WO1995035360A1 - Farbstoffübertragungsinhibitoren für wasch- und reinigungsmittel - Google Patents
Farbstoffübertragungsinhibitoren für wasch- und reinigungsmittel Download PDFInfo
- Publication number
- WO1995035360A1 WO1995035360A1 PCT/EP1995/002111 EP9502111W WO9535360A1 WO 1995035360 A1 WO1995035360 A1 WO 1995035360A1 EP 9502111 W EP9502111 W EP 9502111W WO 9535360 A1 WO9535360 A1 WO 9535360A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymers
- water
- polymer
- vinylimidazole
- washing
- Prior art date
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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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
-
- 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
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
Definitions
- the invention relates to the use of water-insoluble, crosslinked polymers as an additive for detergents and cleaning agents to prevent dye transfer during the washing process, and detergents and cleaning agents which contain these polymers.
- the proportion of crosslinking agents in the copolymer should therefore preferably be less than 5 mol%.
- the polymers should be soluble in water or dispersible by incorporating hydrophobic monomer units, so that the use of water-insoluble crosslinked polymers is not recommended. The examples given prove this.
- the object of the invention is to provide dye transfer inhibitors for detergents and cleaning agents which can be eliminated to a high degree from the waste water compared to the known inhibitors.
- the invention also relates to detergents and cleaning agents based on surfactants and, if appropriate, builders and other customary constituents, the detergents and cleaning agents being 0.1 to 10% by weight, based on the respective formulation, of water-insoluble substances , contain crosslinked polymers, the units of 1-vinylpyrrolidone and / or 1-vinylimidazoles of the formula
- H 2 C CH N ⁇ N
- Water-insoluble crosslinked polymers have hitherto not been used as dye transfer inhibitors for reasons of sorption kinetics. Surprisingly, it has now been found that water-insoluble crosslinked polymers which have a particle size of 0.1 to 500 ⁇ m are excellent dye transfer inhibitors and in some cases even outperform the water-soluble polymers in their effectiveness.
- R 2 Rl in which R, R X and R 2 are the same or different and stand for H, -C ⁇ to C 4 alkyl or phenyl.
- the substituents R, R 1 and R 2 are preferably H, CH 3 and C 2 H 5 .
- Monomers of group (a) are, for example, 1-vinylimidazole, 2-methyl-1-vinylimidazole, 2-ethyl-1-vinylimidazole, 2-propyl-1-vinylimidazole, 2-butyl-1-vinylimidazole, 2, 4-dimethyl l-vinylimidazole, 2,5-dimethyl-l-vinylimidazole, 2-ethyl-4-methyl-l-vinylimidazole, 2-ethyl-5-methyl-l-vinylimidazole, 2,4,5-trimethyl-l- vinyl imidazole,
- 2-methyl-1-vinylimidazole, 2-ethyl-1-vinylimidazole, 2-ethyl-4-methyl-1-vinylimidazole, 4-methyl-1-vinylimidazole or mixtures of 1-vinylpyrrolidone are used and 1-vinylimidazole or mixtures of 1-vinyl-pyrrolidone and 2-methyl-l-vinylimidazole as the monomer
- the polymers contain the monomers of group (a) preferably polymerized in amounts of 40 to 100% by weight.
- the monomers of group (a) can optionally be copolymerized with the monomers of group (b).
- This is to be understood as meaning monoethylenically unsaturated monomers which are different from the monomers of group (a), e.g. Acrylamides,
- (meth) acrylic acid esters as monomer (b), which are derived from amino alcohols. These monomers contain a basic nitrogen atom. They are used either in the form of the free bases or in neutralized or quaternized form. Further preferred monomers are monomers which contain a basic nitrogen atom and an amide group in the molecule.
- Monomers are N, N'-dialkylaminoalkyl (meth) acrylates, for example dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropylacrylate and diethylaminopropyl methacrylate.
- N, N'-dialkylaminoalkyl (meth) acrylates for example dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropylacrylate and diethyla
- Basic monomers which additionally contain an amide group in the molecule are N, N'-dialkylaminoalkyl (meth) acrylamides, for example N, N'-di-C ⁇ - to C 3 -alkylamino-C2- to C ⁇ -alkyl (meth) acrylamides, such as dimethylaminoethyl acrylamide, dimethylaminoethyl methacrylamide, diethylaminoethyl acrylamide, diethylaminoethyl methacrylamide, dimethylaminopropylacrylamide and dimethylaminopropyl methacrylamide.
- N, N'-dialkylaminoalkyl (meth) acrylamides for example N, N'-di-C ⁇ - to C 3 -alkylamino-C2- to C ⁇ -alkyl (meth) acrylamides, such as dimethylaminoethyl acrylamide, dimethylaminoethyl methacrylamide
- monomers which have a basic nitrogen atom are 4-vinylpyridine, 2-vinylpyridine, diallyldi- (C 1 -C 1 to C 2 ⁇ alkyl) ammonium compounds and diallyl-C 1 to C 2 -alkylamines.
- the basic monomers are used in the copolymerization in the form of the free bases, the salts with organic or inorganic acids or in quaternized form.
- alkyl halides with 1 to 18 carbon atoms in the alkyl group are suitable, for example methyl chloride, ethyl chloride or
- Benzyl chloride The quaternization of the nitrogen-containing basic monomers can also be carried out by reaction with dialkyl sulfates, in particular with diethyl sulfate or dimethyl sulfate.
- dialkyl sulfates in particular with diethyl sulfate or dimethyl sulfate.
- Examples of quaternized monomers are trimethylammonium ethyl methacrylate chloride, dimethyl ethyl ammonium ethyl methacrylate ethyl sulfate and dimethyl ethyl ammonium ethyl methacrylamide ethyl sulfate.
- 1-vinylimidazolium compounds which are quaternized, for example, with C 1 -C 4 -alkyl halides, dialkyl sulfates or benzyl chloride or converted into the salt form with an acid.
- Such monomers can, for example, using the general formula
- H 2 C CH N ⁇ NR 3 x ⁇ (II),
- R, R X , R 2 H, Ci to C 4 alkyl or phenyl
- R 3 H, Ci to Cis-alkyl or benzyl
- X® is an anion
- the anion can be a halogen ion, an alkyl sulfate anion or the rest of an inorganic or organic acid.
- Examples of quaternized 1-vinylimidazoles of the formula II are 3-methyl-1-vinylimidazolium chloride, 3-benzyl-1-vinylimidazolium chloride or 3-ethyl-1-vinylimidazolium ethyl sulfate.
- the polymers which contain monomers (a) and optionally 1-vinylimidazole or basic monomers (c) can also be partially quaternized by reaction with customary quaternizing agents such as dimethyl sulfate or methyl chloride. If the monomers (b) are used, they are up to 30% by weight in the monomer mixture.
- the direct preparation of water-insoluble crosslinked polymers is carried out by polymerizing the monomers (a) and, if appropriate (b), in the presence of monomers from group (c). These are monomers which contain at least 2 monoethylenically unsaturated double bonds in the molecule. Compounds of this type are usually used as crosslinking agents in polymerization reactions.
- Suitable crosslinkers of this type are, for example, acrylic esters, methacrylic esters, allyl ethers or vinyl ethers of at least dihydric alcohols.
- the OH groups of the underlying alcohols can be wholly or partially etherified or esterified; however, the crosslinkers contain at least two ethylenically unsaturated groups.
- Examples of the underlying alcohols are dihydric alcohols such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol,
- block copolymers of ethylene oxide or propylene oxide or copolymers which contain built-in ethylene oxide and propylene oxide groups can also be used.
- underlying alcohols with more than two OH groups are trimethylolpropane, glycerol, pentaerythritol, 1, 2, 5-pentanetriol, 1,2, 6-hexanetriol, triethoxycyanoic acid, sorbitan, sugars such as sucrose, glucose, mannose.
- the polyhydric alcohols can of course also be used after the reaction be used with ethylene oxide or propylene oxide as the corresponding ethoxylates or propoxylates.
- crosslinkers are the vinyl esters or the esters of monohydric, unsaturated alcohols with ethylenically unsaturated C to C ß- carboxylic acids, for example acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid.
- examples of such alcohols are allyl alcohol, l-buten-3-ol, 5-hexen-l-ol, l-octen-3-ol, 9-decen-l-ol, dicyclopentenyl alcohol, 10-undecen-l-ol , Cinnamon alcohol, citronellol, crotyl alcohol or cis-9-octadecen-l-ol.
- the monohydric, unsaturated alcohols can also be esterified with polyhydric carboxylic acid, for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.
- polyhydric carboxylic acid for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.
- crosslinkers are esters of unsaturated carboxylic acids with the polyhydric alcohols described above, for example oleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid.
- straight-chain or branched, linear or cyclic, aliphatic or aromatic hydrocarbons which have at least two double bonds which must not be conjugated to aliphatic hydrocarbons, e.g. Divinylbenzene, divinyltoluene, 1,7-octadiene, 1, 9-decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane or polybutadienes with molecular weights from 200 to 20,000.
- Acrylic acid amides, methacrylic acid amides and N-allyl amines are also suitable as crosslinking agents of at least divalent amines.
- Such amines are, for example, 1,2-diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,12-dodecanediamine,
- Piperazine diethylene triamine or isophoronediamine.
- amides of allylamine and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or at least dibasic carboxylic acids, as described above.
- N-vinyl compounds of urea derivatives at least divalent amides, cyanurates or urethanes, for example urea, ethylene urea, propylene urea or tartaric acid diamide.
- crosslinkers are divinyldioxane, tetraallylsilane or tetravinylsilane. Mixtures of the aforementioned compounds can of course also be used.
- the insoluble polymers preferably contain N, N'-divinylethylene urea in copolymerized form as crosslinking agent.
- the monomers of group (c) are used in amounts of up to 40, preferably 0.1 to 10% by weight, based on the monomer mixtures.
- Preferred polymers contain polymers crosslinked with N, N-divinylethyleneurea of 1-vinylpyrrolidone, 1-vinylimidazole and / or 2-methyl-1-vinylimidazole.
- the monomers are usually polymerized using free-radical initiators, generally in an inert gas atmosphere.
- Hydrogen peroxide or inorganic persulfates can be used as radical initiators, as can organic compounds of the peroxide, peroxiester, percarbonate or azo type, such as e.g.
- the water-insoluble crosslinked polymers can be prepared by all known polymerization processes.
- suitable polymerization processes are emulsion and reverse emulsion polymerization.
- suspension polymerisation, reverse suspension polymerisation, precipitation polymerisation and popcorn polymerisation are particularly suitable, as they are easy to carry out and the polymerisation process can be controlled so that the polymer is obtained directly in finely divided form.
- the monomers are dissolved in an aqueous salt solution, e.g. an aqueous sodium sulfate solution, dispersed into droplets by stirring and polymerized by adding a radical-forming starter.
- an aqueous salt solution e.g. an aqueous sodium sulfate solution
- Polymer particles can use protective colloids, inorganic suspending agents or emulsifiers.
- the properties of the polymers can be significantly influenced by adding so-called pore formers such as ethyl acetate, cyclohexane, n-pentane, n-hexane, n-octane, n-butanol, i-decanol, methyl ethyl ketone or i-propyl acetate.
- the particle size can be determined, for example, by the type and concentration of dispersing aid and can be influenced by the selection of the stirrer and the stirring speed.
- the suspension polymer is isolated by filtration or centrifugation, washed thoroughly, dried and, if necessary, ground into particles with a size of less than 500 ⁇ . Milling can also be carried out in the wet state. If the polymers are in the form of fine beads, then the polymer is bead polymerized.
- the monomers are dissolved in water and this phase is suspended and polymerized in an inert organic solvent, for example cyclohexane.
- an inert organic solvent for example cyclohexane.
- Protective colloids or emulsifiers are advantageously added to the system.
- the water can e.g. removed by azeotropic distillation and the product isolated by filtration.
- the precipitation polymerization is based on the use of solvents or solvent mixtures in which the monomers to be polymerized dissolve, but not the resulting polymer.
- the polymer which is insoluble or has only limited solubility, precipitates out of the reaction mixture during the polymerization.
- Dispersions (suspensions) are obtained, which can optionally be stabilized by adding dispersants.
- Suitable solvents are e.g.
- the precipitation polymers are worked up by filtering, washing, drying and, if necessary, grinding or classifying.
- the monomers are polymerized in the absence of solvents or diluents.
- a special method for producing crosslinked polymers is the so-called popcorn polymerization or proliferating polymerization (Encyclopedia of Polymer Science and Engineering, Vol. 13, pp. 453-463, 1988). It can be carried out as precipitation polymerization or as bulk polymerization. The use of a free radical initiator can be partially dispensed with here. The addition of crosslinkers is sometimes not necessary.
- crosslinked polymers of the gel type are formed.
- Crosslinked polymers of the gel type can also be obtained by subsequently crosslinking dissolved polymers, for example with peroxides.
- water-soluble polymers of 1-vinylpyrrolidone and / or 1-vinylimidazoles of the formula I ie homopolymers and copolymers which can each be prepared by polymerizing at least one monomer of groups (a) alone) by subsequent crosslinking with, for example, peroxides or hydroperoxides or by Conversion of high-energy rays, for example UV, ⁇ or electron beams into water-insoluble cross-linked polymers.
- Polymerization regulators which contain sulfur in bound form are preferred.
- Compounds of this type are, for example, sodium disulfite, sodium dithionite, diethanol sulfide, ethylthioethanol, thiodiglycol, di-n-hexyldisulfide, di-n-butyl sulfide, 2-mercaptoethanol, 1,3-mercaptopropanol, ethylthioglycolate, mercaptoacetic acid and thioglycerol.
- the water-insoluble crosslinked polymers are isolated in a customary manner and, if necessary, ground into particles which, in the dry state (moisture content up to a maximum of 2% by weight), have a particle size of 0.1 to 500 ⁇ m, preferably at least 90% by weight 0.1 to 250 and in particular from 0.1 to 50 ⁇ have.
- the particle size is measured on dried polymers using vibrating sieve analysis. For the range 0.1 to 50 ⁇ , laser light diffraction is also used on particles dispersed in air or in cyclohexane (no swelling agent) (Master Sizer, Malvern Instruments GmbH).
- the crushing can be done not only by dry grinding but of course also by wet grinding.
- the cross-linked products which often have an irregular shape, can, if desired, be divided into different grain classes by different classification methods (sieving, sifting, hydroclassification).
- the water-insoluble crosslinked polymers are used in finely divided form, with at least 90% by weight of the polymers having a particle size of 0.1 to 500 ⁇ m, as an additive for detergents and cleaning agents to prevent dye transfer during the washing process.
- the detergents can be in powder form or in fluid attitude.
- the composition of the detergent and cleaning agent formulations can be very different. Detergent and cleaning agent formulations usually contain 2 to 50% by weight of surfactants and optionally builders. This information applies to both liquid and powder detergents.
- detergents and cleaning agent formulations which are common in Europe, the USA and Japan can be found, for example, in Chemical and Engn. News, Volume 67, 35 (1989) presented in table form. Further information on the composition of detergents and cleaning agents can be found in Ullmann's Encyclopedia of Industrial Chemistry, Verlag Chemie, Weinheim 1983, 4th edition, pages 63-160.
- the detergents can optionally also contain a bleach, for example sodium perborate, which, if used, can be present in the detergent formulation in amounts of up to 30% by weight.
- the detergents and cleaning agents can optionally contain other customary additives, for example complexing agents, opacifiers, optical brighteners, enzymes, perfume oils, other color transfer inhibitors, graying inhibitors and / or bleach activators. They contain the water-insoluble, crosslinked polymers to be used according to the invention in amounts of 0.1 to 10% by weight.
- crosslinked polymers which can be used according to the invention can also be used in combination with non-crosslinked water-soluble polymers which are suitable for preventing dye transfer. At least 90, preferably> 95% of the polymers to be used according to the invention can be eliminated from the waste water.
- the percentages in the examples mean percent by weight.
- the polymerization was carried out in accordance with the procedure described in Example 2, but the feed mixture consisted of 90 g of 1-vinylimidazole, 2.3 g of N, N'-divinylethyleneurea and
- the polymerization was carried out in accordance with the procedure described in Example 2, but the feed mixture consisted of 30 g of 1-vinylimidazole, 30 g of 2-methyl-1-vinylimidazole, 1.6 g of N, N'- Divinylethylene urea and 300 g water. The yield of powdered product was 96%.
- reaction mixture In order to keep the reaction mixture stirrable, it was diluted with a total of 600 g of cyclohexane during the polymerization. The resulting product was suction filtered through a suction filter, washed thoroughly with cyclohexane and dried in a vacuum drying cabinet at 50 ° C. A white, fine-grain powder was obtained in a yield of 93%.
- Table 1 contains the washing conditions.
- the composition of the detergent used is given in Table 2.
- the reflection of the washed test fabric was determined using the Data Color Elrepho 2000 measuring device. The evaluation was carried out in the case of direct blue 71 at 600 ⁇ m in the case of director orange 39 at 440 nm.
- Dye concentration 0.001% direct blue 71 or director orange 39 as a 0.25% aqueous solution
- Test fabric cotton polyester / cotton
- Test fabric Cotton detergent with 3% polymer: reflection (%) reflection (%)
- Example test fabric cotton reflection (%) test dye: director orange 39 detergent with 3% polymer:
- Test fabric Cotton polymer content in detergent: 1% by weight
- the K values of the water-soluble polymers were determined in 1% strength aqueous solution (25 ° C., pH 7) according to H. Fikentscher (Cellulose-Chemie, Volume 13, pp. 58-54 and 71-74, 1932)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP95921823A EP0765379B1 (de) | 1994-06-17 | 1995-06-03 | Farbstoffübertragungsinhibitoren für wasch- und reinigungsmittel |
DE59503533T DE59503533D1 (de) | 1994-06-17 | 1995-06-03 | Farbstoffübertragungsinhibitoren für wasch- und reinigungsmittel |
JP8501563A JPH10501573A (ja) | 1994-06-17 | 1995-06-03 | 洗剤用染料移行抑制剤 |
DK95921823T DK0765379T3 (da) | 1994-06-17 | 1995-06-03 | Farvestofoverføringsinhibitorer til vaske- og rensemidler |
US08/750,478 US5830844A (en) | 1994-06-17 | 1995-06-03 | Dye transfer inhibitors for detergents |
AU26741/95A AU2674195A (en) | 1994-06-17 | 1995-06-03 | Color migration inhibitors for washing and cleaning agents |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4421179A DE4421179A1 (de) | 1994-06-17 | 1994-06-17 | Farbstoffübertragungsinhibitoren für Wasch- und Reinigungsmittel |
DEP4421179.1 | 1994-06-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995035360A1 true WO1995035360A1 (de) | 1995-12-28 |
Family
ID=6520810
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1995/002111 WO1995035360A1 (de) | 1994-06-17 | 1995-06-03 | Farbstoffübertragungsinhibitoren für wasch- und reinigungsmittel |
Country Status (10)
Country | Link |
---|---|
US (1) | US5830844A (de) |
EP (1) | EP0765379B1 (de) |
JP (1) | JPH10501573A (de) |
AT (1) | ATE170911T1 (de) |
AU (1) | AU2674195A (de) |
CA (1) | CA2193127A1 (de) |
DE (2) | DE4421179A1 (de) |
DK (1) | DK0765379T3 (de) |
ES (1) | ES2120213T3 (de) |
WO (1) | WO1995035360A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0800570A1 (de) * | 1994-12-29 | 1997-10-15 | The Procter & Gamble Company | Waschmittelzusammensetzung mit wasserunlöslichem, entfärbungshemmendem Polymerwirkstoff |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19519337A1 (de) * | 1995-05-26 | 1996-11-28 | Basf Ag | Verwendugn von wasserunlöslichen, vernetzten Polymerisaten als Additiv für Waschmittel und Waschmittel, die diese Polymerisate enthalten |
DE19519338A1 (de) * | 1995-05-26 | 1996-11-28 | Basf Ag | Mischungen aus Polymeren und Tensiden, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE19532718A1 (de) * | 1995-09-05 | 1997-03-06 | Basf Ag | Pulverförmige, poröse, N-Vinylimidazol-Einheiten enthaltende Polymere, Verfahren zu ihrer Herstellung und ihre Verwendung |
US20020119721A1 (en) * | 2000-10-13 | 2002-08-29 | The Procter & Gamble Company | Multi-layer dye-scavenging article |
US6833336B2 (en) * | 2000-10-13 | 2004-12-21 | The Procter & Gamble Company | Laundering aid for preventing dye transfer |
US6887524B2 (en) * | 2000-10-13 | 2005-05-03 | The Procter & Gamble Company | Method for manufacturing laundry additive article |
US7256166B2 (en) * | 2002-01-18 | 2007-08-14 | The Procter & Gamble Company | Laundry articles |
EP1578821A2 (de) * | 2002-12-23 | 2005-09-28 | Ciba SC Holding AG | Hydrophob modifizierte polymerisate als waschmittelzusatz |
DE10342862A1 (de) * | 2003-09-15 | 2005-04-21 | Basf Ag | Verwendung von polyvinylamin- und/oder polyvinylamidhaltigen Polymeren zur Geruchsverhinderung beim maschinellen Geschirrspülen |
WO2007023862A1 (ja) * | 2005-08-26 | 2007-03-01 | Nippon Shokubai Co., Ltd. | 染料移行防止剤、洗濯用洗剤組成物 |
JP5947918B2 (ja) * | 2012-02-21 | 2016-07-06 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンHenkel AG & Co. KGaA | 着色防止洗剤 |
CA2960158C (en) * | 2014-09-18 | 2019-06-11 | Hymo Corporation | Method for producing polyvinylamine crosslinked polymer particles |
CA3000123C (en) * | 2016-01-20 | 2020-04-07 | Hymo Corporation | Iminodiacetic acid type chelate resin and method for producing same |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0175335A1 (de) * | 1984-09-18 | 1986-03-26 | BASF Aktiengesellschaft | Verfahren zur Herstellung von unlöslichen, nur wenig quellbaren pulverförmigen Polymeren |
DE4000978A1 (de) * | 1990-01-16 | 1991-07-18 | Basf Ag | Verfahren zur entfernung von schwermetallionen aus wein und weinaehnlichen getraenken |
WO1994010281A1 (de) * | 1992-10-23 | 1994-05-11 | Basf Aktiengesellschaft | Verwendung von vinylpyrrolidon- und vinylimidazol-copolymerisaten als waschmitteladditiv sowie deren herstellungsverfahren |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8830235D0 (en) * | 1988-12-24 | 1989-02-22 | Interox Chemicals Ltd | Percarboxylic acids |
CA2047223A1 (en) * | 1989-12-23 | 1991-06-24 | John P. Sankey | Peroxycarboxylic acids |
-
1994
- 1994-06-17 DE DE4421179A patent/DE4421179A1/de not_active Withdrawn
-
1995
- 1995-06-03 DK DK95921823T patent/DK0765379T3/da active
- 1995-06-03 ES ES95921823T patent/ES2120213T3/es not_active Expired - Lifetime
- 1995-06-03 DE DE59503533T patent/DE59503533D1/de not_active Expired - Lifetime
- 1995-06-03 EP EP95921823A patent/EP0765379B1/de not_active Expired - Lifetime
- 1995-06-03 JP JP8501563A patent/JPH10501573A/ja active Pending
- 1995-06-03 CA CA002193127A patent/CA2193127A1/en not_active Abandoned
- 1995-06-03 AT AT95921823T patent/ATE170911T1/de not_active IP Right Cessation
- 1995-06-03 US US08/750,478 patent/US5830844A/en not_active Expired - Fee Related
- 1995-06-03 AU AU26741/95A patent/AU2674195A/en not_active Abandoned
- 1995-06-03 WO PCT/EP1995/002111 patent/WO1995035360A1/de active IP Right Grant
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0175335A1 (de) * | 1984-09-18 | 1986-03-26 | BASF Aktiengesellschaft | Verfahren zur Herstellung von unlöslichen, nur wenig quellbaren pulverförmigen Polymeren |
DE4000978A1 (de) * | 1990-01-16 | 1991-07-18 | Basf Ag | Verfahren zur entfernung von schwermetallionen aus wein und weinaehnlichen getraenken |
WO1994010281A1 (de) * | 1992-10-23 | 1994-05-11 | Basf Aktiengesellschaft | Verwendung von vinylpyrrolidon- und vinylimidazol-copolymerisaten als waschmitteladditiv sowie deren herstellungsverfahren |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0800570A1 (de) * | 1994-12-29 | 1997-10-15 | The Procter & Gamble Company | Waschmittelzusammensetzung mit wasserunlöslichem, entfärbungshemmendem Polymerwirkstoff |
EP0800570A4 (de) * | 1994-12-29 | 1998-01-28 | Procter & Gamble | Waschmittelzusammensetzung mit wasserunlöslichem, entfärbungshemmendem Polymerwirkstoff |
Also Published As
Publication number | Publication date |
---|---|
JPH10501573A (ja) | 1998-02-10 |
DK0765379T3 (da) | 1999-03-01 |
AU2674195A (en) | 1996-01-15 |
EP0765379B1 (de) | 1998-09-09 |
DE59503533D1 (de) | 1998-10-15 |
CA2193127A1 (en) | 1995-12-28 |
ATE170911T1 (de) | 1998-09-15 |
EP0765379A1 (de) | 1997-04-02 |
US5830844A (en) | 1998-11-03 |
DE4421179A1 (de) | 1995-12-21 |
ES2120213T3 (es) | 1998-10-16 |
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