Triazinylaminostilbene disulfone acid mixes

FIELD: chemistry.

SUBSTANCE: invention concerns fluorescent bleach containing a mix of two asymmetrically substituted and one symmetrically substituted triazinylaminostilbene disulfone acid, a new symmetrically substituted derivative, method of their obtaining, and application of the mix in synthetic or natural organic material (especially paper) bleaching and in fluorescent bleaching and sun resistance boost of textile.

EFFECT: high substantivity and light resistance of the claimed fluorescent bleaches and their mixes, and better water solubility of the claimed mixes in comparison to the solubility of each individual bleach.

15 cl, 2 tbl, 12 ex

 

The present invention relates to a fluorescent bleach, containing a mixture of two symmetric and one asymmetrically substituted disulfonic acid triethynylbenzene new asymmetrically substituted derivatives, method for their production and the use of this mixture for whitening synthetic or natural organic materials, primarily paper, and fluorescent whitening and improve factors of sun protection textiles.

The mixture creatinineclearance acid for bleaching paper have been described in the patent US 3132106. However, such mixtures are limited tetrasulfonic acids which are particularly suitable for bleaching paper in the processing of paper pulp, but less desirable for use in modern technology bleaching, such as dyeing or use in sizing presses.

Unexpectedly it was found that mixtures disulfonic acid triethynylbenzene extremely suitable for use not only in the processing of paper pulp, but also for dyeing (or coating) paper and use in sizing presses, where they show a high degree of whiteness and, therefore, can be included in a stable liquid compositions.

Accordingly this invention relates to a fluorescent bleach, to the which contains a mixture of compounds of the formula

in which the radicals R1and R2different and each represents-NH2, -NHC1-C4alkyl, -N(C1-C4alkyl)2, -NHC2-C4hydroxyalkyl, -N(C2-C4hydroxyalkyl)2, -N(C1-C4alkyl)(C2-C4hydroxyalkyl), morpholino-, piperidino or pyrolidine residue or amino acid or amide residue amino acids in which the amino group is removed hydrogen, each radical R3independently represents hydrogen, C1-C4alkyl or C1-C4alkoxygroup, and M denotes hydrogen, an alkali metal atom, ammonium or a cation formed from an amine, and R3preferably represented by hydrogen.

When R1and/or R2denote amino acid or amide residue amino acids, they are preferably represented by the formula

-NR4'-CH(CO2H)-R4(2) or-NR4-CH2CH2CONH2(3),

in which R4and R4' independently denote hydrogen or a group of the formula-CHR5R6in which R5and R6independently represented by hydrogen or C1-C4the alkyl, optionally substituted by one or two substituents selected from the group consisting of hydroxy thio-, methylthio, amino group, carboxypropyl, alphagroup, phenyl, 4-hydroxyphenyl, 3,5-diid-4-hydroxyphenyl, β-indolyl, β-imidazolyl and NH=C(NH2)NH-.

More preferably, if the R1and/or R2derived from glycine, alanine, sarcosine, serine, cysteine, phenylalanine, tyrosine (4-hydroxyphenylglycine), diiodotyrosine, tryptophan (β-indoleamine), histidine (β-imidazolylidene), α-aminobutyric acid, methionine, valine (α-aminosalicilovoj acid), Norvaline, leucine (α-aminoisoquinoline acid), isoleucine (α-aminoβ-methylvaleramide acid), norleucine (α-amino-n-Caproic acid), arginine, ornithine (α,δ-diaminopurine acid), lysine (α,ε-diaminopropionic acid), aspartic acid (amino amber acid), glutamic acid (α-aminoglutaric acid), threonine, hydroxylamino acid and taurine, as well as their mixtures and optical isomers, or from iminodiacetic acid or N-(propionamido)-N-(2-hydroxyethyl)amine. However, most preferably R1and/or R2denote NHC2-C4hydroxyalkyl, -N(C2-C4hydroxyalkyl)2, -N(C1-C4alkyl)(C2-C4hydroxyalkyl), the remainder of the research or the residue of glycine, sarcosine, taurine, glutamic acid, aspartic acid or iminodiacetic acid and in particular, if R1and R2presents mono-(2-hydroxyethyl)amino group, di(2-hydroxyethyl)amino group, di(2-hydroxypropyl)amino group, N-(2-hydroxyethyl)-N-methylaminopropane, aspartic acid, iminodiacetic acid or a residue of the research.

In the compounds of formulas (1A)-(1C) M represents hydrogen, lithium, potassium, sodium, ammonium, mono-, di-, tri - or Tetra-C1-C4alkylammonium, mono-, di - or tri-C1-C4hydroxyethylammonium or ammonium, with two or three substituent selected from a mixture With1-C4alkyl and C1-C4hydroxyalkyl groups, i.e. H2N+(C1-C4alkyl)(C1-C4hydroxyalkyl) and HN+(C1-C4alkyl)m(C1-C4hydroxyalkyl)nwhere n and m denote 1 or 2, but preferably M represents hydrogen, potassium or sodium.

In the most preferred aspect of the invention relates to the fluorescent Brightener containing a mixture of compounds of formulas (1A), (1b) and (1C), in which R1denotes a mono-(2-hydroxyethyl)amino or di-(2-hydroxyethyl)amino group, R2denotes a di-(2-hydroxyethyl)amino group, di(2-hydroxypropyl)amino group, a residue of aspartic acid or iminodiacetic acid, while R1and R2are different, r3presents gorodom and M is represented by sodium.

When R1, R2and/or R3include1-C4alkyl radicals, they can be branched or unbranched and are, for example, methyl, ethyl, n-propyl, isopropyl or n-butyl, isobutyl or tert-butyl, whereas With1-C4alkoxygroup represents, for example, methoxy, ethoxy-, propoxy-, isopropoxy, h-butoxy, isobutoxy - or tert-butoxypropan. With1-C4hydroxyalkyl can be represented, for example, hydroxymethyl, hydroxyethyl, hydroxypropyl or hydroxybutyl.

The mixture of compounds of formulas (1a), (1b) and (1C) can be obtained by the interaction of a known reaction conditions, cyanuric acid chloride acid in any desired sequence, in a row with 4,4'-diaminostilbene-2,2'-disulfonic acid, aniline or its derivative, aminecontaining compound R1H and aminecontaining compound R2H, or, alternatively, a mixture of aminecontaining compounds R1H and R2H, where R1and R2have the meanings given above. However, preferably, if the acid chloride cyanuric acid initially interacts with 4,4'-diaminostilbene-2,2'-disulfonic acid, and then is introduced into the reaction with aniline or its derivatives containing alkyl or alkoxygroup, and finally with a mixture of aminecontaining compounds R1 H and R2H.

Depending on the quantities and ratios of amines R1H and R2H and the conditions they are added, sequentially or simultaneously in the form of a mixture, the ratio of the compounds (1A), (1b) and (1C) can significantly vary. Thus, this invention relates to a fluorescent bleach, containing a mixture of compounds (1A), (1b) and (1C), in which each component is contained in a molar ratio of between 5 and 80%, preferably they are present in the approximate molar ratio of 5 to 45% of the compounds of formula (1A), 15-60% of the compound of formula (1b) and 5-45% of the compound of formula (1C). More preferably the compounds (1A), (1b) and (1C) are contained in the approximate molar ratio of 20-50% of the compounds of formula (1A), 25-50% of the compound of formula (1b) and 5-35% of the compound of formula (1C).

Of course, such compositions can also be obtained by simple mechanical mixing of the individual components in the desired proportions. In this case, you must obtain the individual components in the form of pure substances. While the components of the formulas (1A) and (1C) are known compounds or can be obtained by the known methods, the compounds of formula (1b) are new. In accordance with this, the next object of the invention is a compound of the formula

in which R1, R2, R3and M have the above specified values.

The compound of formula (1b) can be obtained by purification of the mixture obtained as described above or, for example, using the following sequence of reactions:

1) the reaction of the acid chloride cyanuric acid 4-amino-4'-nitrostilbene-2,2'-disulfonic acid with the acid chloride cyanuric acid;

2) reaction dichloropropanol with aniline or aniline derivative;

3) reaction monochloropropane with the amine R1H, or R2N;

4) restore nitrostilbene to aminostilbene;

5) reaction with acid chloride cyanuric acid;

6) the reaction dichloropropanol with aniline or aniline derivative and

7) reaction monochloropropane with the amine R2H, or R1H.

Of course, this sequence of reactions may be carried out in any desired and convenient manner.

The next object of the invention is the use of a composition containing water, a fluorescent bleach, which contains a mixture of compounds (1a), (1b) and (1C) and optional excipients, for whitening synthetic or natural organic materials.

More specifically, such bleaching compositions contain water and above a certain mixture of a fluorescent Brightener in an amount of from 3 to 25 wt.% (in each case based on the weight of the composition), preferably from 5 to 15 wt.%, and auxiliary materials the performance communications substances in quantities of from 0 to 60 wt.%, preferably from 5 to 50 wt.%.

Suitable excipients include, for example, anionic or non-ionic dispersants, belonging to the class of adducts of ethylene oxide and fatty alcohols, higher fatty acids or ALKYLPHENOLS, or adducts of ethylendiaminetetraacetic-propylene oxide, copolymers of N-vinylpyrrolidone and 3-fenilpropionovoy acid, auxiliary funds that hold water, such as ethylene glycol, glycerol or sorbitol, or biocides.

The following excipients used to obtain stable liquid compositions, and to increase the bleaching effect of the compounds represented by, for example, glycols. Such glycols can have an average molecular weight varying within wide limits, for example, from about 200 to about 2000, the most appropriate is the molecular weight of about 1500.

The majority of the compositions containing a mixture of compounds of formulas (1a), (1b) and (1C)are excellent fluorescent brighteners of substrates such as textiles, used to be added to detergent compositions and, in particular, for the fluorescent whitening of paper.

When used for the fluorescent whitening of paper compositions that contain water, a fluorescent bleach, containing a mixture of soybean is ineni (1A), (1b) and (1C) and optional excipients, can be applied in the form of a composition for coating paper for application to a paper substrate in the paper pulp or directly at the size press or plunger presses.

In one preferred aspect of this invention is a method of fluorescent whitening of a paper surface, comprising contacting the paper surface with a composition for coating containing a white pigment, a binder dispersion, optional water-soluble covetous substance and a sufficient amount of fluorescent Brightener containing a mixture of compounds (1A), (1b) and (1C), corresponding to the invention, so that the processed paper contains from 0.01 to 1 wt.% fluorescent Brightener in the calculation of the white pigment.

As a white pigment as a component of the composition for the cover used in accordance with the method of the present invention, can be called a preferably inorganic pigments, such as aluminum silicate and magnesium, such as China clay and kaolin, and, further, barium sulfate, setinit (a mixture of aluminium hydroxide, lime and calcium sulfate), titanium dioxide, calcium carbonate (chalk) or talc, as well as white organic coloring matter.

Compositions for coating paper, used with the availa able scientific C with the method of coating according to this invention, can contain as binders, among others, plastic dispersions based on copolymers of butadiene/styrene, Acrylonitrile/butadiene/styrene, esters of acrylic acid, esters of acrylic acid/styrene/Acrylonitrile, ethylene/vinyl chloride and ethylene/vinyl acetate or homopolymers, such as polyvinyl chloride, grades, polyethylene and polyvinyl acetate or polyurethane. Preferred binders are composed of copolymers of styrene/butyl acrylate or styrene/butadiene/acrylic acid or styrene/butadiene rubbers. Other polymeric grating are disclosed, for example, in the descriptions of the patents US 3265654, 3657174, 3547899 and 3240740.

As an optional water-soluble protective colloid substances include, for example, soy protein, casein, carboxymethyl cellulose, natural or modified starch, chitosan or its derivative, or, in particular, polyvinyl alcohol. The preferred polyvinyl alcohol as a protective colloid component can have levels of saponification and the molecular weight within wide limits, for example, the level of saponification in the range from 40 to 100 and an average molecular weight in the range from 10000 to 100000.

Finished the compositions for coating paper described, for example, in the books J.P.Casey "Pulp and Paper (pulp and paper); Chemistry and Chemical Technology (Chemistry and chemical is a mini-technology), 2nd ed., volume III, s-1649 and "Pulp and Paper Manufacture" (Paper pulp and paper production), 2-nd and 5-th ed., volume II, s (McGraw-Hill).

Compositions for coating paper used in accordance with the method of this invention preferably contain from 10 to 70 wt.% white pigment. The binder is preferably used in a quantity sufficient to maintain the dry content of the polymer compound in the range from 1 to 30 wt.%, preferably from 5 to 25 wt.%, in the calculation of the white pigment. The quantitative composition of the fluorescent Brightener used in accordance with the invention, is calculated so that the fluorescent Brightener is preferably contained in an amount of from 0.01 to 1 wt.%, more preferably from 0.05 to 1 wt.% and most preferably from 0.05 to 0.6 wt.%, in the calculation of the white pigment.

A composition for coating paper used in accordance with the method of this invention can be prepared by mixing the components in any desired sequence at a temperature of from 10 to 100°C, preferably from 20 to 80°C. components In this composition may also include conventional excipients that are added to regulate the rheological properties such as viscosity or the ability of the composition to cover to retain water. As such aircraft is magatelli substances can be called, for example, natural binders, such as starch, casein, protein or gelatin, ethers of cellulose, such as karboksimetilcelljuloza or hydroxyethylcellulose, alginic acid, alginates, polyethylene oxide or simple alkalemia esters of polyethylene oxide, copolymers of ethylene oxide and propylene oxide, polyvinyl alcohol, water-soluble condensation products of formaldehyde with urea or melamine polyphosphates or salts of polyacrylic acid.

Composition for coating used in accordance with the method of the present invention, preferably used for the production of coated paper for printing or writing paper, or special paper, such as ink-jet or photo paper, or thick paper (cardboard).

Composition for coating used in accordance with the method of this invention may be applied to the substrate in any process traditionally used, for example, via an air scraper, blade coating, roller mill, the doctor knife or roll and tip scraper, or size presses, after which the coating is dried at the temperature of the surface of the paper in the range from 70 to 200°C, preferably from 90 to 130°C to a residual moisture content of 3-8%, for example, using infrared drying and/or drying with hot air. This results in sravnitelno high levels of whiteness even at low temperatures drying.

The coatings obtained using the method corresponding to the invention, are of optimal distribution of the dispersion fluorescent Brightener over the entire surface and by increasing the degree of attainable white, high resistance to light and elevated temperatures (e.g., stable for 24 hours at 60-100°C) and excellent resistance to spreading of the components in the water.

In the second preferred aspect of the present invention, a method of the fluorescent whitening of a paper surface, comprising contacting the paper in the size press with an aqueous solution containing an adhesive substance, optional inorganic or organic pigment and from 0.1 to 20 g/l of a fluorescent Brightener containing a mixture of compounds of formulas (1A), (1b) and (1C)of the respective izobreteniya. Preferably an adhesive is starch, a derivative of starch or synthetic adhesive, in particular a water-soluble copolymer.

The following aspect of the invention a mixture of compounds of formulas (1A), (1b) and (1C) ensures the implementation of the method of increasing the degree Stakhanov Ferroalloy plant (sun protection factor) or fluorescent whitening material textile fibers, including the processing of textile fibers by means of from 0.05 to 5.0 wt.% (per the Assu material textile fibers) one or more mixtures of compounds of formulas (1a), (1b) and (1C), corresponding to the invention, as defined above.

Textile fibers treated in accordance with the method of this invention can be of natural or synthetic fibers or mixtures thereof. Examples of natural fibers include plant fibers such as cotton, viscose, linen, viscose fiber or cloth, preferably cotton, and animal fiber such as wool, mohair, cashmere, Angora and silk, preferably wool. Synthetic fibers include polyester, polyamide and polyacrylonitrile fibers. Preferred textile fibers represented by cotton, nylon and wool fibers.

Preferably the textile fibers treated in accordance with the method according to this invention have a density of less than 200 g/m and is not pre-painted in dark tones.

Some mixtures of compounds of formulas (1a), (1b) and (1C)used in the method corresponding to this invention, one can only economically be dissolved in water for use in dispersed form. For this purpose, they can be milled with an appropriate dispersing agent, using the commonly used quartz beads or mixer, until a particle size of 1-2 microns.

As dispersing agents for such sparingly soluble mixture of compounds of formulas (1 is), (1b) and (1C) can be called esters of adducts of alkalinized with acids or their salts, for example, ester of priduct 4-40 moles of ethylene oxide and 1 mole of phenol with the acid or its salt or ester of phosphoric acid with an adduct 6-30 of moles of ethyleneoxide and 1 mol of 4-Nonylphenol, 1 mole of dinonylphenol or, in particular, with 1 mol of the compounds obtained by the addition of 1-3 moles of styrene to 1 pray phenol; polystyrene sulfonates; the Taurids of fatty acids; mono - or disulfonated alkyl diphenyloxide; sulfonates of esters of polycarboxylic acids; products add (adducts) 1-60, preferably 2-30 moles of ethylene oxide and/or propylene oxide to fatty amines, fatty Amida, fatty acids or fatty alcohols having from 8 to 22 carbon atoms, or from three - to hexavalent3-C6the alkanols, with transformation products joining the esters of the acids with organic dicarboxylic acids or inorganic polienovykh acids;

lignin sulfonates and preferably condensation products of formaldehyde, such as condensation products of lignin sulfonates and/or phenol and formaldehyde; condensation products of formaldehyde with aromatic sulfonic acids, for example, the products of simple ether detail sulfonate and formaldehyde; condensation products naphtalenesulfonic acid is/or naphthalenesulfonic acids and formaldehyde; condensation products phenolsulfonic acids and/or from sulphonated of dihydroxydiphenylsulfone and phenols or Cresols with formaldehyde and/or urea; or condensation products derived diphenylacetylene acid with formaldehyde.

Depending on the type of the mixture of compounds of formulas (1a), (1b) and (1C), it may favorably to undergo treatment in a neutral, alkaline or acid bath. Usually the process is carried out at a temperature in the range from 20 to 140°With, for example, at or below the boiling temperature of the water bath, i.e. approximately at 90°C.

Solutions of a mixture of compounds of formulas (1A), (1b) and (1C) or emulsions in organic solvents can also be used in the method corresponding to the invention. For example, can be used in the dyeing apparatus of the so-called methods of dyeing in the solution (the use of dye solution with fusing) or choosing dyes.

If method corresponding to the invention, be combined with fabric finishing and final coloration, such combined treatment may preferably be carried out using appropriate sustainable compositions containing a mixture of compounds of formulas (1A), (1b) and (1C) in such concentrations that attain the desired increase in sun protection factor (so what) or degree of whiteness.

In certain cases, a mixture of compounds of formulas (1A), (1b) and (1C) is made fully effective by subsequent processing. It may include a chemical treatment, for example, treatment with an acid, heat treatment or combined thermal/chemical treatment.

Often beneficial to use a mixture of compounds of formulas (1A), (1b) and (1C) in a mixture with an auxiliary agent or filler such as sodium sulfate, decahydrate sodium sulfate, sodium chloride, sodium carbonate, a phosphate of an alkali metal, such as orthophosphate, sodium or potassium pyrophosphate, sodium or potassium, or sodium tripolyphosphate or potassium, or alkali metal silicate such as sodium silicate.

In addition, with a mixture of compounds of formulas (1a), (1b) and (1C) in a way appropriate for the invention, can also be used in minor proportions of one or more adjuvants. Examples of adjuvants include emulsifiers, perfumes, bleaching agents, enzymes, colorants, chemicals, cloud emulsions, other optical bleaching agents, bactericides, nonionic surfactants, components for fabric care agents against gel formation, such as nitrites or nitrates, in particular sodium nitrate, and corrosion inhibitors such as sodium silicate.

The number is in each of these optional adjuvants should not exceed 1 wt.%, and preferably is in the range from 0.01 to 1 wt.% the treated tissue.

The method corresponding to the invention, in addition to protecting the skin also increases the useful life of textiles treated in accordance with the proposed invention. In particular, can be improved resistance to tearing, and/or light resistance of the treated material textile fibers.

The present invention also proposed a textile fabric made from fibers treated in accordance with the method of this invention, as well as item of clothing made from this fabric.

Such textile fabrics and clothing items made from these fabrics usually have a degree North-West branch of 20 or higher, while raw cotton is usually characterized by the degree of North-West branch of, for example, from 2 to 4.

Fluorescent brighteners, corresponding to this invention, are particularly preferred because they are not only extremely high whitening capacity, superior properties substantively and stability, but, in addition, in many cases highly desirable property of solubility in water, which makes it easy to prepare from them a stable concentrated liquid compositions.

The following examples serve for illustration and is gaining and not intended to limit the nature of the invention; unless otherwise noted, given the mass part and the percent.

Preparative examples

Example 1

11,0 g disodium salt of 4,4'-bis[(4-aniline-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid is stirred in 120 ml of water. To the resulting suspension added 1.64 g diethanolamine and 2.07 g of diisopropanolamine. The mixture is then heated to 95°C and stirred for 3 hours at this temperature, maintaining a pH of 8.0 to 8.5 by adding overall 3.0 g of a 32% aqueous sodium hydroxide solution. The mixture is then cooled, and during this time it is divided into two phases. The lower phase is separated, diluted with 50 ml of acetone and acidified to pH 4-5 by addition of 4 N. aqueous hydrochloric acid. Precipitated solid precipitate is filtered and washed with water. The filtered material is stirred in water and bring the pH to 10 by adding 2 N. aqueous sodium hydroxide solution with the formation of a transparent solution. The water evaporated and the residue is dried under vacuum at 80°obtaining a fluorescent Brightener (101), which contains a mixture containing 41% of the compound (101A), 26% of the compound (101b) and 24% of the compound (s), as well as 4.5% water and 0.5% sodium chloride.

Example 2

The method described in Example 1, but with the use of 1.76 g of diethanolamine and 1.60 g disap is anolamine, get fluorescent bleach (102), which contains a mixture containing 42% of compound (101A), 44.5% of the compound (101b) and 6.5% of the compound (101), and 2% of water and 0.07% sodium chloride.

Example 3

The method described in Example 2, but using instead of the phase separation processing of the entire reaction mass, which is acidified with 4 N. hydrochloric acid to pH 4, add 50 ml of acetone, filtered off solids, diluted with water and 32% aqueous solution of sodium hydroxide, evaporated water, dried the product at 80°With under reduced pressure and get a fluorescent bleach (103), which contains a mixture containing 32.5% of compound (101A), 44.5% of the compound (101b) and 14.5% of the compound (s), and 3.5% water and 0.03% sodium chloride.

Example 4

15.0 g of disodium salt of 4,4'-bis[(4-aniline-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid are suspended in 14.0 g of polyethylene glycol 300 and 29.6 g of water. Then to the stirred suspension added 2.15 g of aspartic acid, 1.7 g diethanolamine and 1.2 g of 50% aqueous sodium hydroxide solution. The reaction mixture is heated to 90°and continue stirring at this temperature for 7 hours, maintaining a pH of 8.5 and 9.3 by addition of 32% aqueous sodium hydroxide solution. The reaction mixture is cooled and filtered to form a liquid composition containing 24.6% of a fluorescent Brightener (104)to the second contains the mixture, containing 39% of the compound (101A), 22% of the compound (104b) and 33% of the compound (s).

Example 5

30.0 g disodium salt of 4,4'-bis[(4-aniline-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid are suspended in 28,0 g of polyethylene glycol 300 and 58,0 g of water. Then to the stirred suspension add 4.26 deaths g iminodiacetic acid and 3,37 g of diethanolamine. The reaction mixture is heated to 95°and continue stirring at this temperature for 7 hours, having first pH to 8.5-9.0 in addition 5,07 g 50% aqueous sodium hydroxide solution and maintaining this value by the addition of 7.8 g of a 32% aqueous sodium hydroxide solution. The reaction mixture is cooled and filtered to form a liquid composition containing 25% of a fluorescent Brightener (105), which contains a mixture containing 28% of compound (101A), 44% of the compound (105b) and 26% of the compound (105c).

Example 6

16.3 g disodium salt of 4,4'-bis[(4-aniline-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid (91,7%)and 1.15 g of monoethanolamine and 1.96 g of diethanolamine are suspended in 50 ml of water. The mixture is heated to 95-100°and continue stirring for 5 hours at this temperature the re, maintaining a pH value of between 8.6 and 8.9 in the addition of 32% aqueous sodium hydroxide solution. After cooling to room temperature the reaction mixture is poured into 500 ml of acetone and bring the pH to 2-3 by adding 6 N. hydrochloric acid. The yellow suspension was filtered, washed with demineralized water and the resulting solid is dried under vacuum at 80°C. Gain of 14.7 g of the fluorescent Brightener (106), which contains a mixture containing 20% of compound (101A), 45% of compound (106b) and 35% of the compound (s).

Example 7

The method described in Example 6, but replacing a 1.96 g of diethanolamine on of 2.51 g of diisopropanolamine, obtain 17.3 g of the fluorescent Brightener (107), which contains a mixture containing 22% of the compound (s), 44% of the compound (107b) and 34% of the compound (s).

Example 8 - Synthesis of compounds (104b)

Stage 1

To a stirred suspension of 9.8 g of the acid chloride cyanuric acid in 100 g of ice water and 50 ml of acetone is added a mixture of 25 g 84,9% of 4-amino-4'-nitrostilbene-2,2'-disulfonic acid. After adding continue stirring for 40 minutes at 5°maintaining the pH at 4.0 to 4.5 by adding in celeryville 60 ml of a 1M aqueous solution of sodium carbonate. After that add is 4.93 g of aniline and the mixture is heated to 50°maintaining a pH value of 6.5 to 7.0 by adding 28 ml of a 1M aqueous solution of sodium carbonate. To the resulting suspension type of 7.25 g of diethanolamine in 30 ml of water, the temperature rises to 95°then distilled acetone and maintain the pH value of 7.5 to 8.0 by adding a total of about 20 ml of 1M aqueous solution of sodium carbonate. After cooling to maintain the pH to 3.0 by adding 6 N. aqueous solution of hydrochloric acid, filtered precipitated in the sediment solid and dried in vacuum at 80°obtaining 4-[(4-aniline-6-diethanolamine-1,3,5-triazine-2-yl)amino]-4'-nitrostilbene-2,2'-disulfonic acid.

Stage 2

of 0.02 mol of 4-[(4-aniline-6-diethanolamine-1,3,5-triazine-2-yl)amino]-4'-nitrostilbene-2,2'-disulfonic acids restore 0,3 the moles of iron shavings and 11 g of glacial acetic acid in 400 ml of water, in accordance with the method of Bechamp, and receive 4-[(4-aniline-6-diethanolamine-1,3,5-triazine-2-yl)amino]-4'-aminostilbene-2,2'-disulfonic acid.

Stage 3

To a stirred suspension of 3.6 g of the acid chloride cyanuric acid in 50 ml of methyl ethyl ketone and 50 g of ice are added dropwise within 30 minutes a solution of 13.3 g of 86% 4-[(4-aniline-6-diethanolamine-1,3,5-triazine-2-yl)amino]-4'-aminostilbene-2,2'-disulfonic acid in 160 g of ice water. Within 1 hour the temperature is rises to 10° With support value of pH at 6.0 to 6.5 by the addition of a total of approximately 4 ml of 1M aqueous solution of sodium carbonate. To the resulting suspension is added 1.7 g of aniline, the temperature rises to 30°C. After stirring for 1 hour, during which maintain the pH in the 6.5 to 7.0 by addition of 1M aqueous solution of sodium carbonate, add 0.33 g of aniline and continue the stirring for the next 1 hour at 30°C. the mixture is Then cooled and acidified, and the product is filtered to obtain 4- [(4-aniline-6-diethanolamine-1,3,5-triazine-2-yl)amino]-4'-[(4-aniline-6-chloro-1,3,5-Trizin-2-yl)amino]stilbene-2,2'-disulfonic acid.

Stage 4

2 g of 4-[(4-aniline-6-diethanolamine-1,3,5-triazine-2-yl)amino]-4'-[(4-aniline-6-chloro-1,3,5-Trizin-2-yl)amino]stilbene-2,2'-disulfonic acid is introduced into reaction with 0.6 g of aspartic acid in 25 ml of water at 95°C for 4 hours, maintaining the pH value of 8.0 to 8.5 by adding a General 1.1 g of a 32% aqueous sodium hydroxide solution. The product is precipitated by adding the reaction solution mixture of ethanol and isopropanol, the precipitate is filtered off and dried to obtain compound (104b).

Examples of the application

Used in paper pulp - Examples 9-11

To the dispersion of the fibres, containing 2 g of a mixture of 50% of bleached beech wood and 50% of bleached pine fibers 35° SR (Schoper-Riegler) in water with hardness German 10° add 10% filler of calcium carbonate. Then add 0.2% of the respective fluorescent Brightener, calculated as 100% active substance in aqueous solution. After stirring for 15 minutes, add 0.03% of a cationic polyacrylamide as agent for holding the liquid, and using the system and methods of Rapid-Koethen form paper sheets. After drying register whiteness CIE and fluorescently ISO. The results are summarized in Table 1, below.

Table 1
Example No.Fluorescent

bleach
White CIEFluorescently

ISO
9(101)12919,4
10(102)13120,2
11(103)13020,3

Application for coverage - Example 12

To kasashima matter for coating, containing 62% solids, consisting of 60% calcium carbonate and 40% clay, add 0.2 part of polyvinyl alcohol and 9 parts SBR binder, based on the weight of the pigment, and then add 0.2 parts of fluorescent Brightener (103) according to Example 3. After stirring for 15 minutes for homogenization painting the th substance for coating the base paper without fluorescent Brightener cover using laboratory devices with a doctor blade coating with a speed drawing of 50 m/min to obtain the mass of the coating 12 g/m2. After drying measure the magnitude of the CIE whiteness and fluorescently ISO.

White CIE - 95,4

Fluorescently ISO - 7.

Solubility in water

Solubility in water is determined by preparing saturated solutions of the corresponding fluorescent brighteners, the obtained values are summarized in Table 2 below.

Table 2
Fluorescent bleachSolubility in water
(101a)3-3,5%
(101)9%
(102)12%
(103)7%

The results clearly demonstrate the excellent solubility of mixtures corresponding to the invention, compared with the solubility of a single component.

1. Fluorescent Brightener containing a mixture of compounds of the formula

in which R1and R2different and each represents-NH2, -NHC1-C4alkyl, -N(C1-C4alkyl)2, -NHC2-C4hydroxyalkyl, -N(C2-C4hydroxyalkyl)2, -N(C1-C4alkyl)(C2-C hydroxyalkyl), the remains of morpholino, piperidino or pyrrolidino, or amino acid residues or amide amino acids in which the amino group is removed hydrogen, each of R3independently represented by hydrogen, C1-C4the alkyl or C1-C4alkoxygroup and M denotes hydrogen, an alkali metal atom, ammonium or a cation formed from an amine.

2. Bleach according to claim 1, in which R3denotes hydrogen.

3. Bleach according to claim 1 or 2, in which the residue of aliphatic amino acids or amide amino acids represented by the formula

-NR4'-CH(CO2H)-R4(2) or-NR4-CH2CH2CONH2(3),

in which each R4and R4' independently denote hydrogen or a group of the formula-CHR5-R6in which R5and R6independently represented by hydrogen or C1-C4the alkyl, optionally substituted by one or two substituents selected from the group consisting of hydroxy-, thio-, methylthio-, carboxy-, alphagroup, phenyl, 4-hydroxyphenyl, 3,5-diid-4-hydroxyphenyl, β-indolyl, β-imidazolyl and NH=C(NH2)NH-.

4. Bleach according to claim 3, in which the residues R1and/or R2derived from glycine, alanine, sarcosine, serine, cysteine, phenylalanine, tyrosine (4-hydroxyphenylethyl), diiodotyrosine, tryptophan (β-indoleamine), wasted is on (β -imidazolylidene), α-aminobutyric acid, methionine, valine (α-aminosalicilovoj acid), Norvaline, leucine (α-aminoisoquinoline acid), isoleucine (α-aminoβ-methylvaleramide acid), norleucine (α-amino-n-Caproic acid), arginine, ornithine (α,δ-diaminopurine acid), lysine (α,ε-diaminopropionic acid), aspartic acid (amino amber acid), glutamic acid (α-aminoglutaric acid), threonine, hydroxylamino acid and taurine, as well as their mixtures and optical isomers, or from iminodiacetic acid or N-(propionamido)-N-(2-hydroxyethyl)amine.

5. Bleach according to claim 1 or 2, in which R1or R2mean-NHC2-C4hydroxyalkyl, -N(C2-C4hydroxyalkyl)2, -N(C1-C4alkyl)(C2-C4hydroxyalkyl), the remainder of morpholino or a residue derived from glycine, sarcosine, taurine, glutamic acid, aspartic acid or iminodiacetic acid.

6. Bleach according to claim 5, in which R1and R2denote mono-(2-hydroxyethyl)amino, di-(2-hydroxyethyl)amino, di-(2-hydroxypropyl)amino, N-(2-hydroxyethyl)-N-methylamino, aspartic acid, iminodiethanol acid or a residue of morpholino.

7. Bleach according to one of claims 1 and 2, in which M denotes adored; lithium, potassium, sodium, ammonium, mono-, di-, tri - or Tetra-C1-C4alkylammonium, mono-, di - or tri-C1-C4hydroxyethylammonium or ammonium that has two or three deputies in the form of a mixture With1-C4alkyl and C1-C4hydroxyalkyl groups.

8. Bleach according to claim 7, in which M represents hydrogen, potassium or sodium.

9. The method of obtaining a mixture of compounds of formulas (1a), (1b) and (1C), including the interaction of 4,4'-bis[(4-aniline-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid or a salt thereof in succession in any desired sequence, with aminoguanidinium R1H, aminoguanidinium R2H, or mixtures thereof, where R1and R2have the meanings given in claim 1.

10. The compound of the formula

in which R1, R2, R3and M have the meanings defined in claim 1, except for the case when R1and R2different and each independently means-NHC1-C4alkyl, -N(C1-C4alkyl)2, -NHC2-C4hydroxyalkyl.

11. The use of a composition containing water, a fluorescent bleach, which contains a mixture of compounds (1a), (1b) and (1C), corresponding to any one of claims 1 to 8, and optional excipients for whitening synthetic or natural organic materials.

12. the label according to claim 11 as an optical Brightener of paper in the paper pulp, sizing press, dosing or press coverage.

13. The application of item 11 to improve the degree of sun protection factor (Stakhanov Ferroalloy plant) or for the fluorescent whitening of textile materials fiber.

14. Paper, optically brightened, through a mixture of compounds of formulas (1A), (1b) and (1C), corresponding to any one of claims 1 to 8.

15. Textile fabric made from fibers treated with a mixture of compounds of formulas (1A), (1b) and (1C), corresponding to any one of claims 1 to 8.



 

Same patents:

FIELD: organic chemistry, paper industry.

SUBSTANCE: invention relates to compositions used for coating paper covers. Invention describes a composition for coating paper cover comprising whitening pigment comprising: (a) product of melamine formaldehyde or phenol-formaldehyde polycondensation, and (b) water-soluble fluorescent whitening agent of the formula:

wherein R1 and R2 represent independently of one another -OH, -Cl, -NH2, -O-(C1-C4)-alkyl, -O-aryl, -NH-(C1-C4)-alkyl, -N-(C1-C4-alkyl)2, -N-(C1-C4)-alkyl-(C1-C4-hydroxyalkyl)- -N-(C1-C4-hydroxyalkyl)2 or -NH-aryl, for example, anilino-, anilinemono- or disulfonic acid or aniline sulfone amide, morpholino-, -S-(C1-C4)-alkyl(aryl) or radical of amino acid, for example, aspartic acid or iminoacetic acid that is replaced with radical in amino-group; M means hydrogen, sodium, potassium, calcium, magnesium atom or ammonium, mono-, di-, tri- or tetra-(C1-C4)-alkylammonium, mono-, di- or tri-(C1-C4)-hydroxyalkylammonium, or ammonium di- or tri-substituted with a mixture of (C1-C4)-alkyl and (C1-C4)-hydroxyalkyl groups. Covers prepared on coating paper elicit high photostability and enhanced whiteness degree.

EFFECT: improved method for preparing, improved properties of covers.

7 cl, 1 tbl, 3 ex

FIELD: paper-and-pulp industry.

SUBSTANCE: formulation includes optic bleacher and low-viscosity water-soluble nonionic polysaccharide derivative, whose 5% aqueous solution exhibits at ambient temperature Brookfield viscosity below about 1500 cP.

EFFECT: increased brightness of coated paper.

34 cl, 9 tbl, 2 ex

The invention relates to new compounds of the number of 4,4'-diaminostilbene-2,2'-disulfonic acid, which can be used as fluorescent whitening tools

The invention relates to a new method of obtaining compounds distributionally

FIELD: household chemistry, in particular compositions for bleaching of white and random dyeing textile made of natural, artificial, synthetic and mixed fibers.

SUBSTANCE: claimed composition contains (mass %): hydrogen peroxide 7-11; oxanole 0.5-1.0; oxyethylidenediphosphonic acid 0.1-0.3; optical bleaching agent, namely mixture of benzoxyzaryl derivative 0.1-0.2 and stilbenesulfo acid 0.1-0.2; and balance: water.

EFFECT: non-layered composition during storage; decreased chemical failure of materials.

2 tbl, 12 ex

FIELD: organic chemistry, paper industry.

SUBSTANCE: invention relates to compositions used for coating paper covers. Invention describes a composition for coating paper cover comprising whitening pigment comprising: (a) product of melamine formaldehyde or phenol-formaldehyde polycondensation, and (b) water-soluble fluorescent whitening agent of the formula:

wherein R1 and R2 represent independently of one another -OH, -Cl, -NH2, -O-(C1-C4)-alkyl, -O-aryl, -NH-(C1-C4)-alkyl, -N-(C1-C4-alkyl)2, -N-(C1-C4)-alkyl-(C1-C4-hydroxyalkyl)- -N-(C1-C4-hydroxyalkyl)2 or -NH-aryl, for example, anilino-, anilinemono- or disulfonic acid or aniline sulfone amide, morpholino-, -S-(C1-C4)-alkyl(aryl) or radical of amino acid, for example, aspartic acid or iminoacetic acid that is replaced with radical in amino-group; M means hydrogen, sodium, potassium, calcium, magnesium atom or ammonium, mono-, di-, tri- or tetra-(C1-C4)-alkylammonium, mono-, di- or tri-(C1-C4)-hydroxyalkylammonium, or ammonium di- or tri-substituted with a mixture of (C1-C4)-alkyl and (C1-C4)-hydroxyalkyl groups. Covers prepared on coating paper elicit high photostability and enhanced whiteness degree.

EFFECT: improved method for preparing, improved properties of covers.

7 cl, 1 tbl, 3 ex

The invention relates to exhaust the forms of optical brighteners, designed for optical bleaching of cellulosic textile materials and paper

The invention relates to new compounds of the number of 4,4'-diaminostilbene-2,2'-disulfonic acid, which can be used as fluorescent whitening tools

FIELD: chemistry.

SUBSTANCE: polynucleotide is obtained, coding chromo- or fluorescen mutant wild type DsRed (SEQ ID N0:2), where chromo- or fluorescent mutant contains a substitute in the amino acid position 42 SEQ ID N0:2, and optionally one or more substitutes in the amino acid positions, chosen from a group, consisting of 4, 2, 5, 6, 21, 41, 44, 117, 217, 145. Using the polynucleotide in the vector, the host cells which express chromo- or fluorescent mutant DsRed are transformed. The invention allows for obtaining chromo- or fluorescent polypeptide DsRed, which matures faster than wild type DsRed.

EFFECT: increased effectiveness.

26 cl, 10 dwg, 2 tbl, 4 ex

FIELD: print engineering.

SUBSTANCE: invention provides ink containing first fluorescent color material emitting fluorescence at specified emission wavelength used for measurement or determination of excitement at specified excitement wavelength; and second fluorescent color material emitting fluorescence when excited at specified excitement wavelength, said second color material being contained in larger amount than said first color material. To obtain fluorescence at desired emission wavelength, excitement spectrum of the first color material in ink should have peak wavelength range adjoining specified fluorescent wavelength, and emission fluorescence spectrum of the second color material has emission wavelength range that includes at least above-mentioned peak wavelength range.

EFFECT: enhanced fluorescence intensity due to presence of several fluorescent coloring substances.

9 cl, 26 dwg, 3 tbl, 6 ex

FIELD: organic chemistry.

SUBSTANCE: invention relates to novel derivatives of some N,N'-bis-(9-anthrylmethyl)-substituted alkanediamines, namely, to N,N'-bis-(9-anthrylmethyl)cyclohexane-1,2-diamine of the formula (I): . This compounds possesses properties of highly selective fluorescent hemosensor for cations Zn2+ in neutral medium. Proposed N,N'-bis-(9-anthrylmethyl)cyclohexane-1,2-diamine as compared with its analog by structure and using, i. e. N,N'-bis-(9-anthrylmethyl)ethane-1,2-diamine, elicits more effective and selective hemosensor properties with respect to ions Zn2+.

EFFECT: improved and valuable chemical properties of compound.

1 dwg, 2 ex

FIELD: luminescent substances, organic chemistry.

SUBSTANCE: invention relates to electroluminescent materials containing organic luminescent substance. Invention describes novel electroluminescent material consisting of injection layer, active luminescent layer based on chelate metal complex, hole-transporting layer and hole-injecting layer. Material comprises metal complexes based on sulfanyl derivatives of 8-aminoquinoline as a luminescent substance, in particular, zinc complexes of 8-(methylsulfanylamino)-quinoline and 8-(3,5-difluorophenylsulfanylamino)-quinoline. Material comprises a mixture of triphenylamine oligomers as a hole-transporting layer. Invention provides creature of electroluminescent material showing the enhanced moisture resistance, enhanced resistance to crystallization and enhanced thermal stability.

EFFECT: improved and valuable properties of material.

4 cl, 5 ex

FIELD: polymer items possessing fluorescent properties and property of reflection in opposite direction; information and signaling appliances.

SUBSTANCE: proposed sheet item has sublayer of film coated with fluorescent paint at concentration of from 0.001 to 1.5 wt-% relative to polymer matrix of sublayer, film of overlayer coated with fluorescent paint at concentration of from 0.001 to 1.5 wt-% relative to polymer matrix of overlayer. Fluorescent film of overlayer coated with paint possesses higher resistance to light as compared with sublayer film. Sheet of painted fluorescent film of overlayer lies over sheet of sublayer fluorescent film. Sheet item has selected fluorescent color different from color of overlayer fluorescent film and from color of sublayer fluorescent film. Specification gives description of production of such items.

EFFECT: enhanced resistance to action of atmospheric conditions; enhanced durability of color; wide range of color.

53 cl, 17 dwg, 8 tbl, 15 ex

FIELD: polymer material.

SUBSTANCE: invention relates to polymeric multilayer fluorescently stained particles widely applicable for distribution of visible information and provides sheet-shaped fluorescence-emitting articles. These have at least two film layers, each of which contains fluorescent dye in polymer matrix. Stained film of the upper layer is characterized by higher resistance to UV emission than stained sublayer film, and article itself has specified fluorescent coloration differing both from coloration of said stained fluorescent sublayer film and from coloration of said stained fluorescent upper layer. Manufacturing process for such articles is also described. Articles may optionally contain light-returning elements suitable as warning signs such as pedestrian crossing signs and signs indicating school zones, which emit fluorescent yellow color.

EFFECT: ensured resistance to weather conditions, increased color durability, and improved coloration characteristics regulated by industrial standards for particular conditions.

37 cl, 14 dwg, 3 tbl, 11 ex

FIELD: capillary luminescent flaw detection, possible use in aviation, automobile, shipbuilding and other branches of mechanical engineering, and also power engineering, chemical and nuclear industries for detection of surface defects, cracks, pores, foliating, abscesses, inter-crystallite corrosion and other defects of material discontinuity flaw type, primarily with small dimensions, in case of especially precise control of products.

SUBSTANCE: penetration agent includes organic phosphor, non-ionic surfactant and solvent, while as organic phosphor a mixture of phosphors from the class of coumarin colorants is used - mixture of donor-coumarin and acceptor-coumarin, as nonionic surfactant a specially defined substance is used, and as solvent a mixture of dibutyl phthalate and propylene carbonate is used with mass ratio ranging from 1:1,5 to 1:0,8. As donor-coumarin, 4-methyl-7-dethyl amine coumarin (K-47) may be used, and as coumarin-acceptor, at least one coumarin of yellow-green luminescence, with mass ratio ranging from 1,1:1 to 1,8:1.

EFFECT: increased sensitivity and reliability of flaw detection, while simultaneously reducing fire hazard and toxicity of used composition.

1 ex, 1 tbl

FIELD: organic chemistry.

SUBSTANCE: invention relates to novel compounds, namely zinc bis-[2-(tosylamino)benzylidene-N-alkyl(aryl, hetaryl)aminates] of the general formula (I): wherein Ts means tosyl; R means (C1-C6)-alkyl with exception isopropyl, (C1-C6)-alkyl-substituted phenyl, (C1-C6)-alkoxy-substituted phenyl with exception para- and ortho-methoxyphenyl, pyridyl, (C1-C6)-alkylpyridyl, or R + R form in common disulfidodialkyl group -(CH2)n-S-S-(CH2)n- wherein n = 1-3, but preferably to zinc bis-[2-(tosylamino)benzylidene-N-alkylidenemercaptoaminates] of the general formula (Ia): Compounds can be used for synthesis of light-radiating organic diode of white and visible light. Fluorescence can be observed in blue region of spectrum with fluorescence bands maximum at 428-496 nm. Quantum yields are 0.2-0.25.

EFFECT: valuable physical properties of compounds.

5 cl, 8 ex

FIELD: organic chemistry, luminophores.

SUBSTANCE: invention relates to colorless at daylight organic luminophores, in particular, to novel, water-soluble, colorless luminophores A of the formula:

wherein X means oxygen (O) or sulfur (S) atom; Q means compounds of the formulas and wherein R1 and R2 taken separately or in common mean compounds of the formulas: -NHCH2COOM, -N(CH2COOM)2, Cl wherein M means Na, K, NH4. As comparing with the known colorless organic luminophores - optical whitening agents possessing with blue-sky blue fluorescence only, novel luminophores show fluorescence in the range from blue to yellow-orange color and can be used as components of fluorescent, colorless at daylight, inks for jet printers or stamp dyes.

EFFECT: improved and valuable properties of luminophores.

14 ex

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