TW200303358A - Process for the treatment of textile fibre materials - Google Patents

Abstract

A detergent composition comprising at least one compound of formula 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; C1-C8alkyl which is unsubstituted or substituted by hydroxy, carboxy, cyano, -CONH2 or phenyl and wherein the C1-C8alkyl group is uninterrupted or interrupted by -O-; unsubstituted or C1-C4alkyl-substituted C5-C7cycloalkyl; or R3 and R4, together with the nitrogen atom linking them, form an unsubstituted or C1-C4alkyl-substituted morpholino, piperidine or pyrrolidine ring; R5 is C1-C8alkyl which is unsubstitued or substituted by hydroxy, and M is hydrogen or a cation, and wherein the detergent contains a peroxide, a peroxide activator and/or a bleaching catalyst.

Description

200303358 (ii) Description of the invention Field of the invention The present invention is directed to detergent formulations containing certain fluorescent whitening agents and peroxides, peroxide activators and / or bleach catalysts. 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 the compound of the following formula (1) has excellent properties in terms of, for example, solubility, cumulative properties, degree of whiteness, light resistance, and the like, and has an excellent white state in a solid state. Whiteness properties, such as whiteness maintenance, can even be improved by using compounds of formula (1) in detergents containing peroxides, peroxide activators and / or bleach catalysts. 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 (1):

200303358 R and R2 are independently hydrogen or unsubstituted or substituted cr c 8 fluorenyl, and X, x2, x3 and x4 are independently -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 Ci-Cs alkyl is not interrupted or -0- interrupted; C5-C7 cycloalkyl substituted or crc4 alkyl substituted; or R3 and R4 together with the nitrogen atom to which they are attached form an unsubstituted or cvc4 alkyl substituted morpholinyl, amidin or pyrrolidine ring 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 a peroxide, a peroxide activator, and / or a bleach catalyst. Embodiments are defined above Within the range, crc8 alkyl may be methyl, ethyl, n- or iso-propyl, n-, second or third butyl, or straight-chain or branched-chain pentyl, hexyl, heptyl or octyl. The preferred is CrC4 alkyl. If the alkyl group given to Ri and R2 is substituted, examples of possible substituents are: hydroxyl, halogen, such as fluorine , Chlorine or bromine, sulfo, sulfate, carboxyl, and Ci-G alkoxy, such as methoxy and ethoxy. Other substituents of this type of alkyl group are, for example: cyano, -CONH2 and benzene Preferred substituents are hydroxy, carboxyl, cyano, -CONH2 and phenyl, especially hydroxy and carboxyl. Furthermore, excellent substituents are hydroxy and crc4 alkoxy, especially hydroxy. These alkyl groups It can also be uninterrupted or -0-interrupted (in the case of alkyl groups containing two or more carbon atoms 200303358). Examples of c5-c7 cycloalkyl are cyclopentyl and especially cyclohexyl. These groups The group may be substituted with a crc4-alkyl group such as methyl. Preferred is a corresponding unsubstituted cycloalkyl group. Within the above definition, Ci-C # alkyl group may be methyl, ethyl, n- or isopropyl Radical, n-, second or third butyl, especially methyl. If R3 and R4 together with the nitrogen atom form a morpholinyl, pimidine or p-pyrrolidine ring, this ring system may be unsubstituted or Substituted by alkyl, especially methyl. Preferred is unsubstituted ring system. Cationic M is preferably alkali metal atom, alkaline earth metal atom, ammonium A cation formed from an amine. Preferred are Na, K, Ca, Mg, Qian, mono, di, tri or tetra CrC4 alkyl ammonium, mono, di or tri C2-C4-hydroxyalkyl ammonium, or CrC4 -A mixture of an alkyl group and a C2-C4-hydroxyalkyl group, a di- or tri-substituted ammonium. The most preferred is sodium. R and R 2 are preferably hydrogen or crc 4 alkyl, especially hydrogen. R 3 and R 4 are preferably: hydrogen ; Cyano; Ci-Cs alkyl, which is unsubstituted or substituted with hydroxy, carboxy, cyano, -CONH2 or phenyl, especially with hydroxy or fluorenyl, and where the crc8 alkyl system is not interrupted or- 〇-discontinued; c5-c7 cycloalkyl, especially cyclohexyl, unsubstituted or substituted with crc4 alkyl; or R3 and R4 together with the nitrogen atom to which they are attached form an unsubstituted or crc4 alkyl substituted A phosphono, piperidine, or pyrrolidine ring. More preferably, r3 and r4 are hydrogen, crc8 alkyl unsubstituted or substituted with hydroxy, c5-c7 cycloalkyl unsubstituted or substituted with crc4 alkyl, or R3 and R4 and the nitrogen to which they are attached The atoms together form an unsubstituted 200303358 or substituted by a cvc: 4k group, a molyl group, a pyridinyl group, or a pyrrolidine ring. Excellent meaning for & and R4 is hydrogen, unsubstituted or hydroxy-substituted q-Q alkyl, or R3 and R4 together with the nitrogen atom to which they are attached form an unsubstituted or CrC4 alkyl substituted Modyl, piperidine or pyrrolidine ring. The most preferred are morpholinyl, pyridinyl, or pyrrolidine rings, especially morphyl, which are unsubstituted or substituted with C4c4 alkyl, which are formed by the combination of: and ^ with the nitrogen atom to which they are attached. Examples of N (R3) R4 groups are: -NH2, -NHCH3, -NHC2H5, -NH (n-C3H7), -NH (i-C3H7), -NH (i-C4H9), · N (ΟΗ3) 2 , -N (C2H5) 2, -N (Bu C3H7) 2, NH (CH2CH2OH), -N (CH2CH2OH) 2, · N (αΗ2ΟΗ (ΟΗ) ΟΗ3) 2, N (CH3) (CH2CH2OH), _N (C2H5 ) (CH2CH2OH), _N (i_C3H7) (CH2CH2CH2OH), -NH (CH2CH (OH) CH3), -N (C2H5) (CH2CH (OH) CH3), -NH (CH2CH2OCH3), -NH (CH2CH2〇CH2CH2OH), -NH (CH2COOH), -NH (CH2CH2COOH), -N (CH3) (CH2COOH), -NH (CN),

10 200303358

——NH-CH-COOH

—-NH—CH—COOH CHj—〇—NH2 〇

NH

II ch2ch2ch2-nh-c-nh2 R5 is preferably a CrC8 alkyl group, especially a C "C4 alkyl group, which is unsubstituted or substituted with a hydroxyl group. For R5, methyl or ethyl, especially fluorenyl .

Xi, X2, X3 and X4 are preferably groups of the formula -N (R3) R4. X, and X3 are preferably the same. In addition, it is preferable that X2 and X4 have the same meaning. Furthermore, it is preferred that the four groups X :, X2, Y3 and X4 do not have the same meaning. Preferred is a compound of formula (1), in which h and R2 are hydrogen or CrC4 alkyl, R3 and R4 are hydrogen, amino, C ^ -Cg fluorenyl 'which is unsubstituted or substituted by hydroxyl, carboxyl, cyano , -Conh2 or phenyl substituted and wherein Cl_c8 alkyl is not interrupted or -0- interrupted; c5-c7 cycloalkyl is unsubstituted or substituted with crc4 alkyl; or R3 and R4 are together with the nitrogen atom to which they are attached To form an unsubstituted or substituted crc4 alkyl group, piperidinyl, or sulfonyl ring; and r5 is crc8 alkyl, which is unsubstituted or substituted with a hydroxy group. As for R3, 114 and R5, the above preferences apply. Excellent is the compound of formula (1), of which 11 200303358 乂! And X3 are amine groups, and 乂 2 and x4 are groups of the formula -N (R3) R4, where r3 and r4 are: hydrogen; cyano; crcs alkyl, which is unsubstituted or substituted with hydroxyl or carboxyl and Wherein the alkyl group is uninterrupted or interrupted by -0-; unsubstituted or cyclohexyl substituted with (^ "alkyl; or 113 and R4 together with the nitrogen atom to which they are attached form an unsubstituted or c" c4 Alkyl substituted morpholinyl, piperidine, or pyrrolidine rings. As for R3 and R4, the above preferences are applicable. Of particular interest are compounds of formula (1), where Xi and χ3 are amine groups, and X2 And X4 is a group of the formula -N (R3) R4, wherein r3 and r4 are hydrogen, unsubstituted or hydroxy substituted CrC8 alkyl, unsubstituted or substituted with crC4 alkyl, cyclopentyl or cyclohexyl, Or R4 and R4, together with the nitrogen atom to which they are attached, form an unsubstituted or substituted pyridine, pyridinyl, or pyrrolidine ring. The most interesting compounds of formula (1) are 113 and r4 together with the nitrogen atom to which they are attached forms an unsubstituted or (^ -alkylidene-substituted morpholinyl, a pyridine, or a pyrrolidine ring. As for R3 and R4, the above preferences are applicable. The compound of formula (1) is known or can be prepared in a similar manner. The compound of formula (1) can be prepared as follows: under known reaction conditions, cyanuric acid Chlorine reacts sequentially with 4,4'-diaminostilbene diphenylene-2,2'-disulfonic acid and amine compounds capable of introducing the groups Xi, x2, x3 and X4, in any desired order. Preferably, 2 mol cyanuric acid is initially reacted with 1 mol 4,4'-diaminostilbene diphenylene-2,2'-disulfonic acid, and then the obtained intermediate is subjected to arbitrary The sequence is reacted with an amine compound 12 200303358 capable of introducing the groups X :, X2, X3 and X4. For the preparation of compounds in which 乂: and 乂 3 have the same meaning and X2 and X4 have the same meaning, it is best to make The resulting intermediate is first reacted with an amine compound capable of introducing fluorene 1 and x3, and finally with an amine compound capable of introducing x2 and x4. It is also possible to react the intermediate with a mixture of amine compounds in one step The reaction with the amine compound is carried out in this case; in this case, the corresponding formula (1) is usually obtained 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 reacted with 4,4'-diamine groups. Diphenylethylene-2,2'-disulfonic acid is reacted, and then the intermediate is reacted with other compounds capable of introducing the remaining groups of Xi, X2, X3 and X4. The last reaction is preferably performed with the corresponding amine. The detergent composition used preferably comprises: i) 1-70% anionic surfactant and / or non-ionic surfactant, ii) 0-75% builder, iii) 0.5-30% peroxide Iv) 0.5-10% peroxide activator and / or 0.1-2% bleach catalyst; v) 0.001-5% compound of formula (1); and vi) at least one selected from 0-5% Enzymes in a group of cellulase, protease, amylase and lipase. More preferably, the detergent composition used comprises: i) 5-70% anionic surfactant and / or non-ionic surfactant 13 200303358 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 (1); and vi) 0.05-5% At least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase. Generally speaking, the compound of formula (1) is used in an amount of 0.001-5%, especially 0.01-5%. An excellent amount is 0.05-5%, especially 0.05 to 2%. Generally speaking, amounts expressed as percentages should be understood as percentages by weight, based on total weight, unless otherwise stated. The detergent can be formulated into a solid, an aqueous liquid containing, for example, 5-50, preferably 10-35% water, or a non-aqueous liquid detergent, which contains no more than 5, preferably 0-1% by weight Water is based on a suspension of the builder in a non-ionic surfactant, as described, for example, in GB-A-2158454. The anionic surfactant component may be, for example, an alkylbenzene sulfonate, an alkyl sulfate, an alkyl ether sulfate, an olefin sulfonate, an alkane sulfonate, a fatty acid salt, an alkyl or an alkenyl ether sulfonate, or Alpha-sulfo fatty acid salts or esters thereof. Preferred are: alkylbenzene sulfonates having 10 to 20 carbon atoms in the alkyl group, alkyl sulfates having 8 to 18 carbon atoms, and ether ether sulfates having 8 to 18 carbon atoms' And fatty acid salts derived from palm oil or tallow with ^ to 18 carbon atoms. The average number of ethylene oxide molecules added to the alkyl ether sulfate is preferably 1 to 20, and more preferably 1 to 10. These 200303358 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-CCKROCI ^ COOM1, where R is an alkyl or alkenyl group having 9-17 carbon atoms in the alkyl group, or an alkenyl group, and R1 is C "C4 alkyl, and M1 is an alkali metal, especially sodium. Non-ionic surfactant components can be, for example, primary and secondary alcohol ethoxylates, especially 1 to 20 moles of ethylene oxide per mole of alcohol. Alkyl ethoxylated C8-C2 () aliphatic alcohols, more particularly C1Q-C15-grade and secondary aliphatic alcohols ethoxylated with an average of 1 to 10 mol ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers, and polyhydroxyamidamine (glucosamine). The total amount of anionic surfactant and nonionic surfactant is preferably 5- 50% by weight, preferably 5-40% by weight and more preferably 5-30% by weight. As for these surfactants, the lower limit is preferably 10% by weight. The builder component may be an alkali metal phosphate, especially Tripolyphosphate; carbonate or bicarbonate, especially its sodium salt; silicate or disilicate; aluminosilicate; polycarboxylic acid salt; polycarboxylic acid; Phosphonates; or aminoalkyl poly (alkylene phosphonates); or mixtures of these. Preferred silicates are crystalline layers of the formula NaHSim02m + 1.pH20 or Na2Sim〇2m + 1.pH20. Sodium silicate, where M is a number of 1.9 to 4 and ρ is 0 to 20. Preferred aluminosilicates are commercially available synthetic materials named zeolites A, B, X and HS, or a mixture of these Zeolite A is preferred. Preferred polycarboxylic acid salts include: hydroxy polycarboxylic acid salts, especially citrates, polyacrylates, and their copolymers with maleic anhydride. 15 200303358 Preferred polycarboxylic acids Including nitrilotriacetic acid and ethylenediaminetetraacetic acid. Preferred organic phosphonates or aminoalkylene poly (alkylene phosphonates) are alkali metal ethane 1-hydroxydiphosphonates, nitrites The amount of methyltrimethylenephosphonate, diethylenediaminetetramethylenephosphonate and diethylenetriaminepentamethylenephosphonate 0 ΓΤΤΪ ′ builder is preferably 5-70% 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. Appropriate Peroxide components, for example, include 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 for bleaching Textile materials. In detail, organic peroxides are, for example: single or multiple peroxides having an alkyl chain of at least 3, preferably 6 to 20 carbon atoms; in particular, 6 to 12 C atom diperoxydicarboxylates, such as diperoxyperazelaate, diperoxypersebacate, diperoxyphthalate, and / or diperoxydodecane di Acid salts, especially their corresponding free acids, are of particular interest. However, it is best to use very reactive inorganic peroxides, such as persulfates, 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 1 to 15% by weight. If peroxide is used, the lower limit is preferably 2% by weight, especially 5% by weight. Peroxides, especially inorganic peroxides, are preferably activated by the inclusion of a bleaching agent. Preferred are compounds which produce unsubstituted or substituted perbenzoic acid and / or peroxycarboxylic acid having 1 to 10 carbon atoms, especially 2 to 4 carbon atoms under the conditions of hydrogen peroxide hydrolysis. Suitable compounds include those which carry a 0- and / or N-fluorenyl group having such a carbon number and / or an unsubstituted or substituted benzamidine group. Preferred are polyfluorenated alkylene diamines, especially tetraethylfluorinated ethylenediamine (TAED), fluorinated glycolurils, especially tetraethylfluorenyl glycoluril (TAGU), N, N-di Acetyl-N, N-dimethyl-o- (DDU), fluorenated triphine derivatives, especially 1,5-diethylfluorenyl-2,4 · dioxo-1,3, 5-three ploughing (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 tetraethylamidinoethylenediamine and nonanoyloxybenzenesulfonate. The amount of bleach activator is preferably 0-10% by weight, and more preferably 0-8% by weight 17 200303358%. 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 (see also formula VII and subsequent definitions on lines 7 to 30 on page 1; especially on page 2 on line 29 To the formula (I) and its definition given on line 11 on page 11). 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 subsequent definitions given on pages 2 and 3). -WO-A-01 / 05925 (ie see formula (1) and subsequent definitions on the last paragraph of page 1 to the first paragraph of page 2. 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). Furthermore, the detergent may contain an enzyme if necessary. Enzymes can be added to detergent detergents. These enzymes often improve the performance of proteins or starch-based stains 18 200303358, such as those caused by blood, milk, forage juice or fruit juice. 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 . Enzymes can be present in the detergent as needed. When used, the enzyme is generally 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 N-oxides, which may have been modified by incorporating anionic or cationic substituents, especially having a molecular weight of 5000 to 60 000, more preferably between 10 000 and 50 19 200303358 000. Such polymers are generally used in an amount of from 0.01 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 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 form of concentrated pellets suitable for adding 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 a large amount of active substance. In order to minimize energy consumption during the washing program, compact detergents must be operated efficiently at temperatures as low as 40 ° C, or even at room temperature such as 25.0. Such detergents usually contain only low amounts of excipients or processing aids, such as sodium sulfate or sodium chloride. The amount of this kind of mash is usually 0-10% by weight, preferably 0-5 20 200303358% by weight, especially 0-1% by weight, based on the total weight of the detergent. Such detergents usually have a bulk density of 650-1000 g / l, preferably 700-1000 g / l and especially 750-1000 g / l. Detergents can also be in the form of nine tablets. The relevant features of the nine tablets are the ease of distribution and the ease of handling. Nine tablets are the most closely delivered solid detergents and have a bulk density of, for example, 0.9 to 1.3 kg / liter. To enable rapid disintegration, the nine tablets of laundry detergents generally contain special disintegrating agents:-effervescent agents such as carbonate / hydrocarbonate / 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-soluble, water-soluble hard coatings, such as dicarboxylic acids. These nine tablets may also contain any combination of the aforementioned disintegrants. The detergent can also be formulated as an aqueous liquid containing 5-50, preferably 10-35% water, or a non-aqueous liquid detergent containing not more than 5, preferably 0-1% by weight of water. Non-aqueous liquid detergent compositions may contain other solvents as carriers. Low-molecular-weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable. Monoalcohols are preferred for dissolving surfactants, but 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, 1,2-propanediol). The composition may contain 5% to 90% of such carriers, typically 10% to 50%. Detergents can also be in the form of so-called "unit liquid doses". This fabric detergent treatment can be manipulated into a domestic treatment in a conventional washing machine. 21 200303358 The textile fibers treated can be natural or synthetic fibers or mixtures thereof. Examples of natural fibers include plant fibers, such as cotton, viscose silk, linen, rayon, or linen, preferably cotton, and animal fibers, such as wool, mohair, cashmere, angora rabbit hair, and silk, preferably wool . Synthetic fibers include polyester, polyamide and polyacrylonitrile fibers. The 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 / m2. According to this method, the compound of formula (1) is usually used in an amount of 0.01 to 3.0% by weight, especially 0.05 to 3.0% by weight, based on the weight of the textile fiber material. The method is usually carried out at a temperature ranging from 5 to 100 ° C, especially 5 to 60 ° C. The temperature range is preferably 5 to 40 ° C, especially 5 to 35 ^ 0 and more preferably 5 to 30 ° C. The detergent composition herein is preferably formulated such that during use in an aqueous cleaning operation, the sewage will have a pH between about 6.5 and about 11, preferably between about 7.5 and 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 washing solution having a volume of 5 to 85 liters, as is the typical product dosage and washing solution commonly used in conventional machine laundry methods. volume. Examples are: 22 200303358-a 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 the washing tank, and the washing cycle is about 10 to about 60 minutes. 'Washing water temperature is about 30 to about 95 ° C;-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. An excellent ratio is a solution ratio of 1 ·· 4 to 1:10, especially 1: 5 to 1: 9. A further object of the present invention is to provide a method for domestic washing treatment of a textile fiber material, wherein the textile fiber material is in contact with an aqueous solution of a detergent containing the compound of the above formula (1), and wherein the detergent contains a peroxide, a peroxide Oxide activators and / or bleach catalysts, and wherein the solution temperature is between 5 ° C and 40 ° C throughout the process, preferably between 5 ° C and 3 ° C. As for the formula ( 1) The compounds and the definitions and preferences given above in terms of detergents and washing methods are applicable. The compounds used according to the invention are particularly advantageous in that they not only exhibit a very high whitening capacity, In addition, in many cases, it also exhibits very ideal water solubility and has excellent white appearance in the solid state. A further advantage of the present invention is that the detergent composition delivery improves 23 200303358 whiteness performance and fabric touch. In addition, compounds show very good results in terms of depletion. These compounds have the advantage that they are present in the presence of active chlorine donors such as hypochlorite It is also very effective and can be used without substantial loss of effectiveness in a water bath containing non-ionic detergents, such as alkylphenol polyglycol ether. It is also used in perboric acid or peracids and activators such as tetraethylfluorenylgan The compounds are stable in both powdered detergents and water wash tanks in the presence of urea or ethylenediaminetetraacetic acid. In addition, they give a brilliant appearance in the sun. The following examples are used to illustrate the invention Parts and percentages are by weight unless otherwise specified. Preparation Example 1:

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

(52205-59-1) (102) is mixed with 600 ml of water and heated to a temperature of 60 ° C. Then 24 200303358 9.2 g of 2-ethylaminoethanol was added and the reaction mixture was heated to a temperature of 98 ^ 0; during the heating, the pH was maintained at 8.5 and 9 by adding a 4-mole sodium hydroxide aqueous solution The number between. The reaction mixture was cooled to 50 ° C, and the pH was adjusted to a value of 4.5 by adding a 6 mol aqueous hydrochloric acid solution. The precipitate was filtered off, washed with 100 ml of a 10% aqueous sodium chloride solution and dried in vacuo. In this way, 30.5 g of a pale yellow product were obtained. Preparation Examples 2 to 15: Compounds of the 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 amount of the corresponding amine. X is defined in Table 1 below. After cooling to 50 ° C, the precipitated compound 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,)? 3 1 4 -N (CH,) CH2CH? 0H 25 200303358 5 V NH I 6 -NHCH, CH? OH 7 -NHCH? CH? OCH, 8 -nhch, ch9cooh 9 -nhch2ch, 10 -N (CH,) CH? COOH 11 -N (CH2CH2OH) 2 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: 26 200303358

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 period, the pH was maintained at a value between 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 "J 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. 27 200303358 Table 2 Example X 17 -N (CH2CH〇CH2CH2OH 18 1 19 -N (CH7CH7OH) 7 Preparation Example 20:

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. Over a period of 30 minutes, 185 ml of an aqueous solution of 4,4'-diaminostilbene-2,2'-disulfonic acid (as the disodium salt) (at a concentration of 100 g / l) was added dropwise, The temperature is between -8 and + 5 ° C. The pH was maintained at a value between 4.5 and 5 by the addition of an aqueous sodium carbonate solution. A light yellow suspension was obtained. Then, by using a dropping funnel, 27.2 g of ethanolamine (99%) was added. The pH is increased to a few 値, and then lowered to a lower 値, at which time the temperature is increased 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. During heating to 98 ° C in 30 minutes, the mixture of methyl ethyl ketone and water was distilled off; the pH was maintained at a value between 8.5 and 9 by adding an aqueous sodium hydroxide solution. After no further addition of aqueous sodium hydroxide was required to maintain the pH at a fixed number of 値, the reaction mixture was cooled to 50 ° C. The pH was adjusted to a value of 5.5, and the pale yellow crystalline precipitate was filtered off. After drying, 29 g of a pale yellow product were obtained. Preparation Example 21:

In a 1 liter pressure vessel, 0.037 mole N, N'-bis- (4-morpholinyl-6-chloro-1,3,5-triphin-2 · yl) -4,4, diamine group Stilbene-2,2, disulfonic acid (disodium salt) was suspended in 500 ml of water. 15 g of an ethylamine aqueous solution (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 off, 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

(107) The compound of formula (107) can be prepared in a similar manner to that given in Preparation Example 21, 29 200303358, but replacing a 15 g solution of ethylamine in water (70%) with a corresponding solution containing an equivalent molar amount of diethylamine. Preparation Example 23:

In a 1 liter flask, add 0.05 mols > 1, _bis- (4-morpholinyl-6-chloro-1,3,5-triphin-2-yl) -4,4, · diamine Base stilbene-2,2, -disulfonic acid (as 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 several 値 between 8.5 and 9 by the addition of a 4-mole aqueous sodium hydroxide solution. The reaction mixture was cooled to 25.0 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 under vacuum at 70 ° C. In this way, 41.8 g of a pale yellow powder was obtained. 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 tank and the strip was washed at 40 ° C for 15 minutes', then rinsed, dried and ironed at 160 ° C. 200303358 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 powders A and B) A Β sodium laurylbenzenesulfonate (LAS) 10 g 10 g 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 5 grams of sodium, 5 grams of sodium sulfate, 11 grams of 17 grams of perborate, and 10 grams of TAED. 3 grams of 3 grams of polycarboxylate (co-builder). 4 grams of carboxymethyl cellulose. 2 grams of 2 grams of perfume. Gram ΐ g water 5 g 5 g fluorescent whitening agent used X g X g mb (washing powder used) amount of fluorescent whitening agent washing powder Preparation Example 1 Compound 0.2 g A Preparation Implementation 0.1 g of compound of Example 2 0.3 g of compound of Example 3 Preparation of 0.2 g of compound of Example 4 0.4 g of compound of Example 5 0.4 g of compound of Example 12 0.15 g of compound of Preparation Example 13 Compound 0.1 g B Compound of Preparation Example 16 0.3 g B Compound of Preparation Example 18 0.2 g A 0.3 g of compound of Preparation Example 21 0.2 g of compound of Preparation 22 0.2 g of compound of Example 23 0.1 g of compound of formula (109) 0.3 g of compound of formula (109): ( 109) (109) 200303358

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 detergent powder (the amounts given in Tables 4a and 4b below are weight percentages based on the total weight of the detergent): Table 4a (components of detergent powders 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% Polycarboxylic acid salt (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% 32 200303358 Sodium perborate monohydrate 15% 15% TAED 5% 5% Soap 2% 2% The fluorescent brightener X% X% used in each of the above detergents to obtain a sufficient amount of water 100%. Table 4b (Washing powder used)

Amount of fluorescent whitening agent Washing powder Preparation of compound of Example 1 0.2% C Preparation of compound of Example 3 0.2% C Preparation of compound of Example 6 0.3% C Preparation of compound of Example 7 0.2% D of Preparation Example 8 Compound 0.2% C Compound 0.4% C of Preparation Example 9 Compound 0.2% D of Preparation Example 10 Compound 0.2% C of Preparation Example 0.3 Compound 0.3% of D Preparation Example 15 0.2% of Compound C Preparation Compound of Example 17 0.4% C Preparation of Compound of Example 19 0.3% C Preparation of Compound of Example 0.5% C Compound of Formula (109) 0.3% D For the structure of the compound of Formula (109), see Application Example 1.

Cotton fabrics washed according to the general procedure with the detergents listed in Table 4b show good whiteness properties. 33

Claims (1)

β 200303358 Patent application scope 1. A detergent composition comprising: at least one compound of formula (1), "X2 Wherein: Xin and R2 are independently of each other hydrogen or unsubstituted or substituted < -08 alkyl, Xi, x2, x3, and x4 are independently _n (r3) r4 or -〇r5, where r3 and r4 are hydrogen; cyano; crc8 alkyl, which is unsubstituted or substituted by hydroxyl, carboxyl, cyano , -CONH2 or phenyl substituted in which the CVC8 alkyl system is not interrupted or -0- interrupted; c5-c7 cycloalkyl, unsubstituted or substituted with crc4 alkyl, or 113 and 114 and the nitrogen atom to which they are attached Together form a morpholinyl, eridine, or pyrrolidine ring that is unsubstituted or substituted with a crc4 alkyl group; 115 is a crc8 alkyl group, which is unsubstituted or substituted with a hydroxyl group, and M is hydrogen or a cation, and wherein Detergents contain peroxides, peroxide activators and / or bleach catalysts. 2. The composition according to item 1 of the scope of patent application, wherein Xi, X2, X3, and X4 are groups of the formula -N (R3) R4. 3. The composition according to any one of the scope of claims 1 and 2 '34 200303358 where XjD 乂 3 is an amine group, X2 and X4 疋 -N (R3) R4 group' where r3 and r4 are Nitrogen; amino or crc8 alkyl 'which is unsubstituted or substituted with a hydroxyl or carboxyl group, and wherein CrC8 alkyl is not interrupted or -0- interrupted; cyclohexyl unsubstituted or substituted with crC4 alkyl; or R3 And R4 together with the nitrogen atom to which they are attached form an unsubstituted or CVC4 alkyl-substituted morpholinyl, perididyl or pyrrolidine ring, and M is hydrogen, an alkali metal or a metal or metal, preferably sodium. 4. The composition according to item 3 of the scope of patent application, the center and R4 of which together with the nitrogen atom to which they are attached form an unsubstituted or substituted CrC4 alkyl group, piperidine or pyrrolidine ring, preferably A morpholinyl ring. 5. The composition according to any one of claims 1 and 2 of the scope of the patent application, which contains = i) 1-70% of anionic surfactant and / or non-ionic surfactant j ii) 0-75% of Builders; iii) 0.5-30% peroxide; iv) 0.5-10% peroxide activator and / or 0.1-2% bleach catalyst; ν) 0.001-5% formula (1 ) A compound; and vi) at least one enzyme selected from the group consisting of cellulase, protease, amylase, and lipase at 0-5%. 35 200303358 6. The composition according to any one of items 1 and 2 of the scope of the patent application, which includes: i) 5-70% anionic surfactant and / or non-ionic surfactant j 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% formula (1 ) A compound; and vi) at least one enzyme selected from the group consisting of cellulase, protease, amylase, and lipase at 0.05-5%. 7. The composition according to any one of claims 1 and 2 of the scope of the patent application, wherein the composition comprises at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase. 8. The composition according to item 7 of the scope of patent application, wherein the enzyme is a protease enzyme. 9. A composition according to any one of the scope of claims 1 and 2 ', wherein the composition comprises a peroxide. 10. The composition according to any one of the claims 1 and 2, wherein the composition comprises a peroxide and a peroxide activator. 11. The composition according to claim 10, wherein the peroxide activator is TAED. 12. —A method for domestic washing treatment of textile fiber material, wherein the textile fiber material is in contact with an aqueous detergent solution containing a compound of formula (1): 36 200303358 # ⑴ where 1 and r2 are independently hydrogen or unsubstituted or substituted CP c8 alkyl, and Xi, x2, X3, and X4 are independently -N (R3) R4 or -〇R5, where R3 and r4 is hydrogen; cyano; crc8 courtyard, which is unsubstituted or substituted with hydroxyl, carboxyl, cyano, -CONH2 or phenyl and wherein crc8 alkyl is not interrupted or -0- interrupted; unsubstituted or C5-C7 cycloalkyl substituted with C "C4 alkyl; or R3 and 114 together with the nitrogen atom to which they are attached form a morpholinyl, pyridine, or pyrrolidine ring that is unsubstituted or substituted with crc4 alkyl; 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 a peroxide, a peroxide activator, and / or a bleach catalyst, and wherein the The temperature is between 5 ° C and 4 ° C throughout the method, preferably between 3 ° C and 13. ° C. 13. According to the method of claim 12 in the scope of patent application, where Xι, X2, X3 and X4 are of the formula- A group of N (R3) R4. 14. The method according to any one of items 12 and 13 of the scope of patent application, wherein: 37 200303358 \ and x3 is X2 and x4 are groups of the formula -N (R3) R4, whose center and R4 are hydrogen; cyano or Ci-Cs alkyl, which are unsubstituted or substituted with a hydroxyl or carboxyl group, and where "C8 Alkyl is uninterrupted or 10-interrupted; unsubstituted or cyclohexyl substituted with (^ -alkyl); or 113 and R4 together with the nitrogen atom to which they are attached form an unsubstituted or crc4 alkyl substituted Morpholinyl, piperidine, or pyrrole ring, and M is hydrogen, alkali metal or alkaline earth metal or gold, preferably sodium. 15. The method according to item 14 of the scope of patent application, wherein R3 and R4 are connected to The nitrogen atoms together form an unsubstituted or substituted CVC4 alkyl group, pyridyl or pyrrolidine ring, preferably a morpholinyl ring. 16. According to any one of claims 12 and 13 of the scope of the patent application A method, wherein the textile fiber material is treated with a compound of formula (1) that accounts for 0.05 to 3.0% by weight of the textile fiber material. 17. The method according to any one of claims 12 and 13 of the scope of the applied patent, wherein the detergent comprises at least One selected from the group consisting of cellulase, protease, amylase and lipase Groups of enzymes. 18. The method according to item 17 of the patent application, wherein the enzyme is a protease enzyme. 19. The method according to any of item 12 and 13 of the patent application, wherein the detergent comprises a peroxide 20. A method according to any one of claims 12 and 13 in the scope of the patent application, wherein the detergent comprises a peroxide and a peroxide activator. 38 200303358 21. A method according to the scope of the patent application, wherein 20 Peroxide live 'all together! J is TAED ° Pick, schema (none) 39 200303358 Lu, (I), the designated representative of this case is: (No) Figure (II), the representative symbols of this representative diagram are simply explained: Chai, if there is a chemical formula in this case, please reveal the chemistry that can best show the characteristics of the invention 5