Dyes and mixtures for tainting during washing

FIELD: chemistry.

SUBSTANCE: claimed invention relates to method of tainting during washing by means of special flue or violet bis-azo dyes, separately or in combination with photocatalyst. Other objects of claimed invention represent composition, containing at least one photocatalyst and at least one of special bis-azo dyes. Composition in accordance with claimed invention is especially suitable for tainting fabrics during washing. Other objects of claimed invention represent detergent composition, fabric-softening composition, containing said dyes or mixtures of said dyes and photocatalysts, and new blue or violet bis-azo dyes.

EFFECT: reduction of dye accumulation on fabric after several washing cycles.

15 cl, 3 tbl, 36 ex

 

The present invention relates to a method of color in the wash with a special blue or purple bis-azo dyes alone or in combination with a photocatalyst. Other objects of the present invention is a composition containing at least one photocatalyst and at least one of the particular bis-azo dyes. The composition of the present invention is particularly suited to color fabrics during washing. Other objects of the present invention are detergent composition, composition of fabric softeners containing a mixture of these dyes and photocatalysts, and new blue or purple bis-azo dyes.

A frequently used method of whitening and bleaching is the simultaneous use of purple or blue dyes to enhance brightening or whitening effect. If this dye is used in conjunction with optical Brightener, this can be achieved with two different goals. On the one hand, it is possible to try to achieve a higher degree of whiteness, to compensate yellow hue of the fabric, and in this case on the cloth remains white shade obtained with optical Brightener. On the other hand, the aim might be the impact of the specified dye to change the tone of white fabric, reached number�ICDO with optical Brightener, and in this case also attempts to further increase the degree of whiteness. Thus, it is possible to adjust the desired shade of white.

The object of the present invention is to provide a particularly suitable bis-azo dyes to color during washing, which can be used separately or in a mixture with at least one photocatalyst.

These dyes and mixtures of dyes with the photocatalyst should not lead to the staining of fabrics after repeated use. In other words, the dye must not accumulate on the fabric after multiple wash cycles. Other requirements are that these dyes were equally suitable for raw cotton and for pre-wyswietlanego cotton. Also they should not accumulate on other synthetic fibers such as polyamide.

This goal is achieved by using special bis-azo dyes, which are unstable when exposed to sunlight. In a particular embodiment, the data of the dyes used in conjunction with at least one photocatalyst. This means that the components of the mixture, when applied to fabric, decompose when exposed to light, in particular sunlight. Although the colours are also to some extent decomposed when exposed to light, uka�this effect is much stronger in the application, together with the photocatalyst.

One object of the present invention lies in a method of color textile fabrics or fibers, wherein the method comprises applying bis-azo dye of formula (I), (II) or (III) on the fabric or fiber during washing

,

or

where

a is 0,1 or 2;

b is 0 or 1;

c is 0 or 1;

d is 0 or 1;

A represents the CH3or SO3X

X represents H, Na or K, and

R is a group

,,,and

,

where the arrows indicate the point of attachment;

provided that in the formula (I) R is different from R2if a is 1 and b is 0.

In a specific embodiment is a method of color textile fabrics or fibers, where the method comprises applying the photocatalyst, which is a water-soluble phthalocyanine Zn, Fe(II), Ca, Mg, Na, K, Al, Si(IV), P(V), Ti(IV), Ge(IV), Cr(VI), Ga(III), Zr(IV), In(III), Sn(IV) or Hf(VI), and bis-azo dye of formula (I), (II) or (III) on the fabric or fiber is in the process of washing

,

or

where

a is 0, 1 or 2;

b is equal� 0 or 1;

c is 0 or 1;

d is 0 or 1;

A represents the CH3or SO3X

X represents H, Na or K, and

R is a group

,,,and

where the arrows indicate the point of attachment.

The mass ratio of the photocatalyst and bis-azo dye is from 1000:1 to 1:1000, preferably from 50:1 to 1:50 and in particular from 1:10 to 10:1.

Examples of suitable woven textile materials that can be processed by this arrangement, the material of silk, wool, acrylics or polyurethanes and, in particular, cellulose woven materials and a mixture of all types of materials. Such woven materials are, for example, fabrics made from natural cellulose, such as cotton, flax, jute and hemp, and regenerated cellulose. Preference is given to cotton woven textile materials. Also suitable hydroxy-containing fibers, which are contained in mixed fabrics, for example blends of cotton with polyester fibers or polyamide fibers.

In a preferred embodiment of the present invention, the total number-SO3X groups per molecule of bis-azo dyes is 3. This provides the perfect balance between races�foremostly and substantive.

Preferably, the specified bis-azo dye is a compound of formula

,

,,

,,

,,

,,

and.

Acid sulfopropyl in the above formulas presented in the form of the free acid. But with the same success can be present corresponding salts of Na and K, which can also be formed under suitable pH values.

Particular preference is given to compounds of examples 3, 16, 26, 31 and 32. Most preferred are compounds 3 and 32.

The above dyes can be used alone or in mixtures with each other. By using mixtures of two dyes, the weight ratio between them is, for example, from 1:10 to 10:1, preferably 1:1.

Composition and method comprising a water-soluble phthalocyanine and bis-azo dye of formula (I), (II) or (III) give the relative angle of the color tone of 220-320°, and compounds of formulas (I), (II) or (III) are not svetoustojchivyh, especially in the presence of water-soluble phthalocyanine. This means that the compounds of formula (I), (II) or (II) in the composition to color decompose under the action of light. The term "light" refers to visible light (400-800 nm). Preferably, the sunlight.

For example, a coloring component is decomposed by the action of the composition of sunlight. The decomposition of this component can be monitored spectrophotometrically.

Preferably, the decomposition of the dye in the presence of the above-mentioned photocatalyst is more than 40% after 1 cycle of washing/drying under the conditions described in the application examples.

In a specific embodiment of the present invention, the photocatalyst is a water-soluble phthalocyanine of the formula (X)

where

PC represents a phthalocyanine cyclic system;

Me represents Zn; Fe(II); Ca; Mg; Na; K; Al-Zi; Si(IV); P(V); Ti(IV), Ge(IV); Cr(VI); Ga(III); Zr(IV); In(III); Sn(IV) or Hf(VI);

Z1is a halide; sulfate; nitrate; a carboxylate or Alkonost-ion or a hydroxy group;

q is 0, 1 or 2;

r = 1-8;

Q2represents a hydroxy group; C1-C22alkyl; branched C3-C22alkyl; C2-C22the alkenyl; branched C3-C22the alkenyl and mixtures thereof; C1-C22alkoxy; sulfo or carboxy group; a radical of the formula

;

;;; ; -SO2(XH2)v-OSO3M; -SO2(CH2)v-SO3M;

;;;

;;

;;;;

branched alkoxy radical of the formula

;

;

alkylacrylate-fragment of formula(T1)d-(CH2)b(OCH2CH2)a-B3

or an ester of the formula COOR18,

where

B2represents a hydrogen atom; hydroxy group; C1-C30alkyl; C1-C30alkoxy; -CO2H; -CH2COOH; -SO3-M1; -OSO3-M1; -PO32-M1; -OPO32-M1; and mixtures thereof;

B3represents a hydrogen atom; hydroxy group; -COOH; -SO3-M1; -OSO3-M1or C1-C6alkoxy;

M1is a water soluble cation;

T1represents-O-; or-NH-;

X1and X4independently from each other represent-O-; -NH - or-N-C1-C6alkyl;

R11and R12independently from each other represent an atom of water�ode; sulfopropyl and its salts; carboxy group and its salts, or hydroxy group; wherein at least one of the radicals R11and R12represents a sulfo or carboxy group or salts thereof,

Y2represents-O-; -S-; -NH - or-N-C1-C5alkyl;

R13and R14independently from each other represent a hydrogen atom; C1-C6alkyl; hydroxy-(C1-C6alkyl; cyano-C1-C6alkyl; sulfo-C1-C6alkyl; carboxy or halogen-C1-C6alkyl; unsubstituted phenyl or phenyl substituted by a halogen atom, a C1-C4the alkyl or C1-C4alkoxy group; a sulfo or carboxy group, or R13and R14together with the nitrogen atom to which they are linked, form a saturated 5 - or 6-membered heterocyclic cycle, which may also optionally contain a nitrogen atom or an oxygen atom as a member of the cycle;

R15and R16independently from each other represents C1-C6alkyl or aryl-C1-C6alkyl radicals;

R17represents a hydrogen atom; unsubstituted C1-C6alkyl or C1-C6alkyl substituted by halogen atom, hydroxy group, cyano group, phenyl, carboxy group, carb-C1-C6alkoxy or C1-C6alkoxy-group;

R18�predstavljaet a C 1-C22alkali, branched C3-C22alkyl; C1-C22the alkenyl or branched C3-C22the alkenyl; C3-C22glycol; C1-C22alkoxy group; a branched C3-C22alkoxy group; and mixtures thereof;

M represents a hydrogen atom; or an alkali metal ion or ammonium ion,

Z2-represents a chlorine atom; a bromine atom; alkylsulfate or aralkylated ion;

a is 0 or 1;

b is from 0 to 6;

c is from 0 to 100;

d is 0 or 1;

e is from 0 to 22;

v is an integer from 2 to 12;

w is 0 or 1; and

where phthalocyanine cyclic system may also contain additional solubilizers group.

The number of Vice-Q2in the formula (X) is from 1 to 8, preferably from 1 to 4, and not mandatory, as in General in the case of phthalocyanines that this number was an integer (the degree of substitution). If there are other nakatingin deputies, their total number cationogenic substituents is from 1 to 4. The minimum number of alternates, who must be present in the molecule, is dictated by the solubility of the final molecule in water. This molecule is quite soluble in water, dissolves when a sufficient amount of phthalocyanine with�of unity for the effects on photodynamic catalyzed oxidation on the fabric. May be sufficient even this low level of solubility as 0.01 mg/l, although the solubility of from 0.001 to 1 g/l is usually a top priority.

The halogen atom means a fluorine atom, bromine or in particular chlorine atom.

In all of these substituents, phenyl, nattily and aromatic heterocycles can be substituted by one or two further radicals, for example C1-C6the alkyl, C1-C6alkoxy group, halogen atom, carboxy group, carb-C1-C6alkoxy group, hydroxy group, amino group, cyano group, sulfopropyl, sulfonamideubul, etc.

Preferred substituent selected from the group consisting of C1-C6of alkyl, C1-C6alkoxy group, halogen atom, carboxy group, carb-C1-C6alkoxy groups or hydroxy groups.

All of the above nitrogen heterocycles may also be substituted by alkyl groups or by a carbon atom or another nitrogen atom in the ring. The alkyl group preferably represents a methyl group.

C1-C6alkyl and C1-C6alkoxy group are alkyl or alkoxy radicals, straight-chain or branched, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-�mil or hexyl, or methoxy, ethoxy, n-propoxy, isopropoxy, butoxy, Deut-butoxy, tert-butoxy, amyloxy, isoamylase, tert-amyloxy or hexyloxy.

C2-C22the alkenyl is, for example, allyl, methallyl, Isopropenyl, 2-butenyl, 3-butenyl, Isobutanol, n-Penta-2,4-dienyl, 3-methyl-but-2-enyl, n-Oct-2-enyl, n-dodec-2-enyl, ISO-dodecenyl, n-dodec-2-enyl or n-octadec-4-enyl.

Other potootvedeniya tools that can be used in accordance with the present invention, have the formula

where

PC represents a phthalocyanine cyclic system;

Me represents Zn; Fe(II); Ca; Mg; Na; K; Al-Zi; Si(IV); P(V); Ti(IV), Ge(IV); Cr(VI); Ga(III); Zr(IV); In(III); Sn(IV) or Hf(VI);

Z1is a halide; sulfate; nitrate; a carboxylate or Alkonost-ion; or a hydroxy group;

q is 0, 1 or 2;

Y3'represents a hydrogen atom; an alkali metal ion or ammonium ion; and

r represents any number from 1 to 4.

Particularly preferred phthalocyanine compounds have the formula (4A),

where

Me is a Zn or Al-Z1;

Z1is a halide; sulfate; nitrate; a carboxylate or Alkonost; or hydroxy group;

PC represents a phthalocyanine cyclic system,

q is 0, 1 or 2;

Y 'represents a hydrogen atom; an alkali metal ion or ammonium ion; and

r represents any number from 1 to 4.

Other interest phthalocyanine compounds which can be used in accordance with the present invention, have the formula

,

where

PC, Me and q correspond to the definitions given for formula (XI);

R12'and R13'independently from each other represent a hydrogen atom; phenyl; sulfophenyl; carboxyphenyl; C1-C6alkyl; hydroxy-(C1-C6alkyl; cyano-C1-C6alkyl; sulfo-C1-C6alkyl; carboxy (C1-C6alkyl or halogen-(C1-C6alkyl, or R12'and R13'together with the nitrogen atom form morpholinyl cycle;

q' is an integer from 2 to 6; and

r is a number from 1 to 4;

where, if r>1, present in the molecule radicals

may be the same or different.

Other interest phthalocyanine compounds which can be used in accordance with the present invention, have the formula

,

where PC, Me and q correspond to the definitions given for formula (XI),

Y3'represents a hydrogen atom; an alkali metal ion or ammonium ion,

q' p�establet an integer from 2 to 6;

R12'and R13'independently from each other represent a hydrogen atom; phenyl; sulfophenyl; carboxyphenyl; C1-C6alkyl; hydroxy-(C1-C6alkyl; cyano-C1-C6alkyl; sulfo-C1-C6alkyl; carboxy (C1-C6alkyl or halogen-(C1-C6alkyl, or R12'and R13'together with the nitrogen atom form morpholinyl cycle;

m' is 0 or 1; and

r and r1independently from each other represent any number from 0.5 to 3, wherein the sum of r+r1equal to at least 1 but not more than 4.

Particularly preferred phthalocyanine compounds are compounds, commercially available and used in detergent compositions. Usually anionic phthalocyanine compounds are in the form of alkali metal salts, especially sodium salts.

Of particular interest are the following compounds

where there are 2-4 of the sulfonate group, and Z1is a halide, sulfate, nitrate, carboxylate or Alkonost or hydroxy group, preferably Cl-. These compounds may be present individually or as a mixture in virtually any ratio.

In the formulas of compounds 101 and 102 depicts four sulfonate groups. However, when you can�to otstavat also less than 4 sulfonate groups. Overall, there is a mixture containing 2-4 sulfonate group.

In another specific embodiment of the present 2-3 sulfonate group, and in the second specific embodiment of the present 3-4 sulfonate group. Depending on the desired application of the first or second embodiment may be advantageous.

In a specific embodiment, the composition contains at least one fluorescent Brightener.

Fluorescent whitening agents (optical brighteners) can be selected from a large number of chemical types, such as 4,4'-bis-(creatininemia)-stilbene-2,2'-disulfonate acid, 4,4'-bis(triazole-2-yl)stilbene-2,2'-disulfonate acid, 4,4'-(diphenyl)-stilbene, 4,4'-DISTEARYL-biphenyls, 4-phenyl-4'-benzoxazolyl-stilbene, stilbene-avtotriada, 4-styryl-stilbene, derivatives of bis-(benzoxazol-2-yl) derivatives, bis-(Basilicata-2-yl), coumarins, pyrazoline, naphthalimide, triazinyl-pyrene derivatives, 2-styryl-benzoxazole or-naftussya, derivative benzimidazol-benzofuran or derivatives oxanilide. These optical brighteners are known and commercially available. Among others they are described in WO 2006/024612.

Another object of the present invention is a composition containing:

(a) bis-azo dye of formula (I), (II) or (III)

or

where a is 0, 1 or 2;

b is 0 or 1;

c is 0 or 1;

d is 0 or 1;

A represents the CH3or SO3X

X represents H, Na or K, and

R is a group

,,,and,

where the arrows indicate the point of attachment, and

(b) water-soluble phthalocyanine Zn, Fe(II), Ca, Mg, Na, K, Al, Si(IV), P(V), Ti(IV), Ge(IV), Cr(VI), Ga(III), Zr(IV), In(III), Sn(IV) or Hf(VI).

Composition containing at least one photocatalyst and at least one bis-azo dye, can be used in solid or liquid detergent composition.

Preferred solid composition are granulates. Preferred is a granular composition containing:

a) from 2 to 75 wt.% as described above composition, based on the total weight of the granulate,

b) from 10 to 95 wt.% at least one further additive, based on the total weight of the granulate, and

c) from 0 to 15 wt.% water, based on the total weight of the granulate.

Granulates receive in accordance with known methods. Any known method suitable for the production of pellets containing a mixture of the present invention. Used batch and continuous methods,the continuous methods, such as spray drying or granulation in a fluidized bed, are preferred.

The granulates of the present invention may be encapsulated or unencapsulated.

Encapsulating materials in features include water soluble and dispersible in water, polymers and waxes. Such preferred materials are polyethylene glycols, polyamides, polyacrylamides, polyvinyl alcohols, polyvinylpyrrolidone, gelatin, hydrolyzed polyvinyl acetate, copolymers of vinylpyrrolidone and vinyl acetate, as well as polyacrylates, waxes, fatty acids, copolymers of acrylate and methacrylate with methacrylic acid and polymethacrylates.

The granulates of the present invention contain from 2 to 75 wt.%, preferably from 2 to 60 wt.%, especially from 5 to 55 wt.% compounds (a), based on the total weight of the granulate.

The granules in the compositions of the present invention preferably have an average particle size <500 microns. More preferred particle size of the granulates from 40 to 400 microns.

The granules in the compositions of the present invention contain from 10 to 95 wt.%, preferably from 10 to 85 wt.%, especially from 10 to 80 wt.% at least one additional additive (component C), based on the total weight of the granulate.

Such additional additives may present with�Oh anionic or nonionic dispersing means; the water-soluble organic polymers; inorganic salt; low-molecular organic acid or its salt; wetting agents; disintegrants, such as, for example, powdery or fibrous cellulose, microcrystalline cellulose; fillers such as, for example, dextrin, soluble or water-insoluble dyes or pigments; and the dissolution accelerators and optical brighteners. Aluminum silicates, such as zeolites, as well as compounds such as talc, kaolin, TiO2, SiO2or magnesium trisilicate, can also be used in small amounts.

Used anionic dispersing means are, for example, commercially available water-soluble anionic dispersing means for dyes, pigments, etc.

In particular, consider the following products: condensation products of aromatic sulfonic acids and formaldehyde, condensation products of aromatic sulfonic acids with unsubstituted or chlorinated biphenyl or biphenyl oxides and optionally formaldehyde, (mono-/di-)alkylnaphthalene, sodium salts of polymerised organic sulfonic acids, sodium salts of polymerized alkylnaphthalene acids, sodium salts of polymerized alkylbenzenesulfonic sour�, alkylarylsulfonate, sodium salts of alkyl polyglycolether sulfates, polyallylamine polynuclear arylsulfonate, methylene-linked condensation products arylsulfonic acids and gidroksikislotny acid, sodium salt diallylmalonate acids, sodium salts of alkyl diglycolamine sulfates, sodium salts polynaphthalenesulfonate, ligno - or oxyegn-sulphonates or heterocyclic polisul acids.

Particularly suitable anionic dispersing funds are the condensation products naphthalenesulfonic acids with formaldehyde, sodium salts of polymerised organic sulfonic acids, (mono-/di-)alkylnaphthalene, polyallylamine polynuclear arylsulfonate, sodium salts of polymerized alkylbenzenesulfonic acid, liposculture, accelignoreauth and condensation products naphtalenesulfonic acid with polychlorinatedbiphenyls.

Suitable nonionic dispersing funds in particular are compounds having a melting point of preferably at least 35°C, these compounds are emulsifiable, dispersible or soluble, for example the following compounds:

1. Fatty alcohols containing 8 to 22 C-atoms, especially cetyl alcohol;

2. Products join�tion, preferably 2-80 mole of accelerated, especially ethylene oxide, where some parts of ethylene oxide may be replaced by substituted epoxides, such as stimulated and/or propylene oxide, with higher unsaturated or saturated monoalcohols, fatty acids, fatty amines or fatty Amida containing 8 to 22 C-atoms, or benzyl alcohols, phenyl-phenols, benzyl-phenols or alkyl phenols, alkyl radicals which contain at least 4 C-atoms;

3. The condensation products of accelerated, especially propyl of anoxia (block polymers);

4. Adducts of ethylene oxide/propylene oxide with diamines, especially with Ethylenediamine;

5. Reaction products of fatty acids containing 8 to 22 C-atoms and a primary or secondary amine containing at least one hydroxy-lower alkyl or lower alkoxy-lower alkyl group, or addition products accelerated such hydroxyalkyl-containing reaction products;

6. Esters sorbitan, preferably long-chain ester groups, or ethoxylated esters sorbitan, such as polyoxyethylene sorbitan monolaurate containing from 4 to 10 ethylene oxide fragments, or polyoxyethylene sorbitan trioleate containing from 4 to 20 ethylene oxide fragments;

7. The addition products of propylene oxide to 3-6-atom aliphatic SP�mouths, containing from 3 to 6 carbon atoms, such as glycerol or pentaerythritol; and

8. Mixed ethers of fatty alcohols with polyglycols, especially the addition products of from 3 to 30 mol of ethylene oxide and from 3 to 30 mol of propylene oxide to aliphatic monoalcohols containing from 8 to 22 C-atoms.

Instead of dispersing funds or funds, or in addition thereto, the granulates of the present invention may contain water-soluble organic polymer, which can also have dipenhydramine properties. Such polymers can be used alone or as mixtures of two or more polymers. As water-soluble polymers (which may be, but need not have film-forming properties) can be seen, for example, gelatin, polyacrylates, polymethacrylates, copolymers of ethyl acrylate, methyl methacrylate and methacrylic acid (ammonium salt), polyvinylpyrrolidone, vinylpyrrolidone, vinylacetate, copolymers of vinylpyrrolidone with long-chain olefins, poly(vinylpyrrolidone/dimethylaminoethyl the methacrylates), copolymers of dipiperidide/dimethylaminopropyl methacrylamide, copolymers vinylpyrrolidone/dimethylaminopropyl the acrylamide free, quaternion copolymers of vinylpyrrolidone and dimethylaminoethyl of methacrylates, terpolymers of vinylcaprolactam/vinylpyrrolidone/dimethylamine�ethyl methacrylates, copolymers vinylpyrrolidone and chloride, terpolymers caprolactam/vinylpyrrolidone/dimethylaminoethyl the methacrylates, copolymers of styrene and acrylic acid, polycarboxylic acids, polyacrylamides, carboxymethyl cellulose, gidroximetil cellulose, polyvinyl alcohols, hydrolyzed and digitalizovane polyvinyl acetate, copolymers of maleic acid with unsaturated hydrocarbons, and mixtures of the products of polymerization of these polymers. Other suitable substances are polyethylene glycol (MW: 2000-20000), copolymers of ethylene oxide with propylene oxide (MW>3500), the condensation products (products block polymerization) of accelerated, especially propylene oxide, copolymers of vinylpyrrolidone with vinyl acetate, the addition products of ethylene oxide-propylene oxide to the diamines, especially Ethylenediamine, polystyrenesulfonate acid, polyarilensulphone acid, copolymers of acrylic acid with sulfonated styrenes, gum Arabic, hydroxypropyl methylcellulose, sodium carboxymethyl cellulose phthalate hydroxypropyl methylcellulose, maltodextrin, starch, sucrose, lactose, modified enzyme and subsequently hydrated sugar, such as available under the trademark "Isomalt", cane sugar, poliasparaginovaya acid and tragakant.

Environments� listed water-soluble organic polymers, especially preferred carboxymethylcellulose, polyacrylamides, polyvinyl alcohols, polyvinylpyrrolidone, gelatin, hydrolyzed polyvinyl acetate, copolymers of vinylpyrrolidone and vinyl acetate, maltodextrins, poliasparaginovaya acid and polyacrylates and polymethacrylates.

For use as inorganic salts can be considered carbonates, bicarbonates, phosphates, polyphosphates, sulfates, silicates, sulfites, borates, halides and pyrophosphates, preferably in the form of salts of alkali metals. Preferred water-soluble salts such as, for example, chlorides of alkali metals, phosphates of alkali metals, carbonates of alkali metals, alkali metal polyphosphates and alkali-metal sulfates, and water-soluble salts used in the compositions of detergents and/or additives to detergents.

Can also be applied liquid composition containing composition which meets the above definition.

Preferred is a liquid composition containing:

(a) 0.01-95 wt.%, preferably 1-80 wt.%, more preferably 5-70 wt.% compositions containing at least one water-soluble phthalocyanine compound and at least one bis-azo dye, which corresponds to the above definition, based on the total weight of the liquid composition,

(c) 0-10 wt.%, preferably 0-5 wt.%, more preferably 0-2 wt.%, based on the total weight of the liquid composition, at least one additional additive.

It is also an object of the present invention is a liquid or solid detergent composition in which uniformly distributed composition described above.

Another object of the present invention is a detergent composition containing:

I) from 5 to 70 wt.% (A) at least one anionic surfactant and/or B) at least one nonionic surfactant, based on the total weight of the cleansing composition,

II) from 5 to 60 wt.% C) at least one binder, based on the total weight of the cleansing composition,

III) from 0 to 30 wt.% (D) at least one peroxide and, optionally, at least one activator, based on the total weight of the cleansing composition, and

(IV) from 0.001 to 1 wt.% E) at least one granulate which contains:

(a) from 2 to 75 wt.% compositions corresponding to the above definition, based on the total weight of the granulate,

b) from 10 to 95 wt.% at least one additional additive, Theor�on the total weight of the granulate, and

c) from 0 to 15 wt.% water, based on the total weight of the granulate,

V) 0 to 60 wt.% F) at least one additional additive, and

VI) 0 to 5 wt.% (G) water.

The sum of the wt.% components (I)-(VI) in the composition is always 100%.

The percentages of components (I)-(VI) in the detergent composition in all cases in this text below is based on the total weight of the detergent composition.

Examples of components A) and B) have already been given above.

In the binder C) can be, for example, phosphates of alkali metals, especially tripolyphosphate, carbonates or bicarbonates, especially sodium salts, silicates, aluminosilicates, polycarboxylates, polycarboxylic acids, organic phosphonates, aminoalkylindole(alkylenediamine) or a mixture of these compounds.

Suitable peroxide components (D) include, for example, organic and inorganic peroxides such as sodium percarbonate or sodium perborate), known in the literature and commercially available, bleach textile materials at conventional washing temperatures, for example, from 5 to 95°C.

The concentration of peroxide or peroxide-forming compound is preferably 0.5-30 wt.%, more preferably 1-20 wt.% and particularly preferably 1-15 wt.%.

However, it is also possible absence of a peroxide or peroxide-obra�following substances.

Used detergents usually contain one or more additives, such as agents for suspending pollution, for example sodium carboxymethylcellulose; salts for pH control, such as silicates of alkali or alkaline earth metals; preregulatory, such as Soaps; salts for controlling characteristics of the spray drying and granulating, such as sodium sulfate; odorants; and, if necessary, an antistatic or emollients; such as smectite clay; potootvedeniya agents; pigments; and/or tools that give shade. These components, of course, must be resistant to any system used bleaching. Listed additives may be present in amounts of, for example, from 0.1 to 20 wt.%, preferably from 0.5 to 10 wt.%, especially from 0.5 to 5.0 wt.%, based on the total weight of the detergent.

Also, the detergent may optionally contain enzymes. The enzymes can be added to detergents to remove stains. Usually the enzymes improve the removability of stains protein or starch origin, such as, for example, the spots of blood, milk, herbs or fruit juices. Preferred enzymes are cellulases, proteases, amylases and lipases. Preferred enzymes are cellulases and proteases, especially proteases. Cellulase represent�t a enzymes, that act on cellulose and its derivatives and hydrolyze them into glucose, cellobiose, caloryguard. Cellulase remove dirt and have the effect of eliminating the coarseness of the surface of the fabric. Examples of enzymes that can be used include (but are not limited to):

Protease, as described in US-B-6,242,405, column 14, lines 21-32;

Lipase, as described in US-B-6,242,405, column 14, lines 33-46; amylase, see previous reference, column 14, lines 47-56; and cellulase, see previous reference, column 14, lines 57-64.

In optional detergent may be present enzymes. In the case of enzymes is usually contained in an amount of 0.01-5.0 wt.%, preferably 0.05-5.0 wt.% and more preferably 0.1-4.0 wt.%, based on the total weight of the detergent.

In addition to the bleaching catalyst corresponding to the formula (1), it is also possible to use other salts or complexes of transition metals, known as the active substance that activates the whitening and/or bleaching activators, i.e. compounds which under the conditions of peligrosa give unsubstituted or substituted, peranso - and/or peroxo-carboxylic acids containing from 1 to 10 C-atoms, in particular 2 to 4 C-atoms. Suitable bleaching activators include traditional bleaching activators mentioned above that containing� O - and/or N-acyl groups with the specified number of C-atoms, and/or unsubstituted or substituted benzolive group. Preferred are polyallylamine alkylenediamine, especially tetraacetylethylenediamine (TAED), acylated glycoluril, especially tetraaceticacid (TAGU), N,N-diacetyl-N,N-dimethylation (DDU), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexane-1,3,5-triazine (DADHT), the compounds of the formula:

where R26represents a sulfonate group, a carboxylic acid group or carboxylate group, and where R27represents a linear or branched (C7-C15)alkyl, especially activators, known under the names of SNOBS, SLOBS and DOBA, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and acylated sorbitol and mannitol and acylated derivatives of sugars, especially pentaacetate (PAG), the sucrose Polyacetal (SUPA), pentaceratops, tetraallylsilane and octatetraene, as well as acetylated, optionally N-alkylated glucamine and gluconolactone. You can also use combinations of traditional bleaching activators known from German patent application DE-A-4443177. Nitrile compounds, which form Perminova acid peroxides, can be also considered as activators from�of Livonia.

It is also an object of the present invention is softening composition containing:

(a) a composition corresponding to the above definition, and

(b) a fabric softener.

The fabric softeners, especially hydrocarbon fabric softeners suitable for use in the present invention, selected from the following classes of compounds:

Cationogenic Quaternary ammonium salts. Counterion for such cationogenic Quaternary ammonium salts may be a halide such as chloride or bromide, methylsulfate, or others well known in the literature ions. Preferably, the counterion is metilsulfate or any alkylsulfate or any halide, wherein metilsulfate is the most preferred for products with a desiccant of the present invention.

These softeners are described in more detail in U.S. patent No. 4,134,838, the description of which is included in this text as a link. The preferred fabric softeners for use in the present invention are acyclic Quaternary ammonium salts. It is also possible to use mixtures of the above fabric softeners.

Composition of fabric softener of the present invention contains 0.001-5.0 wt.%, preferably 0.001-3.0 wt.% the above composition.

Colouring composition of the present invention in specifics�and used in formulations of detergent or softening agents. Such a detergent composition or an emollient may be in solid, liquid, gel-like or pasty form, for example liquid, anhydrous detergent composition containing not more than 5.0 wt.%, preferably 0 to 1 wt.%, water, and has as a basis the slurry binder in nonionic surface-active agent, for example as described in GB-A-2158454.

Liquid detergent composition can also be in the form of powders or (super-)compact powders, view of a single-layer or multi-layer tablets, the type of detergent bars, detergent blocks, cleaning sheets, cleaning detergent pastes or gels, or type of powders, pastes, gels or liquids used in capsules or bags (sachets).

Other objects of the present invention are the use of the above bis-azo dye and applying the above composition to enhance the whiteness of textile materials.

Another object of the present invention is a new bis-azo dyes selected from the group consisting of the following examples,

,

and

All the definitions and preferred embodiments given above, apply equally to all of the objects of the present invention.

The following Examples illustrate the present invention.

A. Examples of preparation

The synthesis of the obtained bis-azo dyes consist of two stages of azocoupling. First, a suitable amine diasterous and injected into a reaction combination with a suitable aromatic amines, yielding mono-azo intermediate connection. In the second stage, the obtained mono-azo compound diasterous and injected into a reaction combination with an aromatic amine. The end product is a bis-azo dye is isolated by precipitation and purified further. Or you can use aqueous solutions of dyes directly in tests for suitability.

Example 1

This compound was obtained according to the literature [N. Sekar, G. Chakko, Rajle, R. N. Colourage(2005) 52 82), 119].

Spectrum in the UV and visible region (UVvis) (H2O) λmax: 555 nm, purity (98% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC. The output of the black dye after treatment was 53%.

Example 2

General procedure for synthesis of bis-azo dyes

a) Synthesis of mono-azo intermediate connection

17.3 g (0.1 mol) of aniline-3-sulfonic acid was dissolved in a mixture of 150 ml of water and 4 g (0.1 mol) of solid sodium hydroxide. To the resulting solution was added 6.9 g (0.1 mol) of solid sodium nitrite dissolved in 15 ml of water. The resulting mixture, with stirring, cooled to 5°C and diazotisable by dropping 70 ml of 50% aqueous HCl solution for 15 minutes. The reaction mixture was stirred at 2-7°C for 90 minutes. A slight excess of nitrous acid was decomposed by adding 10% aqueous solution of sulfamic acid (10 ml) and stirred for another 30 minutes. The suspension obtained diazonium salt for 15 minutes was added at 10°C to a solution containing 14.3 g (0.1 mol) of 1-naphthylamine in 100 ml of water and 4.0 g (0.1 mol) of solid NaOH. The pH of the solution was adjusted to 3-4 by addition of 10% aqueous NaOH solution. After stirring at 10°C for 2 hours the reaction mixture was allowed to stir for 12 hours at room temperature. The precipitate was separated fil�mation. The obtained crude product was suspended in 50 ml of methanol for one hour, and the resulting suspension was filtered. The obtained dark brown solid product was dried in an oven at 55-60°C.

The product was characterized by UV methodvisspectroscopy, and purity was determined by the percentage ratio of the areas of the peaks in the HPLC-chromatogram. HPLC was performed on a reversed-phase column (Inertsil® ODS-2, GL Sciences Inc. Mode in the gradient elution: Mobile phase 'A' represents 0.2% Tetra-butylammonium bromide in water, mobile phase 'B' is a 100% MeOH (HPLC). The initial ratio of A:B is 80:20, and then, in the mode of stepwise gradient of the content of the mobile phase 'B' is increased to 100% within 30 minutes.

Was allocated 18 g of mono-azo compound 94% purity (determined at a wavelength of 254 nm), having the molecular formula C16H13N3O3S, with a yield of 56%.

(b) obtaining a bis-azo dye

In a mixture of 20 ml of water and 0.3 g (7.6 mmol) of solid NaOH was dissolved 2.5 g (7.6 mmol) of mono-azo compound obtained in Example 1A). To the resulting solution is added with stirring to a solution of 0.52 g (7.6 mmol) of solid NaNO2in 2 ml of water. The reaction mixture was cooled to 5°C and pinned 5 ml of 50% aqueous HCl solution for 15 minutes. The temperature in the reaction medium was maintained equal to 2-7°SV for 90 minutes. Excess nitrous acid was decomposed by adding 10% aqueous solution of sulfamic acid (1.5 ml) and stirred for another 30 minutes. The suspension obtained diazonium salt was added at 10°C to a solution of 1.69 g (7.6 mmol) of 8-amino-1-naphthalene-2-sulfonic acid (1.7-acid Kleve) in 20 ml of water and 0.3 g (7.6 mmol) of solid NaOH, maintaining the pH in the range 8-9 by addition of 10% aqueous NaOH solution. After stirring at 10°C for 3 hours the mixture was heated to 70°C for 1 hour. The completion of the reaction was monitored by the method of reversed-phase TLC (RP-18 (F254S, Merck), using as mobile phase a 1:1 mixture of water and methanol (original substance has Rf0.8; product - Rf0.6). In the reaction mixture was added 7 g (10% wt./about.) NaCl. The reaction mixture was stirred for 8 hours at room temperature. Precipitated solid precipitate was separated by filtration, and were additionally treated with 25 ml of a mixture of 1:1 methanol/water. The filtered solid was dried in an oven at 55-60°C. the Product was characterized by UV methodvisspectroscopy (λmax526 nm, H2O). Purity (92.6% at 254 nm) was determined according to the percentage ratio of the areas of the peaks in the HPLC-chromatogram. Black bis-azo dye was isolated with a yield of 57%.

Example 3

(a) mono-azo derivative of 8-amino-5-(3-sulfo-phenylazo)-naphthalene-2-Sultonova� acid:

According to the General methodology described in Example 2, 17.3 g (0.1 mol) of aniline-3-sulfonic acid and 22.3 g (0.1 mol) of 8-amino-naphthalene-2-sulfonic acid was injected into the reaction mix, getting 8-amino-5-(3-sulfo-phenylazo)-naphthalene-2-sulfonic acid with the molecular formula C16H13N3O6S2. The product was characterized by UV methodvisspectroscopy, and purity (91% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC. The output of the black dye after treatment was 60%.

(b) obtaining a bis-azo dye: According to the General methodology described in Example 2, the reaction was carried out between 17.4 g (0.04 mol) of 8-amino-5-(3-sulfo-phenylazo)-naphthalene-2-sulfonic acid and 8.4 g (0.04 mol) of 8-amino-naphthalene-1-sulfonic acid (peri acid) and treated with the reaction mixture.

UVvis(H2O) λmax: 563 nm, purity (91% at 254 mi) was determined according to the percentage ratio of the areas of peaks in HPLC, the output of the black dye after treatment was 52%.

Example 4

According to the method described in Example 2, 3.1 g (0.0076 mol), the reaction was carried out between 8-amino-5-(3-sulfophenylazo)-naphthalene-2-sulfonic acid and 1.7 g (0.0076 mol) of 8-amino-naphthalene-2-sulfonic acid (1.7-acid Kleve) and treated with the reaction mixture.

UVvis(H2O) λmax: 535 nm, purity (85% at 254 mi) was determined by the percent�/ the ratio of the areas of peaks in HPLC.

Example 5

According to the General methodology described in Example 2 was injected into the reaction combinations of 3.1 g (0.0076 mol) of 8-amino-5-(3-sulfophenylazo)-naphthalene-2-sulfonic acid and 1.7 g (0.0076 mol) of 5-amino-naphthalene-1-sulfonic acid (acid Laurent) and treated with the reaction mixture, yielding bis-azo dye in the form of a greenish-black solid.

UVvis(H2O) λmax: 536 nm, purity (95% at 254 mi) was determined according to the percentage ratio of the areas of peaks in HPLC, the output of the substances after treatment was 10%.

Example 6

According to the method described in Example 2, the reaction was carried out between 3.1 g (0.0076 mol) of 8-amino-5-(3-sulfophenylazo)-naphthalene-2-sulfonic acid and 2.3 g (0.0076 mol) of 8-phenylamino-naphthalene-1-sulfonic acid (N-phenyl peri acid). The crude product was treated with 30 ml of 20% solution of methanol and acetone to remove impurities. Bis-azo dye was obtained in pure form.

UVvis(H2O) λmax: 576 nm, purity (89% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC. The output of the black dye after treatment was 44%.

Example 7

(a) mono-azo derivative of 8-amino-(5-phenylazo)-naphthalene-2-sulfonic acid:

The reaction was carried out between 9.5 g (0.1 mol) of aniline and 22.3 g (0.1 mol) of 8-amino-naft�Lin-2-sulfonic acid according to the General method described in Example 2. The product was characterized by UV methodvisspectroscopy; purity (95.1% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC. Yield a dark brown solid dye after treatment was 84%.

(b) obtaining a bis-azo dye:

According to the General methodology described in Example 2, the reaction was carried out between 10 g (0.3 mol) of 8-amino-(5-phenylazo)-naphthalene-2-sulfonic acid and 6.8 g (0.3 mol) of 8-amino-naphthalene-1-sulfonic acid (peri acid) and treated with the reaction mixture.

UVvis(H2O) λmax: 554 nm, purity (91% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC. The output of the black dye after treatment was 29%.

Example 8

The reaction was carried out between 2.5 g (0.0076 mol) of 8-amino-(5-feelso)-naphthalene-2-sulfonic acid and 1.7 g (0.0076 mol) of 8-amino-naphthalene-2-sulfonic acid (1.7-CI slot Kleve) and the treatment of the reaction mixture according to the General methodology described in Example 2.

UVvis(H2O) λmax: 526 nm, purity (94% at 254 mi) was determined according to the percentage ratio of the areas of peaks in HPLC. The output black colorant substances after treatment was 5%.

Example 9

(a) Obtaining a mono azo 2-(4-amino-6-sulfo-naphthalene-1-ylazo)-benzene-1,4-disulfonic acid:

According to the General method described� in Example 2, the reaction was carried out between 10 g (0.039 mol) of aniline-2,5-disulfonic acid and 8.9 g (0.039 mol) of 8-amino-naphthalene-2-sulfonic acid. The obtained mono-azo intermediate product was characterized by UV methodvisspectroscopy, and purity (91%) was determined according to the percentage ratio of the areas of peaks in HPLC. The output of the black dye after treatment was 47%.

(b) obtaining a bis-azo dye:

According to the General methodology described in Example 2, the reaction was carried out between 3.5 g (0.0072 mol) of mono-azo compound obtained in (a) and 2.16 g (0.0072 mol) of 8-phenylamino-naphthalene-1-sulfonic acid (N-phenyl peri acid). After the reaction, the mixture was heated to 70°C for 1 hour and lowered the temperature to 50°C, after which was added 20% wt./about. salt. The mixture was cooled to room temperature and the solid residue was filtered. The crude bis-azo dye was treated with a 1:1 mixture of methanol and acetone to remove impurities. Bis-azo dye was obtained in pure form.

UVvis(H2O) λmax: 587 nm, purity (82% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC. The output of the black dye after treatment was 30%.

Example 10

a) preparation of the mono-azo derivative:

The first intermediate compound was obtained according to literature methods [M. Wojciechowska, G. Wojciechowska, W. Wasiak: J. of Molecular Structure 658 (2003) 125-133). In the reaction mixture containing 40 ml of water and 0.76 g (0.011 mol, a 10% excess) NaNO2added 40 ml of a solution of 4.46 g (0.02 mol) of 8-amino-naphthalene-2-sulfonic acid and 4 ml of concentrated HCl at room temperature. Bring the pH of the reaction mixture to 2 and heated for 30 min at 55°C. the reaction mixture was added 24 g of sodium chloride and was kept for 8 hours at room temperature. The precipitate was filtered, washed with water (12 ml) and dried in a drying Cabinet at 50°C. Yield: 4.2 g, quantitative.

(b) obtaining a bis-azo dye:

According to the General methodology described in Example 2, the reaction was carried out between 4.57 g (0.01 mol) ISPO-azo 8-amino-5,8'-azo-bis-naphthalene-2-sulfonic acid and 2.23 g (0.01 mol) of 8-amino-naphthalene-1-sulfonic acid (peri acid). The crude bis-azo dye was mixed with 20 ml of a mixture of 1:1 methanol and water and filtered. The filtrate was poured in 150 ml of acetone. The precipitate was filtered, and the filtrate was again concentrated to remove solvent. The sludge precipitated from aqueous layer was filtered and dried in a drying oven at 55°C.

UVvis(H2O) λmax: 568 nm, purity (98% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC. The output of the black dye after treatment was 10%.

Example 11

a) preparation of 3-(4-amino-2-methyl-phenylazo)-a mixture of Benzenesulfonic acid:

According to the General methodology described in Example 2, show�and reaction between 8.65 g (0.05 mol) of aniline-3-sulfonic acid and 5.3 g (0.05 mol) of m-toluidine and treated with the reaction mixture. The product was characterized by UV methodvisspectroscopy, and purity was determined by the percentage ratio of the areas of peaks in HPLC. The output of the black dye after treatment was 50%.

(b) obtaining a bis-azo dye:

According to a common methodology, introduced in the reaction of a combination of 2.9 g (0.01 mol) of 3-(4-amino-2-methyl-phenylazo)-a mixture of Benzenesulfonic acid and 2.23 g (0.01 mol) of 8-amino-naphthalene-1-sulfonic acid (peri acid), the pH was adjusted to 3.0-3.5. After the reaction, the solid precipitate was filtered and treated with an additional 25 ml of a 1:1 mixture of methanol and acetone to remove impurities. Pure bis-azo dye was obtained as a greenish-black solid.

UVvis(H2O) λmax: 541 them, purity (85% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC, the output of the substances after treatment was 21%.

Example 12

Obtain 5-[3-methyl-4-(3-sulfo-phenylazo)-phenylazo]-8-phenylamino-naphthalene-1-sulfonic acid:

According to the General methodology described in Example 2, the reaction was carried out between 2.9 g (0.01 mol) of 3-(4-amino-2-methyl-phenylazo)-a mixture of Benzenesulfonic acid, obtained in Example 11a, and 3.0 g (0.01 mole) of 8-phenylamino-naphthalene-1-sulfonic acid (N-phenyl peri acid), and treated with the reaction mixture.

UVvis(H2O) λmax: 541 nm, purity (87% at 254 nm) determined�and the percentage of the areas of peaks in HPLC, the output of the substances after treatment was 32%, greenish-black solid.

Example 13

(a) mono-azo derivative of 8-amino-5-(4-sulfo-phenylazo)-naphthalene-2-sulfonic acid:

According to the General methodology described in Example 2, the reaction was carried out between 19.5 g (0.1 mol) of the sodium salt of aniline-4-sulfonic acid and 22.3 g (0.1 mol) of 8-amino-naphthalene-2-sulfonic acid, and treated with the reaction mixture. The product was characterized by UV methodvisspectroscopy, and purity (92% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC. The output of the black dye after treatment was 60%.

(b) obtaining a bis-azo dye:

According to the General methodology described in Example 2, the reaction was carried out between 4.07 g (0.01 mol) of 8-amino-5-(4-sulfo-phenylazo)-naphthalene-2-sulfonic acid and 3.0 g (0.01 mole) of 8-phenylamino-naphthalene-1-sulfonic acid (N-phenyl peri acid), and treated with the reaction mixture.

UVvis(H2O) λmax; 581 nm, purity (91% at 254 mi) was determined according to the percentage ratio of the areas of peaks in HPLC, the output of the substances after treatment was 28%.

Example 14

(a) mono-azo derivative 4-(4-amino-naphthalene-1-ylazo) a mixture of Benzenesulfonic acid:

According to the General methodology described in Example 2, the reaction was carried out between 19.5 g (0.1 mol) of nutrie�Oh salt of aniline-4-sulfonic acid and 14.3 g (0.1 mol) of 1-aminonaphthalene, and was treated with the reaction mixture. The product was characterized by UV methodvisspectroscopy, and purity (92% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC. The yield of dark red dye after treatment was 50%.

(b) obtaining a bis-azo dye:

According to the General methodology described in Example 2, the reaction was carried out between 3.27 g (0.01 mol) of 4-(4-amino-naphthalene-1-ylazo) a mixture of Benzenesulfonic acid and 3.0 g (0.01 mole) of 8-phenylamino-naphthalene-1-sulfonic acid (N-phenyl peri acid), and treated with the reaction mixture.

UVvis(H2O) λmax: 569 nm, purity (97% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC, the output of the substances after treatment was 15%, a dark solid.

Example 15

According to the General methodology described in Example 2, the reaction was carried out between 4.07 g (0.01 mol) of 8-amino-5-(4-sulfo-phenylazo)-naphthalene-2-sulfonic acid, obtained in Example 13, and 2.23 g (0.01 mol) of 8-amino-naphthalene-1-sulfonic acid (peri acid), and treated with the reaction mixture.

UVvis(H2O) λmax: 566 nm, purity (95% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC, the output of the substances after treatment was 15%, black solid.

Example 16

According to the General methodology described in Example 2, Prov�Dili reaction between 4.07 g (0.01 mol) of 8-amino-5-(3-sulfophenylazo)-naphthalene-2-sulfonic acid and 2.2 g (0.01 mol) of 8-amino-naphthalene-3-sulfonic acid (1,6-acid Kleve). After the reaction, the reaction mixture was heated to 70°C for 1 hour, and the temperature was lowered to 50°C, after which was added sodium chloride (20% wt./vol.). After cooling the reaction mixture to room temperature dropped a solid precipitate, which was filtered. The crude product was treated with a 1:1 mixture of methanol and water to remove impurities. Bis-azo dye was obtained in pure form as a black solid.

UVvis(H2O) λmax: 532 nm, purity (88% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC, the output of the substances after treatment was 27%, black solid.

Example 17

According to the literature method mentioned in Example 1, reaction was carried out between 3.27 g (0.01 mol) of 4-(4-amino-naphthalene-1-ylazo) a mixture of Benzenesulfonic acid and 2.23 g (0.01 mol) of 8-amino-naphthalene-1-sulfonic acid (peri acid), and treated with the reaction mixture.

UVvis(H2O) λmax: 560 nm, purity (98% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC, the output of the substances after treatment was 20%, black solid.

Example 18

According to the General methodology described in Example 2, the reaction was carried out between 3.27 g (0.01 mol) of 4-(4-amino-naphthalene-1-ylazo)a mixture of Benzenesulfonic acid (described in Example 14) and 2.23 g (0.01 mol) of 8-amino-patta�in-2-sulfonic acid (1.7-acid Kleve), and was treated with the reaction mixture.

UVvis(H2O) λmax: 532 nm, purity (90% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC, the output of the substances after treatment was 25%, black solid.

Example 19

According to the literature methods [A. Ono, K. Watanabe, S. Yamate, Jpn. Kokai Tokyo Koho (2001)], the reaction was carried out between 2.5 g (0.005 mol) of 2-(4-amino-6-sulfo-naphthalene-1-ylazo)-benzene-1,4-disulfonic acid and 1.11 g (0.005 mol) of 8-amino-naphthalene-1-sulfonic acid (peri acid). The crude dye was washed with 1:1 mixture of methanol and acetone to remove impurities.

UVvis(H2O) λmax: 556 nm, purity (75% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC, the output of the substances after treatment was 14%, black solid.

Example 20

According to the General methodology described in Example 2, the reaction was carried out between 4.07 g (0.01 mol) of 5-amino-8-(3-sulfo-phenylazo)-naphthalene-2-sulfonic acid and 2.23 g (0.01 mol) of 8-amino-naphthalene-1-sulfonic acid (peri acid), and treated with the reaction mixture.

UVvis(H2O) λmax: 561 nm, purity (92% at 254 mi) was determined according to the percentage ratio of the areas of peaks in HPLC, the output of the substances after treatment was 23%, black solid.

Example 21

According to the General methodology described in Example 2, the reaction was carried out between 2.5 g (0.0076 mol) of 8-amino-5-(phenylazo)-naphthalene-2-sulfonic acid and 1.7 g (0.0076 mol) of 5-amino-naphthalene-1-sulfonic acid (acid Laurent), and treated with the reaction mixture.

UVvis(H2O) λmax531 them, purity (92% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC, the output of the substances after treatment was 26%, greenish-black solid.

Example 22

According to the General methodology described in Example 2, the reaction was carried out between 2.5 g (0.0076 mol) of 3-(4-amino-naphthalene-1-ylazo)-a mixture of Benzenesulfonic acid and 1.7 g (0.0076 mol) of 5-amino-naphthalene-1-sulfonic acid (acid Laurent), and treated with the reaction mixture.

UVvis(H2O) λmax: 527 nm, purity (91% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC, the output of the substances after treatment was 20%, black solid.

Example 23

(a) mono-azo derivative of 8-amino-5-(5-sulfo-Naftali-1 ylazo)-naphthalene-2-sulfonic acid: According to the General methodology described in Example 2, the reaction was carried out between 6.6 g (0.029 mol) of 5-amino-naphthalene-1-sulfonic acid and 6.6 g (0.029 mol) of 8-amino-naphthalene-2-sulfonic acid, and treated with the reaction mixture. The obtained mono-azo derivative ha�was acharitable method UV visspectroscopy, and purity (92% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC. The yield of dark green dye after treatment was 84%.

(b) obtaining a bis-azo dye: According to the General methodology described in Example 2, the reaction was carried out combinations between 3.6 g (0.0076 mol) of 8-amino-5-(5-sulfo-naphthalene-1-ylazo)-naphthalene-2-sulfonic acid and 3.0 g (0.01 mole) of 8-phenylamino-naphthalene-1-sulfonic acid (N-phenyl peri acid). The crude dye was washed with a 1:1 mixture of methanol and acetone to remove impurities.

UVvis(H2O) λmax: 582 nm, purity (90% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC, the output of the substances after treatment was 12%, solid dark color.

Example 24

a) preparation of 5-amino-8-(3-sulfo-phenylazo)-naphthalene-2-sulfonic acid:

According to the General method described in Example 2A, the reaction was carried out between 8.65 g (0.05 mol) of aniline-3-sulfonic acid and 14.3 g (0.1 mol) of 5-amino-naphthalene-2-sulfonic acid, and treated with the reaction mixture. The resulting product was characterized by UV methodvisspectroscopy. Purity (96% at 254 mi) was determined according to the percentage ratio of the areas of peaks in HPLC. The output of the black-and-green dye after treatment was 98%.

(b) obtaining a bis-azo dye:

Using the methodology described in 2b, the reaction was carried out between 4.07 g (0.01 mol) of 5-amino-8-(3-sulfo-phenylazo)-naphthalene-2-sulfonic acid and 3.0 g (0.01 mole) of 8-phenylamino-naphthalene-1-sulfonic acid (N-phenyl peri acid), and treated with the reaction mixture.

UVvis(H2O) λmax: 577 nm, purity (99% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC, the output of the substances after treatment was 26%, black solid.

Example 25

This bis-azo dye obtained by well-known methods (for example, S. Batchelor, J. Bird, WO 2009087032].

UVvis(H2O) λmax: 577 nm, purity (98.8% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC, the output of the substances after treatment was 26%, black solid.

Example 26

According to the General methodology described in Example 2, the reaction was carried out between 4.07 g (0.01 mol) of 5-amino-8-(3-sulfo-phenylazo)-naphthalene-2-sulfonic acid and 2.23 g (0.01 mol) of 8-amino-naphthalene-2-sulfonic acid (1.7-acid Kleve), and treated with the reaction mixture.

UVvis(H2O) λmax: 536 them, purity (94% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC, the output of the substances after treatment was 78%, black solid.

Example 27

According to the General methodology described in Example 2, PR�drove reaction between 4.07 g (0.01 mol) of 5-amino-8-(3-sulfo-phenylazo)-naphthalene-2-sulfonic acid and 2.23 g (0.01 mol) of 5-amino-naphthalene-2-sulfonic acid (1.6-acid Kleve), and was treated with the reaction mixture.

UVvis(H2O) λmax: 536 nm, purity (89% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC, the output of the substances after treatment was 7%, black solid.

Example 28

(a) mono-azo derivative of 5-amino-8-(4-sulfo-phenylazo)-naphthalene-2-sulfonic acid:

According to the General method described in Example 2A, the reaction was carried out between 8.65 g (0.05 mol) of aniline-4-sulfonic acid and 11.2 g (0.05 mmol) 5-amino-naphthalene-2-sulfonic acid, and treated with the reaction mixture. The resulting product was characterized by UV methodvisspectroscopy, and purity (97% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC. The yield of dark green dye after treatment was 85%.

(b) obtaining a bis-azo dye:

According to the method described in Example 2b, the reaction was carried out between 4.07 g (0.01 mol) of mono-azo derivative of 5-amino-8-(4-sulfo-phenylazo)-naphthalene-2-sulfonic acid and 2.23 g (0.01 mol) of 8-amino-naphthalene-1-sulfonic acid (peri acid), and treated with the reaction mixture.

UVvis(H2O) λmax: 566 nm, purity (98% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC, the output of the substances after treatment was 17%, black solid.

Example 29

According to the General methodology described in Example 2, the reaction was carried out between 4.07 g (0.01 mol) of 5-amino-8-(4-sulfo-phenylazo)-naphthalene-2-sulfonic acid and 2.23 g (0.01 mol) of 8-amino-naphthalene-2-sulfonic acid (1.7-acid Kleve), and treated with the reaction mixture.

UVvis(H2O) λmax: 536 nm, purity (84% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC, the output of the substances after treatment was 10%, black solid.

Example 30

According to the General methodology described in Example 2, the reaction was carried out between 4.07 g (0.01 mol) of 5-amino-8-(4-sulfo-phenylazo)-naphthalene-2-sulfonic acid and 3.0 g (0.01 mole) of 8-phenylamino-aftalen-1-sulfonic acid (N-phenyl peri acid), and treated with the reaction mixture.

UVvis(H2O) λmax: 581 nm, purity (93% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC, the output of the substances after treatment was 12%, black solid.

Example 31

According to the General method described in Example 2b, the reaction was carried out between 3.79 g (0.01 mol) of the sodium salt of 4-amino-1,1'-azobenzene-3,4'-disulfonic acid (acid yellow 9) and 2.83 g (0.01 mol) of 8-amino-naphthalene-1-sulfonic acid (peri acid). After completion of the reaction, the crude dye was extracted by adding 30% (weight/weight) of sodium chloride. More about�amityvale water to remove impurities and excess sodium chloride.

UVvis(H2O) λmax: 514 nm, purity (89% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC, the output of the substances after treatment was 31%, greenish-black solid.

The structure was confirmed by the method of ESI-LC-MS.

Molecular weight (g/mol)Structure
592 (component Side)
591 (Main product)

Example 32

According to the General methodology described in Example 2, the reaction was carried out between 3.79 g (0.01 mol) of the sodium salt of 4-amino-1,1'-azobenzene-3,4'-disulfonic acid (acid yellow 9) and 3.0 g (0.01 mole) of 8-phenylamino-naphthalene-1-sulfonic acid (N-phenyl peri acid). The reaction product constituting the crude dye was isolated by addition of 30% (wt./weight.) salt. The product is further processed twice a 1:1 mixture of methanol and water to remove impurities.

UVvis(H2O) λmax: 558 nm, purity (90% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC, the output of the substances after treatment was 42%, black solid.

The structure was confirmed methods�ω ESI-LC-MS.

Molecular weight (g/mol)Structure
591 (traces)
667 (main peak)

Example 33

According to the General methodology described in Example 2, the reaction was carried out between 3.79 g (0.01 mol) of the sodium salt of 4-amino-1,1'-azobenzene-3,4'-disulfonic acid (acid yellow 9) and 3.0 g (0.01 mol) of 5-amino-naphthalene-2-sulfonic acid (1,6-acid Kleve). After completion of the reaction, the crude dye was isolated by addition of 30% (wt./weight.) salt. Additionally, treated with methanol to remove impurities.

UVvis(H2O) λmax: 507 nm, purity (84% at 254 mi) was determined according to the percentage ratio of the areas of peaks in HPLC, the output of the substances after treatment was 50%, black solid.

The structure was confirmed by the method of ESI-LC-MS.

Molecular weight (g/mol)Structure
591 (main component)
592 (traces)

Example 36

According to the General procedure described in Example 28, received mono-azo derivative of 5-amino-8-(4-sulfophenylazo)naphthalene-2-sulfonic acid. The reaction was carried out between 4.07 g (0.01 mol) of mono-azo compounds and 2.23 g (0.01 mol) of 5-Amii-naftalin-2-sulfonic acid (1,6-acid Kleve), and the reaction mixture was treated according to the General method described in Example 2b.

UVvis(H2O) λmax: 539 nm, purity (86% at 254 nm) was determined according to the percentage ratio of the areas of peaks in HPLC, the output of the substances after treatment was 21%, black solid.

The structure was confirmed by the method of ESI-LC-MS.

Molecular weight (g/mol)Structure
641 (main component)
641Detected two isomers of the main component

The resulting dyes are shown in Table 1.

Table 1
Example No.Structure
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36

Acid sulfo group in the above formulas presented in the form of the free acid. But with the same success can be present corresponding salts of Na and K, which can also be formed under suitable pH values.

V. application Examples

Use when washing

Bleached cotton washed for 15 minutes at 30°C with detergent containing the dye, giving shade, with or without adding a mixture of photocatalysts, connections 101 and 102 described on page 10. The amount of detergent used was 40 g per kg of tissue, the ratio of tissue and water was 1 to 10.

After washing, the samples were dried in the light (incandescent lamp with a tungsten spiral, 200 W) for 1 hour. Control blank experiments were carried out in the form of drying without lighting. The washing/drying was repeated 5 times for drawing the profile of the concentration�ation of the dye, giving shade, and the photocatalyst in the conditions of everyday washing.

After the fifth cycle was determined relative amount of dye on the fabric, dried in the dark, and the fabric dried in the light, by measuring the reflection from optically opaque exfoliation. Applying the equation of Kubelka-Munch (1), determine the values of K/S and relative dye concentration after irradiation. The following table shows the percentage concentration of the dye after irradiation with and without photocatalyst of the photocatalyst.

KS=(1-R)22R(1)

Table 2
% Of photodegradation of the dye after 1 cycle of washing/drying
Dye% dye in detergent% Of photocatalyst in detergent% of photodegradation of dye
1 0,0050,0010
0,0050,0455
20,020,006
0,020,1033
30,020,0017
0,020,0456
40,020,0022
0,020,1055
60,020,0013
0,020,0452
70,020,0012
0,020,0438
80,020,004
0,020,0416
100,010,008
0,010,0233
110,010,0013
0,010,0647
120,010,0019
0,010,0539
140,020,006
0,020,0430
150,010,004
0,010,0357
160,040,005
0,040,0847
170,010,006
0,010,0231
180,0080,004
0,0080,0419

Table 3
% Of photodegradation of the dye after 1 and 5 cycles of washing/drying
Dye% dye in detergent% Of photocatalyst in detergentThe relative concentration of the dye after 1 cycle of washing/dryingThe relative concentration of the dye after 5 cycles of washing/drying
10,010,001.003.51
0,010,020.560.56
30,010,001.004.09
0,010,010.120.97
40,020,001.004.05
0,020,100.691.27
60.020.001.003.77
0.020.040.701.28
120.010.001.004.17
0.010.050.641.52
140.02 0.001.004.17
0.020.040.641.52

The results obtained clearly show the degradation of bis-azo dyes in the presence of the photocatalyst.

The values in Table 2 show that the concentration of the dye is low, when the substrate is present photocatalyst, preventing a build.

1. Method give shade textile fabrics or fibers, which comprises applying bis-azo dye of formula (I), (II) or (III) on the fabric or fiber is in the process of washing

where
a is 0, 1 or 2;
b is 0 or 1;
with 0 or 1;
d is 0 or 1;
A represents CH3or SO3X
X represents H, Na or K, and
R is a group

where the arrows indicate the point of attachment;
provided that in the formula (I) R is different from R2if a is 1 and b is 0.

2. Method give shade textile fabrics or fibers, which comprises applying the photocatalyst, which is a water-soluble phthalocyanine Zn, Fe(II), CA, Mg, Na, K, Al, Si(IV), P(V), Ti(IV), Ge(IV), Cr(VI), Ga(III), Zr(IV), In(III), Sn(IV) or Hf(VI), and bis-azo dye of formula (I), (II) or (III) on a cloth or �Alekno in the process of washing


where
a is 0, 1 or 2;
b is 0 or 1;
with 0 or 1;
d is 0 or 1;
A represents CH3or SO3X
X represents H, Na or K, and
R is a group

where the arrows indicate the point of attachment.

3. Method give shade according to claim 1 or 2, where the bis-azo dye is selected from the group consisting of

4. Method give shade according to claim 1 or 2, where indicated bis-azo dye is a compound according to examples 3, 16, 26, 31 and 32.

5. Method give shade according to claim 2, where the said photocatalyst is a water-soluble phthalocyanine of the formula (X)

where
PC represents a phthalocyanine cyclic system;
Me represents Zn; Fe(II); CA; Mg; Na; K; Al-Z1Si(IV); P(V); Ti(IV), Ge(IV); Cr(VI); Ga(III); Zr(IV); In(III); Sn(IV) or Hf(VI);
Z1is a halide; sulfate; nitrate; a carboxylate or Alkonost-ion; or a hydroxy group;
q is 0, 1 or 2;
r = 1-8;
Q2represents a hydroxy group; C1-C22alkyl; branched C3-C22alkyl; C2-C22the alkenyl; branched C3-C22the alkenyl and mixtures thereof; C1-C22alkoxy group; a sulfo or carboxy radical; the radical of the formula

branched alkoxy radical of the formula

alkylacrylate-fragment of formula(T1)d-(CH2)b(OCH2CH2)a-B3or
the ester of the formula COOR18
where
In2represents a hydrogen atom; hydroxy group; C1-C30alkyl; C1-C30alkoxy group; -CO2H; -CH2COOH;-SO3-M1;-OSO3-M1;-PO32-M1;-OPO32-M1; and mixtures thereof;
In3represents a hydrogen atom; hydroxy group; -COOH;-SO3-M1;-OSO3-M1 or C1-C6alkoxy-group;
M1is a water soluble cation;
T1represents-O-; or-NH-;
X1and X4independently from each other represent-O-; -NH - or-N-C1-C6alkyl;
R11and R12independently from each other represent a hydrogen atom; a sulfo group and its salts; carboxy group and its salt or a hydroxy group; wherein at least one of the radicals R11and R12represents a sulfo or carboxy group or salts thereof,
Y2represents-O-; -S-; -NH - or-N-C1-C5alkyl;
R13and R14independently from each other represent a hydrogen atom; C1-C6alkyl; hydroxy-(C1-C6alkyl; cyano-C1-C6alkyl; sulfo-C1-C6alkyl; hydroxy - or halo-C1-C6alkyl; unsubstituted phenyl or phenyl substituted by a halogen atom, a C1-C4the alkyl or C1-C4alkoxy group; sulfo group or carboxy group, or R13and R14together with the nitrogen atom to which they are linked, form a saturated 5 - or 6-membered heterocyclic cycle, which may also optionally contain a nitrogen atom or an oxygen atom as a member of a loop;
R15and R16independently from each other represent�t a C 1-C6alkyl or aryl-C1-C6alkyl radicals;
R17represents a hydrogen atom; unsubstituted C1-C6alkyl or C1-C6alkyl substituted by halogen atom, hydroxy group, cyano group, phenyl, carboxy group, carb-C1-C6alkoxy group or a C1-C6alkoxy-group;
R18represents a C1-C22alkyl; branched C3-C22alkyl; C1-C22the alkenyl or branched C3-C22the alkenyl; C3-C22glycol; C1-C22alkoxy group; a branched C3-C22alkoxy group; and mixtures thereof;
M represents a hydrogen atom; or an alkali metal ion or ammonium ion,
Z2-represents chlorine; bromine; alkylsulfate - or aralkylated-ion;
a is 0 or 1;
b is from 0 to 6;
C is from 0 to 100;
d is 0 or 1;
e is equal to from 0 to 22;
v is an integer from 2 to 12;
w is 0 or 1; and
where phthalocyanine cyclic system may also contain additional solubilizers group.

6. Method give shade according to claim 2, where the said photocatalyst is a water-soluble phthalocyanine formulas

or their mixture�, where the degree of sulfonylurea equal to 2-4, and Z1is a halide, sulfate, nitrate, carboxylate or Alkonost-ion or a hydroxy group.

7. Method give shade according to claim 1 or 2, comprising applying at least one fluorescent whitening agent.

8. Composition to color textile fabrics or fibres containing
(a) bis-azo dye of formula (I), (II) or (III)

where
a is 0, 1 or 2;
b is 0 or 1;
with 0 or 1;
d is 0 or 1;
A represents CH3or SO3X
X represents H, Na or K, and
R is a group

where the arrows indicate the point of attachment, and
(b) water-soluble phthalocyanine Zn, Fe(II), CA, Mg, Na, K, Al, Si(IV), P(V), Ti(IV), Ge(IV), Cr(VI), Ga(III), Zr(IV), In(III), Sn(IV) or Hf(VI).

9. The granular composition for use in the process of giving shade textile fabric or fiber containing:
(a) from 2 to 75 wt.% the composition according to claim 8, based on the total weight of the granulate,
b) from 10 to 95 wt.% at least one further additive, based on the total weight of the granulate, and
c) from 0 to 15 wt.% water, based on the total weight of the granulate.

10. A liquid composition for use in the process of giving shade textile fabrics or fibers containing a composition according to claim 8.

11. The detergent composition for prom�VNOM or emollient, contains:
I) from 5 to 70 wt.% A) at least one anionic surface-active agents and/or B) at least one nonionic surface-active agents, based on the total weight of the cleansing composition,
II) from 5 to 60 wt.% (C) at least one detergent component, based on the total weight of the cleansing composition,
III) from 0 to 30 wt.% (D) at least one peroxide and, optionally, at least one activator, based on the total weight of the cleansing composition, and
(IV) from 0.001 to 1 wt.% (E) at least one granulate which contains
a) from 2 to 75 wt.% the composition according to claim 8, based on the total weight of the granulate,
b) from 10 to 95 wt.% at least one further additive, based on the total weight of the granulate, and
c) from 0 to 15 wt.% water, based on the total weight of the granulate,
V) 0 to 60 wt.% F) at least one additional additive, and
VI) 0 to 5 wt.% (G) water.

12. Liquid or solid detergent composition in which homogeneously distributed in the composition according to claim 8.

13. The use of bis-azo dye according to claim 1, 3, and 4 to enhance the whiteness of textile materials.

14. Use of the composition according to claim 8 to enhance the whiteness of textile materials.

15. Bis-azo dye selected from the group consisting of the following compounds described in the examples:




 

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