WO2003070869A1 - Process for the treatment of textile fibre materials - Google Patents
Process for the treatment of textile fibre materials Download PDFInfo
- Publication number
- WO2003070869A1 WO2003070869A1 PCT/EP2003/001618 EP0301618W WO03070869A1 WO 2003070869 A1 WO2003070869 A1 WO 2003070869A1 EP 0301618 W EP0301618 W EP 0301618W WO 03070869 A1 WO03070869 A1 WO 03070869A1
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- Prior art keywords
- alkyl
- unsubstituted
- substituted
- hydrogen
- formula
- Prior art date
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- BKGUERUEBWCOMX-ONEGZZNKSA-L COc1nc(N2CCOCC2)nc(Nc2ccc(/C=C/c(ccc(Nc3nc(OC)nc(N4CCOCC4)n3)c3)c3S([O-])(=O)=O)c(S([O-])(=O)=O)c2)n1 Chemical compound COc1nc(N2CCOCC2)nc(Nc2ccc(/C=C/c(ccc(Nc3nc(OC)nc(N4CCOCC4)n3)c3)c3S([O-])(=O)=O)c(S([O-])(=O)=O)c2)n1 BKGUERUEBWCOMX-ONEGZZNKSA-L 0.000 description 1
- 0 Cc1nc(N(*)C2=CC(*)[C@](C=Cc(cc3)c(*)cc3N(*)c3nc(*)nc(*)n3)C=C2)nc(*)n1 Chemical compound Cc1nc(N(*)C2=CC(*)[C@](C=Cc(cc3)c(*)cc3N(*)c3nc(*)nc(*)n3)C=C2)nc(*)n1 0.000 description 1
- BPCBXRFTRYZBPB-OWOJBTEDSA-L Nc1nc(Nc2ccc(/C=C/c(ccc(Nc3nc(N)nc(Cl)n3)c3)c3S([O-])(=O)=O)c(S([O-])(=O)=O)c2)nc(Cl)n1 Chemical compound Nc1nc(Nc2ccc(/C=C/c(ccc(Nc3nc(N)nc(Cl)n3)c3)c3S([O-])(=O)=O)c(S([O-])(=O)=O)c2)nc(Cl)n1 BPCBXRFTRYZBPB-OWOJBTEDSA-L 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
- C11D3/42—Brightening agents ; Blueing agents
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3932—Inorganic compounds or complexes
Definitions
- the present invention is directed to detergent formulations containing certain fluorescent whitening agents or mixtures of fluorescent whitening agents, as well as to mixtures of fluorescent whitening agents.
- the present invention provides, as a first aspect, a detergent composition comprising at least one compound of formula
- Rt and R 2 are, independently of each other, hydrogen or unsubstituted or substituted d-C ⁇ alkyl
- X X 2 , X 3 and X 4 are, independently of each other, -N(R 3 )R 4 or -OR 5 , wherein R 3 and R 4 are hydrogen, cyano, unsubstituted or substituted C C ⁇ alkyl or C 5 -C 7 cycloaIkyl, or R 3 and R , together with the nitrogen atom linking them, form a heterocyclic ring, and R 5 is unsubstituted or substituted CrC ⁇ alkyl, and
- M is hydrogen or a cation, together with at least one compound of formula
- R 6 and R 7 independently of each other, are hydrogen, d-C 8 alkyl, d-C 8 alkoxy or halogen, and M is as defined above under formula (1).
- d-C 8 alkyl may be methyl, ethyl, n- or isopropyl, n-, sec- or t-butyl, or linear or branched pentyl, hexyl, heptyl or octyl.
- Preferred are C C 4 alkyl groups.
- the alkyl groups are substituted examples of possible substituents are hydroxyl, halogen, like fluorine, chlorine or bromine, sulfo, sulfato, carboxy and d-C 4 alkoxy, like methoxy and ethoxy.
- Other substituents of such alkyl groups are, for example, cyano, -CONH 2 and phenyl.
- Preferred substituents are hydroxy, carboxy, cyano, -CONH 2 and phenyl, especially hydroxy and carboxy. Furthermore, highly preferred substituents are hydroxy and C r C alkoxy, especially hydroxy.
- the alkyl groups can also be uninterrupted or interrupted by -O- (in case of alkyl groups containing two or more carbon atoms).
- C 5 -C 7 cycloalkyl groups are cyclopentyl and especially cyclohexyl. These groups can be unsubstituted or substituted by, for example, d-C -alkyl, like methyl. Preferred are the corresponding unsubstituted cycloalkyl groups.
- d-C 8 alkoxy may be methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec.-butoxy, tert.-butoxy, or linear or branched higher alkoxy groups.
- Halogen may be fluorine, chlorine, bromine or iodine, preferably chlorine. If R 3 and R 4 together with the nitrogen atom form a heterocyclic ring such a ring system can be, for example, morpholino, piperidine or pyrrolidine.
- the heterocyclic ring can be unsubstituted or substituted.
- An example for such substituents is d-C 4 alkyl, especially methyl.
- 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-, di-, tri- or tetra-d-dalkylammonium, mono-, di- or tri-C 2 -C 4 -hydroxyalkylammonium or ammonium that is di- or tri-substituted with a mixture of C r C 4 -alkyl and C 2 -C 4 -hydroxyalkyl groups.
- Highly preferred is sodium.
- R and R 2 are preferably hydrogen or d-C 4 alkyl, especially hydrogen.
- R 3 and R are preferably hydrogen; cyano; d-C 8 alkyl which is unsubstituted or substituted by hydroxy, carboxy, cyano, -CONH 2 or phenyl, especially by hydroxy or carboxy, and wherein the d-C 8 alkyl group is uninterrupted or interrupted by -O-; unsubstituted or d-C 4 alkyl- substituted C 5 -C 7 cycloalkyl, especially cyclohexyl; or R 3 and R 4 , together with the nitrogen atom linking them, form an unsubstituted or C C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring.
- R 3 and R 4 are hydrogen, unsubstituted or hydroxy-substituted C r C 8 alkyl, unsubstituted or d-C 4 alkyl-substituted C 5 -C 7 cycloalkyl, or R 3 and R 4 , together with the nitrogen atom linking them, form an unsubstituted or C C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring.
- R 3 and R 4 are hydrogen, unsubstituted or hydroxy-substituted d-C 8 alkyl, or R 3 and R 4 , together with the nitrogen atom linking them, form an unsubstituted or d-C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring. Most preferred are unsubstituted or C r C 4 alkyl-substituted morpholino, piperidine or pyrrolidine rings, especially morpholino, formed by R 3 and R 4 together with the nitrogen atom linking them.
- Examples of -N(R 3 )R 4 groups are -NH 2 , -NHCH 3 , -NHC 2 H 5) -NH(n-C 3 H 7 ), -NH(i-C 3 H 7 ), -NH(i-C 4 H 9 ), -N(CH 3 ) 2 , -N(C 2 H 5 ) 2 , -N(i-C 3 H 7 ) 2 , -NH(CH 2 CH 2 OH), -N(CH 2 CH 2 OH) 2 , -N(CH 2 CH(OH)CH 3 ) 2 , -N(CH 3 )(CH 2 CH 2 OH), -N(C 2 H 5 )(CH 2 CH 2 OH), -N(i-C 3 H 7 )(CH 2 CH 2 CH 2 OH), -NH(CH 2 CH(OH)CH 3 ), -N(C 2 H 5 )(CH 2 CH(OH)CH 3 ), -NH(CH 2 CH(OH)CH
- R 5 is preferably d-C 8 alkyl, especially C ⁇ -C 4 alkyl, which is unsubstituted or substituted by d- C 4 alkoxy or especially hydroxy. Highly preferred for R 5 is methyl or ethyl, especially methyl.
- Xi, X 2 , X 3 and X 4 are preferably a radical of formula -N(R 3 )R 4 .
- Xi and X 3 have preferably the same meanings.
- X 2 and X 4 have preferably the same meanings.
- the four radicals X 1 f X 2 , X 3 and X 4 do not have identical meanings.
- R T and R 2 are hydrogen or C ⁇ -C 4 alkyl
- R 3 and R are hydrogen; cyano; d-C 8 alkyl which is unsubstituted or substituted by hydroxy, carboxy, cyano, -CONH 2 or phenyl and wherein the C ⁇ -C 8 alkyl group is uninterrupted or interrupted by -O-; unsubstituted or d-C 4 alkyl-substituted C 5 -C 7 cycloalkyl; or R 3 and R 4 , together with the nitrogen atom linking them, form an unsubstituted or C ⁇ -C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring; and R 5 is d-C 8 alkyl which is unsubstituted or substituted by hydroxy.
- R 3 , R 4 and R 5 the above preferences apply.
- X 2 and X 4 are a radical of formula -N(R 3 )R 4 , wherein R 3 and R 4 are hydrogen; cyano; C C 8 alkyl which is unsubstituted or substituted by hydroxy or carboxy, and wherein the d- C 8 alkyl group is uninterrupted or interrupted by -O-; unsubstituted or C ⁇ -C 4 alkyl-substituted cyclohexyl; or R 3 and R 4 , together with the nitrogen atom linking them, form an unsubstituted or d-C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring.
- R 3 and R 4 the above preferences apply.
- R 6 and R 7 are preferably hydrogen. Each of the sulfo groups indicated in formula (2) are preferably bonded in ortho position. Interesting compounds of formula (2) are those wherein R 6 and R 7 are hydrogen and each of the sulfo groups indicated in formula (2) are bonded in ortho position.
- M is preferably hydrogen, an alkaline- or alkaline earth-metal, or ammonium, especially sodium.
- the molar ratio of compound (1) to compound (2) is usually in the range of from 0.1 :99.9 to 99.9:0.1 , preferably from 1 :99 to 99:1 and more preferably from 5:95 to 95:5. Highly preferred is a molar ratio of from 10:90 to 90:10, especially 20:80 to 80:20. Most important is a molar ratio of from 30:70 to 70:30, especially 40:60 to 60:40.
- Compounds of formula (1 ) may be produced by reacting, under known reaction conditions, cyanuric chloride, successively, in any desired sequence, with each of 4,4'-diaminostilbene-2,2'- disulfonic acid, and amino compounds capable of introducing the groups Xi, X 2 , X 3 and X 4 .
- cyanuric chloride a compound capable of introducing the groups Xi, X 2 , X 3 and X 4 .
- 2 moles of cyanuric chloride are initially reacted with 1 mole of 4,4'-diaminostilbene-2,2'- disulfonic acid and then reacting the intermediate obtained in any order with amino compounds capable of introducing the groups Xi, X 2 , X 3 and X 4 .
- Compounds of formula (1 ) containing a radical of formula -OR 5 can for example be prepared by first reacting cyanuric chloride with the correponding alcohol HOR 5 , reacting the product obtained with 4,4'-diaminostilbene-2,2'- disulfonic acid and then reacting the intermediate with further compounds capable of introducing the remaining groups of Xi, X 2 , X 3 and X 4 . The last reaction is preferably carried out with the corresponding amines.
- the present invention is directed to mixtures of compounds of formulae (1) and (2).
- compounds of formulae (1) and (2) the preferences given above apply.
- Compounds of formula (2) wherein R 6 and R are hydrogen and each of the sulfo groups indicated in formula (2) are bonded in ortho position are preferred.
- the molar ratio of compound (1) to compound (2) is usually in the range of from 0.1:99.9 to 99.9:0.1 , preferably from 1 :99 to 99:1 and more preferably from 5:95 to 95:5.
- Highly preferred is a molar ratio of from 10:90 to 90:10, especially 20:80 to 80:20.
- Most important is a molar ratio of from 30:70 to 70:30, especially 40:60 to 60:40.
- the detergent compositions used preferably comprise i) 1 -70% of an anionic surfactant and/or a nonionic surfactant; ii) 0-75% of a builder; iii) 0-30% of a peroxide; iv) 0-10% of a peroxide activator; and v) 0.001 -5% of a mixture of compounds of formulae (1) and (2), each by weight, based on the total weight of the detergent.
- the detergent compositions used comprise i) 5-70% of an anionic surfactant and/or a nonionic surfactant; ii) 5-70% of a builder; iii) 0.5-30% of a peroxide; iv) 0.5-10% of a peroxide activator and/or 0.1 -2% of a bleaching catalyst; and v) 0.01-5% of a mixture of compounds of formulae (1) and (2), each by weight, based on the total weight of the detergent.
- an amount of a mixture of compounds of formulae (1) and (2) of 0.001-5%, especially an amount of 0.01-5% is used. Highly preferred is an amount of 0.05-5%, especially 0.05 to 2%.
- amounts given in percent are to be understood as being percent by weight, based on the total weight, unless otherwise stated.
- the detergent may be formulated as a solid, as an aqueous liquid comprising, e.g., 5-50, preferably 10-35% water or as a non-aqueous liquid detergent, containing not more than 5, preferably 0-1 wt.% of water, and based on a suspension of a builder in a non-ionic surfactant, as described, e.g., in GB-A-2158454.
- the anionic surfactant component may be, e.g., an alkylbenzenesulfonate, an alkylsulfate, an alkylethersulfate, an olefinsulfonate, an alkanesulfonate, a fatty acid salt, an alkyl or alkenyl ether carboxylate or an ⁇ -sulfofatty acid salt or an ester thereof.
- alkylbenzenesulfonates having 10 to 20 carbon atoms in the alkyl group
- alkylsulfates having 8 to 18 carbon atoms
- alkylethersulfates having 8 to 18 carbon atoms
- fatty acid salts being derived from palm oil or tallow and having 8 to 18 carbon atoms.
- the average molar number of ethylene oxide added in the alkylethersulfate is preferably 1 to 20, preferably 1 to 10.
- the salts are preferably derived from an alkaline metal like sodium and potassium, especially sodium.
- alkali metal sarcosinates of formula R-CO(R 1 )CH 2 COOM 1 in which R is alkyl or alkenyl having 9-17 carbon atoms in the alkyl or alkenyl radical, R 1 is C C 4 alkyl and M 1 is alkali metal, especially sodium.
- the nonionic surfactant component may be, e.g., primary and secondary alcohol ethoxylates, especially the C 8 -C 20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -C 15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
- Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
- 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 to these surfactants it is preferred that the lower limit is 10% by weight.
- the builder component may be an alkali metal phosphate, especially a tripolyphosphate; a carbonate or bicarbonate, especially the sodium salts thereof; a silicate or disilicate; an aluminosilicate; a polycarboxylate; a polycarboxylic acid; an organic phosphonate; or an aminoalkylene poly (alkylene phosphonate); or a mixture of these.
- Preferred silicates are crystalline layered sodium silicates of the formula NaHSi m O 2m+ ⁇ .pH 2 O or Na 2 Si m O 2m+ ⁇ .pH 2 O in which m is a number from 1.9 to 4 and p is 0 to 20.
- Preferred aluminosilicates are the commercially-available synthetic materials designated as
- Zeolites A, B, X, and HS or mixtures of these. Zeolite A is preferred.
- Preferred polycarboxylates include hydroxypolycarboxylates, in particular citrates, polyacrylates and their copolymers with maleic anhydride.
- Preferred polycarboxylic acids include nitrilotriacetic acid and ethylene diamine tetra-acetic acid.
- Preferred organic phosphonates or aminoalkylene poly (alkylene phosphonates) are alkali metal ethane 1 -hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates and diethylene triamine penta methylene phosphonates.
- the amount of builders is preferably 5-70% by weight, preferably 5-60% by weight and more preferably 10-60% by weight. As to the builders it is preferred that the lower limit is 15% by weight, especially 20% by weight.
- Suitable peroxide components include, for example, the organic and inorganic peroxides (like sodium peroxides) known in the literature and available commercially that bleach textile materials at conventional washing temperatures, for example at from 5 to 95°C.
- the organic peroxides are, for example, monoperoxides or polyperoxides having alkyl chains of at least 3, preferably 6 to 20, carbon atoms; in particular diperoxydicarboxylates having 6 to 12 C atoms, such as diperoxyperazelates, diperoxypersebacates, diperoxyphthalates and/or diperoxydodecanedioates, especially their corresponding free acids, are of interest.
- very active inorganic peroxides such as persulphate, perborate and/or percarbonate. It is, of course, also possible to employ mixtures of organic and/or inorganic peroxides.
- the amount of peroxide is preferably 0.5-30% by weight, preferably 1-20% by weight and more preferably 1-15% by weight.
- the lower limit is preferably 2% by weight, especially 5% by weight.
- the peroxides are preferably activated by the inclusion of a bleach activator.
- a bleach activator Preferred are such compounds that, under perhydrolysis conditions, yield unsubstituted or substituted perbenzo- and/or peroxo-carboxylic acids having from 1 to 10 carbon atoms, especially from 2 to 4 carbon atoms.
- Suitable compounds include those that carry O- and/or N-acyl groups having the said number of carbon atoms and/or unsubstituted or substituted benzoyl groups.
- polyacylated alkylenediamines especially tetraacetylethylenediamine (TAED), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N,N-diacetyl-N,N-dimethyl-urea (DDU), acylated triazine derivatives, especially 1 ,5-diacetyl-2,4-dioxohexahydro-1 ,3,5-triazine (DADHT), compounds of formula
- R is a sulfonate group, a carboxylic acid group or a carboxylate group, and wherein R' is linear or branched (C 7 -C ⁇ 5 )alkyl; also activators that are known under the names SNOBS, SLOBS, NOBS and DOBA, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and acetylated sorbitol and mannitol and acylated sugar derivatives, especially pentaacetylglucose (PAG), sucrose polyacetate (SUPA), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, and acetylated, optionally N-alkylated, glucamine and gluconolactone.
- PAG pentaacetylglucose
- the amount of bleach activator is preferably 0-10% by weight, preferably 0-8% by weight.
- the lower limit is preferably 0.5% by weight, especially 1% by weight.
- Bleaching catalysts which may be added, include, e.g., enzymatic peroxide precursors and/or metal complexes.
- Preferred metal complexes are manganese, cobalt or iron complexes such as manganese or iron phthalocyanines or the complexes described in EP-A- 0509787.
- the amount is preferably 0.005 to 2% by weight, more preferably 0.01 to 2% by weight, especially 0.05 to 2% by weight. Highly preferred is an amount of 0.1-2% by weight.
- bleaching catalysts As examples for bleaching catalysts the following are mentioned:
- the detergent can optionally contain enzymes. Enzymes can be added to detergents for stain removal.
- the enzymes usually improve the performance on stains that are either protein- or starch-based, such as those caused by blood, milk, grass or fruit juices.
- Preferred enzymes are cellulases, proteases, amylases and lipases.
- Preferred enzymes are cellulases and proteases, especially proteases.
- Cellulases are enzymes which act on cellulose and its derivatives and hydrolyze them into glucose, cellobiose, cellooligosaccharide. Cellulases remove dirt and have the effect of mitigating the roughness to the touch.
- enzymes to be used include, but are by no means limited to, the following: proteases as given in US-B-6,242,405, column 14, lines 21 to 32; lipases as given in US-B-6,242,405, column 14, lines 33 to 46; amylases as given in US-B-6,242,405, column 14, lines 47 to 56; and cellulases as given in US-B-6,242,405, column 14, lines 57 to 64.
- the enzymes can optionally be present in the detergent.
- the enzymes are usually present in an amount of 0.01-5% by weight, preferably 0.05-5% and more preferably 0.1-4% by weight, based on the total weight of the detergent.
- Further preferred additives for the detergents according to the invention are polymers that, during the washing of textiles, inhibit staining caused by dyes in the washing liquor that have been released from the textiles under the washing conditions (dye fixing agents, dye transfer inhibitors).
- Such polymers are preferably polyvinylpyrrolidones, polyvinylimidazoles or polyvinylpyridine N-oxides which may have been modified by the incorporation of anionic or cationic substituents, especially those having a molecular weight in the range from 5000 to 60 000, more especially from 10 000 to 50 000.
- Such polymers are usually used in an amount of from 0.01 to 5 %, preferably 0.05 to 5 % by weight, especially 0.1 to 2 % by weight, based on the total weight of the detergent.
- Preferred polymers are those given in WO-A-02/02865 (see especially page 1 , last paragraph and page 2, first paragraph).
- the detergents used will usually contain one or more auxiliaries such as soil suspending agents, for example sodium carboxymethylcellulose; salts for adjusting the pH, for example alkali or alkaline earth metal silicates; foam regulators, for example soap; salts for adjusting the spray drying and granulating properties, for example sodium sulphate; perfumes; and also, if appropriate, antistatic and softening agents; such as smectite clays; photobleaching agents; pigments; and/or shading agents.
- auxiliaries can be present in an amount of, for example, 0.1 to 20% by weight, preferably 0.5 to 10 % by weight, especially 0.5 to 5 % by weight, based on the total weight of the detergent.
- the detergent compositions can take a variety of physical forms including powder, granular, tablet and liquid forms. Examples thereof are conventional powder heavy-duty detergents, compact and supercompact heavy-duty detergents and tablets, like heavy-duty detergent tablets.
- One important physical form is the so-called concentrated granular form adapted to be added to a washing machine.
- compact detergents Of importance are also the so-called compact (or supercompact) detergents.
- compact detergents In the field of detergent manufacture, a trend has developed recently towards the production of compact detergents, which contain increased amounts of active substance.
- the compact detergents In order to minimize energy expenditure during the washing process, the compact detergents are required to operate efficiently at temperatures as low as 40°C, or even at room temperatures, e.g. at 25°C.
- Such detergents usually contain only low amounts of fillers or processing aids, like sodium sulfate or sodium chloride.
- the amount of such fillers is usually 0-10% by weight, preferably 0-5 % 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.
- the detergents can also be present in the form of tablets. Relevant characteristics of tablets are ease of dispensing and convenience in handling. Tablets are the most compact delivery of solid detergents and have a bulk density of, for example, 0.9 to 1.3 kg/litre. To enable fast disintegration laundry detergent tablets generally contain special disintegrants:
- the tablets can also contain combinations of any of the above disintegrants.
- the detergent may also be formulated as an aqueous liquid comprising 5-50, preferably 10- 35% water or as a non-aqueous liquid detergent, containing not more than 5, preferably 0-1 wt.% of water.
- Non-aqueous liiquid detergent compositions can contain other solvents as carriers.
- Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
- Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1 ,3-propanediol, ethylene glycol, glycerine, and 1 ,2-propanediol) can also be used.
- the compositions may contain from 5% to 90%, typically 10% to 50% of such carriers.
- the detergents can also be present as the so-called "unit liquid dose" form.
- This detergent treatment of textiles can be conducted as a domestic treatment in normal washing machines.
- the textile fibres treated may be natural or synthetic fibres or mixtures thereof.
- natural fibres include vegetable fibres such as cotton, viscose, flax, rayon or linen, preferably cotton and animal fibres such as wool, mohair, cashmere, angora and silk, preferably wool.
- Synthetic fibres include polyester, polyamide and polyacrylonitrile fibres.
- Preferred textile fibres are cotton, polyamide and wool fibres, especially cotton fibres.
- textile fibres treated according to the method of the present invention have a density of less than 200 g/m 2 .
- the process is usually conducted in the temperature range of from 5 to 100°C, especially 5 to 60°C.
- Preferred is a temperature range of 5 to 40°C, especially 5 to 35°C and more preferably 5 to 30°C.
- the detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 11 , preferably between about 7.5 and 11. Laundry products are typically at pH 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
- Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accordance with the invention.
- an effective amount of the detergent composition it is meant, e.g., from 20 g to 300 g of product dissolved or dispersed in a wash solution of volume from 5 to 85 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods. Examples are
- the liquor ratio is preferably 1 :4 to 1 :40, especially 1 :4 to 1 :15. Highly preferred is a liquor ratio of 1 :4 to 1 : 10, especially 1 :5 to 1 :9.
- the present invention is directed to a detergent composition
- a detergent composition comprising at least one compound of formula
- R T and R 2 are, independently of each other, hydrogen or unsubstituted or substituted C C 8 alkyl
- Xi, X 2 , X 3 and X are, independently of each other, -N(R 3 )R 4 or -OR 5) wherein R 3 and R 4 are hydrogen; cyano; d-C 8 alkyl which is unsubstituted or substituted by hydroxy, carboxy, cyano, -CONH 2 or phenyl and wherein the C C 8 alkyl group is uninterrupted or interrupted by
- R 5 is C C 8 alkyl which is unsubstitued or substituted by hydroxy
- M is hydrogen or a cation
- the detergent contains at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase.
- Xi. X 2 . X3 and X 4 are, independently of each other, -N(R 3 )R 4 or -OR 5 , wherein R 3 and R 4 are hydrogen, unsubstituted or hydroxy-substituted CrC 8 alkyl, unsubstituted or C ⁇ -C 4 alkyl- substituted C 5 -C 7 cycloalkyl, or R 3 and R 4 , together with the nitrogen atom linking them, form an unsubstituted or d-C 4 alkyl-substitued morpholino, piperidine or pyrrolidine ring, and R 5 is unsubstituted or hydroxy-substituted C C 8 alkyl, and M is hydrogen or a cation.
- corresponding detergent compositions which contain enzymes as well as peroxide, peroxide activator and/or bleaching catalyst.
- Preferred are detergent compositions comprising i) 1 -70% of an anionic surfactant and/or a nonionic surfactant; ii) 0-75% of a builder; iii) 0-30% of a peroxide; iv) 0-10% of a peroxide activator; v) 0.001 -5% of a compound of formula (1a); and vi) 0.05-5% of at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase, especially protease.
- detergent compositions comprising i) 5-70% of an anionic surfactant and/or a nonionic surfactant; ii) 5-70% of a builder; iii) 0.5-30% of a peroxide; iv) 0.5-10% of a peroxide activator and/or 0.1-2% of a bleaching catalyst; v) 0.01 -5% of a compound of formula (1a); and vi) 0.05-5% of at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase, especially protease.
- the compounds of formula (1a) can be used in the same way as given above for the mixture of compounds of formulae (1) and (2).
- a further object of the present invention is to provide a process for the domestic washing treatment of a textile fibre material wherein the textile fibre material is contacted with an aqueous solution of a detergent comprising a compound of formula (1a) as defined above, and wherein the detergent contains at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase, and wherein the temperature of the solution is between 5°C and 40°C, preferably between 5°C and 30°C, throughout the process.
- the above washing treatment of textile fibers can also be conducted with the mixture of compounds of formulae (1) and (2).
- the compounds and mixtures used according to the present invention are particularly advantageous in that they exhibit not only extremely high whitening ability, but, in addition, in many cases highly desirable water solubilities and also possess excellent white aspects in the solid state.
- a further advantage of the present invention is that the detergent composition delivers improved whiteness performance and fabric feel.
- the compounds and especially the mixtures show very good results with respect to exhaustion properties.
- the compounds have the advantage that they are also effective in the presence of active chlorine donors, such as, for example, hypochlorite and can be used without substantial loss of the effects in washing baths with non-ionic washing agents, for example alkylphenol polyglycol ethers.
- tetraacetylglycoluril or ethylenediamine-tetraacetic acid are the compounds and mixtures of compounds stable both in pulverulent washing agent and in washing baths. In addition, they impart a brilliant appearance in daylight.
- textile fibres treated according to this embodiment of the present invention may be natural or synthetic fibres or mixtures thereof.
- natural fibres include vegetable fibres such as cotton, viscose, flax, rayon or linen, preferably cotton and animal fibres such as wool, mohair, cashmere, angora and silk, preferably wool.
- Synthetic fibres include polyester, polyamide and polyacrylonitrile fibres.
- Preferred textile fibres are cotton, polyamide and wool fibres.
- textile fibres treated according to the present invention have a density of less than 1000 g/m 2 , especially less than 500 g/m 2 and most preferred less than 250 g/m 2 .
- X is as defined in the following Table 2.
- Compounds having high solubility are treated with a 6-molar aqueous solution of hydrochloric acid in order to adjusted the pH to a value of 4.5 before cooling to 50°C.
- the pH increases to a value of 10 and then drops to a lower value, whereby the temperature increases to 10 to 15°C. Then the reaction mixture is warmed to a temperature of 45°C and held at this temperature for 20 minutes. During heating to 98°C within 30 minutes a mixture of methylethylketone and water is distilled off; the pH is maintained at a value between 8.5 and 9 by addition of an aqueous sodium hydroxide solution. After no further addition of aqueous sodium hydroxide solution is necessary in order to maintain the pH at a constant value the reaction mixture is cooled to 50°C. The pH is adjusted to a value of 5.5 and a yellowish crystalline precipitate can be filtered off. After drying 29g of a yellowish product are obtained.
- the compound of formula (107) can be prepared in analogy to the process given in Preparation Example 21 , by replacing 15 g of an aqueous solution of ethylamine (70%) with a corresponding solution containing an equimolar amount of diethylamine.
- Preparation Example 23
- a wash liquor is prepared by dissolving 0.8 g of a washing powder in 200 ml of tap water. 10 g of bleached cotton fabric is added to the bath and washed at 40°C over 15 minutes and then rinsed, spin-dried and ironed at 160°C.
- washing powders A and B are used (amounts given in the following Tables 3a and 3b are in g):
- a wash liquor is prepared by dissolving 0.8 g of a washing powder in 200 ml of tap water. 10 g of bleached cotton fabric is added to the bath and washed at 30°C over 15 minutes and then rinsed, spin-dried and ironed at 160°C.
- washing powders are used (amounts given in the following Tables 4a and 4b are percent by weight, based on the total weight of the detergent):
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Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03702652A EP1485460B1 (en) | 2002-02-25 | 2003-02-18 | Process for the treatment of textile fibre materials |
AU2003205777A AU2003205777B2 (en) | 2002-02-25 | 2003-02-18 | Process for the treatment of textile fibre materials |
JP2003569763A JP4567975B2 (en) | 2002-02-25 | 2003-02-18 | Method of processing fiber material |
BR0306187-6A BR0306187A (en) | 2002-02-25 | 2003-02-18 | Process for the treatment of textile fiber materials |
DE60308661T DE60308661T2 (en) | 2002-02-25 | 2003-02-18 | PROCESS FOR THE TREATMENT OF TEXTILE FIBER MATERIALS |
BRPI0306187-6A BRPI0306187B1 (en) | 2002-02-25 | 2003-02-18 | detergent compositions and mixture of compounds for the treatment of textile fiber materials |
ZA2004/02942A ZA200402942B (en) | 2002-02-25 | 2004-04-19 | Process for the treatment of textile fibre materials |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02405136 | 2002-02-25 | ||
EP02405136.9 | 2002-02-25 | ||
EP02405876 | 2002-10-11 | ||
EP02405876.0 | 2002-10-11 |
Publications (1)
Publication Number | Publication Date |
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WO2003070869A1 true WO2003070869A1 (en) | 2003-08-28 |
Family
ID=27758773
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2003/001618 WO2003070869A1 (en) | 2002-02-25 | 2003-02-18 | Process for the treatment of textile fibre materials |
PCT/EP2003/001619 WO2003070870A1 (en) | 2002-02-25 | 2003-02-18 | Process for the treatment of textile fibre materials |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/EP2003/001619 WO2003070870A1 (en) | 2002-02-25 | 2003-02-18 | Process for the treatment of textile fibre materials |
Country Status (12)
Country | Link |
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EP (4) | EP1485460B1 (en) |
JP (2) | JP4567976B2 (en) |
CN (2) | CN1294248C (en) |
AR (3) | AR038583A1 (en) |
AT (2) | ATE340847T1 (en) |
AU (2) | AU2003205777B2 (en) |
BR (3) | BR0306187A (en) |
DE (2) | DE60308661T2 (en) |
ES (3) | ES2556971T3 (en) |
TW (2) | TWI332045B (en) |
WO (2) | WO2003070869A1 (en) |
ZA (2) | ZA200402942B (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004085594A1 (en) * | 2003-03-24 | 2004-10-07 | Ciba Specialty Chemicals Holding Inc. | Detergent compositions |
WO2005068597A1 (en) * | 2004-01-20 | 2005-07-28 | Ciba Specialty Chemicals Holding Inc. | Triazinylaminostilbene disulphonic acid mixtures |
WO2005103220A1 (en) * | 2004-04-20 | 2005-11-03 | Ciba Specialty Chemicals Holding Inc. | Amphoteric fluorescent whitening agents in detergent formulations |
US9885095B2 (en) | 2014-01-31 | 2018-02-06 | Goldcorp Inc. | Process for separation of at least one metal sulfide from a mixed sulfide ore or concentrate |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BR0306187A (en) * | 2002-02-25 | 2004-10-19 | Ciba Sc Holding Ag | Process for the treatment of textile fiber materials |
KR101253657B1 (en) * | 2004-08-30 | 2013-04-10 | 시바 홀딩 인코포레이티드 | Shading Process |
WO2007135003A1 (en) * | 2006-05-23 | 2007-11-29 | Ciba Holding Inc. | A detergent composition for textile fibre materials |
CN104801511B (en) * | 2014-01-26 | 2018-09-18 | 艺康美国股份有限公司 | Ex-situ cleaning process and clean-in-place system |
CN105001671A (en) * | 2015-06-29 | 2015-10-28 | 纳爱斯丽水日化有限公司 | Compound brightening agent and washing agent composition containing compound brightening agent |
CN107857738A (en) * | 2017-11-28 | 2018-03-30 | 贺州学院 | The synthesis and application of hexadecylamino pyrrolotriazine derivatives |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4460485A (en) * | 1983-07-15 | 1984-07-17 | Lever Brothers Company | Polyester fabric conditioning and whitening composition |
WO1995013354A1 (en) * | 1993-11-10 | 1995-05-18 | The Procter & Gamble Company | Detergent compositions which provide dye transfer inhibition benefits |
EP0682145A2 (en) * | 1994-05-12 | 1995-11-15 | Ciba-Geigy Ag | Textile treatment |
EP0728749A2 (en) * | 1995-02-22 | 1996-08-28 | Ciba-Geigy Ag | Triazine derivatives, their preparation and use |
EP0850934A1 (en) * | 1996-12-24 | 1998-07-01 | Ciba SC Holding AG | Triazinylaminostilbene ultra-violet absorbing agents |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1107667B (en) * | 1959-07-30 | 1961-05-31 | Wolfen Filmfab Veb | Process for the preparation of optical brightening agents |
JPS515308A (en) * | 1974-07-03 | 1976-01-17 | Kao Corp | HAKUSHOKUGOSEISENZAISOSEIBUTSU |
DE2962980D1 (en) * | 1978-02-14 | 1982-07-22 | Bayer Ag | Composition comprising optical brightening agents for use in the whitening of paper coating compositions |
US4364845A (en) * | 1978-07-17 | 1982-12-21 | Ciba-Geigy Corporation | Concentrated aqueous solutions of sulfo group-containing fluorescent brighteners which are stable on storage |
JPS5817199A (en) * | 1981-07-23 | 1983-02-01 | 花王株式会社 | Detergent composition |
GB2158454B (en) | 1984-04-06 | 1988-05-18 | Colgate Palmolive Co | Liquid laundry detergent composition |
GB9108136D0 (en) | 1991-04-17 | 1991-06-05 | Unilever Plc | Concentrated detergent powder compositions |
DE4416438A1 (en) | 1994-05-10 | 1995-11-16 | Basf Ag | Mononuclear or multinuclear metal complexes and their use as bleaching and oxidation catalysts |
GB9409465D0 (en) * | 1994-05-12 | 1994-06-29 | Ciba Geigy Ag | Protective use |
DE4443177A1 (en) | 1994-12-05 | 1996-06-13 | Henkel Kgaa | Activator mixtures for inorganic per compounds |
DE69615582T2 (en) | 1995-12-29 | 2002-07-11 | Novozymes As | PARTICLE CONTAINING ENZYME AND LIQUID DETERGENT CONCENTRATE |
JPH09241693A (en) * | 1996-03-05 | 1997-09-16 | Lion Corp | Production of high-bulk density granular detergent composition |
ZA974226B (en) * | 1996-05-17 | 1998-12-28 | Procter & Gamble | Detergent composition |
GB9610832D0 (en) * | 1996-05-23 | 1996-07-31 | Ciba Geigy Ag | Stilbene compounds and their use |
GB2318360A (en) * | 1996-10-15 | 1998-04-22 | Ciba Geigy Ag | Fluorescent whitening agent formulation |
AU6156200A (en) | 1999-07-14 | 2001-02-05 | Ciba Specialty Chemicals Holding Inc. | Metal complexes of tripodal ligands |
DE60033522T8 (en) | 1999-07-28 | 2008-03-27 | Ciba Specialty Chemicals Holding Inc. | WATER-SOLUBLE GRANULES OF MANGANIC COMPLEXES FROM THE SALT TYPE |
US6294047B1 (en) * | 1999-07-30 | 2001-09-25 | Institute Of Paper | Methods for reducing fluorescence in paper-containing samples |
JP2001342495A (en) * | 2000-06-05 | 2001-12-14 | Kao Corp | Detergent composition |
US20040034938A1 (en) | 2000-07-04 | 2004-02-26 | Hauke Rohwer | Method for treating textile fibre materials or leather |
JP4414653B2 (en) | 2001-04-30 | 2010-02-10 | チバ ホールディング インコーポレーテッド | Metal complex compounds and their use as oxidation catalysts |
BR0306187A (en) * | 2002-02-25 | 2004-10-19 | Ciba Sc Holding Ag | Process for the treatment of textile fiber materials |
-
2003
- 2003-02-18 BR BR0306187-6A patent/BR0306187A/en active IP Right Grant
- 2003-02-18 BR BRPI0306187-6A patent/BRPI0306187B1/en unknown
- 2003-02-18 DE DE60308661T patent/DE60308661T2/en not_active Expired - Lifetime
- 2003-02-18 ES ES06118792.8T patent/ES2556971T3/en not_active Expired - Lifetime
- 2003-02-18 AT AT03702652T patent/ATE340847T1/en active
- 2003-02-18 AT AT03706527T patent/ATE340242T1/en active
- 2003-02-18 CN CNB038016168A patent/CN1294248C/en not_active Expired - Lifetime
- 2003-02-18 BR BRPI0306184-1B1A patent/BR0306184B1/en active IP Right Grant
- 2003-02-18 JP JP2003569764A patent/JP4567976B2/en not_active Expired - Fee Related
- 2003-02-18 JP JP2003569763A patent/JP4567975B2/en not_active Expired - Fee Related
- 2003-02-18 EP EP03702652A patent/EP1485460B1/en not_active Expired - Lifetime
- 2003-02-18 DE DE60308485T patent/DE60308485T2/en not_active Expired - Lifetime
- 2003-02-18 CN CNB038016044A patent/CN1294247C/en not_active Expired - Lifetime
- 2003-02-18 ES ES03706527T patent/ES2271534T3/en not_active Expired - Lifetime
- 2003-02-18 EP EP03706527A patent/EP1478724B1/en not_active Expired - Lifetime
- 2003-02-18 EP EP06118792.8A patent/EP1715029B1/en not_active Expired - Lifetime
- 2003-02-18 AU AU2003205777A patent/AU2003205777B2/en not_active Ceased
- 2003-02-18 AU AU2003208870A patent/AU2003208870B2/en not_active Ceased
- 2003-02-18 WO PCT/EP2003/001618 patent/WO2003070869A1/en active IP Right Grant
- 2003-02-18 WO PCT/EP2003/001619 patent/WO2003070870A1/en active IP Right Grant
- 2003-02-18 ES ES03702652T patent/ES2271529T3/en not_active Expired - Lifetime
- 2003-02-18 EP EP06118810A patent/EP1724333A1/en not_active Withdrawn
- 2003-02-21 AR ARP030100573A patent/AR038583A1/en active IP Right Grant
- 2003-02-21 AR ARP030100572A patent/AR038582A1/en active IP Right Grant
- 2003-02-24 TW TW092103771A patent/TWI332045B/en not_active IP Right Cessation
- 2003-02-24 TW TW092103773A patent/TWI324177B/en not_active IP Right Cessation
-
2004
- 2004-04-19 ZA ZA2004/02942A patent/ZA200402942B/en unknown
- 2004-04-19 ZA ZA2004/02941A patent/ZA200402941B/en unknown
-
2007
- 2007-08-14 AR ARP070103604A patent/AR067835A2/en active IP Right Grant
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4460485A (en) * | 1983-07-15 | 1984-07-17 | Lever Brothers Company | Polyester fabric conditioning and whitening composition |
WO1995013354A1 (en) * | 1993-11-10 | 1995-05-18 | The Procter & Gamble Company | Detergent compositions which provide dye transfer inhibition benefits |
EP0682145A2 (en) * | 1994-05-12 | 1995-11-15 | Ciba-Geigy Ag | Textile treatment |
EP0728749A2 (en) * | 1995-02-22 | 1996-08-28 | Ciba-Geigy Ag | Triazine derivatives, their preparation and use |
EP0850934A1 (en) * | 1996-12-24 | 1998-07-01 | Ciba SC Holding AG | Triazinylaminostilbene ultra-violet absorbing agents |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004085594A1 (en) * | 2003-03-24 | 2004-10-07 | Ciba Specialty Chemicals Holding Inc. | Detergent compositions |
US7863236B2 (en) | 2003-03-24 | 2011-01-04 | Ciba Specialty Chemicals Corp. | Detergent compositions |
WO2005068597A1 (en) * | 2004-01-20 | 2005-07-28 | Ciba Specialty Chemicals Holding Inc. | Triazinylaminostilbene disulphonic acid mixtures |
US7585333B2 (en) | 2004-01-20 | 2009-09-08 | Ciba Specialty Chemicals Corporation | Triazinylaminostilbene disulphonic acid mixtures |
WO2005103220A1 (en) * | 2004-04-20 | 2005-11-03 | Ciba Specialty Chemicals Holding Inc. | Amphoteric fluorescent whitening agents in detergent formulations |
US9885095B2 (en) | 2014-01-31 | 2018-02-06 | Goldcorp Inc. | Process for separation of at least one metal sulfide from a mixed sulfide ore or concentrate |
US10370739B2 (en) | 2014-01-31 | 2019-08-06 | Goldcorp, Inc. | Stabilization process for an arsenic solution |
US11124857B2 (en) | 2014-01-31 | 2021-09-21 | Goldcorp Inc. | Process for separation of antimony and arsenic from a leach solution |
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