ES2271529T3 - PROCEDURE FOR THE TREATMENT OF TEXTILE FIBER MATERIALS. - Google Patents

Abstract

A detergent composition comprising at least one compound of the formula wherein R1 and R2 are independently hydrogen or unsubstituted or substituted C1-C8 alkyl and X2 and X4 are independently -N (R3) R4 wherein R3 and R4 are hydrogen, cyano, C1-C8 alkyl, which is unsubstituted or substituted by hydroxyl or carboxyl and wherein the C1-C8 alkyl group is uninterrupted or interrupted by -O-; cyclohexyl unsubstituted or substituted by C1-C4 alkyl; or R3 and R4 together with the nitrogen atom that bonds them form a morpholino, piperidine or pyrrolidone ring unsubstituted or substituted by C1-C4 alkyl, M is hydrogen or a cation, together with at least one compound of the formula in wherein R6 and R7, independently, are hydrogen, C1-C8 alkyl, C1-C8 alkoxy or halogen, and M is as defined above under formula (1).

Description

Procedure for the treatment of materials of textile fiber.

The present invention relates to formulations detergents containing certain fluorescent bleaching agents or mixtures of fluorescent bleaching agents, as well as mixtures of fluorescent bleaching agents.

The employment of agents of fluorescent bleaching in detergent formulations. These will deplete during the treatment on the material to be washed and, by virtue of its special light absorption / emission property, It results in the elimination of yellowish tones.

However, there is still a need to find fluorescent bleaching agents for this application. It has been now found that mixtures of the following compounds of the formulas (1) and (2), or compounds of formula (1), possess superior properties with respect to, for example, solubility, properties of formation, degree of solidity in the light of bleaching and also have excellent aspects of whiteness in the solid state.

Favorable results are still obtained at low wash temperatures

Thus, the present invention provides, as a first aspect, a detergent composition comprising minus a compound of the formula

one

in where

R1 and R2 are, independently, hydrogen or unsubstituted C 1 -C 8 alkyl or replaced and

X_ {2} and X_ {4} are, independently, -N (R 3) R 4 where R 3 and R 4 are hydrogen, cyano, C 1 -C 8 alkyl, which is not substituted or substituted by hydroxyl or carboxyl and wherein the C 1 -C 8 alkyl group is not interrupted or interrupted by -O-; unsubstituted cyclohexyl or substituted by C1-C4 alkyl; or R 3 and R4 together with the nitrogen atom that bonds them form a unsubstituted morpholino, piperidine or pyrrolidone ring or substituted by C 1 -C 4 alkyl,

M is hydrogen or a cation,

along with at least one compound of the formula

2

in where

R 6 and R 7, independently, are hydrogen, C 1 -C 8 alkyl, alkoxy C 1 -C 8 or halogen, and M is as has been defined above under the formula (1).

Within the scope of the definitions above, C 1 -C 8 alkyl may be methyl, ethyl, n- or isopropyl, n-, sec.- or t-butyl, or pentyl, hexyl, heptyl or linear octyl or branched. Alkyl groups are preferred C_ {1} -C_ {4}. in case the groups alkyl are substituted examples of possible substituents are hydroxyl, halogen, such as fluorine, chlorine or bromine, sulfo, sulfate, carboxyl and alkoxy C 1 -C 4 alkyl as methoxy and ethoxy. Other substituents of these alkyl groups they are, for example, cyano, -CONH2 and phenyl. Substituents Preferred are hydroxyl, carboxyl, cyano, -CONH2 and phenyl, essentially hydroxyl and carboxyl. Also substituents highly preferred are hydroxy and alkoxy C 1 -C 4, especially hydroxyl. The alkyl groups may also be uninterrupted or interrupted by -O- (in the case of alkyl groups containing two or more carbon atoms).

Examples of cycloalkyl alkyl groups C 5 -C 7 are cyclopentyl and especially cyclohexyl These groups may be unsubstituted or substituted by, for example, alkyl alkyl C 1 -C 8, as methyl. The ones are preferred corresponding unsubstituted cycloalkyl groups.

Within the scope of the definitions Above C 1 -C 6 alkoxy may be methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec.-butoxy, tert-butoxy, or linear higher alkoxy groups  or branched. Alkoxy groups C 1 -C 4 are, especially methoxy or ethoxy. Methoxy is highly preferred.

Halogen can be fluorine, chlorine, bromine or iodine, preferably chlorine.

In case that R 3 and R 4 together with the atom of nitrogen form a heterocyclic ring such as a system of ring of this nature can be, for example, morpholino, piperidine or pyrrolidine. The heterocyclic ring may be unsubstituted or replaced. An example of these substituents is alkyl C 1 -C 4, especially methyl.

The cation M is preferably a metal atom alkaline, an alkaline earth metal atom, ammonium or a cation formed from an amine. Na, K, Ca, Mg, ammonium, is preferred. mono-, di-, tri- or tetra-alkylammonium C 1 -C 4, mono-, di- or tri-hydroxyalkylammonium C 2 -C 4 or ammonium which is di- or tri-substituted by a mixture of alkyl groups C 1 -C 4 and hydroxyalkyl C_ {2} -C_ {4}. Sodium is highly preferred.

R 1 and R 2 are preferably hydrogen or C 1 -C 4 alkyl, especially hydrogen.

R 3 and R 4 are hydrogen; cyano; I rent C_ {1} -C_ {8} which is unsubstituted or substituted by hydroxyl, where the alkyl group C_ {1} -C_ {6} is uninterrupted or interrupted by -O-; cyclohexyl unsubstituted or substituted by alkyl C 1 -C 4; or R_ {3} and R_ {4}, together with the nitrogen atom that bonds them, they form a morpholino ring, piperidine or pyrrolidine unsubstituted or substituted by alkyl C_ {1} -C_ {4}.

More preferably R 3 and R 4 are hydrogen, unsubstituted C 1 -C 6 alkyl or hydroxy-substituted cycloalkyl C 5 -C 7 substituted by alkyl C 1 -C 4, or R 3 and R 4 together with the nitrogen atom that bonds them, they form a morpholino ring, piperidine or pyrrolidine unsubstituted or substituted by alkyl C 1 -C 4, or R 3 and R 4, together with the nitrogen atom that bonds them, they form a morpholino ring, piperidine or pyrrolidine unsubstituted or substituted by alkyl C_ {1} -C_ {4}.

More preferred are morpholino rings, piperidine or pyrrolidine unsubstituted or substituted by alkyl C 1 -C 4, especially morpholino, formed by R 3 and R 4 together with the nitrogen atom that bind

Examples of groups -N (R 3) R 4 are -NH 2, -NHCH 3, -NHC 2 H 5, -NH (n-C 3 H 7 }), -NH (i-C 3 H 7), -NH (i-C 4 H 9), -N (CH 3) 2, -N (C_ {2 H 5) 2, -N (i-C 3 H 7), -NH (CH 2 CH 2 OH), -N (CH 2 CH_ {2 OH) 2, -N (CH 2 CH (OH) CH 3) 2, -N (CH 3) CH 2 CH 2 OH), -N (C 2 H 5) (CH 2 CH 2 OH), -N (i-C 3 H 7) CH 2 CH 2 OH), - NH (CH 2 CH (OH) CH 3), -N (C 2 H 5) (CH 2 CH (OH) CH 3), -NH (CH 2) CH_ {2}
OCH 3), -NH (CH 2 CH 2 (OCH 2 CH 2 OH), -NH (CH 2 COOH), -NH (CH 2 CH 2) COOH), -N (CH 3) CH 2 COOH), -NH (CN),

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3

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4

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5

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6

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The most interesting compounds of the formula (1) are those where R 3 and R 4, together with the atom of nitrogen that binds them, they form a morpholino ring, piperidine or pyrrolidine unsubstituted or substituted by alkyl C_ {1} -C_ {4}.

Regarding R_ {3} and R_ {4}, the preferences indicated above.

Also interesting compounds of formula (1) are those of the formula (1a) given below.

R 6 and R 7 are preferably hydrogen. Each of the sulfo groups indicated in formula (2) are of preference linked in ortho position. Interesting compounds of formula (2) are those in which R 6 and R 7 are hydrogen and each of the sulfo groups indicated in the formula (2) They are linked in ortho position.

M is preferably hydrogen, an alkali metal or alkaline earth, or ammonium, especially sodium.

In the mixtures of compounds of formulas (1) and (2) the molar ratio of compound (1) to compound (2) it is usually in the range of 0.1: 99.9 to 99.9: 0.1, preferably 1:99 to 99: 1 and more preferably from 5:95 to 95: 5. It preferred highly a molar ratio of 10:90 to 90:10, especially 20:80 to 80:20 More important is a molar ratio of 30:70 to 70:30, especially 40:60 to 60:40.

The compounds of formulas (1) and (2) are known or can be prepared analogously to the procedures known.

The compounds of formula 1) can occur by reacting under reaction conditions known, cyanuric chloride, successively, in any sequence desired, with each acid 4,4'-diaminoestilben-2,2'-disulfonic  and amino compounds capable of introducing NH2 groups X 1 and X 3 and the amino groups X 3 and X 4. From preference 2 moles of cyanuric chloride are reacted initially with 1 mol of acid 4,4'-diaminoestilben-2,2'-disulfonic and then reacting the intermediate obtained in any order with amino compounds suitable for introducing the groups X_ {1}, X_ {2} and X_ {4}. For the preparation of compounds in where X_ {1} and X_ {3} have the same meaning and also X_ {2} and X_ {4} have the same meaning, it is preferred to do react the intermediate obtained first with an amino compound suitable for entering X_ {1} and X_ {2} and finally with a amino compound capable of introducing X2 and X4. It is also possible to carry out the reaction with the amino compounds in a stage by reacting the intermediate with a mixture of amino compounds; in this case mixtures are usually obtained corresponding compounds of formula (1).

In addition the present invention relates to mixtures of compounds of formulas (1) and (2). Regarding the compounds of formulas (1) and (2) the preferences indicated above apply. Compounds of formula (2) wherein R 6 and R 7 are hydrogen and each of the sulfo groups indicated in the formula (2) are linked in ortho position. In these mixtures the molar ratio of compound (1) versus compound (2) is usually in the range of 0.1: 99.9 to 99.9: 0.1, preferably between 1:99 to 99: 1 and more preferably from 5:95 to 95: 5. It preferred highly a molar ratio of 1 =: 90 to 90:10, especially 20:80 to 80:20 More important is a molar ratio of 30:70 to 70:30, especially 40:60 to 60:40.

The detergent compositions used preferably understand

i) 1-70% of a surfactant anionic and / or a non-ionic surfactant;

ii) 0-75% of a trainer;

iii) 0-30% of a peroxide;

iv) 0-10% of an activator of peroxide; Y

v) 0.001-5% of a mixture of compounds of formulas (1) and (2), each by weight, based on the total weight of the detergent.

More preferably the compositions detergents used comprise

i) 5-70% of a surfactant anionic and / or a non-ionic surfactant;

ii) 5-70% of a trainer;

iii) 0.5-30% of a peroxide;

iv) 0.5-10% of an activator of peroxide and / or 0.1-2% of a bleaching catalyst, Y

v) 0.01-5% of a mixture of compounds of formulas (1) and (2), each by weight, based on the total weight of the detergent.

In general an amount of a mixture is used of compounds of the formulas (1) and (2) of 0.001-5%, especially an amount of 0.01-5%. It preferred highly an amount of 0.05-5%, especially of 0.05 to 2%. In general, the amounts given in percent must understood as being percent by weight, based on total weight, unless otherwise indicated.

The detergent can be formulated as a solid, as an aqueous liquid comprising, for example 5-50, preferably 10-35% water or as a non-bullying liquid detergent, containing no more than 5, of preference 0-1% by weight of water, and based on a suspension of a former in a non-ionic surfactant, as describe, for example in GB -A-215854.

The anionic surfactant component may be, for example, an alkylbenzenesulfonate, an alkyl sulfate, a alkylene ether sulfate, an olefin sulfonate, an alkanesulfonate, a salt of fatty acid, an alkyl or alkenyl ether carboxylate or a salt of α-sulfograse acid or a respective ester. Be they prefer alkylbenzenesulfonates having 10 to 20 atoms carbon in the alkyl group, alkyl sulfates having from 8 to 18 carbon atoms, alkylether sulfates having from 8 to 18 atoms of carbon, and by deriving the fatty acid salts from an oil of palm or tallow and with 8 to 18 carbon atoms. The average molar number of ethylene oxide added in the alkylene sulfate is preferably 1 to 20, preferably 1 to 10. The salts are they are preferably derived from an alkali metal such as sodium and potassium, especially sodium. Highly preferred carboxylates are  alkali metal sarcosinates of the formula R-CO (R 1) CH 2 COOM 1 in where R is alkyl or alkenyl having 9 to 17 carbon atoms in the alkyl or alkenyl radical, R1 is alkyl C 1 -C 4 and M 1 is alkali metal, especially sodium

The nonionic surfactant component may be, for example, primary and secondary alcoholic ethoxylates, especially aliphatic alcohols C_ {8} -C_ {20} with an average of 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially alcohols primary and secondary aliphatic C 10 -C 15 ethoxylated with an average of 1 to 10 moles per mole of alcohol. Non-ethylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).

The total amount of anionic surfactant and nonionic surfactant is preferably 5-50% in weight, preferably 5-40% by weight and more preferably 5-30% by weight. Regarding these surfactants it is preferred that the lower limit be 10% in weight.

The forming component may be a phosphate of alkali metal, especially a tripolyphosphate; a carbonate or bicarbonate, especially its sodium salts; a silicate or disilicate; an aluminosilicate; a polycarboxylate; an acid polycarboxylic; an organic phosphonate; or an aminoalkylene poly (alkylene phosphonate); or a mixture of these.

Preferred silicates are crystalline layered sodium silicates of the formula NaHSi {m} O 2m + 1} • H 2 O or Na 2 Si_ {m}
O_ {2m + 1} \ cdotpH_ {2} where m is a number from 1.9 to 4 and p is 0 to 20.

Preferred aluminosilicates are the materials synthetics found in commerce designated as Zeolites A, B, X and HS or mixtures thereof. Zeolite is preferred TO.

Preferred polycarboxylates include hydroxypolycarboxylates, in particular citrates, polyacrylates and their copolymers with maleic anhydride.

Preferred polycarboxylic acids include nitrilotriacetic acid and ethylene diamin acid tetra-acetic

Organic phosphonates or aminoalkylene poly (preferred alkylene phosphonates) are ethan 1-hydroxy alkali metal diphosphonates, nitrile trimethylene phosphonates, ethylene diamin tetra methylene phosphonates and diethylene triamine penta methylene phosphonates.

The number of trainers is preferably 5-70% by weight, preferably 5-60% by weight and more preferably 10-60% by weight. Regarding the trainers, it is preferred that the lower limit be 15% by weight, especially 20% by weight.

Appropriate peroxy components include, for example, organic and inorganic peroxides (such as peroxides sodium) known in the literature and found in the trade whitening textile materials at wash temperatures conventional, for example between 5 and 95 ° C. In particular the organic peroxides are, for example, monoperoxides or polyperoxides having alkyl chains of at least 3, preferably 6 to 20, carbon atoms; in particular they are of interest diperoxydicarboxylates with 6 to 12 atoms, such as diperoxiperazelates, diperoxy persebacates, diperoxyphthalates and / or diperoxidedecandioates, especially their corresponding free acids. However it is preferred to use very active inorganic peroxides, such as persulfate, perborate and / or percarbonate. Obviously it is also possible to use mixtures of organic and / or inorganic peroxides.

The amount of peroxide is preferably 0.5-30% by weight, preferably 1-20% by weight and more preferably 1-15% by weight. If a peroxide is used, the lower limit is preferably 2% by weight, especially 5% in weigh.

Peroxides, especially peroxides inorganic, are preferably activated by the inclusion of a bleaching actuator. Compounds such that, under perhydrolysis conditions, provide perbenzo- and / or acids peroxo-carboxylic acids unsubstituted or substituted with 1 to 10 carbon atoms, especially 2 to 4 carbon atoms.  Appropriate compounds include those that involve O- and / or groups N-acyl having said number of atoms of unsubstituted or substituted carbon and / or benzoyl groups. Is given preference to polycylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N, N-diacetyl-N, N-dimethyl-urea (DDU), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triacin (DADHT), compounds of the formula

7

where R is a sulfonate group, a carboxylic acid group or a carboxylate group, and wherein R ' it is linear or branched C 7 -C 15 alkyl; also activators that are known by the names of SNOBS, SLOBS, NOBS and DOBA, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran  and sorbitol and acetylated mannitol derived from acylated sugar, especially pentaacetylglucose (PAG), sucrose polyacetate (SUPA), pentaacetyl fruit, tgetraacetylxylose and octaacetylactose, and glucamine and acetylated gluconolactone, optionally N-rented. The activator combinations of conventional bleaching described in the German patent DE-A-44 43 177 can be used too. Nitrile compounds that form peroxyimidic acids with peroxides they are also suitable as bleach activators. Tetraacetyl ethylenediamine and nonoyloxybenzenesulfonate.

The amount of bleach activator is preferably 0-10% by weight, preferably 0-8% by weight. In the case of using a bleach activator the lower limit is preferably 0.5% in weight, especially 1% by weight.

Bleaching catalysts that can be added include, for example, enzymatic peroxide precursors and / or metal complexes Preferred metal complexes are manganese, cobalt or iron complexes such as manganese phthalocyanines or iron or the complexes described in EP-A-0509787. If used  bleaching catalyst the amount is preferably 0.005 to 2% by weight, more preferably from 0.01 to 2% by weight, especially from 0.05 to 2% by weight. A quantity of 0.1-2% by weight.

As examples of bleaching catalysts, They cite the following:

-

WO-A-95/30681 (see for example the formula (I) and the following definition in the page 1, lines 7 to 30; especially formula (I) and the following definitions given on page 2, lines 29 to page ll, line 11). Preferred ligands are those given on the page 13, line 12 to page 26, line 11.

-

WO-A-01/09276 (see for example formulas (1), (2) and (3) and definitions following on pages 2 and 3).

-

WO-A-01/05925 (see for example the formula (1) and the following definition in page 1, last paragraph to page 2, first paragraph. Are applicable preferences given to metal complexes, see especially those of formula (2) on page 3 and those of formula (3) in  page 4).

-

WO-A-02/088289 (see, for example formula (1) and the following definition on page 2. The preferences given for complexes are applicable metallic, see especially the ligands of formula (3) and also the preferences given on page 3, fourth paragraph a page 4, paragraph 7).

In addition the detergent may contain optionally enzymes. Enzymes can be added to detergents To remove stains. Enzymes usually improve the rendering on stains that are based on protein or starch, such such as those caused by blood, milk, fat or fruit juices. The Preferred enzymes are cellulases, proteases, amylases and lipases. Preferred enzymes are cellulases and proteases, especially proteases Cellulases are enzymes that act on cellulose and their derivatives hydrolyze them into glucose, cellobious, cellooligosaccharide. Cellulases remove dirt and have the effect of mitigating roughness to the touch. Examples of enzymes for be used include, but not imply limitation, the following:

proteases as given in US-B-6,242,405, column 14, lines 21 to 32;

lipase as given in US-B-6,242,405, column 14, lines 33 to 46;

Amylases as they occur in US-B-6,242,405, column 14, lines 47 to 56; Y

cellulases as given in US-B-6,242,405, column 14, lines 57 to 64.

Enzymes may optionally be present. in the detergent. When they are used enzymes are present usually in an amount of 0.01-5% by weight, of preference 0.05-5% and more preferably 0.1-4% by weight, based on the total weight of the Detergent.

Other preferred additives for detergents according to the invention are polymers that, during washing of textiles, inhibit staining caused by dyes in liquor washing that have been released from textiles under conditions washing agents (dye fixing agents, inhibitors of dye transfer). These polymers are preferably polyvinylpyrrolidones, polyvinylimidazoles or N-oxides of polyvinylpyridine that may have been modified by incorporation of anionic or cationic substituents, especially those with a molecular weight in the range of 5000 to 60,000, more especially 10,000 to 50,000. These polymers are they use, usually, in an amount of 0.01 to 5%, preferably 0.05 to 5% by weight, especially 0.1 to 2% by weight, based on The total weight of the detergent. Preferred polymers are those given in WO-A-02/02865 (see especially page 1, last paragraph and page 2, first paragraph).

The detergents used will usually contain one or more auxiliaries such as soil suspension agents, for example sodium carboxymethylcellulose; salts to adjust the pH, for example alkali metal or alkaline earth metal silicates; foam regulators, for example soap; you go out to adjust the spray drying and granulation properties, for example sodium sulfate, perfumes; and also, if appropriate, agents antistatic and softening; such as smectite clays; photobleaching agents; pigments; and / or conferring agents of tonality. These constituents must obviously be stable at Any bleaching system used. These auxiliaries can be present in an amount of, for example, 0.1 to 20% by weight, preferably 0.5 to 10% by weight, especially 0.5 to 5% by weight, based on the total weight of the detergent.

Detergent compositions may take a variety of physical forms including powder forms, granular, tablet and liquids Examples of these are detergents for strong conventional powder effect, strong effect detergents compact and super compact and tablets, such as detergent tablets Of strong effect. Another important physical form is the so-called form concentrated granular suitable for adding to a machine washing machine.

So-called detergents are important compact (or supercompact). In the field of manufacturing detergents, a trend has recently developed towards the production of compact detergents, which contain quantities increased active substance. In order to minimize the expense of energy during the washing process the compact detergents will requires that they operate efficiently at such low temperatures as of 40 ° C, or even at room temperature, for example at 25 ° C. These detergents usually contain only low amounts of filler or processing aids, such as sodium sulfate or chloride sodium The quantity of these fillers is usually of 0-10% by weight, preferably 0.5% by weight, especially 0-1% by weight, based on total weight of detergent. These detergents usually have a density 650-1000 g / l, preferably 700-1000 g / l and especially 750-1000 g / l.

Detergents may also be present. in the form of tablets. The relevant characteristics of the Tablets are ease of supply and convenience of handling.  Tablets are the most compact supply of solid detergents and have a mass density of, for example, 0.9 to 1.3 kg / liter. To facilitate rapid disintegration of detergent tablets They usually contain special disintegrants:

- Effervescent such as carbonate / hydrogencarbonate / citric acid;

- intumescent agents such as cellulose, carboxymethyl cellulose, cross-linked poly (N-vinyl pyrrolidone);

- fast dissolving materials such as Na (K) acetate or NA (K) citrate;

- rigid water soluble coatings of rapid dissolution such as dicarboxylic acids.

The tablets may also contain combinations of any of the above disintegrants.

The detergent can also be formulated as a aqueous liquid comprising 5-50, preferably 10-35% water or as a liquid detergent not aqueous, containing no more than 5, preferably 0-1% by weight of water Non-aqueous liquid detergent compositions They may contain other solvents such as vehicles. Are appropriate primary or secondary low molecular weight alcohols exemplified by methanol, ethanol, propanol and isopropanol. Be they prefer monohydric alcohols for solubilizing surfactants, but polyols such as those containing can also be used from 2 around 6 carbon atoms and from 2 to about 6 groups hydroxy (for example 1,3-propanediol, ethylene glycol, glycerin and 1,2-propanediol). The compositions they can contain from 5% to 90% typically from 10% to 50% of these vehicles. Detergents may also be present as the called the "unit liquid dosage" form.

This textile detergent treatment can be carried out as a domestic treatment in washing machines normal.

The treated textile fibers can be fibers natural or synthetic or mixtures thereof. Examples of natural fibers include vegetable fibers such as cotton, viscose, rayon or linen, preferably cotton and animal fibers such as wool, angora, Cashmere and silk, preferably wool. Synthetic fibers they include polyester, polyamide and polyacrylonitrile fibers. Fibers Preferred textiles are cotton, polyamide and wool fibers, especially cotton fibers. Preferably textile fibers treated in accordance with the method of the present invention have a density of less than 200 g / m2.

In accordance with this procedure it is used usually an amount of 0.01 to 3.0% by weight, especially 0.05 at 3.0% by weight, based on the weight of the textile fiber material, of a mixture of compounds of formulas (1) and (2).

The procedure is usually conducted in the temperature range from 5 to 100 ° C, especially 5 to 60 ° C. Be prefers a temperature range of 5 to 40 ° C, especially 5 to 35 ° C and more preferably 5 to 30 ° C.

Detergent compositions will be formulated from preference so that during use in cleaning operations aqueous, the wash water has a pH between about 6.5 and about 11, preferably between about 7.5 and 11. Laundry products typically have a pH of 9-11.

The techniques to control the pH at levels of Recommended use include the use of buffers, alkalis, acids, etc. and they are well known by the art expert.

Machine wash methods here typically comprise treating soiled clothing with a solution of aqueous washing in a washing machine that has dissolved or dispersed an effective amount of a detergent composition for machine wash clothes in accordance with the invention. By a effective amount of the detergent composition is understood as for example, from 20 g to 300 g of product dissolved or dispersed in a volume washing solution from 5 to 85 liters, such as doses of Typical products and wash solution volumes commonly Used in conventional machine washing methods of clothes. Examples are

- automatic axis washing machines U.S. vertical, with top load, using about 45 to 83 liters of water in the wash bath, a wash cycle of around 10 to about 14 minutes and a wash water temperature from about 10 to about 50 ° C.

- European type automatic washing machine horizontal axis, front loading, using around 8 to 15 liters of water in the wash bath, a wash cycle of around from 10 to about 60 minutes and a wash water temperature from about 30 to about 95 ° C;

- Japanese type automatic washing machine vertical axis, top load, using about 26 to 52 liters of water in the wash bath, a wash cycle of around from 8 to about 15 minutes and a wash water temperature from about 5 to about 25 ° C.

The liquor ratio is preferably 1: 4 a 1:40, especially 1: 4 to 1:15. A relationship is highly preferred of liquor from 1: 4 to 1:10, especially 1: 5 to 1: 9.

The previous fiber wash treatment textiles can also be carried out with the mixture of compounds of the formulas (1) and (2).

The compounds and mixtures used of in accordance with the present invention are particularly advantageous because they exhibit not only extremely bleaching capacity high, but, in addition, in many cases water solubilities highly desirable and also possess excellent aspects of whiteness in the solid state. Another advantage of the present invention is that the detergent composition provides improved whiteness performance and tissue touch In addition, the compounds and especially the mixtures show very good results regarding properties of exhaustion

The compounds have the advantage that they are also effective in the presence of active chlorine donors, such such as hypochlorite and can be used without loss Substantial effects in washing baths with washing agents nonionic, for example polyglycol alkylphenol ethers. Too in the presence of perborate or peracids and activators, for example tetra-acetiglycoluril or acid ethylenediamine tetraacetic are the compounds and mixtures of stable compounds in powder washing agent and in wash baths In addition they impart a bright appearance to light of the day

The compounds of the formula (1) and mixtures of compounds of formulas (1) and (2) have been found to be also useful for fluorescent bleaching of textile materials, in whose connection should be noted particularly polyamides, wool and cotton. Textile fibers treated in accordance with this embodiment of the present invention can be natural or synthetic or their mixtures Examples of natural fibers include plant fibers such as cotton, viscose, linen or rayon. Fiber examples Natural include plant fibers such as cotton, viscose, rayon or linen, preferably cotton and animal fibers such as wool, cashmere, angora and silk, preferably wool. Fibers Synthetic include polyester, polyamide and polyacrylonitrile. Preferred textile fibers are cotton, polyamide and wool fibers. Preferably textile fibers treated in accordance with the present invention have a density less than 1000 g / m2, especially less than 500 g / m2 and more preferably less than 250 g / m.

The following examples serve to illustrate the invention; parts and percentages are by weight, unless indicated else.

Preparation Example one

8

In a 1 liter flask, 0.05 mol of the mixture is mixed compound of formula

9

with 600 ml of water and heated up to a temperature of 60 ° C. Then 9.2 g of 2-ethylaminoethanol and the mixture is heated reactional to a temperature of 98 ° C; during heating the pH is maintained at a value between 8.5 and 9 by the addition of a 4-molar aqueous solution of sodium hydroxide. Be cool the reaction mixture to 50 ° C and adjust the pH to a value of 4.5 by adding a 6 molar aqueous solution of hydrochloric acid. The precipitate is filtered off, washed with 100 ml of a 10% aqueous solution of sodium chloride and dry in a vacuum In this way 30.5 g of a product are obtained yellowish.

Preparation Examples 2 a fifteen

Similarly to the procedure given in the preparation example 1 the following compounds can be prepared of formula

10

replacing 9.2 g of 2-ethylaminoethanol with an equimolar amount of the corresponding amine. X is as defined in table 1 next. Compounds that precipitate after cooling up to 50 ° C they are directly isolated as sodium salts without the addition of hydrochloric acid and then dried in empty.

TABLE 1

eleven

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Preparation Example 16

(Not in accordance with the invention)

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In a 1 liter flask, 0.05 mol of the mixture is mixed compound of formula

13

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with 600 ml of water and heated up to a temperature of 60 ° C. Then 9.2 g of morpholine and the reaction mixture is heated to a temperature of 98 ° C; during heating the pH is maintained at a value between 8.5 and 9 by adding an aqueous solution 4-molar sodium hydroxide. The mixture is cooled reactional to 40 ° C and the precipitate is filtered off, wash with 100 ml of a 10% aqueous solution of sodium chloride and It dries in a vacuum. In this way 30.5 g of a product are obtained yellowish.

Preparation Examples 17 a 19

(Not in accordance with the invention)

The compounds that follow the formula

14

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can be prepared analogously to the procedure given in preparation example 16, replacing 9.5 g of morpholine with an equimolar amount of the amine correspondent. X is as defined in table 2 below. The compounds that have high solubility are treated with a solution 6-molar aqueous hydrochloric acid in order to adjust the pH to a value of 4.5 before cooling to 50 ° C

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TABLE 2

fifteen

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Preparation Example twenty

(Not in accordance with the invention)

16

In a 2-liter flask 130 ml of methyl ethyl ketone, 80 ml deionized water, 150 g of ice and 18.5 g of cyanuric chloride. For a period of 30 minutes it is added dropwise 185 ml of an acid solution 4,4'-diaminoestilben-2,2'-disulfonic (as disodium salt) in water (concentration of 100 g / l), the temperature between -8 and + 5ºC. The pH is maintained at a value between 4.5 and 5 by the addition of an aqueous solution of sodium carbonate.  A yellowish suspension is obtained. Then, with the use of a drip funnel, 27.2 g of ethanolamine (99%) are added. PH increases to a value of 10 and then goes down to a lower value, whereby the temperature rises to 10-15 ° C. The reaction mixture is then heated to a temperature of 45 ° C and maintained at this temperature for 20 minutes. During heating to 98 ° C within 30 minutes is separated by distillation a mixture of methyl ethyl ketone and water; the pH at a value between 8.5 and 9 by adding a solution aqueous sodium hydroxide. After not being necessary to perform further addition of aqueous sodium hydroxide solution to keeping the pH at a constant value the reaction mixture cools up to 50 ° C. The pH is adjusted to a value of 5.5 and a filter can be filtered. yellowish crystalline precipitate. After drying they are obtained 29 g of a yellowish product.

Preparation Example twenty-one

(Not in accordance with the invention)

17

In a 1 liter pressure vessel, 0.037 mol of acid suspended in 500 ml of water N, N'-bis- (4-morpholino-6-chloro-1,3,5-triacin-2-yl) -4,4'-diaminoestylben-2,2'-disulfonic  (disodium salt). 15 g of an aqueous solution of ethylamine (70%) and the reaction mixture is heated to a temperature of 100 to 105 ° C and stir for 4 hours. Be cool the reaction mixture to 25 ° C and filter off the precipitate is washed with 100 ml of an aqueous solution of 10% sodium chloride and dried in vacuo at 70 ° C. In this way they obtain 254.8 g of a yellowish powder.

Preparation Example 22

(Not in accordance with the invention)

18

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The compound of the formula (107) can be prepared analogously to the procedure given in the example of Preparation 21, substituting 15 g of an aqueous solution of ethylamine (70%) with a corresponding solution containing a equimolar amount of diethylamine.

Preparation Example 2. 3

(Not in accordance with the invention)

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19

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In a 1 liter pressure vessel, suspend 0.05 mol of acid in 600 ml of water N, N'-bis- (4-morpholino-6-chloro-1,3,5-triacin-2-yl) -4,4'-diaminoestiben-2,2'-disulfonic (disodium salt) and heated to a temperature of 60 ° C. Be 6.4 g of ethanolamine are added and the reaction mixture is heated up to a temperature of 98ºC. The pH is maintained at a value between 8.5 and 9 by adding a solution of sodium hydroxide 4-molar aqueous. The reaction mixture is cooled up to 25 ° C and 10% by volume of sodium chloride is added. Be filter off the precipitate, wash with 100 ml of a 10% aqueous sodium chloride solution and dried in vacuo at 70 ° C. In this way, 41.8 g of a yellowish powder are obtained.

Application example one

General procedure

A washing liquor is prepared by dissolving 0.8 g of washing powder in 200 ml of tap water. It is added to bath 10 g of bleached cotton fabric and wash at 40 ° C for 15 minutes and then washed, dried by centrifugation and ironed at 160 ° C.

Washing powders A and B are used following (amounts given in Tables 3a and 3b below are in g):

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TABLE 3a Ingredients of washing powders A and B

twenty

twenty-one

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TABLE 3b Washing powders used

22

2. 3

24

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Constitution of the compound of formula (109):

25

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Constitution of the compound of formula (110):

26

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Cotton fabrics washed with detergents given in Table 3b in accordance with the procedure  In general they show good solidity properties.

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Application example 2

General procedure

A washing liquor is prepared by dissolving 0.8 g of washing powder in 200 ml of tap water. It is added to bath 10 g of bleached cotton fabric and wash at 30 ° C for 15 minutes and then washed, dried by centrifugation and ironed at 160 ° C.

The following washing powders are used (amounts given in Tables 4a and 4b below are percent by weight, based on the total weight of the detergent):

TABLE 4a Ingredients of washing powders C and D

27

TABLE 3b Washing powders used

29

30

Regarding the constitution of the compounds of formulas (109) and (110) see application example 1.

Cotton fabrics washed with detergents given in Table 4b in accordance with the procedure  Generally show good whiteness properties.

Claims (15)

1. A detergent composition comprising at least one compound of the formula 31 in where R1 and R2 are, independently, hydrogen or unsubstituted C 1 -C 8 alkyl or replaced and X_ {2} and X_ {4} are, independently, -N (R 3) R 4 where R 3 and R 4 are hydrogen, cyano, C 1 -C 8 alkyl, which is not substituted or substituted by hydroxyl or carboxyl and wherein the C 1 -C 8 alkyl group is not interrupted or interrupted by -O-; unsubstituted cyclohexyl or substituted by C1-C4 alkyl; or R 3 and R4 together with the nitrogen atom that bonds them form a unsubstituted morpholino, piperidine or pyrrolidone ring or substituted by C 1 -C 4 alkyl, M is hydrogen or a cation, along with at least one compound of the formula 32 in where R 6 and R 7, independently, are hydrogen, C 1 -C 8 alkyl, alkoxy C 1 -C 8 or halogen, and M is as has been defined above under the formula (1). 2. A composition, in accordance with the claim 1, wherein R1 and R2 are hydrogen or alkyl C_ {1} -C_ {{}}, R 3 and R 4 are hydrogen; cyano; I rent C_ {1} -C_ {8} which is unsubstituted or substituted by hydroxyl, carboxyl, cyano, -CONH2 or phenyl and wherein the alkyl group C_ {1} -C_ {8} is uninterrupted or interrupted by -O-; cycloalkyl C5 -C7 {unsubstituted or substituted by C1-C4 alkyl; or R 3 and R4, together with the nitrogen atom that bonds them, form a unsubstituted morpholino, piperidine or pyrrolidine ring or substituted by C1-C4 alkyl; Y R 5 is alkyl C_ {1} -C4 {which is unsubstituted or substituted by hydroxyl. 3. A composition, in accordance with the claim 1 or 2, wherein R 3 and R 4, together with the atom of nitrogen that binds them, they form a morpholino ring, piperidine or pyrrolidine unsubstituted or substituted by alkyl C_ {1} -C_ {4}.

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4. A composition, in accordance with the claim 1 to 3, wherein R 6 and R 7 are hydrogen and each of the sulfo groups indicated in formula (2) are linked in ortho position. 5. A composition, in accordance with any one of claims 1 to 4, wherein M is hydrogen, an alkali metal or alkaline earth, or ammonium, preferably sodium. 6. A composition, in accordance with any one of claims 1 to 5, comprising i) 1-70% of a surfactant anionic and / or non-ionic; ii) 0-75% of a trainer; iii) 0-30% of a peroxide; iv) 0-10% of an activator peroxidic; Y v) 0.001-5% of a mixture of compounds of formulas (1) and (2). 7. A composition, in accordance with the claim 6, comprising i) 5-70% of a surfactant anionic and / or non-ionic; ii) 5-75% of a trainer; iii) 0.5-30% of a peroxide; iv) 0.5-10% of an activator peroxidic and / or 0.1-2% of a catalyst of Whitening; Y v) 0.001-5% of a mixture of compounds of formulas (1) and (2). 8. A composition, in accordance with any one of claims 1 to 7, wherein the composition detergent comprises at least one enzyme chosen from the group constituted by cellulase, protease, amylase and lipase, of protease preference. 9. A mixture of compounds comprising, by at least one compound of formula 33 in where R1 and R2 are, independently, hydrogen or unsubstituted C 1 -C 8 alkyl or replaced and X_ {2} and X_ {4} are, independently, -N (R 3) R 4 where R 3 and R 4 are hydrogen, cyano, C 1 -C 8 alkyl, which is not substituted or substituted by hydroxyl or carboxyl and wherein the C 1 -C 8 alkyl group is not interrupted or interrupted by -O-; unsubstituted cyclohexyl or substituted by C1-C4 alkyl; or R 3 and R4 together with the nitrogen atom that bonds them form a unsubstituted morpholino, piperidine or pyrrolidone ring or substituted by C 1 -C 4 alkyl, M is hydrogen or a cation,

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along with at least one compound of the formula 3. 4 in where R 6 and R 7, independently, are hydrogen, C 1 -C 8 alkyl, alkoxy C 1 -C 8 or halogen, and M is as has been defined above under the formula (1). 10. A mixture of compounds, in accordance with claim 11, wherein R1 and R2 are hydrogen or alkyl C_ {1} -C_ {{}}, R 3 and R 4 are hydrogen; cyano; I rent C_ {1} -C_ {8} which is unsubstituted or substituted by hydroxyl, carboxyl, cyano, -CONH2 or phenyl and wherein the alkyl group C_ {1} -C_ {8} is uninterrupted or interrupted by -O-; cycloalkyl C5 -C7 {unsubstituted or substituted by C1-C4 alkyl; or R 3 and R4, together with the nitrogen atom that bonds them, form a unsubstituted morpholino, piperidine or pyrrolidine ring or substituted by C1-C4 alkyl; Y R 5 is alkyl C_ {1} -C4 {which is unsubstituted or substituted by hydroxyl. 11. A mixture of compounds, in accordance with claim 10, wherein R 3 and R 4, together with the atom of nitrogen that binds them, they form a morpholino ring, piperidine or pyrrolidine unsubstituted or substituted by alkyl C 1 -C 4, preferably a ring morpholino 12. A mixture of compounds, in accordance with any of claims 9 to 11, wherein R 6 and R 7 are hydrogen and each of the sulfo groups indicated in formula (2) are linked in position ortho. 13. A mixture of compounds, in accordance with any one of claims 9 to 12, wherein M is hydrogen, an alkali metal or alkaline earth metal, or ammonium, preferably sodium. 14. A procedure for bleaching fluorescent textile materials comprising contacting textile materials with a mixture of compounds of formulas (1) and (2) as defined in claim 1. 15. A procedure, in accordance with the claim 14, wherein the textile materials are polyamides, wool or cotton