WO1995033814A1 - Composition detergente amelioree - Google Patents

Composition detergente amelioree Download PDF

Info

Publication number
WO1995033814A1
WO1995033814A1 PCT/EP1995/001823 EP9501823W WO9533814A1 WO 1995033814 A1 WO1995033814 A1 WO 1995033814A1 EP 9501823 W EP9501823 W EP 9501823W WO 9533814 A1 WO9533814 A1 WO 9533814A1
Authority
WO
WIPO (PCT)
Prior art keywords
detergent
detergent composition
sodium
polymer
bleach
Prior art date
Application number
PCT/EP1995/001823
Other languages
English (en)
Inventor
Suk Hyung Cho
Velayudhan Nair Gopa Kumar
Perincherry Aravindakshan
Iyer Varadarajan Nagarajan
Original Assignee
Unilever N.V.
Unilever Plc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever N.V., Unilever Plc filed Critical Unilever N.V.
Priority to AU25641/95A priority Critical patent/AU2564195A/en
Publication of WO1995033814A1 publication Critical patent/WO1995033814A1/fr

Links

Classifications

    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3788—Graft polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • 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
    • C11D3/3942—Inorganic per-compounds

Definitions

  • the present invention relates to fabric washing compositions having low temperature bleaching efficiency and more particularly to compositions which include polysaccharide graft copolymers for obtaining this efficiency.
  • Fabric bleaching is well known and bleach systems commonly used in the detergent industry are perborate bleaches.
  • the perborate bleaches are a category of oxygen bleaches. From the fabric and colour safety point of view the oxygen bleaches are preferred to the chlorine bleaches.
  • Sodium perborate is widely used as bleaching agent in detergent formulations.
  • the bleaching action of such formulations where perborate alone is used as the active bleaching agent is effective only at high temperatures of about 60°C and above.
  • a detergent formulation containing perborate alone as the active bleach ingredient or similar oxygen bleach compounds such as percarbonate does not exhibit desirable or effective bleach properties at temperatures lower than 60°C.
  • activators for perborates has been suggested and efficient bleaching at lower temperatures could be achieved. These activators combine with the perborates to form perco pounds which have higher bleaching potency at lower temperatures.
  • the activators which are commonly used are N,N,N',N' tetraacetylethylene diamine (TAED) , sodium nonanoyloxybenzene sulphonate (SNOBS) , sodium acetoxybenzene sulphonate (SABS) , sodium benzoyloxybenzene sulphonate (P-15) .
  • transition metal ions e.g. Mn ions
  • peracids e.g., phthaloyl-a ido-percaproic acid (PAP)
  • PAP phthaloyl-a ido-percaproic acid
  • the inventors have surprisingly found that the incorporation of a polysaccharide graft copolymer (e.g., starch graft polymethacrylic acid) into a detergent composition comprising peroxy compound bleach synergistically improves the bleaching efficiency of the detergent composition at low temperatures.
  • a polysaccharide graft copolymer e.g., starch graft polymethacrylic acid
  • the present invention provides a detergent composition
  • a detergent composition comprising: i) a detergent active material; ii) a bleaching system comprising a peroxy bleach, a polysaccharide graft copolymer and, optionally, a bleach activator; and iii) optionally, a detergency builder;
  • the detergent active material may be selected from anionic, cationic, amphoteric, zwitterionic or nonionic detergent active materials or mixtures thereof.
  • the level of detergent active material or materials in the composition is preferably from 2% to 50%, more preferably from 5% to 30% by weight.
  • the preferred detergent compounds which can be used are synthetic anionic and nonionic compounds.
  • the former are usually water soluble alkali metal salts of organic sulphates and sulphonates having alkyl groups containing from about 8 to 22 carbon atoms.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C 8 - C w ) alcohols produced for example from tallow or coconut oil, sodium and potassium alkyl (C 9 - C ⁇ o) benzene sulphonates, particularly from sodium linear secondary alkyl (C ⁇ 0 - C- 5 ) benzene sulphonates, sodium alkyl glyceryl ether sulphates especially the ethers of higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and sulphonates, sodium and potassium salts of sulphuric acid esters of higher (C 8 - C
  • Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • Specific nonionic detergent compounds are alkyl (C 6 - C 22 ) phenols-ethylene oxide poly condensates, containing generally 5 to 25 units of ethylewne oxide (EO) per molecule.
  • nonionic compounds are the poly condensation products of aliphatic (C 8 - C 18 ) primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine.
  • nonionic detergent compounds include long chain tertiary a ine oxides and dialkyl sulphoxides.
  • detergent compounds for example, mixed anionic or mixed anionic and nonionic compounds may be used in the detergent compositions.
  • the latter in particular provide controlled low sudsing properties. This is beneficial for compositions intended for use in suds intolerant automatic washing machines.
  • Amounts of amphoteric or zwitterionic detergent compounds can also be used in the compositions of the invention but this is not normally desired due to their relatively high cost. If any amphoteric or zwitterionic detergent compounds are used, it is generally in small amounts in compositions based on the much more commonly used synthetic anionic and/or nonionic detergent compounds.
  • detergent active compounds are available and fully described in the literature, e.g: Surface active agents and detergents, vols. I and II, by Schwartz, Perry and Berch.
  • the peroxy bleaching agent may be a compound which is capable of yielding hydrogen peroxide in aqueous solution.
  • Hydrogen peroxide sources are well-known in the art. They include the alkali metal peroxides, organic peroxides and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates. Mixtures of two or more such compounds may also be suitable.
  • sodium perborate tetrahydrate and, especially, sodium perborate monohydrate.
  • Sodium perborate monohydrate is preferred because it has excellent storage stability while also dissolving very quickly in aqueous solutions.
  • Sodium percarbonate may also be preferred as peroxide ion source, for environmental reasons.
  • the amount of these inorganic persalts in the composition of the invention will usually be from 5 to 35 % by weight, preferably from 5 to 20% by weight.
  • bleach precursors of this invention are compounds that react with peroxide anion, and form therewith a peracid, percarbonic acid or perimidic acid. These bleach precursors are water soluble materials, being soluble generally to an extent of at least 1%, preferably at least about 5% by weight, at 25°C.
  • N-diacylated and N' N'-polyacylated amines such as, N, N, N , ,N'-tetra acetyl methylene diamine and N, N, N'N'-tetra acetyl ethylene diamine, N, N,-diacetylaniline, N,N-diacetyl-p-toluidine; 1,3- diacylated hydantoins, such as, for example l,3-diacetyl-5, 5-dimethyl hydantoin and 1,3-dipropionyl hydantoin; acetoxy-(N,N,N') - polyacylmalonamide, for example, acetoxy-(N,N)-diacetylmalonamide;
  • N-alkyl-N-sulphonyl carbonamides for example, the compounds N-methyl-N-mesyl-acetamide, N-methyl-N- mesylbenzamide, N-methyl-N-mesyl-p-nitrobenzamide, and N-methyl-N-mesyl-p-methoxybenzamide;
  • N-acylated cyclic hydrazides acylated triazones or urazoles for example onoacetylmaleic acid hydrazide
  • 0,N,N-trisubstituted hydroxylamines such as O-benzoyl-N-N-succinyl hydroxylamine,O-acety1-N-N- succinylhydroxylamine, O-p-methoxy benzoy1-N-N-succinylhydroxylamine, O-p-methoxy benzoyl-N-N-succinylhydroxylamine,O-p-nitrobenzoyl-N, N-succinyl hydroxylamine and 0,N,N,-triacetyl and 0,N,N,-triacetyl hydroxylamine;
  • N,N'diacyl-sulphurylamides for example, N,N'dimethyl-N,N'-diacetyl - sulphuryla ide and N,N'-diethy1-N,N'dipropiony1 sulphurylamide;
  • Tricyanurates for example, triacetyl cyanurate and tribenzoyl cyanurate
  • Carboxylic acid anhydrides such as benzoic anhydride, m-chloro-benzoic anhydride, phthalic anhydride, 4-chloro phthalic anhydride;
  • Esters for example, glucose pentaacetate, xylose tetraacetate, sodium acetyloxybenzene sulfonate, sodium nanoyloxybenzene sulfonate and sodium benzoyloxybenzene-sulfonate;
  • Carbonic acid esters for example, the sodium salts of p-(ethoxycarbonyloxy)-benzoic acid and p-(propoxycarbonyloxy)-benzenesulphonic acid;
  • Quaternary ammonium substituted peroxycarbonic or carboxylic acid esters such as 2-(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl-carbonate.
  • the precursors mentioned under (a), (h) and (j) are of special interest, particularly, N,N,N',N , -tetraacetyl -ethylene-diamine (TAED) , tetraacetyl-glycoluril (TAGU) , glucose pentaacetate, xylose tetraacetate, sodium acetyloxybenzene sulfonate (SABS) and sodium nonanoyloxybenzene sulfonate (SNOBS) .
  • TAED -tetraacetyl -ethylene-diamine
  • TAGU tetraacetyl-glycoluril
  • SABS sodium acetyloxybenzene sulfonate
  • SNOBS sodium nonanoyloxybenzene sulfonate
  • the level of the precursor When present in the detergent composition, the level of the precursor may be up to 12% by weight, preferably from 2-12% by weight.
  • Organic peroxy acids may also be suitable as the peroxy bleaching agent.
  • Such materials have a general formula HOOO-C-R-Y
  • R is an alkylene or substituted alkylene group containing from 1 to about 22 carbons atoms or a phenylene or substituted phenylene group
  • Y is hydrogen, halogen, alkyl, aryl, COOH or COOOH .
  • organic peroxy acids usable in the present invention can contain either one or two peroxy groups and can be either aliphatic or aromatic.
  • Typical monoperoxy acids useful herein include alkyl peroxy acids and aryl peroxy acids such as: i) peroxybenzoic acid and ring substituted peroxybenzoic acids, peroxy- ⁇ -naphthoic acid; ii) aliphatic, substituted aliphatic and arylalkyl monoperoxy acids, e.g., peroxylauric acid, peroxystearic acid, and N,N # -phthaloylamino-peroxycaproic acid (PAP) .
  • PAP N,N # -phthaloylamino-peroxycaproic acid
  • Typical diperoxy acids useful herein include alkyl diperoxy acids and aryldiperoxy acids, such as: iii) 1,12-diperoxy-dodecanedioic acid; iv) 1,9-diperoxyazelaic acid; v) diperoxybrassylic acid; diperoxysebacic acid and diperoxyisophthalic acid; vi) 2-decyldiperoxybutane-l,4-dioic acid; vii) 4,4'sulfonylbisperoxybenzoic acid.
  • alkyl diperoxy acids and aryldiperoxy acids such as: iii) 1,12-diperoxy-dodecanedioic acid; iv) 1,9-diperoxyazelaic acid; v) diperoxybrassylic acid; diperoxysebacic acid and diperoxyisophthalic acid; vi) 2-decyldiperoxybutane-l,4-dio
  • organic peroxy acids are peracetic acid, monoperoxyphthalic acid (magnesium salt hexahydrate) and diperoxydodecanedioic acid. Under certain circumstances hydrogen peroxide itself may directly be employed as the peroxy compound. If organic peroxyacids are used as the peroxy bleaching compound, the amount thereof will normally be within the range of 2-20% by weight, preferably from 4-8% by weight, of the detergent composition.
  • the polysaccharide graft copolymers used in this invention may be prepared according to methods known in the art, particularly as described in Indian patent no. 172039.
  • the process essentially consists of preparing graft copolymer of a polysaccharide and an unsaturated monomer by
  • the polysaccharide graft copolymers used in this invention may be further modified by making them cationic e.g. by reacting with quaternary amine.
  • Fig. 2 gives the representative structure of starch graft polyvinyl acetate, another preferred polysaccharide copolymer.
  • the polymethacrylic acid and the cationic ingredient are both present at a level ranging between 0.1-40% of the polysaccharide graft copolymer.
  • the content of polyvinyl acetate is at a level ranging between 0.1-20% of the starch graft polyvinyl acetate.
  • the level of the polysaccharide graft copolymer in the detergent composition of the invention is preferably from 0.1-10% by weight.
  • the builder may be any material capable of reducing the level of free calcium ions in the wash liquor and will preferably provide the composition with other beneficial properties such as the generation of an alkaline pH, the suspension of soil removed from the fabric and the suspension of the fabric softening clay material.
  • the level of the builder may be from 0.5% to 70% by weight, more preferably from 15% to 50% by weight. In the case of detergent formulations based on nonionic surfactants, it is possible to avoid use of detergent builders.
  • detergency builders include precipitating builders, such as the alkali metal carbonates with or without high surface area calcite, alkali metal bicarbonates, alkali metal pyrophosphates; sequestering builders, such as, the alkali metal tripolyphosphates, citrates or nitrilotriacetates; or ion exchange builders such as amorphous alkali metal aluminosilicates or the zeolites.
  • a detergent composition of the invention can contain any of the conventional additives in the amounts in which such additives are normally employed in fabric washing detergent compositions.
  • these additives include the lather boosters, such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, lather depressants, inorganic salts such as sodium sulphate, other fillers such as kaolin, and the additives usually present in very minor amounts: fluorescent agents, perfumes, enzymes such as proteases, lipases and amylases, germicides and colourants.
  • the detergent composition of the invention is prepared by mixing the various components at desired levels, using the methods known in the art such as spray drying or dry mixing, followed by post dosing of sensitive ingredients.
  • Tapioca starch 1000 g 13% moisture was slurried in urea solution (30 g urea in 1 liter water) maintained at ambient temperature (30°C) in a 5 liter three necked round bottomed flask fitted with a mechanical stirrer. The slurry was stirred for 1 hr and ferrous ammonium sulphate (1.0 g in 10 ml water) and 10 minutes later ascorbic acid solution (5 g in 25 ml water) was added to it under stirring. To this mixture, methacrylic acid (50 g) was added. After 10 minutes, hydrogen peroxide solution (10 ml, 30% solution) was added and the reaction mixture was stirred for 2 hrs. The product was filtered, washed 3 times with equal volumes of water (1 liter) and dried initially in air at room temperature for 18 hours and finally in an oven at 55°C till the moisture content was less than 13%.
  • This copolymer was prepared according to the same procedure as for Copolymer no. 1, the only difference being that the amount of methacrylic acid employed in this case was 100 g instead of 50 g. After stirring for 2 hours, the product slurry was directly used for preparing cationic starch graft polymethacrylic acid.
  • Copolymer No 3 For the preparation of Copolymer No 3 the entire quantity of Copolymer no 2 obtained as per the procedure described above was used.
  • Copolymer no. 2 was slurried in 1500ml of distilled water and reacted with 100 gms of 3-chloro, 2-hydroxypropyl trimethyl ammonium chloride at 50°C for 16 hours at a pH of 11.5-11.8 maintained by the addition of 3% sodium hydroxide solution.
  • the product was neutralised to pH 6.5-7 using 10% HC1, filtered, washed (three times with 1L of water each time) , air dried and finally dried in an oven.
  • Detergent Product The detergent product used for the studies contained about 30% by weight each of detergent active (linear alkyl benzene sulphonate, sodium salt) and phosphate builder (STPP) . It also contained usual components like soda ash (10%) , ARD agent(sodium carboxy methyl cellulose, 1%), fillers (20%), perfume(0.25%) , other minor ingredients (colour, structurant) and water (to 100%) .
  • Bleaching Agent - Sodium perborate or PAP. Activators (for - TAED, SNOBS or P-15 perborates) Polymer - Copolymer no.l to copolymer no. 4. The required amounts of the detergent product (2.5 g/liter for low product concentration and 10 g/liter for high product concentration) along with the required amounts of bleach activators (when perborate is used) and polymer were added and stirred for 5 minutes.
  • the amounts of the bleach/activators were chosen to give 10 ppm available oxygen in solution.
  • 0.22 g PAP alone or 0.25 g of sodium perborate along with, as activators 0.0725 g TAED/0.210 g SNOBS/0.187g P-15 was used.
  • 0.075 g cooked polymer (dissolved by heating in lml of water at 90°C for 20min) as solution in water was also added to the solutions.
  • the stained standard test pieces of fabric were added to the solutions in a Terg-o-tometer and stirred for 30 minutes.
  • the washed fabrics were rinsed three times in 24°FH water and air dried.
  • the test fabrics were conditioned to equilibrium moisture content.
  • the reflectance values of the original stained fabric and the reflectance of the fabric after the bleaching experiment were measured using an Elrepho reflectance spectrophotometer fitted with UV filter and 250 W Xenon lamp. The difference in the reflectance of the original fabric and the washed fabric at 460 n.m. is ⁇ R 460.
  • the test fabrics used were (10cm x 10cm, 3 numbers) standard tea stained BC-l (weight of fabric 4.5g) and wine stained EMPA-114 (weight of fabric 6.0g) fabrics.
  • a combination of sodium perborate and TAED along with polymer no.3 gave synergistic benefits.
  • Test conditions Terg-o-tometer 100 cpm, 30 mins stirring Table - II
  • Test conditions Terg-o-tometer 100 rpm, 30 mins stirring
  • Test fabric BC-l EMPA-114 Temperature 30°C 45°C 30°C 45°C
  • Test conditions Terg-o-tometer at 100 cpm, 30 mins stirring
  • Detergent product 2.5 gms
  • Polymer 0.075 gms
  • Perborate 0.25 gms

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Detergent Compositions (AREA)

Abstract

Composition détergente comprenant un matériau actif détergent, éventuellement un adjuvant de détergence ainsi qu'un système de blanchiment, ce système comportant un agent de blanchiment peroxy ainsi qu'un copolymère greffé de polysaccharide. On a découvert que l'incorporation dans la composition de ce copolymère, notamment l'acide polyméthacrylique greffé d'amidon cationique et l'acétate de polyvinyle greffé d'amidon, améliore l'efficacité de blanchiment de la composition.
PCT/EP1995/001823 1994-06-02 1995-05-15 Composition detergente amelioree WO1995033814A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU25641/95A AU2564195A (en) 1994-06-02 1995-05-15 Improved detergent composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9411079.8 1994-06-02
GB9411079A GB9411079D0 (en) 1994-06-02 1994-06-02 Detergent composition

Publications (1)

Publication Number Publication Date
WO1995033814A1 true WO1995033814A1 (fr) 1995-12-14

Family

ID=10756099

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/EP1995/000766 WO1995033813A1 (fr) 1994-06-02 1995-03-01 Composition detergente amelioree
PCT/EP1995/001823 WO1995033814A1 (fr) 1994-06-02 1995-05-15 Composition detergente amelioree

Family Applications Before (1)

Application Number Title Priority Date Filing Date
PCT/EP1995/000766 WO1995033813A1 (fr) 1994-06-02 1995-03-01 Composition detergente amelioree

Country Status (3)

Country Link
AU (2) AU1947995A (fr)
GB (1) GB9411079D0 (fr)
WO (2) WO1995033813A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9376648B2 (en) 2008-04-07 2016-06-28 The Procter & Gamble Company Foam manipulation compositions containing fine particles

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2322137A (en) * 1997-02-14 1998-08-19 Unilever Plc Detergent composition with soil release agents
CN1255446C (zh) * 2001-03-02 2006-05-10 荷兰联合利华有限公司 去污聚合物以及包含它们的洗衣洗涤剂组合物
GB0117768D0 (en) 2001-07-20 2001-09-12 Unilever Plc Use of polymers in fabrics cleaning
CN115260397B (zh) * 2022-08-17 2023-11-21 深圳百市达生物技术有限公司 一种双氧水漂白无硅型稳定剂

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0404377A1 (fr) * 1989-06-06 1990-12-27 Ausidet S.R.L. Copolymères d'anhydride d'acide maléique
EP0441197A2 (fr) * 1990-02-03 1991-08-14 BASF Aktiengesellschaft Copolymère greffé à base de monosaccharides, oligosaccharides, polysaccharides et de polysaccharides modifiées, procédé de fabrication de celle-ci et son utilisation
EP0465287A1 (fr) * 1990-07-02 1992-01-08 Rhone-Poulenc Chimie Composition détergente contenant un polysaccharide greffé biodégradable
WO1993011214A1 (fr) * 1991-12-03 1993-06-10 Basf Aktiengesellschaft Produits de lavage et detergents
WO1994001476A1 (fr) * 1992-07-02 1994-01-20 Chemische Fabrik Stockhausen Gmbh Copolymeres greffes de monomeres insatures et de sucres, leur procede de fabrication et leur utilisation
DE4239076A1 (de) * 1992-11-20 1994-05-26 Basf Ag Mischungen aus Polymerisaten von monoethylenisch ungesättigten Dicarbonsäuren und Polymerisaten ethylenisch ungesättigter Monocarbonsäuren und/oder Polyaminocarbonsäuren und ihre Verwendung
DE4319807A1 (de) * 1993-05-13 1994-11-17 Huels Chemische Werke Ag Waschmittelformulierungen mit biologisch abbaubaren Polymeren

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0404377A1 (fr) * 1989-06-06 1990-12-27 Ausidet S.R.L. Copolymères d'anhydride d'acide maléique
EP0441197A2 (fr) * 1990-02-03 1991-08-14 BASF Aktiengesellschaft Copolymère greffé à base de monosaccharides, oligosaccharides, polysaccharides et de polysaccharides modifiées, procédé de fabrication de celle-ci et son utilisation
EP0465287A1 (fr) * 1990-07-02 1992-01-08 Rhone-Poulenc Chimie Composition détergente contenant un polysaccharide greffé biodégradable
WO1993011214A1 (fr) * 1991-12-03 1993-06-10 Basf Aktiengesellschaft Produits de lavage et detergents
WO1994001476A1 (fr) * 1992-07-02 1994-01-20 Chemische Fabrik Stockhausen Gmbh Copolymeres greffes de monomeres insatures et de sucres, leur procede de fabrication et leur utilisation
DE4239076A1 (de) * 1992-11-20 1994-05-26 Basf Ag Mischungen aus Polymerisaten von monoethylenisch ungesättigten Dicarbonsäuren und Polymerisaten ethylenisch ungesättigter Monocarbonsäuren und/oder Polyaminocarbonsäuren und ihre Verwendung
DE4319807A1 (de) * 1993-05-13 1994-11-17 Huels Chemische Werke Ag Waschmittelformulierungen mit biologisch abbaubaren Polymeren

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9376648B2 (en) 2008-04-07 2016-06-28 The Procter & Gamble Company Foam manipulation compositions containing fine particles

Also Published As

Publication number Publication date
GB9411079D0 (en) 1994-07-20
WO1995033813A1 (fr) 1995-12-14
AU1947995A (en) 1996-01-04
AU2564195A (en) 1996-01-04

Similar Documents

Publication Publication Date Title
US5106528A (en) Bleach activation and bleaching compositions
JP3450326B2 (ja) 過酸前駆物質としてのアシル化クエン酸エステル
CA2038010C (fr) N-sulfonyloxaziridines, composes de blanchiment
CA2038209C (fr) Compositions de blanchiment a faible temperature
CA2083658C (fr) Catalyseur au manganese
JPH0765074B2 (ja) 漂白剤の活性化
JPH0768543B2 (ja) 洗浄漂白組成物
JPH05263098A (ja) 漂白活性体
EP0775192A1 (fr) Compositions de blanchiment contenant de l'imine et un compose peroxyde ainsi qu'un catalyseur a base de metal de transition
CA2051046A1 (fr) Composition de blanchiment
WO1997041199A1 (fr) Sulfanimines en tant que catalyseurs de blanchiment
JPH10130692A (ja) 漂白触媒としてのスルホニルイミン誘導体
AU615531B2 (en) Bleaching composition
JPS6126958B2 (fr)
WO1998006813A1 (fr) Phosphinoylimines
JPH05209193A (ja) 無機過酸塩又は過酸化水素の漂白効果の増加方法及び漂白及び／又は洗浄組成物
US5041142A (en) Peroxymetallates and their use as bleach activating catalysts
WO1995033814A1 (fr) Composition detergente amelioree
EP0492000B1 (fr) Procédé pour augmenter l'efficacité de blanchiment d'un persel minéral
JPH01306498A (ja) 布洗浄用組成物
US5320775A (en) Bleach precursors with novel leaving groups
KR101139882B1 (ko) 알킬옥시계 및 디아민계 화합물의 혼합물을 함유하는표백활성화제 및 표백 조성물
US5429768A (en) Grignard reaction intermediates as bleach catalysts

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AM AT AU BB BG BR BY CA CH CN CZ DE DK EE ES FI GB GE HU IS JP KE KG KP KR KZ LK LR LT LU LV MD MG MN MW MX NO NZ PL PT RO RU SD SE SG SI SK TJ TM TT UA UG UZ VN

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): KE MW SD SZ UG AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA