TWI332045B - Process for the treatment of textile fibre materials - Google Patents

Description

FIELD OF THE INVENTION The present invention is directed to detergent formulations containing certain blends of fluorescent whitening agents or fluorescent whitening agents, as well as mixtures of fluorescent whitening agents. Prior Art The use of fluorescent whitening agents in detergent formulations is well known. The fluorescent whitening agent is consumed on the material to be washed during the treatment and then, due to its special light absorption/emission properties, results in the elimination of yellowing. However, there is still a need to find improved fluorescent brighteners for this application. It has now been found that a mixture of the following compounds of the formula (1) and (2), or a compound of the formula (la), has excellent properties in terms of, for example, solubility, cumulative properties, degree of whiteness, light resistance, and the like, and is excellent in a solid state. White aspect. Whiteness properties, such as whiteness maintenance, may even be obtained by using a mixture of compounds of formula (1) and (2) or formula (la) in a detergent containing cellulase, protease, amylase or lipase. Increased. Favorable results can even be obtained at low wash temperatures. SUMMARY OF THE INVENTION Accordingly, a first aspect of the present invention provides a detergent composition comprising the following: at least one compound of the formula (1): 1332045 Λ - male ~ k

1\ N where: the heart and the r2 are independently hydrogen or unsubstituted or substituted cr c8,

Xi, x2, X3 and X4 are each independently -N(R3)R4 or -〇115, wherein R3 and R4 are hydrogen; cyano; unsubstituted or substituted CrC8 alkyl or 〇5-07 cycloalkane Or 113 and 114 together with the nitrogen atom to which they are joined form a heterocyclic ring; and R5 is an unsubstituted or substituted CrG alkyl group, and hydrazine is hydrogen or a cation, and at least one compound of formula (2):

Wherein R6 and R7 are each independently hydrogen, Crc8 alkyl, Ci-G alkoxy or halogen, and the oxime is as defined above in formula (1). Embodiments 1332045 Within the scope of the above definition, the crc8' alkyl group may be methyl, ethyl, n- or isopropyl, n-, second or third butyl, or a linear or branched pentyl, hexyl, Heptyl or octyl. Preferred is crc4 alkyl. Examples of possible substituents if the alkyl group is substituted are: a hydroxyl group, a halogen such as fluorine, chlorine or bromine, a sulfo group, a sulfate group, a carboxyl group and a crc4 alkoxy group such as a methoxy group and an ethoxy group. Other substituents of such alkyl groups are, for example, cyano, -CONH2 and phenyl. Preferred substituents are hydroxy, carboxy, cyano, -CONH2 and phenyl, especially hydroxy and carboxy. Further, an excellent substituent is a hydroxyl group and a crc4 alkoxy group, especially a hydroxyl group. These alkyl groups may also be uninterrupted or interrupted by -0 (in the case of an alkyl group containing two or more carbon atoms). Examples of c5-c7 cycloalkyl groups are cyclopentyl groups and especially cyclohexyl groups. These groups may be unsubstituted or substituted by, for example, crc4-alkyl, such as methyl. Preferred are the corresponding unsubstituted cycloalkyl groups. Within the scope of the above definition, the crc8 alkoxy group may be a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a second butoxy group, a third butoxy group. Or a linear or branched higher alkyl group. Preferred is cr c4-alkoxy, especially methoxy or ethoxy. The best is methoxy. The halogen may be fluorine, chlorine, bromine or iodine, preferably chlorine. If the heart and R4 together with the nitrogen atom form a heterocyclic ring, such a ring system can be, for example, a fluorenyl, decyl or pyrrolidine ring. The heterocyclic ring may be unsubstituted or substituted. An example of such a substituent is a crc4 alkyl group, especially a methyl group. The cationic ruthenium is preferably an alkali metal atom, an alkaline earth metal atom, ammonium or a cation formed from an amine. Preferred are Na, hydrazine, Ca, Mg, ammonium, mono, 1332045 di, tri or tetra crc4 alkyl ammonium, mono, di or tri c2-c4-hydroxyalkyl ammonium, or CrC4-alkyl and c2- a mixture of c4-hydroxyalkyl groups of di- or tri-substituted ammonium. The best is sodium. • The heart and R2 are preferably hydrogen or a Ci-G alkyl group, especially hydrogen. R3 and R4 are preferably: hydrogen; cyano; crc8 alkyl, which is unsubstituted or substituted by hydroxy, carboxy, cyano '-CONH2 or phenyl, especially by hydroxy or carboxy, and wherein crc8 is alkyl Uninterrupted or interrupted by -0-: unsubstituted or c5-c7 cycloalkyl substituted by crc4 alkyl, especially cyclohexyl; or the heart and R4 together with the nitrogen atom to which they are attached form an unsubstituted or CVC4 Alkyl substituted morpholinyl, pyridinyl or pyrrolidine ring. More preferably, R3 and R4 are hydrogen, unsubstituted or hydroxy substituted crc8 alkyl, unsubstituted or substituted by CrC4 alkyl (: 5-(:7 cycloalkyl, or, 1 and R4 with The nitrogen atoms linking them together form an unsubstituted or CVC4 alkyl substituted oxime, acridine or pyrrolidine ring. Excellent for R3 and r4 is hydrogen, unsubstituted or substituted by hydroxy (^ - alkalyl' or a ring and R4 together with the nitrogen atom to which they are attached form an unsubstituted or substituted rcolinyl, pyridyl or pyrrolidine ring via a crc4 alkyl group. The most preferred is unsubstituted or crc4 alkane. a morpholino, octazide or pyrrolidine ring, especially a morpholinyl group, which is formed by the combination of a nitrogen atom to which they are bonded via 113 and 1. Examples of the -N(R3)R4 group are:- NH2, -NHCH3, -NHC2H5, ·ΝΗ(η-03Η7), -NH(i-C3H7), -NH(i-C4H9)' -N(CH3)2, -N(C2H5)2, -N(i -C3H7)2, -NH(CH2CH2OH), -N(CH2CH2OH)2, -N(CH2CH(OH)CH3)2, -N(CH3)(CH2CH2OH)'-N(C2H5)(CH2CH2OH), -N( i-C3H7)(CH2CH2CH2OH), -NH(CH2CH(OH)CH3), 11 1332045-N(C2H5)(CH2CH(OH)CH3), -NH(CH2CH2OCH3) ), -NH(CH2CH2OCH2CH2OH), -NH(CH2COOH), -NH(CH2CH2COOH), -N(CH3)(CH2COOH), -NH(CN), CH.CH_

NH——CH—COOH

——NH——CH—COOH ch7—c—nh9 2 II 2 〇

NH

II CH2CH2CH Plant NH-C-NH2 R5 is preferably a Crq alkyl group, especially a CVC4 alkyl group, which is unsubstituted or substituted by a Crq alkoxy group or especially a hydroxyl group. Excellent for R5 is methyl or ethyl, especially methyl.

Xi, X2, X3 and X4 are preferably a group of the formula -State 1^)1^4.

Xi and x3 preferably have the same meaning. In addition, it is preferable that x2 and x4 have the same meaning. Furthermore, it is preferred that the four groups X〆x2, 乂3 and χ4 have no similar meaning. Preferred are compounds of formula (1) wherein 12 1332045 R, and R 2 are hydrogen or CrC 4 alkyl, R 3 and R 4 are: hydrogen; cyano; CrCs alkyl, which is unsubstituted or hydroxy, carboxy, cyanide Substituent, -conh2 or phenyl substituted and wherein the Cl-C8 alkyl group is uninterrupted or interrupted by -0; unsubstituted or C5-C7 cycloalkyl substituted with crc4 alkyl; or 1 and 114 with attached thereto The nitrogen atoms together form an unsubstituted or rcolinyl, piperidine or pyrrolidine ring substituted with a crc4 alkyl group; and the core is a crc8 alkyl group which is unsubstituted or substituted with a hydroxy group. As for R3, 1 and R5, the above preferences are applicable. Particularly preferred are compounds of formula (1) wherein 乂1 and x3 are amine groups, and x2 and x4 are groups of formula -N(R3)R4 wherein R3 and 4 are: hydrogen; cyano; crc8 alkyl , which is unsubstituted or substituted by a hydroxy or carboxy group and wherein the crc8 alkyl group is uninterrupted or interrupted by -0; unsubstituted or via (^-0:4 alkyl substituted cyclohexyl; or 113 and R4 The nitrogen atoms linking them together form an unsubstituted or rcolinyl, guanidinyl or pyrrolidine ring substituted with a crc4 alkyl group. As for the heart and R4, the above preferences are applicable. 1) A compound wherein Xi and χ3 are an amine group, and X2 and χ4 are a group of the formula -N(R3)R4, wherein R3 and R4 are hydrogen, unsubstituted or hydroxy substituted crc8 alkyl' unsubstituted Or via (^-04 alkyl substituted cyclopentyl or cyclohexyl, or 113 and R4 together with the nitrogen atom to which they are attached form an unsubstituted or crc4 alkyl substituted morpholinyl, pyridinyl or pyrrolidine ring The most interesting compound of formula (1) is where 113 and r4 13 1332045 form an unsubstituted or crc4 alkane together with the nitrogen atom to which they are attached. The group is substituted with a fluorenyl group, a # pyridine or a pyrrolidine ring. As for R3 and R4, the above preferences are applicable. Further interesting compounds of the formula (1) are those of the formula (la) given below. The cores 117 are preferably hydrogen. The sulfo groups shown in the formula (2) are each preferably bonded to the ortho position. The compound of the formula (2) is of interest wherein 116 and the core are preferably hydrogen and The sulfo groups shown in (2) are each bonded to the ortho position. Μ is preferably hydrogen, an alkali metal or an alkaline earth metal or ammonium, especially sodium. In a mixture of the compounds of the formulae (1) and (2), The molar ratio of the compound of the formula (1) to the compound of the formula (2) is usually in the range of 0_1: 99.9 to 99.9: 0.1, preferably 1:99 to 99:1 and more preferably 5:95 to 95:5. The best is 10: 90 to 90: 10 'especially 20: 80 to 80: 20 Mobi. The most important is 30: 70 to 70: 30, especially 40: 60 to 60: 40 Mo The compound of the formula (1) and (2) is known or can be prepared by a similarly known method. The compound of the formula (1) can be prepared as follows: under the known reaction conditions, the cyanuric chloride is desired to be any The order of the order is successively with 4 , 4'-diaminostilbene-2,2'-disulfonic acid and an amine compound capable of introducing groups Χι, χ2, χ3 and & preferably, 2 mil cyanide urethane initially Reacts with 1 mol 4,4,-diaminodiphenylethane-2,2'-disulfonic acid, and then the resulting intermediate is introduced in any order with the group X, 'χ2, heart and χ4 Amino compound reaction ❹ For the preparation of a compound in which 1 and Χ3 have the same meaning and χ2 and χ4 have the same meaning, it is preferable to react the obtained intermediate with an amine compound capable of introducing \ and 133 1332045, and finally It is then reacted with an amine compound capable of introducing x2 and X4. It is also possible to carry out the reaction with the amine compound in one step by reacting the intermediate with the mixture of the amine compounds; in this case, the corresponding compound mixture of the formula (1) is usually obtained. The compound of the formula (1) containing a group of the formula -OR5 can be prepared, for example, by first reacting cyanuric chloride with the corresponding alcohol HOR5 to obtain the product and 4,4'-diaminostilbene-2. , 2'-disulfonic acid reaction, and then the intermediate is reacted with other compounds capable of introducing the remaining groups of Χ, X2, 3 and 乂4. The last reaction is preferably carried out with the corresponding amine. Furthermore, the invention is directed to mixtures of the compounds of formula (1) and (2). As for the compounds of the formulae (1) and (2), the preferences given above are applicable. The compound of the formula (2) wherein R6 and 117 are hydrogen and the sulfo group represented by the formula (2) is bonded to the ortho position is preferred. In such a mixture, the molar ratio of the compound of the formula (1) to the compound of the formula (2) is usually in the range of from 0.1:99.9 to 99.9:0.1, preferably from 1:99 to 99:1 and more preferably 5 : 95 to 95 : 5. The best is 10: 90 to 90: 10, especially 20: 80 to 80: 20 Mobi. Most importantly, the detergent composition used in the 30:70 to 70:30, especially 40:60 to 60:40 molar ratio preferably comprises: i) 1-70% anionic surfactant and/or Nonionic surfactant; ii) 0-75% builder; iii) 0-30% peroxide; iv) 0-10 peroxide activator; and v) 〇_〇〇1-5 % of a mixture of compounds of formula (1) and (2), 1332045 by weight, based on the total weight of the detergent. More preferably, the detergent composition used comprises: i) 5-70% anionic surfactant and/or nonionic surfactant; ii) 5-70% builder; iii) 0.5-30 % peroxide; iv) 0.5-10% peroxide activator and / or 0.1-2% bleach catalyst; and v) 0.01-5% mixture of compounds of formula (1) and (2); It is based on the weight of the total weight of the detergent. In general, a mixture of the compounds of the formulae (1) and (2) in an amount of from 0.001 to 5% is used, especially in an amount of from 0.01 to 5%. Excellent is an amount of 0.05 to 5%, especially 0.05 to 2%. In general, the quantity expressed as a percentage should be understood as a percentage by weight based on the total weight unless otherwise stated. The detergent may be formulated as a solid, formulated into an aqueous liquid containing, for example, 5 to 50, preferably 10 to 35%, or formulated as a non-aqueous liquid detergent containing no more than 5, preferably 0 to 1% by weight. Water is based on a suspension of the builder in the nonionic surfactant, as described, for example, in GB-A-2158454. The anionic surfactant component can be, for example, an alkylbenzene sulfonate, an alkyl sulfate, an alkyl ether sulfate, an alkene sulfonate, an alkane sulfonate, a fatty acid salt, an alkyl or alkenyl ether carboxylic acid. a salt or an α-sulfofatty acid salt or an ester thereof. Preferred are alkylbenzenesulfonates having 10 to 20 carbon atoms in the alkyl group, alkyl sulfates having 8 to 18 carbon atoms, alkyl ether sulfates having 8 to 18 carbon atoms, And fatty acid salts derived from palm oil or tallow and having 132045 and having 8 to 18 carbon atoms. The average number of molecules of the ethylene oxide added to the alkyl ether sulfate is preferably from 1 to 20's preferably from 1 to 10. These salts are preferably derived from alkali metals such as sodium and potassium, especially sodium. An excellent carboxylate is an alkali metal sarcosinate of the formula R-CCKR^CH^OOM1 wherein R is an alkyl or alkenyl group having from 9 to 17 carbon atoms in the alkyl group, or an alkenyl group, R1 It is a CrC4 alkyl group, and M1 is an alkali metal, especially sodium. The nonionic surfactant component can be, for example, a graded and a secondary alcohol ethoxylate, especially a C8-C2 nonaliphatic alcohol ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol. More particularly, C1Q-C15 grade and secondary aliphatic alcohols are ethoxylated per mole of 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers, and polyhydroxy decylamine (glucosamine). The total amount of the anionic surfactant and the nonionic surfactant is preferably from 5 to 50% by weight, preferably from 5 to 40% by weight and more preferably from 5 to 30% by weight. As for these surfactants, the lower limit is preferably 10% by weight. The builder component can be an alkali metal phosphate, especially a tripolyphosphate; a carbonate or bicarbonate, especially a sodium salt thereof; a citrate or a dicaprate; a strontium aluminate; a polycarboxylate; a polycarboxylic acid; an organic phosphonate; or an amine-based poly(phosphonate), or a mixture of these. A preferred phthalate salt is a crystalline layered sodium silicate of the formula NaHSira02m+1.pH20 or Na2Sim〇2m+1.pH2〇 wherein m is a number from 1.9 to 4 and P is from 0 to 20. Preferred yttrium aluminates are commercially available synthetic materials designated zeolite A, B' X and HS, or mixtures of these. Zeolite A is preferred. 17 1332045 Preferred polycarboxylates include: hydroxypolycarboxylates, especially citrates, polyacrylates and their copolymers with maleic anhydride. Preferred polycarboxylic acids include nitrilotriacetic acid and ethyldiaminetetraacetic acid. Preferred organic phosphonates or amine alkylene poly(alkylene phosphonates) are alkali metal ethane 1-hydroxydiphosphonates, nitrilotrimethylene phosphonates, ethylidene diamines Methylene phosphonate and di-ethyltriamine penta methylene phosphonate. The amount of III I-builder is preferably from 5 to 70% by weight, preferably from 5 to 60% by weight and more preferably from 10 to 60% by weight. As for the builder, the lower limit is preferably 15% by weight, especially 20% by weight. Suitable peroxide components, for example, include organic and inorganic peroxides (such as sodium peroxides) which are known in the literature and commercially available, and which are conventionally used at wash temperatures such as 5 to 95°. C bleached textile material. In particular, the organic peroxide is exemplified by a monoperoxide or a polyperoxide having an alkyl chain of at least 3, preferably 6 to 20 carbon atoms; in particular, having 6 to 12 C atoms. Diperoxydicarboxylates, such as diperperoxypersalate, diperoxyperpine diphosphate, diperoxyphthalate and/or diperoxydodecanedioate, In particular, their corresponding free acid systems are of particular interest to those. However, it is preferred to use very active inorganic peroxides such as persulfates, perborates and/or percarbonates. Of course, it is also possible to use mixtures of organic and/or inorganic peroxides. The peroxide is preferably from 0.5 to 30% by weight, preferably from 1 to 20% by weight and more preferably from 1 to 15% by weight. If a peroxide is used, the lower limit is preferably 2 18 1332045 wt%, especially 5% wt%. Peroxides, especially inorganic peroxides, are preferably activated via the inclusion of a bleach activator. Preferred are such compounds which, under the conditions of hydrogen peroxide hydrolysis, are substituted, substituted or substituted with perbenzoic acid and/or peroxycarboxylic acid having from 1 to 10 carbon atoms, especially from 2 to 4 carbon atoms. Suitable compounds include those bearing a fluorene- and/or N-fluorenyl group having the carbon number and/or an unsubstituted or substituted benzindenyl group. Preference is given to polyalkylene alkyl diamines, in particular tetraethyl hydrazide ethyl diamine (TAED), thiolated glycoluril, especially tetraethylene guanylurea (TAGU), N, N-di Ethyl-N,N-dimethyl-urea (DDU), a thiolated trimorphine derivative, especially 1,5-diethylindenyl-2,4-dihydrohexahydro-1,3, 5-three tillage (0 people 01^), the compound of the following formula

Wherein R is a sulfonate group, a carboxylic acid group or a carboxylate group, and wherein R' is a linear or branched (C7-C15) alkyl group; and an activator known by the trade names SNOBS, SLOBS, NOBS and D0BA a thiolated polyol, especially triacetin, ethylene glycol diacetate and 2,5-diethoxycarbonyl-2,5-dihydrofuran, and ethoxylated sorbitol and mannitol and Thiolated sugar derivatives, especially pentaethylglucosamine (PAG), sucrose polysuccinate (SUPA), pentaethylene fructose, tetraethyl xylenyl and octadecyl lactose, and acetylation N-alkylated glucosamine and gluconolactone are optionally required. A conventional bleaching agent combination disclosed in German Patent Application No. DE-A-44 43 177 can also be used. A nitrile compound which forms a peroxyimin with a peroxide is also suitable as a bleach activator. Preferred are tetraethylguanidinoethyldiamine and nonyloxybenzenesulfonate 1332045 acid salts. The amount of bleach activator is preferably from 0 to 10% by weight, preferably from 〇 to 8 % by weight. The lower limit is preferably 0.5% by weight, especially 1% by weight, if a bleach activator is used. Bleach catalysts which may be added include, for example, enzymatic peroxide precursors and/or metal complexes. A preferred metal complex is a manganese, cobalt or iron complex complex such as a clock or iron phthalocyanine or a complex as described in EP-A-0509787. If a bleaching transfer agent is used, the amount thereof is preferably from 0.005 to 2% by weight, more preferably from 0.01 to 2% by weight, particularly from 5 to 2% by weight. It is preferably an amount of from 0.1 to 2% by weight. As examples of bleach catalysts, the following may be mentioned: - WO-A-95/30681 (i.e., see formula (1) on page 1, lines 7 to 30 and its definitions; especially on page 2, line 29 Go to Equation (I) given on line 11 on page 11 and later). Preferred ligands are given on page 13, line 12 to page 26, line 11. -WO-A-01/09276 (ie see equations (1), (2) and (3) given on pages 2 and 3 and subsequent definitions). -WO-A-01/05925 (see also the definition of equation (1) and subsequent definitions in the first paragraph of page 1 to the first paragraph of page 2. The preference for metal complexes may apply, see in particular page 3. Equation (2) and Equation (3) on page 4). -WO-A-02/088289 C See also equation (1) on page 2 and its definition. Preference is given to the preference for metal complexes, see in particular the ligands of formula (3) and the preferences given on page 3, paragraph 4 to page 4, paragraph 7. 20 1332045 Furthermore, detergents may contain enzymes as needed. Enzymes can be added to decontamination detergents. These enzymes often increase the effectiveness of protein or starch-based stains, such as those caused by blood, milk, grass juice or fruit juice. Preferred enzymes are cellulases, proteases, amylases and lipases. Preferred enzymes are cellulases and proteases, especially proteases. Cellulase is an enzyme that acts on cellulose and its derivatives and hydrolyzes them into glucose, cellulose disaccharide, and cellulose oligosaccharides. Cellulase removes dirt and has the effect of reducing roughness. Examples of enzymes to be used include, but are not intended to be limited to, the following: the proteases listed in US-B-6, 242, 405, column 14, lines 21 to 32; in US-B-6, 242, 405, column 14, lines 33-46. Lipases listed in; US-B-6, 242, 405, amylases listed in column 14, lines 47 to 56; and fibers listed in US-B-6,242,405, column 14, lines 57-64 Enzyme. Enzymes may be present in the detergent as needed. When used, the enzyme is usually present in an amount of from 0.01 to 5% by weight, preferably from 0.05 to 5% and more preferably from 0.1 to 4% by weight based on the total weight of the detergent. Other preferred additives which can be used in the detergents of the present invention are polymers (fixing agents, dye transfer inhibiting agents) which inhibit coloration caused by dyes which have been released from the fabric under the washing conditions during the washing of the fabric. Such polymers are preferably polyvinylpyrrolidone, polyvinylimidazole or polyvinylpyridine 21 1332045 N-oxide, which may have been modified by the incorporation of anionic or cationic substituents, especially having a molecular weight of from 5,000 to 60 Å. Hey, better from the range of 1 to 50 000. Such polymers are generally employed in amounts of from 〇1 to 5% by weight, preferably from 0.05 to 5% by weight, especially from 0.1 to 2% by weight, based on the total weight of the detergent. Preferred polymers are those listed in WO-A-02/02865 (see especially the first paragraph on page 1 and the first paragraph on page 2). The detergent to be used usually contains one or more auxiliaries, such as soil suspending agents, such as sodium carboxymethylcellulose; salts for pH adjustment, such as alkali metal or alkaline earth metal citrate; foam regulators, such as soap; Adjusting salts for spray drying and granulating properties, such as sodium sulfate; perfumes; and, where appropriate, antistatic and softening agents, such as smectite clays; photobleaches; pigments: and/or toners. These components should of course be stable to any bleaching system used. Such auxiliaries may be present in an amount of from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight, especially from 0.5 to 5% by weight, based on the total weight of the detergent. The detergent composition can take a variety of physical forms, including powders, granules, nine pieces, and liquids. Examples thereof are conventional powdered heavy duty detergents, compact and ultra-tight heavy duty detergents and nine sheets, such as nine heavy duty detergents. An important physical form is the so-called concentrated particle form suitable for addition to a washing machine. Also important are so-called tight (or ultra-compact) detergents. In the field of detergent manufacture, a trend has recently been developed towards the manufacture of compact detergents containing incremental actives. In order to minimize energy consumption during the washing process, the compact detergent must be operated at temperatures as low as 40 ° C, or even at room temperature, such as 25 ° C. This type of detergent usually contains only 22 1332045 with low amounts of dips or processing aids such as sodium sulfate or sodium chloride. The amount of such a stock is usually from 0 to 10% by weight, preferably from 0 to 5% by weight, especially from 0 to 1% by weight, based on the total weight of the detergent. Such detergents typically have a bulk density of from 650 to 1000 grams per liter, preferably from 700 to 1000 grams per liter and especially from 750 to 1000 grams per liter. The detergent can also be present in nine pieces. The relevant characteristics of the nine pieces are the ease of distribution and the convenience of handling. Nine sheets are the most closely delivered solid detergent and have a bulk density of, for example, 0.9 to 1.3 kg/liter. In order to enable rapid disintegration, nine pieces of laundry detergent generally contain special disintegrants: - effervescent agents, such as carbonates / hydrogen carbonate / citric acid; - swelling agents, such as cellulose, carboxymethyl cellulose, Cross-linked poly(N-vinylpyrrolidone); - fast-dissolving material such as sodium acetate (potassium) or sodium citrate (potassium); - instant soluble water-soluble hard coating such as dicarboxylic acid. These nine sheets may also contain any combination of the above disintegrants. The detergent may also be formulated as an aqueous liquid containing 5 to 50, preferably 10 to 35%, or as a non-aqueous liquid detergent containing not more than 5, preferably 0 to 10% by weight of water. The non-aqueous liquid detergent composition may contain other solvents as a carrier. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol 'propanol and isopropanol are suitable. The unit alcohol is preferred for dissolving the surfactant, but polyols such as those having from 2 to about 6 carbon atoms and from 2 to about 6 hydroxyl groups (e.g., U-propylene glycol, ethylene glycol, glycerin, and 1, may also be used. 2-propanediol). The composition may contain from 5% to 90% 'typically from 10% to 50% of such carriers. Detergents can also be present in the form of so-called "unit liquid doses". 23 1332045 This fabric detergent treatment can be manipulated into a household treatment in a conventional washing machine. The textile fibers treated can be natural or synthetic fibers or mixtures thereof. Examples of natural fibers include vegetable fibers such as cotton, viscose, linen, crepe or linen, preferably cotton, and animal fibers such as wool, mohair, cashmere, angora, and silk, preferably wool. . Synthetic fibers include fibers such as polyester, polyamide, and polyacrylonitrile. Preferred textile fibers are fibers such as cotton, polyamide, and wool, especially cotton fibers. Preferably, the textile fibers treated in accordance with the method of the present invention have a density of less than 200 grams per square meter. According to the process, it is customary to use a mixture of the compounds of the formulae (1) and (2) in an amount of from 0.01 to 3.0% by weight, especially from 0.05 to 3.0% by weight, based on the weight of the textile fibre material. The process is generally carried out at temperatures ranging from 5 to 100 ° C, especially 5 to 60 ° C. It is preferably in the range of 5 to 40 ° C, especially 5 to 35 ° C and more preferably 5 to 30 ° C. Preferably, the detergent compositions herein are formulated such that the sewage will have a pH of between about 6.5 and about 11, preferably between about 7.5 and 11, during use in an aqueous cleaning operation. Laundry products are usually at pH 9-11. Techniques for controlling pH to the recommended standards of use include the use of buffers, bases, acids, and the like, and are well known to those skilled in the art. The machine laundry process herein generally comprises treating the soiled laundry with a wash water solution of the machine laundry detergent composition of the present invention dissolved or suspended in the washing machine. By effective amount of detergent composition is meant, for example, that from 20 grams to 300 grams of product is dissolved or dispersed in a volume of from 5 to 85 liters of a wash 24 1332045 detergent solution, as is typically used in conventional machine laundry methods. And the volume of the wash solution. Examples are: - Top-mounted vertical shaft American type automatic washing machine, which uses about 45 to 83 liters of water in a washing tank, a washing cycle of about 10 to about 14 minutes, and a washing water temperature of about 10 to about 50 ° C; A horizontal axis European type automatic washing machine, which uses about 8 to 15 liters of water in a washing tank, a washing cycle of about 10 to about 60 minutes, and a washing water temperature of about 30 to about 95 ° C;

- Top-mounted vertical shaft Japanese type automatic washing machine which uses about 26 to 52 liters of water in a washing tank, a washing cycle of about 8 to about 15 minutes, and a washing water temperature of about 5 to about 25 °C. The ratio of the solution is preferably from 1:4 to 1:40, especially from 1:4 to 1:15. The preferred ratio is 1:4 to 1:10, especially 1:5 to 1:9. Furthermore, the present invention is directed to a detergent composition comprising: at least one compound of formula (la):

(1a)

Wherein: the heart and R2 are independently of each other hydrogen or unsubstituted or substituted C,-c8 alkyl, 25 1332045 X!, X2, X3 and X4 are independently of each other -N(R3)R4 or - OR5, wherein R3 and R4 are hydrogen; cyano; crc8 alkyl, which is unsubstituted or substituted by hydroxy, carboxy, cyano, -conh2 or phenyl and wherein c"c8 alkyl is uninterrupted or is -0 - interrupted; unsubstituted or c5-c7 cycloalkyl substituted by CVC4 alkyl; or R3 and R4 together with the nitrogen atom to which they are attached form an unsubstituted or substituted crc4 alkyl group, piperidine or a pyrrolidine ring; the rule 5 is a CrC8 alkyl group which is unsubstituted or substituted by a hydroxyl group, and the hydrazine is hydrogen or a cation, and wherein the detergent contains at least one selected from the group consisting of cellulase, protease, amylase and An enzyme consisting of a group of lipases. As for the compound of formula (la) and its substituents, the above meanings and preferences for the compound of formula (1) apply. The compound of formula (la) of interest is: its central R2 is independently of each other hydrogen or unsubstituted or substituted CrC8 alkyl, X, X2, X3 and X4 are independently of each other Is -N(R3)R4S-OR5, wherein ampules 3 and R4 are hydrogen, unsubstituted or hydroxy substituted CrC8 alkyl, unsubstituted or substituted by (^-decylalkyl) C5-C7 cycloalkyl, Or the core and R4 together with the nitrogen atom to which they are attached form an unsubstituted or crc4 alkyl substituted morpholinyl, guanidine or pyrrolidine ring, and R5 is unsubstituted or hydroxy substituted crc8 alkyl, And the hydrazine is hydrogen or a cation. It is preferably a corresponding detergent composition containing an enzyme and a peroxide, a peroxide activator and/or a bleach catalyst. Preferred are detergent compositions comprising the following: 26 1332045 i) 1-70% anionic surfactant and / or nonionic surfactant; ii) 0-75% builder; iii) 0-30% peroxide; iv) 0-10% a peroxide activator; v) 0.001 to 5% of the compound of the formula (la); and vi) 0.05 to 5% of at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase Very preferred are detergent compositions comprising: i) 5-70% anionic surfactant and/or nonionic surfactant; ii ) 5-70% builder; iii) 0.5-30% peroxide; iv) 0.5-10% peroxide activator and / or 0.1-2% bleach catalyst; v) 0.01-5% a compound of the formula (la); and vi) 0.05 to 5% of at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase. As for the enzyme, the detergent and the components thereof, the above The definitions and preferences given apply. The compound of the formula (la) can be used in the same manner as given above for the mixture of the compounds of the formulae (1) and (2). It is a further object of the present invention to provide a method for household laundry treatment of textile fiber materials wherein the textile fiber material is contacted with an aqueous solution of a detergent comprising a compound of formula (la) as defined above, and wherein the detergent contains at least one selected An enzyme consisting of a group consisting of cellulase, protease, amylase and lipase, and wherein the temperature of solution 27 1332045 is between 5 ° C and 40 ° C throughout the process, preferably 5 Between °C and 30 °C. As regards the compounds of formula (la) and in terms of detergents and washing methods, the definitions and preferences given above apply. The washing treatment of the above textile fibers can also be carried out using a mixture of the compounds of the formula (1) and (2). The compounds and mixtures used according to the invention are particularly advantageous in that they not only exhibit an extremely high whitening ability, but in addition, they exhibit very desirable water solubility in many cases and are excellent in solid state. White aspect. A further advantage of the present invention is that detergent composition delivery improves whiteness performance and fabric feel. Furthermore, the compounds and especially the mixtures show very good results in terms of depletion properties. These compounds have the advantage that they are also effective in the presence of active chlorine donors such as hypochlorite and have no substantial effect loss in water wash tanks containing nonionic detergents such as alkylphenol polyglycol ethers. Use in case. Also in the presence of perboric acid or peracids and activators such as tetraethylglycoluril or ethyldiaminetetraacetic acid, the compounds and compound mixtures are stable in both powdered detergents and water wash tanks. In addition, they give the sun a brilliant appearance. Mixtures of the compound of formula (1) and the compounds of formula (1) and (2) have also been found to be useful for the fluorescent whitening of textile materials, in which case the polyamide, wool and cotton should be specifically isolated. The textile fibers treated in accordance with this embodiment of the invention may be natural or synthetic fibers or mixtures thereof. Examples of natural fibers include vegetable fibers such as cotton, viscose, linen, crepe or linen, preferably cotton and animal fibers such as wool, mohair, cashmere, Angora 28 1332045 wool and silk, preferably For wool. Synthetic fibers include fibers such as polyester, polyamide, and polyacrylonitrile. Preferred textile fibers are fibers such as cotton, polyamide, and wool. Preferably, the textile fibers treated in accordance with the invention have a density of less than 1000 g/m2, especially less than 500 g/m2 and most preferably less than 250 g/m2. The following examples are intended to illustrate the invention; parts and percentages are by weight unless otherwise indicated. Preparation Example 1:

In a 1 liter flask, 0.05 mole of the compound of the formula:

Mix with 600 ml of water and heat it to a temperature of 60 °C. Then 9.2 g of 2-ethylaminoethanol was added and the reaction mixture was heated to a temperature of 98 ° C; during heating, the pH was maintained at 8, 5 and 9 by the addition of a 4-mole aqueous solution of sodium hydroxide. The number between the two. The reaction mixture was cooled to 29 1332045 50 ° C, and the pH was adjusted to a number of 4.5 by adding a 6 molar aqueous solution of hydrochloric acid. The precipitate was filtered off, washed with 1 mL of a 1% aqueous sodium chloride aqueous solution and dried in vacuo. In this way, 30.5 g of a pale yellow product was obtained. Preparation Example 2: Xin 15 : Compound of the formula:

It can be prepared by a method similar to that described in Preparation Example 1, except that 9.2 g of 2-ethylaminoethanol is substituted with an equivalent molar amount of the corresponding amine. X is as defined in Table 1 below. The compound precipitated after cooling to 50 ° C was directly isolated into a sodium salt without adding hydrochloric acid, followed by drying in a vacuum.

Table 1

Example ~X 2 •N(C,hU. 3 1 4 -N(CH,)CH,CH,OH 5 P NH 1 6 -NHCH,CH,OH 30 1332045 7 -NHCH,CH?0CH, 8 -NHCH ,CH,COOH 9 -NHCH?CH, 10 -N(CHs)CH?COOH 11 -N(CH?CH?OH), 12 -〇13 I 14 -NHCH^COOH 15 -NH -CH-COOH NH II ch2ch2ch"nh-c-nh2

Preparation Example 16:

(103) 0.05 mM compound in a 1 liter flask

(104) Mix with 600 ml of water and heat it to a temperature of 60 °C. Then 9.5 grams of morpholine was added and the reaction mixture was heated to a temperature of 98 ° C; during heating, the pH was maintained at 31 1332045 between 8.5 and 9 by the addition of a 4-mole aqueous sodium hydroxide solution. . The reaction mixture was cooled to 4 (TC), then the precipitate was filtered, washed with 100 ml of 10% aqueous sodium chloride and dried in vacuo. In this way, 30 g of pale yellow product was obtained. Preparation Example 17 To 19 : Compound of the formula:

It can be prepared by a method similar to that described in Preparation Example 16, except that 9.5 g of morpholine is substituted with an equivalent molar amount of the corresponding amine. X is as defined in Table 2 below. The compound with high solubility was treated with a 6-mole aqueous solution of hydrochloric acid to adjust the pH to a number of 4.5 before cooling to 50 °C. Table 2 Example X 17 -N(CH,CHXH,CH?OH 18 I 19 -N(CH,CH,OH), Preparation Example 20: 32 (105) (105) 1332045

In a 2 liter flask, 130 ml of methyl ethyl ketone, 80 ml of ionized water, 150 g of ice and 18.5 g of cyanuric chloride were mixed. During 30 minutes, 185 ml of an aqueous solution of 4,4'-diaminostilbene-2,2'-disulfonic acid (as a disodium salt) (concentration of 100 g/L) was added dropwise, at a temperature system. Between ~8 % +5 °C. The pH was maintained at a number between 4.5 and 5 & by adding an aqueous solution of sodium carbonate. A light yellow suspension was obtained. Then, by using a drip drain 4, 27.2 g of ethanolamine (99%) was added. The pH is increased to a number of 10, and after #, it is lowered to a lower number, and the temperature is increased to 10 to 15 °C. The reaction mixture was then warmed to a temperature of 45 ° C and maintained at this temperature for 20 minutes. & During heating in 30 minutes to 98 ° C, the mixture of methyl ethyl ketone and water was distilled off; the pH was maintained at a number between 8.5 and 9 by the addition of an aqueous sodium hydroxide solution. The reaction mixture was cooled to 50 after further addition of aqueous sodium hydroxide solution to a pH of the stomach at a fixed number of hydrazines. (: The pH was adjusted to a number of 5.5, and the pale yellow crystal precipitate was filtered off. After drying; to give 29 g of pale yellow product. Preparation Example 21: 33 1332045

0.037 mol of N,N,-bis-(4-morpholinyl-6-chloro-1,3,5-trimorph-2-yl)-4,4,-diamine in a 1 liter pressure vessel The stilbene-2,2-disulfonic acid (as the disodium salt) was suspended in 500 ml of water. 15 g of an aqueous solution of ethylamine (70%) was added and the reaction mixture was heated to a temperature of 100 to 105 ° C, followed by stirring for 4.5 hours. The reaction mixture was cooled to 25 ° C, and the precipitate was filtered, washed with 100 ml of 10% aqueous sodium chloride and dried at 70 ° C in vacuo. In this way, 25.8 g of a pale yellow powder was obtained. Preparation Example 22:

(107)

The compound of formula (107) can be prepared analogously to the procedure given for the preparation of Example 21, but 15 g of an aqueous solution of ethylamine (70%) was replaced with a corresponding solution containing an equimolar amount of diethylamine. Preparation Example 23 = 34 (108) (108) 1332045

In a 1 liter flask, 0.05 moles of Ν'-bis-(4-morpholinyl-6-chloro-1,3,5-triment-2-yl)-4,4,-diamino group The stilbene-2,2, disulfonic acid (as the disodium salt) was suspended in 600 ml of water and heated to a temperature of 60 °C. 6.4 grams of ethanolamine was added and the reaction mixture was heated to a temperature of 98 °C. The pH was maintained between 8.5 and 9 by the addition of a 4-mole concentration aqueous sodium hydroxide solution. The reaction mixture was cooled to 25 ° C and 10% by volume of sodium chloride was added. The precipitate was filtered, washed with 100 mL of 10% aqueous sodium chloride and dried in vacuo. In this way, 41.8 g of a pale yellow powder was obtained. Application Example 1: General procedure: A lotion was prepared by dissolving 0.8 g of washing powder in 200 ml of tap water. Ten grams of the bleached cotton fabric was added to the tank and washed at 40 ° C for 15 minutes, then rinsed, dried and ironed at 160 °C. The following washing powders A and B (in the amounts given in Tables 3a and 3b below) are used: Table 3a (components of washing powders A and B) AB sodium laurylbenzene sulfonate (LAS) ίο克 10 g 35 1332045 Sodium lauryl ether sulfate (AES) 3 g 3 g Dobanol 23-6.5 (nonionic ethoxylated alcohol) 4 g 4 g sodium tripolyphosphate 30 g zeolite A 20 g sodium carbonate 15 g 15 g citric acid Sodium 5 g 5 g sodium sulfate 11 g gram cellulose enzyme 1.5 g protease 1.5 g polycarboxylate (co-builder) 4 g carboxymethyl cellulose 2 g 2 g perfume 0.1 g 0.1 g water 5 g 5 g Fluorescent whitening agent or fluorescent whitening agent mixture X g X g

Table 3b (Washing Powder Used) Fluorescent Brightener or Fluorescent Brightener Mixture Amount of Washing Powder Preparation Compound of Example 1 0.2 g A Preparation of Compound of Example 2 0.1 g B Preparation of Compound 0.3 of Example 3克A Preparation of the compound of Example 4 0.2 g A Preparation of the compound of Example 5 0.4 g A Preparation of the compound of Example 12 0.15 g B Preparation of the compound of Example 13 0.1 g B Preparation of the compound of Example 16 0.3 g B Preparation Example Mixture of 6 compound and compound of formula (109) [7: 3 by weight] 0.2 g A Preparation of a mixture of the compound of Example 12 and a compound of the formula (109) [7: 3 by weight] 0.4 g B Preparation of the compound of Example 14 and (109) Mixture of the compound [7:3 by weight] 0.3 g A Preparation of a mixture of the compound of Example 17 and the compound of the formula (109) [1 : 1 by weight] 0.2 g of B Preparation of the compound of Example 18 and the compound of the formula (109) Mixture [1: 2 by weight] 0.5 g B Preparation of a mixture of the compound of Example 1 and a compound of the formula (109) [1: 5 by weight] 0.3 g B Preparation of a mixture of the compound of Example 2 and the compound of the formula (109) [5 : 1 weight Ratio] 0.2 g B Preparation of a mixture of the compound of Example 3 and the compound of the formula (109) [1 : 1 by weight] 0.2 g B Preparation of a mixture of the compound of Example 20 and the compound of the formula (109) [3: 7 by weight] 0.1 g A 36 1332045

Preparation of a mixture of the compound of Example 21 and the compound of the formula (109) [1: 9 by weight] 0.1 g of B Preparation of a mixture of the compound of Example 22 and the compound of the formula (109) [9: 1 by weight] 0.2 g B Preparation Example 23 a mixture of a compound and a compound of the formula (109) [1 : 1 by weight] 0.4 g of a mixture of a compound of the formula (110) and a compound of the formula (109) [1: 1 by weight] 0.3 g of a compound of the formula (109)

,S03Na Na03S, (109)

The structure of the compound of formula (110):

(110) Cotton fabrics which have been washed according to the general procedure with the stripping agents listed in Table 3b show good whiteness properties. Application Example 2: General procedure: A lotion was prepared by dissolving 0.8 g of washing powder in 200 ml of tap water. Ten grams of bleached cotton fabric was added to the tank and washed at 30 ° C for 15 minutes, then rinsed, de-dried and ironed at 160 °C. The following washing powders were used (the amounts given in Tables 4a and 4b below are the weights of 37 1332045 ,, based on the total weight of the washing agent): ' Table 4a (components of washing powders C and D) CD lauryl benzene Sodium sulfonate (LAS) 8% 8% Sodium sulphate (AES) 3% 3% Dobanol 23-6.5 (nonionic ethoxylated alcohol) 5% 5% Zeolite A 20% 20% Polycarboxylate ( Co-builder) 5% 5% soda ash 18% 18% sodium citrate 4% 4% sodium sulphate 5% 5% hydroxyethane diphosphonic acid (complex) 0.5% 0.5% cellulase 1.5% protease 1.5% carboxy Methylcellulose 1% 1% Sodium perborate monohydrate 15% 15% TAED . 5% 5% Soap 2% 2% Fluorescent whitening agent or fluorescent whitening agent mixture X% X% used above In each detergent, a sufficient amount of water was used to obtain 100%. Table 4b (washing powder used)

Amount of Fluorescent Brightener or Fluorescent Brightener Mixture Washing Powder Preparation Compound of Example 1 0.2% C Preparation of Compound of Example 3 0.2% C Preparation of Compound of Example 7 0.2% D Preparation of Compound of Example 8 0.2 % C Preparation of compound of Example 9 0.4% C Preparation of compound of Example 10 0.2% C Preparation of compound of Example 11 0.2% C Preparation of compound of Example 17 0.4% C Preparation of compound of Example 20 0.5% C Formula (110 Compound 0.3% D Preparation of a mixture of the compound of Example 1 and a compound of the formula (109) [10: 1 by weight 1 0.2% D Preparation of a mixture of the compound of Example 3 and the compound of the formula (109) [5: 1 by weight] 0.4% C 38 1332045 嚤

Preparation of a mixture of the compound of Example 5 and a compound of the formula (109) [1: 5 by weight] 0.15% C Preparation of a mixture of the compound of Example 11 and a compound of the formula (109) [1 : 1 by weight] 0.2% C Preparation Example 15 Mixture of compound and compound of formula (109) [1:9 by weight] 0.4% C Preparation of a mixture of the compound of Example 16 and a compound of formula (109) [9: 1 by weight] 0.3% D Preparation of compound of Example 19 and formula ( 109) Mixture of compounds [1: 5 by weight] 0.2% D For the structures of the compounds of the formulae (109) and (110), see Application Example 1

Cotton fabrics washed according to the general procedure with the detergents listed in Table 4b showed good whiteness properties.

39

Claims (1)

1332045 ^ > :: Pick up, apply for a range of 1. A detergent composition comprising: at least one compound of formula (1): Wherein: 1 and R 2 are independently of each other hydrogen or unsubstituted or substituted CVCs alkyl, 1 and are amine groups, and χ 2 and X 4 are groups of the formula -N(R3)R4 wherein 113 and R4 together with the nitrogen atom to which they are attached form a morpholinyl ring, and hydrazine is hydrogen, an alkali metal or alkaline earth metal or ammonium, and at least one compound of formula (2): Wherein R6 and R7 are each independently hydrogen, CVC8 alkyl, Ci-Cs alkoxy or halogen, and the oxime is as defined above in formula (1). 2. The composition according to claim 1, wherein R6 and R7 are hydrogen, and each sulfo group shown in formula (2) is bonded to the ortho position 40 1332045 3. According to the scope of claim 1 or A composition of 2 comprising: i) 1-70% anionic surfactant and/or nonionic surfactant; ii) 0-75% builder; iii) 0-30% peroxide W) 0-10% of a peroxide activator; and v) 0.001-5% of a mixture of compounds of formula (1) and (2). 4. A composition according to item 3 of the scope of the patent application, comprising: i) 5-70% anionic surfactant and/or nonionic surfactant; ii) 5-70% builder; iii) 0.5 -30% peroxide; iv) 0.5-10% peroxide activator and/or 0.1-2% bleach catalyst; and v) 0.01-5% mixture of compounds of formula (1) and (2) . 5. The composition according to claim 1 or 2, wherein the detergent composition comprises at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase. 6. A detergent composition comprising: at least one compound of formula (la): (1a) 41 1332045 wherein: the core and the r2 are independently hydrogen or unsubstituted or substituted Cl_Cs alkyl, and χ3 is an amine ' χ 2 and X 4 is a group of the formula -N(R3)R4 a group, wherein hydrazine and R4 together with the nitrogen atom to which they are attached form a morpholinyl ring, and hydrazine is hydrogen, an alkali metal or an alkaline earth metal or ammonium, and wherein the detergent contains at least one selected from the group consisting of cellulase, protease, An enzyme group consisting of amylase and lipase. 7. The composition of claim 6 wherein the composition comprises a peroxide, a peroxide activator and/or a bleach catalyst. 8. The composition according to claim 6 or 7 of the patent application's comprising: i) l-70% of an anionic surfactant and/or a nonionic surfactant; ii) 0-75% builder; iii 0-30% peroxide; iv) 0-10% peroxide activator; v) 0.001-5% of the compound of formula (la); and vi) 0.05-5% of at least one selected from the group consisting of fibers An enzyme group consisting of a protease, a protease, an amylase, and a lipase. 9. The composition according to claim 6 or 7, comprising: i) 5-70% of an anionic surfactant and/or a nonionic surfactant; ii) 5-70% builder; Iii) 0.5-30% peroxide; iv) 0.5-1% peroxide activator and/or 0.1-2% bleach catalyst; 42 1332045 V) 0.01-5% of the compound of formula (la); And vi) 0.05-5% at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase. 10. The composition according to claim 6 or 7, wherein the enzyme is a protease enzyme. 11. A method for household laundry treatment of textile fiber materials, wherein the textile fiber material is contacted with an aqueous detergent solution comprising a compound of the formula: (1a) Wherein: 1 and r2 are independently of each other hydrogen or an unsubstituted or substituted CVC8 alkyl group, χβα χ3 is an amine group, and χ2 and χ4 are groups of the formula -n(r3)r4, wherein 尺3 and r4 Forming a morpholino ring together with the nitrogen atom to which they are attached, and the hydrazine is hydrogen, an alkali metal or an alkaline earth metal or ammonium, and wherein the detergent contains at least one selected from the group consisting of cellulase, protease, amylase and lipase The enzymes that make up the group, and wherein the temperature of the solution is at 5 in the entire process. (: and 40. (: between. 12. According to the method of claim 11, wherein the knotted fiber material 43 1332045 is treated with a compound of the formula (la) in an amount of 0.05 to 3.0% by weight based on the weight of the textile fiber material ^ 13. A compound mixture comprising: at least one compound of formula (1) Wherein = 1 and R2 are independently of each other hydrogen or unsubstituted or substituted OC8 alkyl, \! and X3 are amine groups, and χ2 and χ4 are groups of the formula -N(R3)R4, wherein the ruler 3 And R4 together with the nitrogen atom to which they are attached form a morpholinyl ring, and hydrazine is hydrogen, an alkali metal or alkaline earth metal or ammonium, and at least one compound of the formula (2): so3m so3m Wherein Re and R7 are independently of each other, oxime, Ci-Cs, or Ci-Ce, or halogen, and the lanthanide is as defined above in formula (1). 44 "32045 U. Mixture according to Clause 13 of the patent application, wherein I and R are hydrogen, and each sulfo group shown in formula (2) is bonded to the ortho position. I5·- is used in textiles A method of fluorescent whitening of a material comprising contacting a textile material with a mixture of compounds of the formulae (1) and (2) as defined in claim 1 of the patent application. 16. According to the method of claim 15 of the patent application, Among them, the woven fabric is polyamide, wool or cotton. ' Pick up, pattern (none) 45