a 4-point scale. In this regard, when the color measurement used part gradation 55% of each test sample. The average value of the optical density in the reflected light Dc of each of the test samples before the test was 0.6.

◎: ΔΕ less than 10, 5.

○: ΔΕ is 10.5 or more and less than 11,5.

Δ: ΔΕ is equal to 11,5 or more and less 12.5.

X: ΔΕ equal to 12.5 or more.

A smaller value of ΔΕ means less color change and better ozone resistance. The results are presented in the following table 3.

3. The Dc value of the tested sample

Using the above Colo is metricheskuyu system, part gradation of 100% in each test sample was measured value of optical density in the reflected light Dc blue. This value was evaluated on a 4-point scale.

◎: The value of Dc is equal to 2.40 or more.

○: The value of Dc is equal to 2.30 or more and less 2,40.

Δ: the Value of Dc is of 2.20 or more and less 2,30.

X: the Dc Value is less than 2,20.

The greater the numerical value of Dc means a higher print density (dark) and the best quality as the blue paint. The results are presented in the following table 4.

4. Evaluation bronze sheen

Using the same printer and glossy paper for ink jet recording described above (B), was carried out by the inkjet recording densities 100%, 85%, 70%, 55%, 40% and 25% by installing a printer, and was received written material with six gradations of density. To this recorded material evaluation was carried out by visual observation, for which the gradation of the print density is the effect of bronze shimmer. The following table 4 "OK" described in the case where the effect of a bronze tint does not occur, and the lowest density with the effect of a bronze tint in the above 6 gradations of density printing is described in the case where the effect of bronze shimmer. The inkjet image recording without bronze shimmer has a great quality. The results are presented in the description of the authorized below table 4.

5. Test resistance

Using the same printer and glossy paper for ink jet recording described above (B)received written material having the lattice structure consisting of 100% and 0% density printing (corresponding printed part and not printed parts, respectively). Received recorded material was dried, leaving him for a week at ordinary temperature, and this material was used as the test sample.

A drop of ion-exchange water was poured on each of the obtained test sample, and this drop of water evaporated by direct drying during the day. Status of spreading the coloring matter of the printed parts on neotitanium part after the test was judged by visual observation. Evaluation criteria below.

Spreading on neotitanium part not see ...
See easy spreading on neotitanium part ...
Spreading on neotitanium part clear ...Δ

The results are presented in the following table 3.

Table 3
Ozone resistanceWater resistance
High concentration*Low concentration**
Example 9
Example 10
Example 11
Example 12
Example 13ΔΔ
Compare. example 1XX
Compare. example 2X
High concentration*: High concentration of the coloring matter
Low concentrat the I**: Low concentration of the coloring matter
Compare. example: Comparative example

Table 4
The Dc valueThe effect of a bronze sheen
Example 9OK
Example 10100%
Example 11OK
Example 12OK
Example 13OK
Compare. example 1OK
Compare. example 2Δ70%
Compare. example: Comparative example

As can be seen from table 3, each Example that is used as a compound of the present invention, has good ozone resistance at both high and low concentrations of cu is generating substance in comparison with Comparative example 1. This means that, for example, using paint high concentration containing the coloring matter of the present invention as a normal blue paint, and using paint low concentration containing the coloring matter of the present invention as a light blue paint, you can get a set of colors, where as usual cyan ink and light cyan ink contains coloring matter of the present invention. In addition, it becomes clear that the coloring matter of the present invention, where X in the above formula (1) represents a substituted group of aniline, in particular sulfo-substituted group of aniline, has a much better ozone resistance than the coloring matter of the present invention, where X in the above formula (1) represents a substituted group naphthylamine.

However, as for the composition of the ink of Example 10 (a paint composition containing the compound of Example 2), the resistance is "○", and the effect of the bronze tint is 100%, which shows slightly worse results compared to the other Examples considered that this is because the salt content of the compound of Example 2 was higher and had an impact.

In addition, it is confirmed that Comparative example 2 has good ozone resistance, but the very discovolante compared with Examples and, therefore, the Examples show excellent properties as ozone resistance, and water resistance. In addition, as can be seen from table 4, it is clear that the Examples have essentially excellent properties as the values of the print density Dc and resistance to the effect of a bronze tint in comparison with Comparative example 2.

Based on the above results confirmed that the recorded image of each Sample obtained from porphyrinogen the coloring matter of the present invention and the composition of the paints containing him, magnificent in respect of the balance of properties of durability and quality, such as density printing.

Example 14

(Stage 1)

The synthesis of compounds represented by the following formula (22), where 1.00 rings A to D is a pyridine ring fused at the 3 - and 4-position, the rest of 3.00 are benzene rings, the position of substitution of sulfopropyl is beta-position on the benzene ring, and Q is equal to 3.00

In chetyrehosnuju flask was added 250 parts of sulfolane, 73,86 part 4-sulfophthalic acid (used a commercial product is available in the form of a 50% aqueous solution), and 11.0 parts of 28% aqueous ammonia solution, the liquid temperature was raised to 200°C., and the reaction was carried out at this temperature for 2 hours. Then the reaction liquid was cooled to 65°C and EXT is ulali it 8,35 part of Tikhomirova acid, 72 parts of urea, and 9.1 parts of copper acetate (II) and 1 part of ammonium molybdate. The liquid temperature was again raised to 200°C., and the reaction was carried out at this temperature for 5 hours. After completion of the reaction, the reaction liquid was cooled to 65°C. and added thereto 50 parts of methanol. The precipitated solid was separated by filtration and washed with 200 parts of methanol to obtain 106,1 part of the wet sludge. The whole volume of the obtained wet sediment was added to a solution consisting of 343 parts of water, 57 parts of hydrochloric acid and 100 parts of sodium chloride, the liquid temperature was raised to 60°C., and the solution was stirred at this temperature for one hour. The precipitated solid was separated by filtration and washed with 200 parts of 20% aqueous solution of sodium chloride with getting wet sediment.

The obtained wet sediment was added to a mixed solvent of 400 parts of methanol and 100 parts of 25% aqueous sodium hydroxide solution, the liquid temperature was raised to 60°C., and the mixture was stirred at this temperature for 1 hour. The precipitated solid was separated by filtration and washed with 200 parts of methanol to obtain a 76.5 parts of wet sediment. The obtained wet sediment was added to a mixed solvent of 540 parts of methanol and 60 parts of water, the liquid temperature was raised to 60°C, and liquid premesis is whether at this temperature for 1 hour. A solid substance was separated by filtration and washed with 200 parts of methanol to obtain 72,0 part of the wet sludge. The obtained wet precipitate was dried at 80°C To produce 31,2 part of the target compounds represented by the above formula (22), in the form of a blue solid.

λmax=623 nm (in aqueous solution).

(Stage 2)

The synthesis of compounds represented by the above formula (2), where 1.00 rings A to D is a pyridine ring fused at the 3 - and 4-position, the rest of 3.00 are benzene rings, the position of substitution chlorosulfonyl group is beta-position on the benzene ring and n is equal to 3.00

To 39,8 parts of chlorosulfonic acid, adjusting so that the liquid temperature did not exceed 60°C, was slowly added 6,65 part of the connection represented by the above formula (22)obtained in example 14 (stage 1). Then the liquid temperature was raised to 120°C., and the reaction was carried out at this temperature for 4 hours. The reaction liquid was cooled to 70°C., was added dropwise to 13.4 parts of thionyl chloride for 30 minutes and then the reaction was conducted at 80°C for 3 hours. The reaction liquid was cooled to 30°C or less and slowly poured into 1000 parts of ice water. The precipitated solid was separated by a filter, the cation and washed with 100 parts of cold water with the receipt of 33.3 parts of wet sediment target compound, represented by the above formula (2) (n=3).

(Stage 3)

Synthesis porphyrinogen the coloring matter of the present invention represented by the following formula (23) [coloring matter of the above formula (1), where 1.00 rings A to D is a pyridine ring fused at the 3 - and 4-position, the rest of 3.00 are benzene rings, E represents ethylene, X represents a 2.5 desultorily, R1represents methyl, and any one of a substituted and unsubstituted sulfamoyl groups substituted in the beta position]

To 50 parts of ice water was added to 33.3 parts of the wet precipitate obtained in example 14 (stage 2), and the mixture was suspended by stirring at 5°C or less. Ten minutes later, while maintaining the liquid temperature at 10°C or less, to this suspension was added to the solution, dissolving 1,6 part of the organic amine represented by the formula (6)obtained in accordance with Example 1 (stage 3), in a mixed liquid of 1 part of 28% aqueous ammonia solution and 40 parts of water, and maintaining the pH at 9.0 to further add to it 28% aqueous ammonia solution, the reaction. While maintaining the pH of the suspension liquid temperature was raised to 20°C for 1 hour, and the reaction was conducted further at this temperature for 8 the aces. The volume of liquid in the reaction liquid at this time was 175 parts. The liquid temperature of this reaction liquid was raised to 50°C., was added 35 parts of sodium chloride, and the mixture was stirred for 30 minutes and then was added concentrated hydrochloric acid for 20 minutes to bring the pH to 1.0. The precipitated solid was separated by filtration and washed with 100 parts of 20% aqueous solution of sodium chloride with getting 61,2 part of the wet sludge. The obtained wet sediment was added to 130 parts of water, and thereto was added 25% aqueous solution of sodium hydroxide to bring the pH to 9.0, resulting in the wet precipitate was dissolved. The volume of liquid at this time was 200 parts. The temperature of this solution was raised to 50°C., was added 10 parts of sodium chloride, and then the solution was stirred for 30 minutes. Then added concentrated hydrochloric acid for 20 minutes to bring the pH of the solution to 1.0. The precipitated solid was separated by filtration and washed with 100 parts of a 5% aqueous solution of sodium chloride with getting 40,1 part of the wet sludge. The obtained wet sediment was added to a mixed liquid of 360 parts of methanol and 40 parts of water, the liquid was stirred at 50°C for 1 hour and then the solid substance was separated by filtration receipt of 18.6 parts of wet sediment. The obtained wet sediment visos the Vali with the receipt of 8.1 parts of free acid, the coloring matter of the present invention, represented by the above formula (23) (coloring matter, where b is equal to 2.5 and equal to 0.5) in the form of a blue powder.

λmax: 609,8 nm.

Example 15

(Stage 1)

The synthesis of compounds represented by the above formula (22), where 1,50 rings A to D are pyridine rings fused at the 3 - and 4-position, the remaining 2.50 each represent a benzene ring, the position of substitution of sulfopropyl is beta-position of the benzene ring, and Q is 2,50

In chetyrehosnuju flask was added 200 parts of sulfolane, 61,55 part 4-sulfophthalic acid (used a commercial product is available in the form of a 50% aqueous solution) and 9.1 parts of 28% aqueous ammonia solution, the liquid temperature was raised to 200°C., and the reaction was carried out at this temperature for 2 hours. Then the reaction liquid was cooled to 65°C. to this reaction liquid was added to 12.5 parts by Tikhomirova acid, 72 parts of urea, and 9.1 parts of copper acetate (II) and 1 part of ammonium molybdate. The temperature of the reaction liquid was again raised to 200°C., and the reaction was carried out at this temperature for 5 hours. After completion of the reaction, the reaction liquid was cooled to 65°C. and added thereto 50 parts of methanol. The precipitated solid was separated by filtration and washed with 200 parts of methanol to obtain 112,1 part of the wet sludge.

The whole volume of the obtained wet sediment was added to the solution, consisting of 343 parts of water, 57 parts of hydrochloric acid and 100 parts of sodium chloride, the liquid temperature was raised to 60°C., and the liquid was stirred at this temperature for one hour. The precipitated solid was separated by filtration and washed with 200 parts of 20% aqueous solution of sodium chloride with getting wet sediment. The obtained wet sediment was added to a mixed solvent of 400 parts of methanol and 100 parts of 25% aqueous sodium hydroxide solution, the liquid temperature of this solution was raised to 60°C., and the solution was stirred at this temperature for 1 hour. The precipitated solid was separated by filtration and washed with 200 parts of methanol to obtain 78,1 part of the wet sludge. The obtained wet sediment was added to a mixed solvent of 540 parts of methanol and 60 parts of water, the liquid temperature was raised to 60°C., and the liquid was stirred at this temperature for 1 hour. The precipitated solid was separated by filtration and washed with 200 parts of methanol to obtain 78,8 part of the wet sludge. The obtained wet precipitate was dried at 80°C To produce 28,6 part of the target compounds represented by the above formula (22), in the form of a blue solid.

λmax=612,5 nm (in aqueous solution).

(Stage 2)

The synthesis of compounds represented by the above four who Ulai (2), where 1,50 rings A to D are pyridine rings fused at the 3 - and 4-position, the remaining 2.50 each represent a benzene ring, the position of substitution chlorosulfonyl group is beta-position on the benzene ring, and n is 2,50

To 37,7 parts of chlorosulfonic acid, adjusting so that the liquid temperature did not exceed 60°C, was slowly added to 6.3 parts of a compound represented by the formula (22)obtained in example 15 (stage 1), and then the liquid temperature was raised to 120°C., and the reaction was carried out at this temperature for 4 hours. The reaction liquid was cooled to 70°C. to this reaction liquid was added dropwise to 13.4 parts of thionyl chloride for 30 minutes and then the reaction was conducted at 80°C for 3 hours. The reaction liquid was cooled to 30°C. or less, and the reaction liquid was slowly poured into 1000 parts of ice water. The precipitated solid was separated by filtration and washed with 100 parts of cold water with obtaining 33,1 part of the wet sediment target of the connection.

(Stage 3)

Synthesis porphyrinogen the coloring matter of the present invention represented by the above formula (23) [coloring matter of the above formula (1), where 1,50 rings A to D are pyridine rings fused at the 3 - and 4-position, the rest of 2.50 presented Aut a benzene ring, E represents ethylene, X represents a 2.5 desultorily, R1represents methyl, and any one of a substituted and unsubstituted sulfamoyl groups substituted in the beta position]

To 50 parts of ice water was added 33,1 part of the wet precipitate obtained in example 15 (stage 2), and the mixture was suspended by stirring at 5°C or less. Ten minutes later, while maintaining the liquid temperature at 10°C or less, to this suspension was added to the solution, dissolving 1,6 part of the organic amine represented by the formula (6)obtained in accordance with Example 1 (stage 3), in a mixed liquid of 1 part of 28% aqueous ammonia solution and 40 parts of water, and maintaining the pH at 9.0 additional by adding 28% aqueous ammonia solution, the reaction. While maintaining the pH of the suspension liquid temperature was raised to 20°C for 1 hour, the reaction was conducted further at this temperature for 8 hours. The volume of liquid in this reaction liquid at this time was 175 parts. The liquid temperature of the reaction liquid was raised to 50°C., was added thereto, 35 parts of sodium chloride, and the reaction liquid was stirred for 30 minutes. Then to the reaction liquid was added concentrated hydrochloric acid for 20 minutes to bring the pH to 1.0. The precipitated solid was separated by filtration and washed with 100 what authorities 20% aqueous solution of sodium chloride with getting 29,2 part of the wet sludge.

The obtained wet sediment was added to 150 parts of water, and thereto was added 25% aqueous solution of sodium hydroxide to bring the pH to 9.0, resulting in the wet precipitate was dissolved. The volume of liquid at this time was 200 parts. The temperature of this solution was raised to 50°C., was added 10 parts of sodium chloride, the solution was stirred for 30 minutes and then was added concentrated hydrochloric acid for 20 minutes to bring the pH to 1.0. The precipitated solid was separated by filtration and washed with 100 parts of a 5% aqueous solution of sodium chloride with getting 37,1 part of the wet sludge. The obtained wet sediment was added to a mixed liquid of 360 parts of methanol and 40 parts of water, the mixture was stirred at 50°C for 1 hour and then the solid substance was separated by filtration to obtain 19,8 part of the wet sludge. The obtained wet precipitate was dried to obtain 6,6 part of the free acid target the coloring matter of the present invention represented by the above formula (23) (coloring matter, where b is 2.0 and equal to 0.5), in the form of a blue powder.

λmax: 607,6 nm.

Examples 16 and 17

(G) Preparation of paints

Paint (ink) was prepared in the same manner as in Examples 9 to 13, except that he used the dye obtained in Example 14 and Example 15, instead of Kras is the pollutant specific each Example, used in Examples 9-13. Preparations of these colors represent the Example 16 and Example 17, respectively.

(D) an Inkjet recording

Using each of the Example 16, Example 17, and the above-described Comparative example 1, an inkjet recording was carried out as described below glossy paper using an inkjet printer (manufactured by company Canon Inc., trade name: PIXUSRTMip4500).

The inkjet recording pattern image was created this way to get a six gradations of density 100%, 85%, 70%, 55%, 40% and 25%, and was obtained recorded material in a bitmap image, which was used as the test sample.

In this regard, the color measurement of the optical density in the reflected light was performed on the same system and under the same conditions as in the above-described inkjet recording (B).

Glossy paper A: "Kassai Photo-finishing Pro"manufactured by the company Fujifilm Corporation.

(E) Evaluation of the recorded image

1. Test ozone resistance

Using atmospheric ozone chamber (produced by the firm Suga Test Instruments Co., Ltd., model: OMS-H), each tested sample was left under the conditions of an ozone concentration of 80%, and the chamber temperature of 24°C and humidity 60% RH for 4 hours. After testing the optical density in the reflected light of each test sample was measured using the above kolorimetricheskoe the system. The residual ratio of the coloring matter was determined by calculation based on the following calculation: (optical density in the reflected light after the test/optical density of the reflected light before the test) × 100(%), and was evaluated on the following 4-point scale.

In this regard, when tested for ozone resistance measurement was carried out on part of the grading 70%. The results of the evaluation are presented in the table below 5.

The residual ratio of the coloring matter is 85% or more ... ◎

The residual ratio of the coloring matter less than or equal to 85% and 80% or more ... ○

The residual ratio of the coloring matter less than or equal to 80% and 75% or more ... Δ

The residual ratio of the coloring matter less than or equal to 75% ... X

Table 5
The result of evaluatingOzone resistance
Glossy paper And
Example 16
Example 17
Comparative example 1Δ

2. Test tone

The test tone was measured part gradation of 70%using wicheap the sliding colorimetric system, and evaluate the deviation of the color from the standard colors. At this time, the measured Dc value of the tested sample ranged from 1.3 to 1.5.

As the standard blue color used sample (3rd version) solid marker paint Japan Color standard published by the Japan National Committee For ISO/TC130. The results of measurement of L*, a* and b* standard colors are as described below.

Standard color: L*=57,28, and*=-30,49 and b*=-44,67.

When evaluating the measured L*, a* and b* of each test sample, and determined the color difference (ΔΕ) with a standard color on the basis of the following calculation formula.

As a result, the value (ΔΕ) in each image obtained in Examples 16 and 17 of the present invention, ranged from less than 4 to 7, and the value (ΔΕ) in the image obtained in Comparative example 1, ranged from less than 7 to 9. A smaller numerical value of ΔΕ means closer to the standard color.

None of the examples 16 and 17 were not observed effect of a bronze tint at any density.

As it is clear on the basis of the above results, it is confirmed that Examples 14 and 15 are the best both in terms of the ozone resistance, and in the shade than Comparative example 1.

Industrial applicability

The recorded image obtained piperazinonyl dye really hard is retenu and composition of paint, containing it, can give excellent properties of durability and high print density and almost does not cause the effect of a bronze tint, which reduces the quality of the recorded images, and therefore they are very useful as inks for various recording systems, in particular, as the ink (ink for inkjet recording.

1. Porphyrazine dye or its salt represented by the following formula (1)

where the rings A to D represented by broken lines, each independently represents a benzene ring or 6-membered nitrogen-containing heteroaromatic ring fused with piperazinonyl ring, where the number of nitrogen-containing heteroaromatic rings is more than 0.00 and of 3.00 or less as an average value, and the rest are benzene rings,
E represents a C2-C12alkylen,
X represents a group of sulfonanilide, group carboxyaniline, group postroeniya, group alphanaphthylamine, group carboxymethylamino or group of postdonation and may optionally have a substituent at least one group selected from the group consisting of sulfopropyl, carboxypropyl, phosphono group, sulfamoyl group, carbamoyl group, a hydroxy-group, C1-C6alkoxygroup is s, amino, mono-C1-C4alkylamino, di-C1-C4alkylamino, monoarylamino, diarylamino, C1-C3alkylcarboxylic, ureides group, C1-C6alkyl groups, nitro, ceanography, halogen atom, a C1-C6alkylsulfonyl group and C1-C6allylthiourea,
R1represents a C1-C6alkyl group,
b is, as the average value is 0.00 or more and less 3,90,
c as the average value of 0.10 or more and less than 4,00, and
the sum of b and c are equal, as the average value of 1.00 or more and less than 4,00.

2. Porphyrazine dye or its salt according to claim 1, where the 6-membered nitrogen-containing heteroaromatic ring represented by the rings A to D is a pyridine ring or pyrazinone ring.

3. Porphyrazine dye or its salt according to claim 1, which is obtained by reacting compounds of porphyrazine represented by the following formula (2), with an organic amine represented by the following formula (3), in the presence of ammonia,

where rings A-D have the same meanings as described in claim 1, and n is 1.00 or more and less than 4,00

where E, X and R1have the same meanings as described in claim 1.

4. Piperazinone painting is its substance or its salt according to claim 1, where
E represents a C2-C4alkylen,
R1represents a C1-C3alkyl group, and
X represents a group of sulfonanilide, group carboxyaniline, group postroeniya, group alphanaphthylamine, group carboxymethylamino or group of postdonation and additionally has as Deputy from 0 to 3 groups of at least one species selected from the group consisting of sulfopropyl, carboxypropyl, phosphonopropyl, hydroxy-group, C1-C6alkoxygroup, C1-C3alkylcarboxylic, ureides group, nitro group and a chlorine atom.

5. Porphyrazine dye or its salt according to claim 4, where
E represents remotemachine C2-C4alkylen, and
X represents a group of sulfonanilide or group of carboxyaniline and additionally has as Deputy from 0 to 2 groups of at least one species selected from the group consisting of sulfopropyl, carboxypropyl, hydroxy-group, C1-C6alkoxygroup, nitro and chlorine atom.

6. Porphyrazine dye or its salt according to claim 1, where
nitrogen-containing heteroaromatic ring for the rings A to D each independently represents a pyridine ring fused at the 2 - and 3-position or at the 3 - and 4-position; or pyrazinone ring, con is inspirowane in 2 - and 3-position
E represents ethylene or propylene, and
X represents a group of sulfonanilide or group of carboxyaniline and additionally has as Deputy from 0 to 2 groups of at least one species selected from the group consisting of sulfopropyl, carboxypropyl, hydroxy-group, C1-C6alkoxygroup, nitro and chlorine atom.

7. Porphyrazine dye or its salt according to claim 1, where
nitrogen-containing heteroaromatic ring for the rings A to D each independently represents a pyridine ring fused at the 2 - and 3-position or at the 3 - and 4-position.
E represents ethylene or propylene, and
X represents a group of sulfonanilide or group of alphanaphthylamine where the group of sulfonanilide additionally has as Deputy from 0 to 2 groups selected from the group consisting of sulfopropyl, carboxypropyl, hydroxy-group, C1-C6alkoxygroup, amino, mono-C1-C4alkylamino, di-C1-C4alkylamino, C1-C3alkylcarboxylic, C1-C6alkyl group, nitro group, chlorine atom, C1-C6alkylsulfonyl group and C1-C6allylthiourea, and group alphanaphthylamine additionally has as a substituent, 1 or 2 groups selected from the group consisting of soulful uppy, hydroxy-group and nitro group.

8. Porphyrazine dye or its salt according to claim 1, where
nitrogen-containing heteroaromatic ring for the rings A to D each independently represents a pyridine ring fused at the 2 - and 3-position or at the 3 - and 4-position, where their number is equal, as an average, more than 0.00 and of 3.00 or less, and the remaining number of benzene rings as well as the average value of 1.00 or more and less than 4,00,
E represents ethylene,
X represents a group of desultorily or group of alphanaphthylamine where the group of alphanaphthylamine additionally has as a substituent, 1 or 2 groups of one or two kinds selected from the group consisting of sulfopropyl and hydroxy-group,
R1represents a C1-C4alkyl group,
b is, as the average value is 0.00 or more and less 3,90,
c as the average value of 0.10 or more and less than 4,00, and
the sum of b and c as the average value of 1.00 or more and less than 4,00.

9. The composition of the inks for ink jet printing containing porphyrazine dye or its salt according to claim 1 or 8 as the coloring matter.

10. The composition of the ink for inkjet printing according to claim 9, which further comprises an organic solvent.

11. The composition of the ink for inkjet printing according to claim 10, which is for inkjet recording.

12. With rainy the way you write, where recording is carried out on the receiving material for recording by ejection of droplets of the ink composition, the ink containing porphyrazine dye or its salt according to claim 1 in response to the print signal.

13. Inkjet recording method according to item 12, where receiving the print is a reference sheet.

14. Inkjet recording method according to item 13, where the reference sheet is a sheet subjected to surface treatment, and this sheet is a sheet having a receiving layer for ink containing particles of a white inorganic pigment on a substrate.

15. The container containing the composition of the paints containing porphyrazine dye or its salt according to claim 1.

16. An inkjet printer that contains the container according to item 15.

17. Colored product colored paint composition containing porphyrazine dye or its salt according to claim 1.

18. Porphyrazine dye or its salt according to claim 1 or 8, where X is a group of desultorily or group of desulfonation, which may be substituted by a hydroxy-group.

19. Porphyrazine dye or its salt p, where X is a group of desultorily.

20. The composition of the inks for ink jet printing containing porphyrazine dye or its salt according to claim 1, water and organic races of foretell.

21. The composition of the inks for ink jet printing containing porphyrazine dye or its salt according to claim 1 or 8, where X is a group of desultorily or group of desulfonation, which may be substituted by a hydroxy-group, water and an organic solvent.



 

Same patents:

FIELD: printing.

SUBSTANCE: invention relates to an ink set containing chromophoric metals for digital printing on ceramic materials. The ink set comprises liquid colouring compositions (A), (B), (C) and one from (D) and (E). The (A) comprises at least a compound of cobalt. The (B) comprises at least a compound of iron. The (C) comprises at least a compound of a metal selected from chromium, nickel and their mixtures. The (D) comprises at least a compound of cobalt and at least a compound of iron. The (E) comprises one or more compounds of zirconium. The said metal compounds decompose at a temperature of from 500 to 1300°C. When interacting with the ceramic material the metal compounds of compositions (A)-(D) form colured oxides or colured compounds. The compounds of zirconium from the composition (E) with the ceramic material form white oxides or white compounds. Also the method of decorating ceramic materials by digital printing using the specified set of ink and the decorated ceramic products produced using this method are described.

EFFECT: invention provides ceramic materials decorated with digital printing of wide range of colours with the effect of natural stone.

11 cl, 45 tbl, 5 ex

Conductive pastes // 2509789

FIELD: chemistry.

SUBSTANCE: invention relates to conductive pastes for forming metal contacts on the surface of substrates for photovoltaic cells. The conductive paste is substantially free of frit glass. According to one version of the invention, the conductive paste contains organometallic components which form a solid metal oxide phase upon firing and conductive material. The organometallic components are selected from a group which includes metal carboxylates or metal alkoxides, where the metal is boron, aluminium, silicon, bismuth, zinc or vanadium. According to another version, the conductive paste includes multiple precursors which form conductive elements upon firing or heating. The paste is adapted for adhesion to the surface of a substrate and upon firing, forms a solid oxide phase while forming an electrical conductor from conductive materials on the substrate.

EFFECT: use of said conductive paste in a line of a conductive array of photovoltaic cells provides high efficiency and fill factor of the photovoltaic cell.

14 cl, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: composition for making sensor coatings contains antimony-doped tin dioxide of the formula SbxSn1-xO2, where x=0.1-0.3, and water in ratio SbxSn1-xO2:H2O = 89-87:11-13 wt %. The method of preparing the composition involves hydrothermal treatment of tin and antimony hydroxides at 170°C for 48 hours. The tin and antimony hydroxides are obtained by dissolving Sn and Sb metal in concentrated hydrochloric acid, 18-20 wt %, while adding 3-5 wt % concentrated HNO3. The obtained solution is 2-3 times diluted with distilled water and a calculated amount of ammonia solution is added. Using a simple scheme, the disclosed method enables to obtain nanoparticles of said composition SbxSn1-xO2 with size of 30 nm and surface area of 154 m2/g, which can be used as the basic component of electroconductive ink for printing sensor arrays and microcontacts.

EFFECT: low labour and power consumption.

3 cl, 6 dwg, 3 ex

PRINTING PRODUCT AND METHOD OF ITS MANUFACTURING

FIELD: chemistry.

SUBSTANCE: conductive paste contains frit glass, a conductive material, an organic medium and one or more organometallic components which form metal oxides when burnt. The organometallic components are selected from a group comprising a metal carboxylate and a metal alkoxide, where the metal is boron, aluminium, silicon, bismuth, zinc or vanadium. When deposited on antireflecting coating on a substrate, the conductive paste is capable of penetrating the coating to form an ohmic contact with the substrate. Described also is a photovoltaic cell, having a semiconductor substrate, an antireflecting coating and lines of a conductive mesh formed from said conductive paste.

EFFECT: high efficiency of the photovoltaic cell, improved adhesion and ohmic contact between metallic elements and the substrate through antireflecting coatings.

10 cl, 1 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to use of a composition which contains: a) 0.1-20 wt % binder which contains a polycarbonate derivative based on geminally disubstituted dihydroxydiphenyl cycloalkane, b) 30-99.9 wt % solvent, c) 0-10 wt %, with respect to dry mass, dye or mixture of dyes, d) 0-10 wt % functional material or mixture of functional materials, e) 0-30 wt % additives and/or auxiliary substances or a mixture thereof, as jet printing ink. The invention also relates to a method of producing a composite and a composite which contains a polymer layer on which there is a jet printing layer of said composition.

EFFECT: invention is aimed at producing agents which enable to use jet printing in making counterfeit protected documents and/or valuable documents based on polycarbonate layers, and which enable to deposit jet printing layers on layers which meet all optical requirements, which can be coloured, wherein lamination does not deteriorate optical properties of the layers and said layers do not act as a separating layer and facilitate formation of a monolithic composite.

31 cl, 2 tbl, 2 dwg, 8 ex

FIELD: chemistry.

SUBSTANCE: invention relates to jet printing inks, particularly non-aqueous inks for jet printing. The ink for jet printing contains a pigment, binder, polyetheramide resin as a pigment dispersant, an organic solvent and an anti-corrosion agent from an imidazole group or a group of volatile anti-corrosion agents, preferably dicyclohexylamine or cyclohexylammonium cyclohexylcarbamate.

EFFECT: disclosed inks have high dispersion stability and prevent corrosion of print heads of jet printers and nozzle clogging.

8 cl, 8 tbl, 34 ex

FIELD: food industry.

SUBSTANCE: proposed print compound in the form of print ink or print varnish includes a binding substance with a resinous component and a solvent component. The binding substance solvent represents a one-component or multicomponent saturated resin solvent and a food product or food additive of a number of monoglycerides and/or diglycerides and/or triglycerides. Preferably, the binding substance solvent component includes acetylated or esterified monoglycerides and/or acetylated or esterified diglycerides and/or acetylated or esterified triglycerides.

EFFECT: print ink solvent migration degree reduction and treatment simplification in view of the possibility of the print compound drying-out by way of absorption and re-varnishing exclusion.

4 cl, 3 ex

FIELD: printing industry.

SUBSTANCE: proposed invention relates to a printing item comprising a substrate and a combination of printed inks including six colours. Each of colours is defined with a full tone and a half-tone of the specified colour, at the same time each ink has a value of colour difference dE of the combined full tone L-C-H-a-b, which is less than or equal to 2, and a value dE of the combined half-tone, which is less or equal to 3.

EFFECT: invention provides for production of printing items, which reproduce patterns with high accuracy.

7 cl, 1 dwg

FIELD: textiles and paper.

SUBSTANCE: non-woven fabric is proposed, on the visible surface of which the ink composition is applied comprising from about 40 wt % to about 80 wt % of the dry weight of the ink of linking agent - aziridine oligomer with at least two aziridine functional groups. Also an absorbing article is proposed comprising a liquid-permeable upper layer, an absorbing core and a liquid-impermeable lower layer that contains the specified non-woven fabric with the said applied ink composition. The application of ink on the non-woven fabric can be carried out by the method of flexography or a method of ink-jet printing.

EFFECT: printed non-woven fabric has high resistance to abrasion even in case of its contacting with fatty substance.

16 cl, 2 dwg, 2 tbl, 2 ex

FIELD: printing industry.

SUBSTANCE: invention relates to ink for jet printing containing at least one dye-stuff, besides: dye-stuff is a compound represented by the following formula (I), or its salt; dye-stuff content (wt %) is 3.0 wt % or more to the total weight of ink for jet printing; in distributing molecules aggregates in ink for jet printing with dye-stuff concentration determined as 3.0 wt %, according to scatter range, measured using method of small-angle x-ray scattering, scatter distance value (d75 complying with the fact that 75% of distributing is 3.0 wt %) is 6.50 nm or more and 7.10 nm or less: common formula (I) , where M means alkali metal or ammonium; I means from 0 to 1, m means from 1 to 2, and n means from 2 to 3 under condition that l+m+n=3 and position of substituent replacing is position 4 and 4.

EFFECT: obtaining ink for jet printing.

3 cl, 1 ex, 9 tbl, 9 dwg

FIELD: polygraphic industry.

SUBSTANCE: ink for jet printing is described including water, watersoluble organic solvent and coloring substance which is phthalocyanine compound. Content of specified coloring substance is in the range of 0.5 wt % ≤ content < 3.0 wt % relative to ink weight. Watersoluble organic solvent includes 2-pyrrolidone in amount of 50.0% or more relative to ink weight. Value of dispersion distance d75, measured using small angle X-ray scattering method for molecular aggregates in ink corresponds to 75% of dispersion distance distribution. Suggested ink is high resistant to ambient gases, to coloring substance aggregation and provides bronze play-resistant images.

EFFECT: getting ink that is high resistant to ambient gases, to coloring substance aggregation and provides bronze play-resistant images.

12 cl, 9 dwg, 9 tbl, 8 ex

FIELD: organic chemistry.

SUBSTANCE: invention relates, in particular, to new tetrapyrrole macroheterocycles - diphenyloctaalkylporphynes that can be used as a dyeing substance for optical filters. Invention describes 5-(4'-acrylamidophenyl)-10,15,20-triphenylporphyne (I) and 5-(3'-acrylamidophenyl)-10,15,20-triphenylporphyne (II) as a dyeing substance for optical filters. Indicated compounds show the maximum absorption value in the range 650 nm and can be used for preparing colored polymers.

EFFECT: valuable properties of substances.

1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to tetra-(5-acetylamino-7-heptyloxy)anthraquinonoporphyrazines of copper and cobalt of formula .

EFFECT: obtained compounds can be used as dyes and catalysts.

4 ex, 5 dwg,

FIELD: chemistry.

SUBSTANCE: invention relates to tetra-(5-acetylamino-7-hydroxy)anthraquinonoporphyrazines of copper and cobalt of formula

.

EFFECT: compounds can be used as dyes and catalysts.

4 ex, 6 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to novel chemical compounds - tetra-(5-octadecylsulfamoyl)anthraquinone porphirazines of copper and cobalt of formula:

EFFECT: compounds can be used as dye in polymer materials and as a catalyst in different processes.

1 cl, 2 ex, 5 dwg

FIELD: chemistry.

SUBSTANCE: described is a catalyst for oxidative demercaptanisation of oil and oil products which is a derivative of phthalocyanine, distinguished by that it is a supramolecular ion-associate of oppositely charged phthalocyanines with structural formula I, I:(R+)nPcM, where R=-CH2N+(CH3)2CH2CH2OHCl- (choln- PcM), n=2÷8, M=Co, Fe; (pymn-PcM), n=2÷8, M=Co, Fe; (R-)nPcM, where R=-CH2P(=O)(O-Na+)2(phosn-PcM), n=8, M-Co and II, II:(R-)nPcM, where R=R1=R2=-C(O)O-Na+ (carb8-PcM), n=8, M=Co, Fe; R=R1=-C(O)O-Na+, R2=H (carb4-PcM), n=4, M=Co; R= R1=-S(O)2O-Na+ , R2=H (sul4-PcM), n=4, M=Co. Also described is a method of oxidative catalytic demercaptanisation of oil and oil products with atmospheric oxygen in an alkaline medium in the presence of the above described catalyst at room temperature.

EFFECT: carrying out the process in mild conditions with high substrate conversion to 98 percent.

3 cl, 2 tbl, 26 ex

FIELD: chemistry.

SUBSTANCE: invention relates to self-organising supramolecular ion-associates of oppositely charged phthalocyanines and their use for oxidising sodium sulphide. A catalyst for oxidising sodium sulphide is described, where the said catalyst is a phthalocyanine derivative and is distinguished by that, it is a supramolecular ion-associate of oppositely charged phthalocyanines with structural formula I, I:(R+)nPcM, where R=-CH2N+(CH3)2CH2CH2OHCl- (choln- PcM), n=2÷8, M=Co, Fe; (pymn-PcM), n=2÷8, M=Co, Fe; (R-)nPcM, where R=-CH2P(=O)(O-Na+)2(phosn-PcM), n=8, M-Co and II, II:(R-)nPcM, where R=R1=R2=-C(O)O-Na+ (carb8-PcM), n=8, M=Co, Fe; R=R1=-C(O)O-Na+, R2=H (carb4-PcM), n=4, M=Co; R= R1=-S(O)2O-Na+ , R2=H (sul4-PcM), n=4, M=Co. Also described is a method of oxidising sodium sulphide with oxygen in the presence of the above described catalyst.

EFFECT: achieved complete substrate conversion corresponding to activity 3.1x103 mol(Na2S)/mol (catalyst) min.

3 cl, 2 tbl, 44 ex

FIELD: chemistry.

SUBSTANCE: catalyst for oxidative demercaptanisation of oil and oil products is described, where the said catalyst is phthalocyanine deposited activated carbon and is distinguished by that, it contains charged phthalocyanine with structural formula I or its supramolecular ion-associates with oppositely charged phthalocyanine with structural formula I, I:(R+)nPcM, where R=-CH2N+(CH3)2CH2CH2OHCl- (choln- PcM), n=2÷8, M=Co, Fe; (pymn-PcM), n=2÷8, M=Co, Fe; (R-)nPcM, where R=-CH2P(=O)(O-Na+)2(phosn-PcM), n=8, M-Co or II, II:(R-)nPcM, where R=R1=R2=-C(O)O-Na+ (carb8-PcM), n=8, M=Co, Fe; R=R1=-C(O)O-Na+, R2=H (carb4-PcM), n=4, M=Co; R= R1=-S(O)2O-Na+ , R2=H (sul4-PcM), n=4, M=Co. Also described is a method of oxidative catalytic demercaptanisation of oil and oil products with atmospheric oxygen at room temperature in the presence of the above described catalyst.

EFFECT: carrying out the process in mild conditions with complete substrate conversion.

4 cl, 2 tbl, 59 ex

FIELD: chemistry.

SUBSTANCE: invention concerns novel chemical compound of copper tetra-6-[4-(hexyloxy)benzoyloxy]anthraquinonoporphyrazine of the formula .

EFFECT: application as colourant for polymer materials.

1 cl, 2 ex, 5 dwg

FIELD: organic chemistry of complex compounds.

SUBSTANCE: invention relates to novel derivatives of metalloporphyrazine of the formula (I) that can be used as dyes, catalysts in different processes. Invention provides preparing compounds possessing with coloring properties.

EFFECT: valuable properties of complexes.

5 dwg, 4 ex

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