TW200303386A - Process for the treatment of textile fibre materials - Google Patents

Abstract

Detergent compositions comprising at least one compound of formula (1) wherein R1 and R2 are, independently of each other, hydrogen or unsubstituted or substituted C1-C8alkyl, X1, X2, X3 and X4 are, independently of each other, -N(R3)R4 or -OR5, wherein R3 and R4 are hydrogen, cyano, unsubstituted or substituted C1-C8alkyl or C5-C7cycloalkyl, or R3 and R4, together with the nitrogen atom linking them, form a heterocyclic ring, and R5 is unsubstituted or substituted C1-C8alkyl, and M is hydrogen or a cation, together with at least one compound of formula (2) wherein R6 and R7, independently of each other, are hydrogen, C1-C8alkyl, C1-C8alkoxy or halogen, and M is as defined above under formula (1), the novel mixtures of compounds of formulae (1) and (2) and detergent compositions containing compounds embraced by formula (1).

Description

200303386 (ii) Description of the invention The technical field to which the invention belongs The present invention is directed to detergent formulations containing certain fluorescent whitening agents or mixtures of fluorescent whitening agents, and to 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 property, the result of eliminating yellowing is obtained. However, there is still a need to find improved fluorescent whitening agents for this application. It has now been found that a mixture of the compounds of the following formulae (1) and (2), or a compound of the formula (la), has excellent properties in terms of, for example, solubility, cumulative properties, whiteness and light resistance, and has excellent White appearance. Whiteness properties, such as whiteness maintenance, can even be improved by using a mixture of formula (1) with a hydrazone compound or formula (la) in a detergent containing cellulase, protease, amylase or lipase . Advantageous results can be obtained even at low washing temperatures. SUMMARY OF THE INVENTION Accordingly, a first aspect of the present invention is to provide a detergent composition comprising: at least one compound of formula (I): 200303386

In the formula: d and r2 are independently hydrogen or unsubstituted or substituted cr c8 alkyl, and X, X2, X3, and X4 are independently -N (R3) R4 or -〇R5, and their centers And R4 are hydrogen; cyano; unsubstituted or substituted Ci-C8 alkyl or c5-c7 cycloalkyl; or R3 and R4 together with the nitrogen atom to which they are attached form a heterocyclic ring; A substituted or substituted CVC8 alkyl group, and M is hydrogen or a cation, and at least one compound of formula (2): s〇3m so3m where: R6 and R7 are independently hydrogen, CrC8 alkyl, alkoxy Or halogen, and M is as defined above in formula (1). Embodiment 200303386 Within the scope of the above definition, crc8 alkyl may be methyl, ethyl, n- or iso-propyl, n-, second or third butyl, or straight-chain or branched-chain pentyl, hexyl, heptyl Base or octyl. Preferred is cvc4 alkyl. If alkyl is substituted, examples of possible substituents are: hydroxyl, halogen, such as fluorine, chlorine or bromine, sulfo, sulfate, carboxyl and Cpq alkoxy, such as methoxy and ethoxy. 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. Furthermore, excellent substituents are hydroxyl and crc4 alkoxy, especially hydroxyl. These alkyl groups can also be uninterrupted or -0- interrupted (in the case of alkyl groups containing two or more carbon atoms). Examples of c5-c7 cycloalkyl are cyclopentyl and especially cyclohexyl. These groups may be unsubstituted or substituted with, for example, crc4-alkyl, such as methyl. Preferred is the corresponding unsubstituted cycloalkyl. Within the scope of the above definition, crc8 alkoxy may be methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, second butoxy, third butoxy , Or a straight-chain or branched higher alkyl group. Preferred is CP c4-alkoxy, especially methoxy or ethoxy. An excellent one is methoxy. The halogen may be fluorine, chlorine, bromine or iodine, and chlorine is preferred. If R3 and r4 form a heterocyclic ring together with the nitrogen atom, such a ring system may be, for example, a morpholinyl, pyridine, or pyrrolidine ring. The heterocyclic ring may be unsubstituted or substituted. An example of such a substituent is an alkyl group, especially a methyl group. The cation M is preferably an alkali metal atom, an alkaline earth metal atom, ammonium or a cation formed from an amine. Preferred are Na, K, Ca, Mg, ammonium, mono, 10 200303386 di-, tri- or tetra-CrC4 alkylammonium, mono-, di- or tri-c2-c4-hydroxyalkylammonium, or via CrC4-alkyl and c2 -c4-hydroxyalkyl mixtures of di- or tri-substituted ammonium. Excellent is sodium. R and r2 are preferably hydrogen or crc4 alkyl, especially hydrogen. R3 and R4 are preferably: hydrogen; cyano; crc8 courtyard, which is unsubstituted or substituted with hydroxyl, carboxyl, cyano, -CONH2 or phenyl, especially substituted with hydroxyl or carboxyl, and wherein crc8 alkyl Uninterrupted or -0-interrupted; c5-c7 cycloalkyl, especially cyclohexyl, unsubstituted or substituted with CrG alkyl; or 113 and R4 together with the nitrogen atom to which they are attached form an unsubstituted or CrQ An alkyl group is substituted with a molyl group, a purine or a pyrrolidine ring. More preferably, R3 and R4 are hydrogen, unsubstituted or substituted CrC8 alkyl, unsubstituted or substituted Ci-G alkyl cycloalkyl group, or '1 and 114 and The nitrogen atoms linking them together form an unsubstituted or Crc4 alkyl-substituted morphinyl, piperidine, or pyrrolidine ring. Excellent meaning for r3 and R4 is hydrogen, unsubstituted or substituted with hydroxy (^-(: 8 alkyl, or 113 and R4 together with the nitrogen atom connecting them to form an unsubstituted or crc4 alkyl substituted Morpholinyl, benidine, or pyrrolidine ring. The best is unsubstituted or substituted with crc4 alkyl, morpholinyl, pyridyl or pyrrolidine ring, especially morpholinyl, this is through the heart and 1 and The nitrogen atoms connecting them are formed together. Examples of -N (R3) R4 groups are: -NH2, -NHCH3, -NHC2H5, -NH (n-C3H7), -NH (i-C3H7), -NH (i- C4H9), -N (CH3) 2, -N (C2H5) 2, -N (i-C3H7) 2, -NH (CH2CH2OH), -N (CH2CH2OH) 2, · N (ΟΗ2ΟΗ (ΟΗ) αΗ3) 2, -N (CH3) (CH2CH2OH), -N (C2H5) (CH2CH2〇H), -N (i-C3H7) (CH2CH2CH2〇H), -NH (CH2CH (OH) CH3), 200303386 -N (C2H5) ( CH2CH (〇H) CH3), -NH (CH2CH2OCH3), -NH (CH2CH2OCH2CH2〇H), -NH (CH2C〇OH), -NH (CH2CH2COOH), -N (CH3) (CH2COOH), -NH (CN),

NH—CH—COOH

——NH—CH—COOH ch2—c—nh2 〇NH CH2CH2CH2-NH-C—nh2 CH. 1 CH. 1 NH—C—CHr-OH '1 2 —NH—C—CH.CH. 1 2, ChU CH,

Rs is preferably a CrC8 compound, especially a Ci_C4 alkyl group, which is unsubstituted or substituted with a CrC4 alkoxy group or especially a hydroxyl group. Excellent for R5 is methyl or ethyl, especially methyl.

X1, X2, X3 and X4 are preferably groups of the formula -N (R3) R4.

Xi and X3 preferably have the same meaning. In addition, it is preferable that X2 and X4 have the same meaning. Furthermore, it is preferable that the four groups χ !, χ2, x3, and x4 do not have the same meaning. Preferred are compounds of formula (1), wherein 12 200303386 and R2 are hydrogen or a radical; R3 and R4 are: hydrogen; cyano; Crc8 alkyl, which is unsubstituted or substituted by hydroxyl, carboxyl, cyano, c5-c7 cycloalkyl substituted with -c〇NH2 or phenyl in which the crc8 alkyl system is uninterrupted or interrupted, unsubstituted or substituted with a CrC4 alkyl group; or together with the nitrogen atom to which they are attached forms an unsubstituted A morpholinyl, piperidine, or pyrrolidine ring that is substituted or substituted with a Crc4 alkyl group; and a crc8 alkyl group that is unsubstituted or substituted with a hydroxy group. As for R3, R4 and R5, the above preferences apply. Excellent are compounds of formula (1), in which 乂 1 and x3 are amine groups, and X2 and X4 are groups of formula -N (R3) R4, wherein R3 and R4 are: hydrogen; cyano; crc8 alkyl, It is unsubstituted or substituted with a hydroxy or carboxyl group and in which the CrC8 alkyl system is not interrupted or -0- interrupted; cyclohexyl is unsubstituted or substituted with crc4 alkyl; or R3 and R4 are together with the nitrogen atom to which they are attached Forms an unsubstituted or croc4 alkyl-substituted morpholinyl, peridine, or pyrrolidine ring. As for heart and R4, the above preferences apply. Of particular interest are compounds of formula (1), where Xi and x3 are amine groups, and X2 and X4 are groups of formula -N (R3) R4, where 113 and R4 are hydrogen, unsubstituted or substituted with a hydroxy group. CrC8 alkyl, unsubstituted or crc4 alkyl substituted cyclopentyl or cyclohexyl, or 1 and R4 together with the nitrogen atom to which they are attached to form an unsubstituted or crc4 alkyl substituted morpholinyl, morphine Or pyrrolidine ring. The most interesting compounds of formula (1) are those in which 1 and R4 200303386 together with the nitrogen atom to which they are attached form an unsubstituted or alkyl-substituted morpholinyl, eridine, or pyrrolidine ring. As for & and &, the above preferences apply. Further interesting compounds of formula (1) are those of formula (la) given below. R6 and R7 are preferably hydrogen. Each of the sulfo groups shown in formula (2) is preferably bonded to an ortho position. Of interest are compounds of formula (I) in which 1 and 1 ^ 7 are more preferably hydrogen and each sulfo group shown in formula (2) is bonded to an ortho position. M is preferably hydrogen, an alkali metal or an alkaline earth metal or ammonium, especially sodium. In the mixture of the compounds of formula (1) and (2), the molar ratio of the compound of formula (1) to the compound of 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. Excellent are Mohr ratios of 10:90 to 90:10, especially 20:80 to 80:20. The most important is the molar ratio of 30:70 to 70 ... 30, especially 40:60 to 60:40. The compounds of the formulae (1) and (2) are known or can be prepared in a similar manner. The compound of formula (1) can be prepared as follows: Under known reaction conditions, cyanuric chloride is sequentially reacted with 4,4'-diaminostilbene-2,2'-disulfonic acid in any desired order. The acid reacts with amine compounds capable of introducing groups Xi, χ2, χ3, and X4. Preferably, 2 mole cyanuric acid is initially reacted with 1 mole 4,4'-diaminostilbene-2,2'-disulfonic acid, and then the resulting intermediate is reacted with The amine compounds introduced into the groups Xi, X2, X3 and X4 react. For the preparation of compounds in which 乂 1 and 乂 3 have the same meaning and X2 and the same meaning, it is best to make the resulting intermediate first able to introduce 乂! It reacts with amine compounds of X3 200303386, and finally reacts with amine compounds capable of introducing X2 and X4. It is also possible to perform the reaction with the amine compound in one step by reacting the intermediate with the amine compound mixture; in this case, it is usually to obtain the corresponding compound mixture of formula (1). A compound of formula (1) containing a group of formula -OR5 can be prepared, for example, as follows: First, cyanuric chloride is reacted with the corresponding alcohol HOR5, and the resulting product is 4,45-diaminostilbene-2, The 2'-disulfonic acid is reacted, and the intermediate is then reacted with other compounds capable of introducing the remaining groups of Xi, X2, X3 and X4. The last reaction is preferably carried out with the corresponding amine. In addition, the present invention is directed to a mixture of the formula (1) and a hydrazone compound. As for the compounds of the formulae (1) and (2), the preferences given above are applicable. The compound of formula (2) wherein R6 and R7 are hydrogen and each sulfo group shown in formula (2) is bonded to the ortho position is preferred. In such mixtures, the molar ratio of the compound of formula (1) to compound of 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. Excellent are Molar ratios of 10:90 to 90:10, especially 20:80 to 80:20. The most important is 30:70 to 70:30, especially 40:60 to 60:40. The detergent composition used preferably contains: i) 1-70% anionic surfactant and / Or non-ionic surfactants; ii) 0-75% builder; iii) 0-30% peroxide; W) 0-10 peroxide activator; and v) 0.001-5% formula Mixtures of (1) and (2) compounds, 15 200303386 each by weight, based on the total weight of the detergent. More preferably, the detergent composition used comprises: i) 5-70% anionic surfactant and / or non-ionic 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); each Based on weight, based on total detergent weight. In general, a mixture of a compound of formula (I) and a compound of VII is used in an amount of 0.001-5%, especially in an amount of 0.01-5%. An excellent amount is 0.05-5%, especially 0.05 to 2%. In general, 'an amount expressed as a percentage is understood to be a percentage by weight, based on total weight' unless otherwise stated. Detergents can be formulated as solids 'formulated to contain, for example, 5-50' aqueous liquids preferably 10-35% water 'or formulated as non-aqueous liquid detergents' which contain no more than 5, preferably 0_1 wt% Water is based on a suspension of the builder in a non-ionic surfactant 'as described in, for example, GB-A-2158454. The anionic surfactant component may be, for example: alkylbenzene sulfonate, alkyl sulfate, alkyl ether sulfate, bright hydrocarbon sulfonate, alkane sulfonate, fatty acid salt, alkyl or alkyl ether Acid salt or α-sulfo fatty acid salt or an ester thereof. Preferred are: alkylbenzene sulfonates having 10 to 20 carbon atoms in the alkyl group, and 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 with 16 200303386 having 8 to 18 carbon atoms. The average number of ethylene oxide molecules added to the alkyl ether sulfate is preferably from 1 to 20, more 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-COiRqCH'OOM1, where R is an alkyl or alkenyl group having 9-17 carbon atoms in the alkyl group, or an alkenyl group, and R1 is CrC4 Alkyl, and M1 is an alkali metal, especially sodium. Non-ionic surfactant ingredients may be, for example: primary and secondary alcohol ethoxylates, especially C8-C2Q aliphatic alcohols ethoxylated with an average of 1 to 20 moles of ethylene oxide per mole of alcohol, more specifically The C1Q-C15-grade and secondary aliphatic alcohols are ethoxylated with an average of 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers, and polyhydroxyamidamine (glucosamine). The total amount of the anionic surfactant and the nonionic surfactant is preferably 5 to 50% by weight, preferably 5 to 40% by weight, and more preferably 5 to 30% by weight. As for these surfactants, the lower limit is preferably 10% by weight. Builder ingredients can be alkali metal phosphates, especially tripolyphosphates; carbonates or bicarbonates, especially their sodium salts; silicates or disilicates; aluminosilicates; polycarboxylic acids; Polycarboxylic acids; organic phosphonates; or amino poly (alkylene phosphonates); or mixtures of these. Preferred silicates are crystalline layered sodium silicates of the formula NaHSim〇2m + 1.pH20 or Na2Sim〇2m + 1.pH20, where m is a number of 1.9 to 4 and p is 0 to 20. Preferred aluminosilicates are commercially available synthetic materials under the names Zeolites A, B, X and HS, or mixtures of these. Zeolite A is preferred. 17 200303386 Preferred polycarboxylates include: hydroxypolycarboxylates, especially citrates, polyacrylates and their copolymers with maleic anhydride. Preferred polycarboxylic acids include nitrilotriacetic acid and ethylenediaminetetraacetic acid. Preferred organic phosphonates or aminoalkylene poly (alkylene phosphonates) are alkali metal ethane 1-hydroxydiphosphonate, nitrilotrimethylenephosphonate, and ethylenediamine tetra Methylene phosphonate and diethylene triamine penta methylene phosphonate. The amount of the builder is preferably 5 to 70% by weight, preferably 5 to 60% by weight and more preferably 10 to 60% by weight. As for the builder, the lower limit is preferably 15% by weight, especially 20% by weight. Suitable peroxide ingredients include, for example, organic and inorganic peroxides (such as sodium peroxide) known in the literature and commercially available at conventional washing temperatures such as 5 to 95 ° C bleached textile material. In detail, organic peroxides are exemplified by: single or multiple peroxides having an alkyl chain of at least 3, preferably 6 to 20 carbon atoms; in particular, 6 to 12 C atoms Diperoxydicarboxylates, such as diperoxyazelate, diperoxysebacate, diperoxyphthalate, and / or diperoxydodecane diacid, Particularly interested are their corresponding free acid systems. However, it is preferred to use very reactive inorganic peroxides such as persulfate, perborate and / or percarbonate. Of course, it is also possible to use mixtures of organic and / or inorganic peroxides. The peroxide is preferably 0.5 to 30% by weight, preferably 1 to 20% by weight and more preferably M5% by weight. If peroxide is used, the lower limit is preferably 2 18 200303386% by weight, especially 5% by weight. Peroxides, especially inorganic peroxides, are preferably activated by bleaching and the inclusion of activators. Preference is given to such compounds which, under the conditions of hydrogen peroxide hydrolysis, have unsubstituted to substituted or substituted perbenzoic acids and / or peroxycarboxylic acids having 1 to 10 carbon atoms, especially 2 to 4 carbon atoms. Suitable compounds include those which carry a 0- and / or N-fluorenyl group with the number of carbon atoms and / or an unsubstituted or substituted benzamidine group. Preferred are polyfluorenated alkylene diamines, especially tetraethylfluorinated ethylenediamine (TAED), fluorinated glycoluril, especially tetraethylfluorinated glycerol (TAGU), N, N-di Ethylfluorenyl-N, N-dimethyl-urea (DDU), fluorenated tricotyl derivatives, especially 1,5-diethylfluorenyl-2,4-dioxo-1,3, 5-triorphine (DADHT), a compound of the formula

Where R is a sulfonate group, a carboxylic acid group, or a carboxylate group, and where R 'is a linear or branched (C7-C15) alkyl group; and an activator known under the trade names SNOBS, SLOBS, NOBS, and DOBA , Fluorinated polyols, especially triacetin, ethylene glycol diacetate and 2,5-diethylfluorenyloxy-2,5-dihydrofuran, as well as acetylated sorbitol and mannitol and Amidated sugar derivatives, especially pentaethylfluorinated glucose (PAG), sucrose polyacetate (SUPA), pentaethylfluorenyl fructose, tetraethylfluorinated xylose and octaethylfluorinated lactose, and acetylated N-alkylated glucosamine and gluconolactone as needed. The conventional bleaching agent combination disclosed in German patent application DE-A-44 43 177 can also be used. Nitrile compounds which form peroxyimidic acid with peroxides are also suitable as whitening activators. Preferred are tetraethylamidinoethylene diamine and nonamyloxybenzenesulfonic acid 19 200303386. The amount of the bleach activator is preferably 0-10% by weight, and more preferably 0-8% by weight. If a bleach activator is used, the lower limit is preferably 0.5% by 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 or ferritin, or the complexes described in EP-A-0509787. If a bleach catalyst is used, the amount is preferably 0.005 to 2% by weight, more preferably 0.01 to 2% by weight, and especially 0.05 to 2% by weight. An amount of 0.1 to 2% by weight is excellent. As examples of bleach catalysts, the following may be mentioned:-WO-A-95 / 30681 (ie see formula (I) and subsequent definitions on lines 7 to 30 on page 1; especially on page 2 on page 2 The formula given in lines 29 to 11 on line 11 and subsequent definitions). The preferred ligands are those given on page 13 on line 12 to page 26 on line 11. -WO-A-01 / 09276 (see also formulas (1), (2) and (3) and their definitions given on pages 2 and 3). • WO-A-01 / 05925 (ie see formula (1) in the last paragraph on page 1 to the first paragraph on page 2 and its definitions later. The preference for metal complexes may apply, see page 3 in particular (2) and (3) on page 4). -WO-A-02 / 088289 (ie see formula (1) and subsequent definitions on page 2. Preferred preferences for metal complexes are applicable, see in particular the ligands of formula (3), and (Preferences given on page 3, paragraph 4 to page 4, paragraph 7). 20 200303386 Furthermore, the detergent may contain enzymes as needed. Enzymes can be added to detergent detergents. These enzymes often increase the effectiveness of proteins or starch-based stains, such as those caused by blood, milk, forage juice or fruit juices. Preferred enzymes are cellulases, proteases, amylases and lipases. Preferred enzymes are cellulases and proteases, especially proteases. Cellulases are enzymes that act on cellulose and its derivatives and hydrolyze them into glucose, cellobiose, and cellooligosaccharides. Cellulase removes dirt and has a roughening effect. Examples of enzymes to be used include, but are not intended to be limited to the following: 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, column 14, lines 47 to 56; and amylases listed in US-B-6,242,405, column 14, lines 57-64素 酶。 The enzyme. Enzymes can be present in the detergent as needed. When used, the enzyme is usually present in an amount of 0.01 to 5% by weight, preferably 0.05 to 5% and more preferably 0.1 to 4% by weight, based on the total weight of the detergent. Other preferred additives that can be used in the detergents of the present invention are polymers (fixing agents, dye transfer inhibitors) that can inhibit the coloration caused by dyes already released from the fabric under washing conditions during washing in the fabric. Such polymers are preferably polyvinylpyrrolidone, polyvinylimidazole or polyvinylpyridine 21 200303386 N-oxide, which may have been modified by incorporating anionic or cationic substituents, especially having a molecular weight of 5000 to 60 000 , More preferably in the range of 10,000 to 50,000. Such polymers are generally used in an amount of 0.01 to 5% by weight, 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 listed in WO-A-02 / 02865 (see in particular the first paragraph on page 1 and the first paragraph on page 2). The detergents used will usually contain one or more adjuvants, such as soil suspending agents, such as sodium carboxymethyl cellulose; salts for pH adjustment, such as alkali metal or alkaline earth metal silicates; foaming regulators, such as soap; Salts for adjusting spray drying and granulation 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 adjuvants 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. Detergent compositions can take a variety of different physical forms, including powder, granule, nine-tablet, and liquid forms. Examples are conventional powder heavy-duty detergents, compact and ultra-compact heavy-duty detergents, and nine tablets, such as nine-duty heavy-duty detergents. An important physical form is the so-called concentrated particulate form suitable for addition to a washing machine. Also important are the so-called compact (or ultra-compact) detergents. In the field of detergent manufacturing, a trend has recently been developed towards the manufacture of compact detergents containing bulk active substances. In order to minimize energy consumption during the washing program, compact detergents must be efficiently operated at temperatures as low as 40 ° C, or even at room temperature such as 25 ° C. These detergents usually contain only 22 200303386 in low amounts of additives or processing aids such as sodium sulfate or sodium chloride. The amount of this type of ingredient usually accounts for the total weight of the detergent (M0% by weight, preferably 0-5% by weight, especially 0-1% by weight. Such detergents usually have 650-1000 g / l, Good bulk density of 700-1000 g / L and especially 750-1000 g / L. Detergent can also exist in the form of nine tablets. The related features of nine tablets are the ease of dispensing and the convenience of handling. Nine tablets are the most Tightly delivered solid detergents and have a bulk density of, for example, 0.9 to 1.3 kg / liter. To enable rapid disintegration, nine tablets of laundry detergents typically contain special disintegrating agents: Salts / citric acid;-swelling agents, such as cellulose, carboxymethyl cellulose, cross-linked poly (N-vinylpyrrolidone);-fast-dissolving substances, such as sodium (potassium acetate) or sodium (potassium) citrate;-fast-dissolving Water-soluble hard coatings such as dicarboxylic acids. These nine tablets may also contain any combination of the above disintegrants. The detergent may also be formulated as an aqueous liquid containing 5-50, preferably 10-35% water, or Non-aqueous liquid detergent containing not more than 5, preferably 0 to 1% by weight of water. Non-aqueous liquid washing The 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 preferable for dissolving the surfactant, but it may also be used. Polyols, such as those containing 2 to about 6 carbon atoms and 2 to about 6 hydroxyl groups (such as 1,3-propanediol, ethylene glycol, glycerol, and 1,2-propanediol). The composition may contain 5% to 90 %, Typically 10% to 50% of this type of carrier. Detergents can also exist in the so-called "unit liquid dose" form. 23 200303386 This fabric detergent treatment can be manipulated into a domestic treatment in a normal washing machine. Textile fibers may be natural or synthetic fibers or mixtures thereof. Examples of natural fibers include plant fibers, such as cotton, viscose, linen, hemp or linen, preferably cotton, and animal fibers, such as wool, mohair, goat Wool, Angora rabbit hair 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 according to the method of the present invention have a density of less than 200 g / m 2. According to the method, it is generally used in an amount of 0.01 to 3.0% by weight, especially 0.05 to 3.0% by weight, of the textile fiber material. Mixtures of compounds of formulae (1) and (2). This method is usually carried out at a temperature ranging from 5 to 100 ° C, especially 5 to 60QC. Preferably 5 to 40 ° C, especially 5 to 35 ° C and more preferably a temperature range of 5 to 3 ° C. The detergent composition herein is preferably formulated such that during use in an aqueous cleaning operation, the sewage will have a temperature of about 6.5 and about 11, preferably about 7.5 PH between 11. Laundry products are usually at pH 9-11. Techniques for controlling pH to the recommended standard include the use of buffers, bases, acids, etc. and are well known to those skilled in the art. The machine laundry method herein generally involves treating a dirty laundry with a dissolved or suspended effective amount of a washing water solution of the machine laundry detergent composition according to the present invention in a washing machine. An effective amount of a detergent composition means, for example, that 20 to 300 grams of the product is dissolved or dispersed in a wash solution having a volume of 5 to 85 liters of washing 2003200303386, as is typical for typical product dosages used in conventional machine laundry methods. And wash solution volume. Examples are:-Top-mounted vertical axis 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;

-Front-loading 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;-a top-mounted vertical shaft A Japanese-type automatic washing machine 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 solution ratio is preferably from 1: 4 to 1:40, especially from 1: 4 to 1:15. Excellent is 1: 4 to 1: 10, especially 1: 5 to 1: 9. Solution 0 In addition, the present invention is directed to a detergent composition comprising: at least one compound of formula (la):

(1a) where: X and r2 are independently hydrogen or unsubstituted or substituted cr c8 alkyl, 25 200303386

Xi, X2, X3, and X4 are independently -N (R3) R4 or, OR5, where R3 and R4 are hydrogen, fluorenyl, CpC8, "71: radicals are unsubstituted or substituted by a Cyano, -CONH2 or phenyl substituted and the CVc8 alkyl system is not interrupted or -0- interrupted; C5_C7 cycloalkyl is unsubstituted or substituted with CrC4 alkyl; or R3 and R4 together with the nitrogen atom to which they are attached Form an unsubstituted or CrG alkyl substituted morpholinyl, hydrazine, or pyrrolidine ring; R5 is a crc8 alkyl group, which is unsubstituted or substituted with a group, and. M is hydrogen or a cation, and The detergent contains at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase. The meanings and preferences given to the compound of the formula (1) and the substituents' above apply to the compound of the formula (la) and its substituents. The compounds of formula (la) of interest are: wherein R! And R2 are independently hydrogen or unsubstituted or substituted C "C8Chen" Xι, X2, χ3 and 乂 4 are independently -N (R3) R4 or -OR5 ', where 113 and R4 are hydrogen, unsubstituted or substituted with hydroxy8, crc8 alkyl, unsubstituted or substituted with CrC4 alkyl, or C5-C7 cycloalkyl, or R3 and R4 are connected with Together, their nitrogen atoms form an unsubstituted or substituted morpholinyl, piperidine, or pyrrolidine ring, and the center is an unsubstituted or substituted CrC8 alkyl group, and M is hydrogen. Or cationic. Excellent is a corresponding detergent composition containing enzymes and peroxides, peroxide activators, and / or bleach catalysts. Preferred detergent compositions include the following: 26 200303386 i) 70% of anionic and / or non-ionic surfactants; ii) 0-75% builder; iii) 0-30% peroxide; iv) 0-10% peroxide activation V) 0.001-5% of the compound of formula (la); and W) at least one selected from the group consisting of cellulase, protease, amylase, and 0.05-5% Enzymes of the group consisting of lipases. Excellent are detergent compositions comprising: i) 5-70% anionic surfactants and / or non-ionic surfactants; ii) 5-70% Iii) 0.5-30% peroxide; iv) 0.5-10% peroxide activator and / or 0.1-2% bleach catalyst; v) 0.01-5% formula (la) Compounds; and V1) at least one enzyme selected from the group consisting of cellulase, protease, amylase, and lipase at 0.05-5%. As for enzymes, detergents and their components, the definitions and preferences given above All options are applicable. The compound of formula (la) can be used in the same manner as given above for the mixture of compounds of formulas (1) and (2). A further object of the present invention is to provide a method for domestic washing treatment of textile fiber materials, wherein The textile fiber material is in contact with an aqueous solution of a detergent containing the compound of the formula (la) as defined above, and wherein the detergent contains at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase, And in the whole process of the method Solution 27 200303386 The temperature is between 5 ° C and 40 ° C, preferably between 5 ° C and 30 ° C. As for the compound of formula (la) and in terms of detergents and washing methods, the above are given Both definitions and preferences apply. The washing treatment of the above-mentioned textile fibers can also be performed with a mixture of compounds of the formulae (1) and (2). The compounds and mixtures used according to the invention are particularly advantageous in that they not only exhibit extremely high In addition to its whitening ability, in many cases it also exhibits very good water solubility and has excellent white appearance in the solid state. A further advantage of the present invention is that detergent composition delivery improves whiteness performance and fabric feel. In addition, compounds and especially 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 can be used without substantial loss of effectiveness in water washing tanks containing non-ionic detergents such as alkylphenol polyglycol ether Case. Also in the presence of perboric acid or peracid and an activator such as tetraethylfluorenylglycoluril or ethylenediaminetetraacetic acid, the compounds and compound mixtures are stable in both powdered detergents and water wash tanks. In addition, they give a brilliant appearance in daylight. Compounds of formula (1) and mixtures of compounds of formulas (1) and (2) have also been found to be useful in fluorescent whitening of textile materials, in which polyamide, wool and cotton should be specifically isolated. The textile fibers treated according to this embodiment of the invention may be natural or synthetic fibers or mixtures thereof. Examples of natural fibers include plant fibers, such as cotton, viscose silk, linen, hemp, or linen, preferably cotton, and animal fibers, such as wool, mohair, cashmere, Angora 28 200303386 wool and silk, preferably For wool. Synthetic fibers include fibers such as polyester, polyamide, and polyacrylonitrile. The preferred textile fibers are cotton, polyamide, and wool. Preferably, the textile fibers treated according to 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 provided to illustrate the invention; parts and percentages are by weight unless otherwise specified. Preparation Example 1:

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

(102) was mixed with 600 ml of water and heated to a temperature of 6 ° C. Then 9.2 g of 2-ethylaminoethanol was added and the reaction mixture was heated to a temperature of 98 ° C; during the heating, by Add a molar solution of sodium hydroxide in water to maintain the pH between 8.5 and 9. Cool the reaction mixture to 29 200303386 50 ° C and adjust the pH by adding a 6 molar aqueous hydrochloric acid solution Numbers up to 4.5. The precipitate was filtered off, washed with 100 ml of a 10% aqueous sodium chloride solution and dried in vacuum. In this way, 30.5 g of a pale yellow product were obtained. Preparation Examples 2 to 15: Next Formula:

It can be prepared by a method similar to that given in Production Example 1, but replacing 9.2 g of 2-ethylaminoethanol with an equivalent molar amount of the corresponding amine. X is defined in Table 1 below. The compound precipitated after cooling to 50 ° C was isolated directly into the sodium salt without the addition of hydrochloric acid and then dried in vacuo.

Table 1

Example X 2 -N (C, H,) 9 3 〇1 4 -N (CH,) CH? CH, OH 5 V NH 1 6 -NHCH, CH, OH 30 200303386 7 -NHCHpCH.OCH, 8 -NHCH , CH, C〇〇〇 9 -NHCH.CH, 10 -N (CH,) CH? COOH 11 -N (CH, CH9OH), 12 -〇13 I 14 -NHCH.COOH 15 ——NH——CH— C〇〇H NH II ch2ch2ch2-nh-c-nh2

Preparation Example 16:

(103) In a 1 liter flask, add 0.05 mole of the compound of formula:

(104) Mix with 600 ml of water and heat to 60 ° C. Then 9.5 grams of morpholine was added and the reaction mixture was heated to a temperature of 98 ° C; during the heating, the pH was maintained at a number between 31 200303386 8.5 and 9 by adding a 4-mole sodium hydroxide aqueous solution. . The reaction mixture was cooled to 40 ° C, and the precipitate was filtered off, washed with 100 ml of a 10% aqueous sodium chloride solution and dried in vacuo. In this way, 30 g of a pale yellow product are obtained. Preparation Examples 17 to 19: Compounds of the formula:

It can be prepared by a method similar to that given in Production Example 16, but replacing 9.5 g of morpholine with an equivalent molar amount of the corresponding amine. X is defined in Table 2 below. Compounds with high solubility are treated with a 6-mole aqueous solution of hydrochloric acid to adjust the pH to a value of 4.5 before cooling to 50 ° C.

Table 2 Example X 17 -N (CH? CH,) CHpCH? OH 18 I 19 -N (CH? CH, OH), Preparation Example 20: 32 200303386

In a 2 liter flask, 130 ml of methyl ethyl ketone, 80 ml of deionized water, 150 g of ice cubes, and 18.5 g of cyanuric chloride were mixed. During 30 minutes, 185 ml of 4,4'-diaminostilbene-2,2'-disulfonic acid (as disodium salt) in water (concentration 100 g / l) was added dropwise at a temperature of Between ~ 8 and + 5 ° C. The pH was maintained at a number between 4.5 and 5 $ by the addition of an aqueous sodium carbonate solution. A light yellow suspension was obtained. Then, by using the drip solution Gu4, 27.2 g of ethanolamine (99%) was added. The pH increases to a few 値, and then decreases to a lower 値, at which point the temperature increases to 10 to 15 ° C. The reaction mixture was then warmed to a temperature of 45 ° C and held at this temperature for 20 minutes. While heating to 98 ° C within 30 minutes, distill the mixed solution of methyl ethyl ketone and water; maintain the pH between 8.5 and 9 by adding sodium hydroxide aqueous solution. After no further addition of an aqueous sodium hydroxide solution was required to maintain the pH at a fixed number, the reaction mixture was cooled to 50. (:. The pH is adjusted to a number of 5.5, and the pale yellow crystalline precipitate can be filtered off. After drying, 29 g of a pale yellow product is obtained. Preparation Example 21: 33 200303386

In a 1 liter pressure vessel, 0.037 moles of n, N, -bis- (4-morpholin-6-chloro-1,3,5-triphin-2-yl) -4,4, -diamine Stilbene-2,2, -disulfonic acid (as the disodium salt) was suspended in 500 ml of water. 15 g of an aqueous ethylamine solution (70%) was added and the reaction mixture was heated to a temperature of 1000 to 105 ° C, followed by stirring for 4.5 hours. The reaction mixture was cooled to 25 ° C and the precipitate was decanted, washed with 100 ml of a 10% aqueous sodium chloride solution and dried at 70 ° C in vacuo. In this way, 25.8 g of a pale yellow powder was obtained. Preparation Example 22:

(107) A compound of formula (107) can be prepared similarly to the method given in Preparation Example 21, except that a 15 g solution of ethylamine in water (70%) is replaced with a corresponding solution containing an equivalent molar amount of diethylamine. Preparation Example 23 '' 34 (108) (108) 200303386

In a 1 liter flask, 0.05 mol N, N '· bis- (4-morpholinyl-6-chloro-1,3,5-triamine ^ 2-yl) -4,4, diaminodiphenyl Ethylene-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 were added and the reaction mixture was heated to a temperature of 98 ° C. The pH was maintained at a number between 8.5 and 9 by the addition of a 4-mole-concentrated aqueous sodium hydroxide solution. The reaction mixture was cooled to 25 ° C and 10 vol% sodium chloride was added. The precipitate was filtered off, washed with 100 ml of a 10% aqueous sodium chloride solution and dried in vacuo at 70 ° C. In this way, 41.8 g of pale yellow powder was obtained. Application Example 1: General procedure: Prepare a lotion by dissolving 0.8 g of washing powder in 200 ml of tap water. 10 grams of bleached cotton fabric was added to the bath and washed at 40 ° C for 15 minutes, then rinsed, dried and ironed at 160 ° C. The following laundry powders A and B were used (the amounts given in tables 3a and 3b below are in grams): Table 3a (components of laundry powder A and B) AB sodium laurylbenzenesulfonate (LAS) 10 g 10 g 35 200303386 Sodium lauryl ether sulfate (AES) 3 g 3 g Dobanol 23-6.5 (non-ionic ethoxylated alcohol) 4 g 4 g sodium tripolyphosphate 30 g zeolite A 20 g sodium carbonate 15 g 15 g silicic acid Sodium 5g 5g Sodium sulfate 11g 17g Cellulase 1.5g Protease 1.5g Polycarboxylate (co-builder) 4g Carboxymethylcellulose 2g 2g Perfume 0.1 g 0.1 g Water 5 5 grams of fluorescent brightener or fluorescent brightener mixture used X grams X grams

Table 3b (Washing powder used) Amount of fluorescent whitening agent or mixture of fluorescent whitening agents Washing powder Preparation of the compound of Example 1 0.2 g A Preparation of the compound of Example 0 · ΐg B Preparation of the example 3 0.3 g of compound A 0.2 g of compound of production example 4 0.4 g of compound of example 5 0.4 g of compound of preparation 12 0.15 g of compound of preparation 13 0.1 g of compound of preparation 13 0.3 g of compound of preparation 16 B Preparation Example 6 Mixture of Compound of Formula (109) and Compound of Formula (109) [7: 3 weight ratio] 0.2 g A Preparation Mixture of Compound of Example 12 and Compound of Formula (109) [7: 3 weight ratio] 0.4 g B Preparation Example A mixture of 14 compound and compound of formula (109) [7: 3 weight ratio] 0.3 g A Preparation Example 17 compound of compound with formula (109) [1: 1 weight ratio] 0.2 g B Preparation Example 18 compound with formula (109) A mixture of compounds [1: 2 weight ratio] 0.5 g of B A compound of Preparation Example 1 and a compound of formula (109) [1: 5 weight ratio] 0.3 g of B A compound of preparation example 2 and a compound of formula (109) The mixture [5 : 1 weight ratio] 0.2 g B Preparation Example 3 compound and compound of formula (109) [1: 1 weight ratio] 0.2 g B Preparation Example 20 compound and compound of formula (109) [3: 7 weight ratio 〇 · 1g A 36 200303386

Preparation Example 21: A mixture of a compound of the formula (109) and a compound of the formula (109) [1: 9 weight ratio] 0.1 g B Preparation Example 22: A mixture of a compound of the formula (109) and the compound of formula (109) [9: 1 weight ratio] 0.2 g B Example 23 A mixture of a compound of formula (109) and a compound of formula (109) [1: 1 weight ratio] 0.4 g B A mixture of a compound of formula (11 〇) and a compound of formula (109) [1: 1 weight ratio] 0.3 g of a compound of formula (109) Structure:

(109) (110)

Cotton fabrics washed according to the general procedure with the detergents 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. 10 grams of bleached cotton fabric was added to the bath and washed at 30 ° C for 15 minutes, then rinsed, dried and ironed at 160 ° C. Use the following laundry powder (the amounts given in Tables 4a and 4b below are weight percents 37 200303386, based on the total weight of the detergent) Table 4a (components of laundry powder C and D) CD Sodium Laurylbenzene Sulfonate ( LAS) 8% 8% sodium lauryl ether sulfate (AES) 3% 3% Dobanol 23-6.5 (non-ionic ethoxylated alcohol) 5% 5% zeolite A 20% 20% polycarboxylate (co-builder) 5% 5% soda ash 18% 18% sodium silicate 4% 4% sodium sulfate 5% 5% hydroxyethane diphosphonic acid (combination agent) 0.5% 0.5% cellulase 1.5% protease 1.5% carboxymethyl cellulose 1% 1% Sodium perborate monohydrate 15% 15% TAED 5% 5% Soap 2% 2% The fluorescent brightener or fluorescent brightener mixture used X% X% In each of the above detergents, Use enough water to get 100%. Table 4b (Washing powder used)

Amount of fluorescent whitening agent or mixture of fluorescent whitening agents Washing powder Preparation of the compound of Example 1 0.2% C Preparation of the compound of Example 3 0.2% C Preparation of the compound of Example 7 0.2% D Preparation of the compound of Example δ 0.2 % C Compound of Preparation Example 0.4% C Compound of Preparation Example 10 0.2% C Compound of Preparation Example 11 0.2% C Compound of Preparation Example 0.4% C Compound of Preparation Example 0.5% C Formula (110 ) Compound 0.3% D Preparation Example 1 mixture of compound of formula (109) [10: 1 weight ratio 102% D Preparation Example 3 compound of compound of formula (109) [5: 1 weight ratio] 0.4% C 38 200303386

Mixture of the compound of the preparation example 5 and the compound of the formula (109) [1: 5 weight ratio] 0.15% C Preparation mixture of the compound of the preparation example 11 and the compound of formula (109) [1: 1 weight ratio] 0.2% C Preparation Example 15 Mixture of compound and compound of formula (109) [1: 9 weight ratio] 0.4% C Preparation Example 16 compound of compound and formula (109) mixture [9: 1 weight ratio] 0.3% D Preparation Example 19 compound and formula ( 109) Mixture of compounds [1: 5 weight ratio] 0.2% D As for the structure of the compounds of formulae (109) and (110), see Application Example 1 Cotton fabrics washed with the detergents listed in Table 4b according to the general procedure are shown Good whiteness properties. 39

Claims (1)

200303386 Patent application patent 1. A detergent composition comprising: at least one compound of formula (1): In the formula: 1 ^ and R2 are each independently hydrogen or unsubstituted or substituted cr c8 alkyl, Xi, x2, x3, and x4 are independently -n (r3) r4 or -〇 center, where 1 and R4 are hydrogen; cyano; unsubstituted or substituted CrG alkyl or c5-c7 cycloalkyl; or R3 and R4 together with the nitrogen atom to which they are attached form a heterocyclic ring; and r5 is unsubstituted A substituted or substituted crc8 alkyl group, and M is hydrogen or a cation, and at least one compound of formula (2): In the formula: r6 and r7 are independently of each other hydrogen, c "c8 alkyl, c" c8 alkoxy or halogen, and M is as defined above in formula (1). 200303386 2. According to the scope of patent application The composition of item 1, whose center and R2 are hydrogen or C, C4 alkyl, I and R4 are hydrogen; cyano; CrC8 alkyl, which is unsubstituted or substituted by hydroxyl, carboxyl, cyano, _conh2 or benzene Radicals where crc8 alkyl is uninterrupted or interrupted by -cu; unsubstituted or C5-C7 cycloalkyl substituted with Crc4 alkyl; or r3 and R4 together with the nitrogen atom to which they are attached form an unsubstituted or An alkyl group is substituted by a morpholinyl, eridine, or pyrrolidine ring; and 115 is a C ^ -Cs alkyl group, which is unsubstituted or substituted with a hydroxyl group. 3. Composition according to item 1 or 2 of the scope of patent application X !, X2, and X4 are groups of the formula -N (R3) R4. 4. The composition according to item 1 or 2 of the scope of the patent application, wherein χβα X3 is an amine group, X2 and X4 are formula- A group of N (R3) R4, in which 113 and R4 are hydrogen; cyano; c "c8 alkyl, which is unsubstituted or substituted with a hydroxyl or carboxyl group, and wherein CrCs alkyl is not interrupted Interrupted by -0-; unsubstituted or cyclohexyl substituted with d-alkyl; or 113 and R4 together with the nitrogen atom to which they are attached form an unsubstituted or substituted with cvc4 alkyl, hydrazone Or a pyrrolidine ring. 5. The composition according to item 4 of the scope of the patent application, wherein R3 and R4 together with the nitrogen atom to which they are attached form an unsubstituted or CrC4 alkyl-substituted morpholinyl, morphinyl, or pyrrole Alkanes, preferably morpholinyl rings. 6. The composition according to item 1 or 2 of the scope of patent application, in which 200303386, 6 and R7 are hydrogen, and each of the sulfo linkages in Formula (2) 75 On the adjacent position 07. The composition according to item 1 or 2 of the scope of the patent application, where M is chlorine, metal or soil test metal or money, preferably sodium. 8 · According to item 1 or 2 of the scope of patent application A composition comprising: i) 1-70% anionic surfactant and / or non-ionic surfactant; ii) 0-75% builder; iii) 0-30% peroxide; iv ) 0-10% peroxide activator; and v) 0.001-5% of a mixture of compounds of formula (1) and (2). 9 · According to the patent application The composition of item 8, comprising: i) 5-70% anionic surfactant and / or non-ionic 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). 10. 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. 11. A detergent composition ' comprising: at least one compound of formula (la): 42 200303386 (1a) In the formula: 1 and R2 are independently hydrogen or unsubstituted or substituted Cr c8 alkyl, x !, \, X3, and X4 are independently -N (R3) R4 or -〇1, where R3 and R4 are hydrogen; cyano; Cl_C8 alkyl, which is unsubstituted or substituted by hydroxyl, end, Cyano, _C0NH2 or phenyl substituted and in which the CrC8 alkyl system is uninterrupted or interrupted; C5-C7 cycloalkyl, unsubstituted or substituted with Crc4 alkyl; or D ^ and 1 ^ 4 together with the nitrogen atom to which they are attached Forms an unsubstituted or substituted morpholinyl, piperidine, or pyrrolidine ring; 115 is crc8 alkyl, which is unsubstituted or substituted with a hydroxy group, and M is hydrogen or cation, and the detergent contains at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase. 12. The composition according to item Π of the scope of the patent application, wherein Xi, χ2, X3, and X4 are groups of the formula -N (R3) R4. 13. The composition according to any one of items II and 12 of the scope of patent application, wherein Xi and X3 are amine groups, X2 and X4 are groups of formula -N (R3) R4, wherein R3 and I are hydrogen; Cyan 43 200303386 group or crc8 alkyl group, which is unsubstituted or substituted with hydroxy or carboxyl group, and wherein c "c8 alkyl group is not interrupted or interrupted by -0-; unsubstituted or via (^-(: 4 alkyl Substituted cyclohexyl; or R4 and R4 together with the nitrogen atom to which they are attached form an unsubstituted or crc4 alkyl substituted morpholinyl, pyridyl, or pyrrolidine ring, and M is hydrogen, an alkali metal, or an alkaline earth metal Or ammonium, preferably sodium. 14. The composition according to item 13 of the application, wherein R3 and R4 together with the nitrogen atom to which they are attached form an unsubstituted or alkyl-substituted morpholinyl, thioline, or A pyrrolidine ring, preferably a molybdenum ring. 15. The composition according to any one of items 11 and 12 of the scope of patent application, wherein the composition comprises a peroxide, a peroxide activator and / or a bleach Catalyst 16. The composition according to any one of claims 11 and 12 of the scope of patent application, which comprises: i) l-70% anionic surfactant and / or non-ionic surfactant; ii) 0-75% builder; iii) 0-30% peroxide; iv) (M0% peroxide Activator; v) 0.001-5% compound of formula (la); and V1) 0.05-5% at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase. 17. A composition according to any one of claims 11 and 12 of the scope of patent application, which contains = 200303386 i) 5-70% anionic surfactant and / or non-ionic 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% compound of formula (la); and vi) 0.05-5% at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase. 18. The composition according to any one of claims 11 and 12, wherein the enzyme is a protease enzyme. 19. A method for domestic washing treatment of textile fiber material, wherein the textile fiber material is contacted with an aqueous detergent solution containing a compound of the formula: In the formula: Ri and R2 are independently of each other hydrogen or unsubstituted or substituted Cr c8 alkyl, Λ X2, X3 and X4 are independently of each other -N (R3) R4 or -〇115, where R3 and r4 is hydrogen; cyano; crc8 alkyl, which is unsubstituted or substituted with hydroxy, carboxy, cyano, _CONH2 or phenyl and wherein ei_C8 alkyl is not interrupted or -0- interrupted; unsubstituted Or a c5-c7 alkyl group substituted with a κ4 alkyl group; or together with the nitrogen atom to which they are attached forms an un45 200303386 substituted or substituted with a cvc4 alkyl group, a pyridine, or a pyrrolidine ring; 1 Is a C8 alkyl group, which is unsubstituted or substituted with a hydroxyl group, and ^ M is hydrogen or a cation, and wherein the detergent contains at least one member selected from the group consisting of cellulase, protease, amylase, and lipase Group of enzymes, and wherein the temperature of the solution is between 5 ° C and 40 in the whole method. (:, Preferably between 5 ° C and 30 ° C. 20. According to item 19 of the scope of patent application Method, wherein X !, X2, X3 and X4 are groups of the formula -N (R3) R42. 21. According to any one of the items 19 and 20 of the scope of patent application Where X and Xs are amine groups, x2 and x4 are groups of the formula -N (R3) R4, where R3 and R4 are hydrogen; cyano or crc8 alkyl, which is unsubstituted or substituted with a hydroxyl or carboxyl group, And in which the alkyl group is uninterrupted or interrupted by -0-; unsubstituted or cyclohexyl substituted by (^ -alkyl); or 113 and R4 form an unsubstituted or CrC4 Substituted morpholinyl, pyridinyl or pyrrolidine ring, and M is hydrogen, alkali metal or alkaline earth metal or ammonium, preferably sodium. 22. The method according to item 21 of the application, wherein R3 and R4 and The nitrogen atoms linking them together form an unsubstituted or CrC4 alkyl substituted morpholinyl, pyridinyl or pyrrolidine ring, preferably a morpholinyl ring. 23. According to any of claims 19 and 20 of the scope of the patent application One method, 46 200303386, wherein the textile fiber material is treated with a compound of formula (la) which accounts for 0.05 to 3.0% by weight of the textile fiber material. 24. A compound mixture comprising: at least one compound of formula (1) In the formula: X and R2 are independently hydrogen or unsubstituted or substituted Cr C8 alkyl, and X, X2, X3 and X4 are independently -N (R3) R4 or -〇r5, where R3 And R4 are hydrogen; cyano; unsubstituted or substituted CrC8 alkyl or C5-C7 cycloalkyl; or R3 and dagger together with the nitrogen atom to which they are attached form a heterocyclic ring; and R5 is unsubstituted Or substituted CrCs alkyl, and M is hydrogen or a cation, and at least one compound of formula VII: In the formula: 47 200303386 r6 and r7 are independently hydrogen, crc8 alkyl, crc8 alkoxy, or halogen, and M is as defined above in formula (1). 25. The mixture according to item 24 of the scope of patent application, wherein 1 and R2 are hydrogen or eve #, and R3 and R4 are hydrogen; cyano; Ci-Cs alkyl, which is unsubstituted or substituted by hydroxyl, carboxy, Cyano, -connh2 or phenyl substituted in which the crc8 alkyl system is not interrupted or interrupted by -0; unsubstituted or CrC4 alkyl substituted c5-C7 cycloalkyl; or R3 and R4 are connected to them The nitrogen atoms together form an unsubstituted or crc4 alkyl substituted or substituted group, eridine or pyrrolidine ring: and 1 is a crc8 alkyl group, which is unsubstituted or substituted with a hydroxyl group. 26. A mixture according to any one of claims 24 and 25 of the scope of patent application, wherein Xi, X2, X3 and X4 are groups of the formula -N (R3) R42. 27. A mixture according to any one of items 24 and 25 of the scope of patent application, wherein Xi and 乂 3 are amine groups, 乂 2 and X4 are groups of the formula -N (R3) R4, wherein R3 and R4 are hydrogen; Cyano or CrC8 alkyl, which is unsubstituted or substituted with a hydroxy or carboxyl group, and wherein CrC8 alkyl is not interrupted or interrupted by -0-; unsubstituted or cyclohexyl substituted by (^ -alkyl); Alternatively, 1 and R4 together with the nitrogen atom to which they are attached form an unsubstituted or CrC4 alkyl-substituted morpholinyl, morphinyl, or pyrrole ring. 28. A mixture according to item 27 of the scope of patent application, of which 48 200303386 1 And R4 together with the nitrogen atom to which they are attached form an unsubstituted or CrG alkyl substituted morpholinyl, eridine or pyrrolidine ring, preferably a morpholinyl ring. 29. According to the scope of application for patents No. 24 and A mixture of any one of 25 items, in which R6 and R7 are hydrogen, and each sulfo group shown in formula (I) is bonded to the ortho position. 30. According to any one of the items 24 and 25 of the scope of patent application A mixture, wherein M is hydrogen, an alkali metal or an alkaline earth metal or ammonium, preferably sodium. 31.-for spinning A method for fluorescent whitening a woven material, comprising contacting a textile material with a mixture of compounds of formulas (1) and (2) as defined in item 1 of the scope of the patent application. 32. Method according to item 31 of the scope of patent application , Wherein the textile material is polyamide, wool or cotton. Pick up, diagram (none) 49 200303386 Lu, (a), the designated representative of the case is: (none) (b), the representative symbol of the representative diagram is briefly explained: 柒, if there is a chemical formula in this case, please Reveal the chemical formula that best characterizes the invention: 6