TWI324177B - Process for the treatment of textile fibre materials - Google Patents

Description

1324177 发明, INSTRUCTION DESCRIPTION FIELD OF THE INVENTION The present invention is directed to detergent formulations containing certain camping whiteners as well as 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 properties, results in the elimination of yellowing. However, there is still a need to find improved fluorescent brighteners for this application. It has now been found that the compound of the following formula (1) has excellent properties in terms of, for example, solubility, cumulative properties, whiteness, light resistance, and the like, and has an excellent white state in a solid state. Whiteness properties, such as whiteness maintenance, can be enhanced even by the use of a compound of formula (1) in a detergent containing a peroxide, a peroxide activator and/or a bleach catalyst. Favorable results can even be obtained at low wash temperatures. SUMMARY OF THE INVENTION Accordingly, a first aspect of the invention provides a detergent composition comprising at least one compound of formula (1):

Wherein the 1324177 core and the r2 are independently hydrogen or unsubstituted or substituted cr C8, and the X!, X2, X3 and X4 are independently of each other -N(R3)R4 or -ORs, wherein R3 and R4 is hydrogen; cyano; crc8 alkyl, which is unsubstituted or substituted by hydroxy, carboxy, cyano, -CONH2 or phenyl, and wherein the CVC8 alkyl is uninterrupted or interrupted by -0; unsubstituted Or a C5-c7 cycloalkyl group substituted by a CrG alkyl group; or R3 and R4 together with a nitrogen atom to which they are bonded form an unsubstituted or substituted crc4 alkyl group, a fluorenyl or pyrrolidine ring is Crq An alkyl group which is unsubstituted or substituted by a hydroxy group and which is a hydrogen or a cation, and wherein the detergent contains a peroxide, a peroxide activator and/or a bleach catalyst. Embodiments Within the scope of the above definition, 匕-(:8 alkyl may be methyl, ethyl, n- or isopropyl, n-, second or third butyl, or a linear or branched pentyl group, Hexyl, heptyl or octyl. Preferred is CVC4 alkyl. If alkyl groups of ruthenium and r2 are substituted, examples of possible substituents are: hydroxy, halogen, such as fluorine, chlorine or bromine, sulfo group , a sulfate group, a carboxyl group, and a crc4 alkoxy group such as a methoxy group and an ethoxy group. Other substituents of such an alkyl group are, for example, a cyano group, -CONH 2 and a phenyl group. Preferred substituents are a hydroxyl group. , a carboxyl group, a cyano group, -C0NH2 and a phenyl group, especially a hydroxyl group and a carboxyl group. Further, an excellent substituent is a hydroxyl group and a (:, -〇 (alkoxy group, especially a hydroxyl group. These alkyl groups may also be Interrupted or interrupted by -0- (in the case of alkyl group 1324177 containing two or more carbon atoms). Examples of c5-c7 cycloalkyl are cyclopentyl and especially cyclohexyl. These groups can be crc4 - an alkyl group such as a methyl group, preferably a corresponding unsubstituted ring-based group. Within the scope of the above definition, the CrG alkyl group may be a methyl group, an ethyl group, Or isopropyl, positive 'second or third butyl, especially methyl. If R3 and the heart together with the nitrogen atom form a morpholinyl, pyridinyl or pyrrolidine ring, this ring system can be unsubstituted Or substituted by a CVC4 alkyl group, especially a methyl group. Preferred is an unsubstituted ring system. The cationic ruthenium is preferably an alkali metal atom, an alkaline earth metal atom, ammonium or a cation formed from an amine. , hydrazine, Ca, Mg, ammonium, mono-, di-, tri- or tetra-Crq alkylammonium, mono-, di- or tri-C2-C4-hydroxyalkylammonium, or via 4-alkyl and C2-C4-hydroxyalkyl Mixture of di- or tri-substituted ammonium. Excellent sodium. Heart and R2 are preferably hydrogen or crc4 alkyl, especially hydrogen. R3 and R4 are preferably: hydrogen; cyano; CrC8 alkyl, which is not Substituted or substituted by hydroxy, carboxy, cyano, -conh2 or phenyl, especially by hydroxy or carboxy and wherein c"c8 alkyl is uninterrupted or interrupted by -〇-; unsubstituted or substituted by crc4 alkyl a c5-c7 cycloalkyl group, especially a cyclohexyl group; or r3 and r4 together with a nitrogen atom to which they are bonded form an unsubstituted or crc4 alkyl substituted morpholine More preferably, R3 and R4 are hydrogen 'unsubstituted or hydroxy substituted CrCs alkyl, unsubstituted or alkyl substituted ^:5-(:7 naphthenic Or, R3 and R4 together with the nitrogen atom to which they are attached form an unsubstituted 1324177 or CrC4 alkyl substituted fluorenyl, piperidine or flttrolidine ring. The best idea for r3 and R4 is hydrogen. Substituting an unsubstituted or substituted base for a CiIC8 alkyl group, or R3 and & together with the nitrogen atom to which they are attached form an unsubstituted or substituted C"C4 thiol group? The most preferred are morpholinyl, guanidinyl or pyrrolidine rings which are unsubstituted or substituted with a Crc4 alkyl group, especially a thiol group which is formed via the heart and 1 together with the nitrogen atom to which they are attached. Examples of the -N(RS)R4 group are: ΝΗ2, _ΝΗ(:;Η广νη〇2η5, -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(CH2CH(OH)CH3)2, -N(CH3 )(CH2CH2OH), -N(C2H5)(CH2CH2OH), -N(i-C3H7)(CH2CH2CH2OH), -NH(CH2CH(OH)CH3), -N(C2H5XCH2CH(OH)CH3), -NH(CH2CH2OCH3) -NH(CH2CH2OCH2CH2OH), -NH(CH2COOH), -NH(CH2CH2COOH), -N(CH3)(CH2COOH), -NH(CN),

10 1324177

—N

-NH-CH

NH-CH-COOH

NH——CH—COOH CHj—C—NH〇 2 II 〇

NH CH, CH, CH, -NH-C-NH, R5 is preferably a hospital base, especially a C!-C4 hospital base, which is unsubstituted or substituted with a hydroxyl group. It is excellent for methyl or ethyl', especially methyl. X, x2, x3 and x4 are preferably a group of the formula -n(r3)r4. X: and x3 preferably have the same meaning. Other than that, it is preferable that A and X4 have the same meaning. Further, it is preferable that the four groups X1, X2, and x3 have the same meaning. Preferred are compounds of formula (1) wherein

Rjn R2 is nitrogen or Ci-C^, and R3 and R4 are: hydrogen; cyano; CrCs alkyl, which is unsubstituted or substituted by hydroxy, carboxy 'cyano, -CONH2 or phenyl and wherein crc8 alkane The base is uninterrupted or interrupted by -0; unsubstituted or C5-C7 cycloalkyl substituted by crc4 alkyl; or R3 and R4 together with the nitrogen atom to which they are attached form an unsubstituted or CrQ alkyl substituted a morpholinyl, piperidine or aglycon ring; and the rule 5 is a CrC8 alkyl group which is unsubstituted or substituted with a hydroxy group. As for R3, 1 and R5, the above preferences are applicable. Particularly preferred are compounds of formula (1) wherein 11 1324177 乂, and X 3 are amine groups, and x 2 and x 4 are groups of the formula -N(R 3 ) R 4 wherein r 3 is: hydrogen; cyano; CpC: 8 An alkyl group which is unsubstituted or substituted by a hydroxy or carboxy group and wherein the CVC8 alkyl group is uninterrupted or interrupted by -〇-; unsubstituted or substituted by a cyclyl group; or 1^3 and R4 are linked thereto. The nitrogen atoms together form a morpholinyl, piperidine or fluorene ring that is unsubstituted or substituted with a crc4 alkyl group. As for R3 and R4, the above preferences are applicable. Of particular interest are compounds of formula (1) wherein Xi and indole 3 are amine groups, and X2 and X4 are groups of formula -N(R3)R4 wherein the ampules 3 and r4 are hydrogen, unsubstituted or substituted by hydroxy groups. Is the CrC8 alkyl group unsubstituted or substituted by a cyclopentyl group or a cyclohexyl group, or is the core and R4 together with the nitrogen atom to which they are attached form an unsubstituted or substituted by a crc4 alkyl group? Amidino, acridine or pyrrolidine ring. The most interesting compound of formula (1) is one in which 113 and r4 together with the nitrogen atom to which they are attached form an unsubstituted or rcolinyl group substituted with a crc4 alkyl group. Acridine or pyrrolidine ring. As for the heart and R4, the above preferences may be applied. The compound of formula (1) is known or can be prepared by a similarly known method. The compound of formula (1) can be prepared as follows: Under the reaction conditions, cyanuric chloride is successively combined with 4,4'-diaminostilbene-2,2'-disulfonic acid and an amine capable of introducing a group and X4 in any desired order. The base compound is reacted. Preferably, the 2 molar cyanuric hydrazine is initially reacted with 1 mol of 4,4'-diamino stilbene-2,2'-disulfonic acid. The resulting intermediate should then be reacted in any order with the amine group 12 1324177 capable of introducing groups Χι, X2, A and A. It is prepared in which 乂1 and X3 have the same meaning and x2 and x4 have the same meaning. In the case of a compound, it is preferred to react the obtained intermediate with an amine compound capable of introducing ", and X3, and finally with an amine compound capable of introducing x2 and x4. It is also possible to make an intermediate with an amine group. The compound mixture is reacted, and the reaction with the amine compound is carried out in one step; in this case, a corresponding compound mixture of the formula (1) is usually obtained. The compound of the formula (1) having a group of the formula -OR5 is, for example, It can be prepared as follows: First, cyanuric chloride is reacted with the corresponding alcohol HOR5, and the obtained product is reacted with 4,4'-diaminostilbene-2,2'-disulfonic acid, and then the intermediate is made. It is reacted with other compounds capable of introducing the remaining groups of Xi, χ2, χ3 and χ4. The last reaction is preferably carried out with the corresponding amine. The detergent composition used preferably comprises: i) 1 - 70% anion Surfactant and/or non-separating Surfactant 9 ii) 0-75% builder; iii) 0.5-30% peroxide; iv) 0.5-10% peroxide activator and/or 0.1-2% bleach catalyst; 0.001 to 5% of the compound of the formula (1); and vi) 0 to 5% of at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase. More preferably, the detergent composition used comprises: i) 5-70% anionic surfactant and/or nonionic surfactant 13 1324177 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% of the compound of formula (1); and W) 0.05-5% At least one enzyme selected from the group consisting of cellulase, protease, amylase, and lipase. In general, a compound of the formula (1) is used in an amount of from 0.001 to 5%, especially in an amount of from 0.01 to 5%. Excellent is an amount of 0.05 to 5%, especially 0.05 to 2%. In general, the amount expressed as a percentage should be understood as a percentage by weight based on the total weight unless otherwise stated. The detergent may be formulated as a solid, formulated into an aqueous liquid containing, for example, 5 to 50, preferably 10 to 35%, or formulated as a non-aqueous liquid detergent containing no more than 5, preferably 0 to 1% by weight. Water is based on a suspension of the builder in the nonionic surfactant, as described, for example, in GB-A-2158454. The anionic surfactant component can be, for example, an alkylbenzene sulfonate, an alkyl sulfate, an alkyl ether sulfate, an alkene sulfonate, an alkane sulfonate, a fatty acid salt, an alkyl or alkenyl ether carboxylate or An α-sulfofatty acid salt or an ester thereof. Preferred are alkylbenzenesulfonates having 10 to 20 carbon atoms in the alkyl group, alkyl sulfates having 8 to 18 carbon atoms, alkyl ether sulfates having 8 to 18 carbon atoms, And fatty acid salts derived from palm oil or tallow and having from 8 to 18 carbon atoms. The average number of molecules of the epoxy group added to the alkyl ether sulfate is preferably from 1 to 20, preferably from 1 to 1 unit. These 14 1324177 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-CCHRyCH/OOM1 wherein R is an alkyl or alkenyl group having from 9 to 17 carbon atoms in the alkyl group, or an alkenyl group 'R1 is an alkane M, and M1 is an alkali metal, especially sodium. The nonionic surfactant component can be, for example, primary and secondary alcohol ethoxylates, especially C8-C2 nonaliphatic alcohols which are ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol. In particular, C1Q-C15 grade and secondary aliphatic alcohols are ethoxylated per mole of 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers, and polyhydroxy decylamine (glucosamine). The total amount of the anionic surfactant and the nonionic surfactant is preferably from 5 to 50% by weight, preferably from 5 to 40% by weight and more preferably from 5 to 30% by weight. As for these surfactants, the lower limit is preferably 10% by weight. The builder component can be an alkali metal phosphate, especially a tripolyphosphate; a carbonate or bicarbonate, especially a sodium salt thereof; a citrate or a dicaprate; a strontium aluminate; a polycarboxylate; a polycarboxylic acid; an organic phosphonate; or an amine-based poly(phosphonic acid alkyl ester or a mixture of these. The preferred decanoate is a crystal of the formula NaHSim02m+1.pH20 or Na2Sim〇2m+1.pH20 Layered sodium niobate, where Μ is a number from 1.9 to 4 and ρ is from 〇 to 20. Preferred yttrium aluminates are commercially available synthetic materials known as zeolite A, hydrazine, X and HS' or these A mixture of zeolites is preferred. Preferred polycarboxylates include: hydroxypolycarboxylates, particularly the citrate salt 'polyacrylates and their copolymers with maleic anhydride. 15 1324177 Preferred The polycarboxylic acid includes nitrilotriacetic acid and ethyldiaminetetraacetic acid. The preferred organic phosphonate or amine alkylene poly(alkyl phosphonate) is an alkali metal ethane hydroxy diphosphonate, Nitrilotrimethylenephosphonate, ethyldiaminetetramethylenephosphonate and diethylenetriaminepentamethylenephosphine Rr^rg [jfm 助 The amount of the builder is preferably from 5 to 70% by weight, preferably from 5 to 60% by weight and more preferably from 10 to 60% by weight. As for the builder, the lower limit is preferably 15% by weight. %, especially 20% by weight. Suitable peroxide components, for example, include organic and inorganic peroxides (such as sodium peroxides) which are known in the literature and commercially available, which are conventional The washing temperature is, for example, 5 to 95 ° C bleaching the textile material. In detail, the organic peroxide is exemplified by a single peroxide or a plurality of alkyl chains having at least 3, preferably 6 to 20 carbon atoms. a peroxide; in particular a diperoxydicarboxylate having 6 to 12 C atoms, such as diperperoxypersalate, diperoxyperpine, diperoxyphthalate And/or diperoxydodecanedionate, especially those of which the corresponding free acid is of particular interest. However, it is preferred to use very active inorganic peroxides such as persulfates, perborates and/or Or percarbonate. Of course, it is also possible to use a mixture of organic and/or inorganic peroxides. The peroxide is preferably 0.5-3. 0% by weight, preferably 1% to 20% by weight and more preferably 1% to 15% by weight. If a peroxide is used, the lower limit is preferably 2% by weight, especially 5% by weight. Peroxide, especially inorganic The peroxide, preferably activated via the inclusion of a bleaching activity 1324177. Preferably, it is produced under the conditions of hydrogen peroxide hydrolysis, substituted or substituted having from 1 to 10 carbon atoms, especially from 2 to 4 a compound of the carbon atom which is a perbenzoic acid and/or a peroxycarboxylic acid. Suitable compounds include a 0- and/or N-fluorenyl group having the carbon number and/or an unsubstituted or substituted benzyl group. A preferred group is a polythiol alkylene diamine, especially tetraethyl hydrazide ethyl diamine (TAED), thiolated glycoluril, especially tetraethylene guanylurea (TAGU), N , N-diethyl fluorenyl-indole, fluorene-dimethyl-dens (DDU), thiolated trimorphine derivatives, especially 1,5-diethyl fluorenyl 2,4-dihydro hexahydro-hydrogen 1,3,5-trimorphine (DADHT), a compound of the formula

Wherein R is a sulfonate group, a carboxylic acid group or a carboxylate group, and wherein R' is a linear or branched (C7-C15) alkyl group; and an activator known by the trade names SNOBS, SLOBS, NOBS and D0BA a thiolated polyol, especially triacetin, ethylene glycol diacetate and 2,5-diethoxycarbonyl-2,5-dihydrofuran, and ethoxylated sorbitol and mannitol and Thiolated sugar derivatives, especially pentaethylglucosamine (PAG), sucrose polysuccinate (SUPA), pentaethylene fructose, tetraethyl xylenyl and octadecyl lactose, and acetylation N-alkylated glucosamine and gluconolactone are optionally required. A conventional bleaching agent combination disclosed in German Patent Application No. DE-A-44 43 177 can also be used. A nitrile compound which forms a peroxyimin with a peroxide is also suitable as a bleach activator. Preferred are tetraethyl hydrazide ethyl diamine and decyloxybenzene sulfonate. The amount of bleach activator is preferably from 0 to 10% by weight, preferably from 0 to 8 by weight, from 17 to 1324177%. If a bleach activator is used, the lower limit is preferably 0.5% by weight, especially 1% by weight. Bleach catalysts which may be added include, for example, enzymatic peroxide precursors and/or metal complexes. Preferred metal complexes are manganese, cobalt or iron complex complexes such as manganese or iron peptidyl, or the complexes described in EP-A-0509787. If a bleach catalyst is used, the amount thereof is preferably from 0.005 to 2% by weight, more preferably from 0.01 to 2% by weight, particularly from 0.05 to 2% by weight. It is preferably an amount of from 0.1 to 2% by weight. As examples of bleach catalysts, the following may be mentioned: - WO-A-95/30681 (i.e., see formula (I) on page 1, lines 7 to 30 and its definitions; especially on page 2 Line 29 to page 11 and line 11 gives the formula (I) and its definition). Preferred ligands are given on page 13, line 12 to page 26, line 11. -WO-A-01/09276 (ie see equations (1), (2) and (3) given on pages 2 and 3 and subsequent definitions). -WO-A-01/05925 (see also the definition of equation (1) and subsequent definitions in the first paragraph of page 1 to the first paragraph of page 2. The preference for metal complexes may apply, see in particular page 3. Equation (2) and Equation (3) on page 4). -WO-A-02/088289 C See also equation (1) on page 2 and its definition. Preference is given to the preference for metal complexes, see in particular the ligand of formula (3) and the preference given on page 3, paragraph 4 to page 4, paragraph 7. Furthermore, the detergent may contain enzymes as needed. Enzymes can be added to decontamination detergents. These enzymes usually increase the effectiveness of protein or starch-based stains 18 1324177, such as those caused by blood, milk, grass juice or fruit juice. Preferred enzymes are cellulases, proteases, amylases and lipases. Preferred enzymes are cellulases and proteases, especially proteases. Cellulase is an enzyme that acts on cellulose and its derivatives and hydrolyzes them into glucose, cellulose disaccharide, and cellulose oligosaccharides. Cellulase removes dirt and has the effect of reducing roughness. Examples of enzymes to be used include, but are not intended to be limited to, the following: the proteases listed in US-B-6, 242, 405, column 14, lines 21 to 32; in US-B-6, 242, 405 'col. 14 columns, lines 33 to 46 Lipases listed in; US-B-6, 242, 405, amylases listed in column 14, lines 47 to 56; and fibers listed in US-B-6,242,405, column 14, lines 57-64 Enzyme. Enzymes may be present in the detergent as needed. When used, the enzyme is usually present in an amount of from 0.01 to 5% by weight, preferably from 0.05 to 5% and more preferably from 0.1 to 4% by weight based on the total weight of the detergent. Other preferred additives which can be used in the detergents of the present invention are polymers (fixing agents, dye transfer inhibiting agents) which inhibit coloration caused by dyes which have been released from the fabric under the washing conditions during the washing of the fabric. Such polymers are preferably polyvinylpyrrolidone, polyvinylimidazole or polyvinylpyridinium N-oxide, which may have been modified by the incorporation of anionic or cationic substituents, especially having a molecular weight of from 5,000 to 60,000. More preferably in the range of 10,000 to 50 19 1324177 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 especially the first paragraph on page 1 and the first paragraph on page 2). The detergent to be used usually contains one or more auxiliaries, such as soil suspending agents, such as sodium carboxymethylcellulose; salts for pH adjustment, such as alkali metal or alkaline earth metal citrate; foam regulators, such as soap; Adjusting salts for spray drying and granulating properties such as sodium sulfate; perfume; and, where appropriate, antistatic and softening agents, such as smectite clay; photobleaches; pigments; and/or toners. These components should of course be stable to any bleaching system used. Such auxiliaries may be present in an amount of from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight, especially from 5% to 5% by weight, based on the total weight of the detergent. The detergent composition can take a variety of physical forms, including powders, granules, nine pieces, and liquids. Examples thereof are conventional powdered heavy duty detergents, compact and ultra-tight heavy duty detergents and nine sheets, such as nine heavy duty detergents. An important physical form is the so-called concentrated particle form suitable for addition to a washing machine. Also important are so-called tight (or ultra-compact) detergents. In the field of detergent manufacture, a trend has recently been developed towards the manufacture of compact detergents containing incremental actives. In order to minimize energy consumption during the washing process, the compact detergent must be as low as 40. (: The temperature, or even at room temperature such as 25. (:: efficient operation. This type of detergent usually only contains low amounts of dips or processing aids, such as sodium sulfate or sodium chloride. The amount of the material is usually 〇-1〇% by weight based on the total weight of the detergent, preferably 0-5 20 1324177% by weight, especially 0_1% by weight. Such detergents usually have 650-1000 g/l. Good bulk density of 700-1000 g / liter and especially 750-1000 g / liter. The detergent can also exist in the form of nine pieces. The characteristics of the nine pieces are the ease of distribution and the convenience of handling. A solid detergent that is delivered in close proximity and has a bulk density of, for example, 0.9 to 1.3 kg/liter. To enable rapid disintegration, nine pieces of laundry detergent generally contain a special disintegrant: - an effervescent agent such as carbonate/hydrocarbonic acid Salt/citric acid; - swelling agent such as cellulose, carboxymethyl cellulose, cross-linked poly(N-vinylpyrrolidone); - fast-dissolving substance such as sodium acetate (potassium) or sodium citrate (potassium); - an instant water soluble hard coating such as a dicarboxylic acid. These nine sheets may also contain any of the above disintegrants. The detergent may also be formulated as an aqueous liquid containing 5-50, preferably 10-35% water, or as a non-aqueous liquid detergent containing no more than 5, preferably 0-1% by weight water. 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 preferred for dissolving the surfactant, but may also be A polyol such as those having from 2 to about 6 carbon atoms and from 2 to about 6 hydroxyl groups (for example, 1,3-propanediol, ethylene glycol, glycerin, and 1,2-propanediol) is used. The composition may contain from 5% to 90%. %, typically from 10% to 50% of such carriers. Detergents may also be present in the form of so-called "unit liquid doses". Such fabric detergent treatments can be manipulated into household treatments in conventional washing machines. 21 1324177 Processed The textile fibers may be natural or synthetic fibers or mixtures thereof. Examples of natural fibers include vegetable fibers such as cotton, viscose, linen, crepe or linen, preferably cotton, and animal fibers such as wool, mohair 'goats Cashmere, Angora rabbit Wool 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. The textile fibres treated according to the process of the invention have a density of less than 200 g/m2. According to the process, it is customary to use formulas of from 0.01 to 3.0% by weight, in particular from 0.05 to 3.0% by weight, based on the weight of the textile fibre material. The compound is usually carried out at a temperature ranging from 5 to 100 ° C, especially 5 to 60 ° C. It is preferably 5 to 40 ° C, especially 5 to 35 ° C and more preferably 5 to Temperature range of 30 ° C. The detergent compositions herein are preferably formulated such that the sewage will have a pH of between about 6.5 and about 11, preferably between about 7.5 and 11, during use in an aqueous cleaning operation. Laundry products are usually at pH 9-11. Techniques for controlling pH to the recommended standards of use include the use of buffers, bases, acids, and the like, and are well known to those skilled in the art. The machine laundry process herein generally comprises treating the soiled laundry with a wash water solution of the machine laundry detergent composition of the present invention dissolved or suspended in the washing machine. By effective amount of detergent composition is meant, for example, that from 20 grams to 300 grams of product is dissolved or dispersed in a wash solution having a volume of from 5 to 85 liters, as is typically used in conventional machine laundry methods for typical product dosages and wash solutions. volume. Examples are: 22 1324177 - Top-mounted vertical shaft American type automatic washing machine, which uses about 45 to 83 liters of water in a washing tank, a washing cycle of about 10 to about 14 minutes, and a washing water temperature of about 10 to about 50 ° C; 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; - top-loading vertical shaft Japan Type automatic washing machine, which uses about 26 to 52 liters of water in a washing tank, a washing period of about 8 to about 15 minutes, and a washing water temperature of about 5 to about 25°. The ratio of the solution is preferably 1:4 to 1:40. Especially 1: 4 to 1: 15. The preferred ratio is 1:4 to 1:10, especially 1:5 to 1:9. It is a further object of the present invention to provide a method for household laundry treatment of textile fiber materials wherein the textile fiber material is contacted with an aqueous solution of a detergent comprising a compound of formula (1) above, and wherein the detergent contains peroxide, Oxide activators and/or bleach catalysts, and wherein throughout the process, the solution temperature is between 5 ° C and 40 ° C, preferably between 5 ° C and 30 ° C. As regards the compounds of the formula (1) and in terms of detergents and washing methods, the above definitions and preferences are applicable. The compounds used according to the invention are particularly advantageous in that they exhibit not only a very high whitening ability. In addition, in many cases, it exhibits a very desirable water solubility, and has an excellent white state in a solid state. A further advantage of the present invention is that the detergent composition delivery improves the whiteness performance and fabric feel of 23 1324177. In addition, the compounds show very good results in terms of depletion. These compounds have the advantage that they are also effective in the presence of active chlorine donors such as hypochlorite and have no substantial effect loss in water wash tanks containing nonionic detergents such as alkylphenol polyglycol ethers. Use in case. Also in the presence of perboric acid or peracids and activators such as tetraethylglycoluril or ethyldiaminetetraacetic acid, the compounds are stable in both the powdered detergent and the water wash tank. In addition, they give the sun a brilliant appearance. The following examples are intended to illustrate the invention; parts and percentages are by weight unless otherwise indicated. Preparation Example 1:

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

Mix with 600 ml of water and heat it to a temperature of 6 °c. Then, 1324177 9.2 g of 2-ethylaminoethanol was added, and the reaction mixture was heated to a temperature of 98 ° C; during heating, the pH was maintained at 8.5 and 9 by adding a 4-mole aqueous solution of sodium hydroxide. The number between the two. The reaction mixture was cooled to 50 ° C, and the pH was adjusted to a number of 4.5 by adding a 6 molar aqueous solution of hydrochloric acid. The precipitate was filtered off, washed with 100 mL of a 10% aqueous sodium chloride solution and dried in vacuo. In this way, 30.5 g of a pale yellow product was obtained.

Preparation Examples 2 to 15: Compounds of the formula:

It can be prepared by a method similar to that described in Preparation Example 1, except that 9.2 g of 2-ethylaminoethanol is substituted with an equivalent molar amount of the corresponding amine. X is as defined in the following table. After cooling to 50 ° C, the precipitated compound was directly isolated into a 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〇CH,CH,OH 25 1324177 5 V NH I 6 -NHCH,CH,OH 7 -NHCH,CH?OCH, 8 -NHCH ,CH,COOH 9 -NHCH,CH,10 -N(CH〇CH,COOH 11 -N(CH,CH,OH), 12 -ό 13 I 14 -NHCH,COOH 15 -NH -CH-COOH NH II ch2ch2ch2-nh-c-nh2 Preparation Example 116:

(103)

In a 1 liter flask, 0.05 moles of the following compound: 26 1324177

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

It can be prepared by a method similar to that described in Preparation Example 16, except that 9.5 g of morpholine is substituted with an equivalent molar amount of the corresponding amine. X is as defined in Table 2 below. The compound with high solubility was treated with a 6-mole aqueous solution of hydrochloric acid to adjust the pH to a number of 4.5 before cooling to 50 °C. 27 1324177 Table 2 Examples X 17 -NCCH,CH,)CH,CH7OH 18 1 19 -N(CH,CH,OH)7 Preparation Example 20:

In a 2 liter flask, 130 ml of methyl ethyl ketone, 80 ml of deionized water, 150 g of ice and 18.5 g of cyanuric chloride were mixed. 185 ml of an aqueous solution of 4,4'-diaminostilbene-2,2'-disulfonic acid (as a disodium salt) (concentration of 100 g/l) was added dropwise over a period of 30 minutes. The temperature is between -8 and +5 °C. The pH was maintained between 4.5 and 5 by the addition of an aqueous solution of sodium carbonate. A light yellow suspension was obtained. Then, 27.2 g of ethanolamine (99%) was added by using a dropping funnel. The pH was increased to a number of 10 and then lowered to a lower number, at which time the temperature was increased to 1 Torr to 15. 0. The reaction mixture was then warmed to a temperature of 45 ° C and maintained at this temperature for 20 minutes. The mixture of methyl ethyl ketone and water was removed by evaporation during heating to 98 ° C in 30 minutes; the pH was maintained between 8.5 and 9 by the addition of an aqueous sodium hydroxide solution. The reaction mixture was cooled to 50 ° C after further addition of aqueous sodium hydroxide was not required to maintain the pH at a fixed number of 28. The pH was adjusted to a number of 値' of 5.5 and the pale yellow crystalline precipitate was filtered off. After drying, 29 g of a pale yellow product was obtained. Preparation Example 21J_

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

29 1324177 However, 15 g of an aqueous solution of ethylamine (70%) was replaced with a corresponding solution containing an equivalent molar amount of diethylamine.

Preparation Example 9.L

In a 1 liter flask, 0.05 mol of bis-(4-morpholinyl-6-chloro-1,3,5-trimethyl-2-yl)-4,4,diamine stilbene The -2,2,-disulfonic acid (as a disodium salt) was suspended in 600 ml of water and heated to a temperature of 60 °C. 6.4 grams of ethanolamine was added and the reaction mixture was heated to 98. (temperature of: The pH was maintained between 8.5 and 9 by the addition of a 4-molar aqueous sodium hydroxide solution. The reaction mixture was cooled to 25 ° C and 10% by volume of sodium chloride was added. The material was filtered, washed with 100 mL of 10% aqueous sodium chloride and dried in vacuo at 70 ° C. In this way, 41.8 g of pale yellow powder was obtained. Example 1: General procedure: A washing solution was prepared by dissolving 0.8 g of washing powder in 200 ml of tap water. 10 g of the bleached cotton fabric was added to the tank and washed at 40 ° C for 15 minutes, then rinsed, dried and ironed at 160 °C. 30 1324177 Use the following washing powders A and B (in grams in the following Tables 3a and 3b): Table 3a (components of washing powders A and B) A 钠 Sodium laurylbenzene sulfonate (LAS) 10 10 g of sodium lauryl ether sulfate (AES) 3 g 3 g Dobanol 23-6.5 (nonionic ethoxylated alcohol) 4 g 4 g sodium tripolyphosphate 30 g zeolite A 20 g sodium carbonate 15 g 15 g 矽Sodium 5 g 5 g sodium sulphate 17 g sodium perborate monohydrate 10 g 10 g TAED 3 g 3 g multi-residual acid salt (co-builder 4 g carboxymethyl cellulose 2 g 2 g perfume 〇_1 g 0.1 g water 5 g 5 g fluorescent brightener X g X g table 3b (washing powder used) fluorescent brightener Preparation of the compound of Example 1 in an amount of 0.2 g of A. Preparation of the compound of Example 2 〇·1 g B Preparation of the compound of Example 3 0.3 g A Preparation of the compound of Example 4 0.2 g A Preparation of the compound of Example 5 0.4 g A Preparation Example 12 Compound 0.15 g Β Preparation Example 13 compound 0.1 g Β Preparation Example 16 compound 0.3 g Β Preparation Example 18 compound 0.2 g A Preparation Example 21 compound 0.3 g A Preparation Example 22 Compound 0.2 g 制备 Preparation of the compound of Example 23 0.1 g Compound of formula (109) 0.3 g 结构 Structure of compound of formula (109): 31 (109) 1324177

Cotton fabrics washed according to the general procedure with the detergents listed in Table 3b showed good whiteness properties. Application Example 2: General procedure: A lotion was prepared by dissolving 0.8 g of washing powder in 200 ml of tap water. Ten grams of bleached cotton fabric was added to the tank and rinsed at 30 ° C for 15 minutes, then rinsed, de-dried and ironed at 160 °C. The following washing powders were used (the amounts given in Tables 4a and 4b below are based on the total weight of the detergent): Table 4a (components of washing powders C and D) CD sodium laurylbenzene sulfonate (LAS) 8% 8% Sodium lauryl ether sulfate (AES) 3% 3% Dobanol 23-6.5 (nonionic ethoxylated alcohol) 5% 5% Zeolite A 20% 20% Polycarboxylate (co-builder) 5% 5% soda ash 18% 18% sodium citrate 4% 4% sodium sulphate 5% 5% hydroxyethane diphosphonic acid (complex) 0.5% 0.5% cellulase 1.5% protease 1.5% carboxymethyl cellulose 1% 1% 32 1324177 Sodium perborate monohydrate 15% 15% TAED 5% 5% Soap 2% 2% Fluorescent brightener X% X% used In each of the above detergents, use a sufficient amount of water to get 100% ^ Table 4b (Washing detergent 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 0.3 0.3% C Preparation of compound of Example 7 0.2% D Preparation Example 8 Compound 0-2% C Preparation of compound of Example 9 0.4% C Preparation of compound of Example 10 0.2% D Preparation of compound of Example 11 0.2% C Preparation of compound of Example 0.3 0.3% D Preparation of compound of Example 15 0.2% C Preparation of compound of Example 17 0.4% C Preparation of compound of Example 19 0.3% C Preparation of compound of Example 20 0.5% C Compound of formula (109) 0.3% D

As for the structure of the compound of the formula (109), see Application Example 1.

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

Claims (1)

1324177. The common tongue book, the year of the bamboo, the month of the bamboo, the 3rd repair (/) original, the patent application scope 1. A detergent composition comprising: at least one compound of the formula (1), (1) wherein: 1 and R2 are each independently hydrogen or unsubstituted or substituted Ci-G alkyl, 乂! And X3 is an amine group, and 乂2 and X4 are a group of the formula -N(R3)R4, wherein R3 and R4 are hydrogen; a cyano group or a CVC8 alkyl group which is unsubstituted or substituted by a hydroxy group or a carboxy group, and wherein CVC8 alkyl is uninterrupted or interrupted by -0; unsubstituted or substituted by ChC% alkyl; or r3 and r4 together with the nitrogen atom to which they are attached form an unsubstituted or Ci-C% alkane The aryl group, the piperidine or the pyrrolidine ring, and the hydrazine are gases, alkali metals or alkaline earth metals or ammonium, and wherein the detergent contains a peroxide, a peroxide activator and/or a bleach catalyst. 2. The composition according to claim 1, wherein R3 and R4 together with the nitrogen atom to which they are attached form an unsubstituted or alkyl-substituted morpholinyl, decyl or pyrrolidine ring. 34 1324177 3. The composition according to claim 1 of the patent application, comprising: 1) 1-70% anionic surfactant and/or nonionic 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% of the compound of formula (1); and vi) 0- 5% of at least one enzyme selected from the group consisting of cellulase, protease, amylase # and lipase. 4. The composition according to claim 1 of the patent application, comprising: i) 5 - 70% of an anionic surfactant and/or a nonionic surfactant » ii) 5-70% builder; iii) 0.5-30% peroxide; W) 0.5-10% peroxide activator and / or 0.1-2% bleach catalyst; v) 0.01-5% of the compound of formula (1); and vi) 0.05 - 5% of at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase. 5. The composition according to claim 1, wherein the composition comprises at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase. 6. The composition according to item 5 of the patent application, wherein the enzyme is egg 35 1324177 white enzyme. 7. The composition according to item 1 of the patent application' wherein the composition contains a peroxide. 8. The composition according to the scope of claim 1 wherein the composition comprises a peroxide and a peroxide activator. 9. The composition according to item 8 of the patent application, wherein the peroxide activator is tetraethylstilbene ethyldiamine. 10. A method for household washing of textile fiber materials, wherein the textile fiber material is contacted with an aqueous detergent solution comprising a compound of formula (1): Wherein 1 and R2 are independently hydrogen or unsubstituted or substituted G-Cs, oxime, and X; are amine groups, and X2 and X4 are groups of the formula -N(R3)R4, wherein R3 And R4 is hydrogen; cyano or Ci-Cs alkyl, which is unsubstituted or substituted by hydroxy or carboxy, and wherein the Ci-C8 alkyl is uninterrupted or interrupted by -〇-; unsubstituted or via Cl_C4 a substituted cyclohexyl group; or R3 and R4 together with a nitrogen atom to which they are bonded form an unsubstituted or Ci-G alkyl-substituted fluorenyl, piperidine or lysine ring, and 36 1324177 hydrazine is hydrogen, An alkali metal or alkaline earth metal or ammonium, and wherein the detergent contains a peroxide, a peroxide activator and/or a bleach catalyst, and wherein the temperature of the solution is at 5 throughout the process. (: and 40. (: between. 11. The method according to claim 10, wherein the temperature of the solution is between 5 ° C and 30 ° C throughout the method. 12. According to the scope of the patent application The method of item 10 or 11, wherein 1 and R 4 together with the nitrogen atom to which they are bonded form an unsubstituted or G-C4 alkyl-substituted morpholinyl, piperidine or pyrrolidine ring. The method of claim 10, wherein the textile fiber material is treated with a compound of the formula (1) in an amount of from 0.05 to 3.0% by weight based on the weight of the textile fiber material. 14. The method of claim 10 or 11, wherein the detergent comprises At least one enzyme selected from the group consisting of a cellulase, a protease, an amylase, and a lipase. 15. The method according to claim 14, wherein the enzyme is a protease enzyme. Or the method of claim 11, wherein the detergent comprises a peroxide. 17. The method of claim 10 or 11, wherein the detergent comprises a peroxide and a peroxide activator. The method of item 17 wherein the peroxide activity 37 1324177 is tetraethyl fluorenyl ethyl diamine. ^ 壹, pattern (none) 38