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WO1996002622A1 - Compositions detergentes liquides concentrees aqueuses stables, contenant des copolymeres hydrophiles - Google Patents

Compositions detergentes liquides concentrees aqueuses stables, contenant des copolymeres hydrophiles Download PDF

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Publication number
WO1996002622A1
WO1996002622A1 PCT/EP1995/002597 EP9502597W WO9602622A1 WO 1996002622 A1 WO1996002622 A1 WO 1996002622A1 EP 9502597 W EP9502597 W EP 9502597W WO 9602622 A1 WO9602622 A1 WO 9602622A1
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WO
WIPO (PCT)
Prior art keywords
monomer
formula
zero
hydrophilic
composition
Prior art date
Application number
PCT/EP1995/002597
Other languages
English (en)
Inventor
Sridhar Gopalkrishnan
John V. Sherman
Kathleen M. Guiney
David T. Durocher
Michael C. Welch
Original Assignee
Basf Corporation
Basf Aktiengesellschaft
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
Priority claimed from US08/274,948 external-priority patent/US5536440A/en
Priority claimed from US08/274,938 external-priority patent/US5534183A/en
Application filed by Basf Corporation, Basf Aktiengesellschaft filed Critical Basf Corporation
Priority to EP95925829A priority Critical patent/EP0770122B1/fr
Priority to JP8504639A priority patent/JPH10502694A/ja
Priority to DE69506551T priority patent/DE69506551T2/de
Priority to AU29814/95A priority patent/AU2981495A/en
Publication of WO1996002622A1 publication Critical patent/WO1996002622A1/fr

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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
    • C11D3/16—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
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid 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
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions

Definitions

  • the present invention relates to hydrophilic copolymers, and more particularly, to stable, aqueous-based, concentrated liquid de ⁇ tergents that contain the hydrophilic copolymers and thus permit the incorporation of builders, polymers and other water— insolu ⁇ ble components to form a stable composition.
  • the invention also relates to a method of stabilizing liquid detergent compositions.
  • the preparation of such polymers are accomplished by copoly- merizing hydrophilic monomers with a hydrophobic monomer.
  • the hy ⁇ drophobic monomer contains a hydrophobic side chain.
  • the polymerization of the hydrophilic monomer and the hydrophobic monomer is conducted in a cosolvent, which is typically water and another solvent in which the hydrophobic monomer is soluble.
  • Another object of the present invention is to provide an aqueous- based laundry detergent formulation which has significant amounts of detergent active matter and builders which shows virtually no phase separation.
  • a further object of the invention is to provide a novel, hydro ⁇ philic copolymer useful in stabilizing liquid laundry detergents.
  • Another object is to provide a method of stabilizing laundry for ⁇ mulations.
  • a stable liquid detergent composition which contains about 5 - 70% of detergent active matter selected from the group consist ⁇ ing of anionic, nonionic, cationic, a photeric and zwitterionic surfactants, as well as about 1 - 60% of one or more electro ⁇ lytes.
  • the detergent composition also has about 0.01 - 5% of at least one hydrophilic copolymer represented by formula I or II:
  • M is a alkali metal such as sodium, or hydrogen and the monomer units are in random order.
  • (x + y):z is from about 5:1 to 1000:1, and y can be any value ranging from zero up to the maximum value of x, and b can be zero
  • R 2 COOM , OCH 3 , S0 3 M, 0-CO-CH 3 , CO-NH 2
  • R 3 CH 2 -0- , CH 2 -N- , COO- , -0- , CH 2 -0-CH 2 -CH-0- , CO-NH-
  • R 4 -CH 2 -CH 2 -0
  • x, y, z, a, and b are inte ⁇ gers and M is a alkali metal such as sodium, or hydrogen, and the monomer units are in random order, (x + y):z is from about 5:1 to 1000:1, and y can be any value ranging from zero up to the maxi ⁇ mum value of x, and b can be zero, and
  • R 4 is ethyleneoxy and R 5 is alkyleneoxy, preferably propyleneoxy or butyleneoxy, with the provision that, if b is different from zero, the values of a and b in the sidechain are such that the combined weights of R 4 and R 5 are such that the monomer has a sol ⁇ ubility of at least about 500 grams/liter in water at 20°C.
  • the remainder of the detergent formulation is water.
  • the liquid de ⁇ tergent composition has a phase separation of less than about 2% over a one month period.
  • Also provided as part of the invention is a method of stabilizing a liquid detergent composition which comprises adding thereto about 0.01 - 5% of at least one hydrophilic copolymer having the above formula(s).
  • hydrophilic copolymer of the invention is represented by For ⁇ mula I or II:
  • x, y, z, a, and b are integers and M is a alkali metal, or hydrogen and the monomer units are in random order
  • (x + y) :z is from about 5:1 to 1000:1
  • y can be any value ranging from zero up to the maximum value of x, and b can be zero.
  • R 3 CH2-O- , CH 2 -N- , C00- , -0- , CH 2 -0-CH 2 -CH-0- , CO-NH-
  • R 4 -CH 2 -CH 2 -0
  • R5 alkyleneoxy group, preferably propyleneoxy or butyleneoxy groups, with the provision that, if b is different from zero, the values of a and b in the sidechain are such the combined weights of R 4 and R5 are such that the monomer has a solubility of at least about 500 grams/liter in water at 20°C
  • x, y, z, a, and b are inte ⁇ gers and M is a alkali metal, or hydrogen and the monomer units are in random order, (x + y):z is from about 5:1 to 1000:1, and y can be any value ranging from zero up to the maximum value of x, and b can be zero and
  • Ri H or CH 3
  • R 2 COOM, OCH 3 , S0 3 M, 0-CO-CH 3
  • R 4 is ethyleneoxy and R5 is alkyleneoxy, preferably propyleneoxy or butyleneoxy, with the provision that, if b is different from zero, the values of a and b in the sidechain are such the com ⁇ bined weights of R 4 and R 5 are such that the monomer has a solu- bility of at least about 500 grams/liter in water. It is within the scope of the invention that R and R 5 be interchangeable in the sidechain.
  • the molar ratio of x + y to z in both For- mulas I and II is within the range of about 5:1 to 1000:1, pre ⁇ ferably about 50:1 to 800:1, and more preferably about 100:1 to 500:1. If b is zero, the value of a is preferably within the range of about 1 to 200, more preferably about 1 to 150, and more preferably about 1 to 100.
  • the total molecular weight of the copolymer will be within the range of about 500 to 500,000, as determined by gel permeation chromatography. It is further desirable that the molecular weight fall within the range of about 1,000 to 100,000, and even more preferably be within the range of about 1,000 to 10,000 (weight average molecular weight - WAMW; unless otherwise specified, mo ⁇ lecular weights herein are given in terms of WAMW) .
  • hydrophilic copolymers of the present invention are prepared by copolymerizing two hydrophilic monomers, an unsaturated hydro ⁇ philic monomer copolymerized with an oxyalkylated monomer. These monomers may be randomly distributed within the polymer backbone. Preparation of oxyalkylated monomers could be carried out in ac ⁇ cordance with Tang, U.S. Patent No. 5,162,475, incorporated herein by reference. In Tang, Example 1 is especially relevant. Gosselink, U.S. Patent No. 4,622,378, is also relevant, and is also incorporated herein.
  • the unsaturated hydrophilic monomer may be selected from the group consisting of acrylic acid, maleic acid, maleic anhydride, methacrylic acid, methacrylate eaters and substituted meth- acrylate esters, vinyl acetate, as well as vinyl acetate copoly ⁇ merized with said oxyalkylated monomer and hydrolyzed to poly- vinyl alcohol, methylvinyl ether, and vinylsulphonate.
  • the unsaturated hydrophilic monomer component of the hydro ⁇ philic copolymer in formula I or II is acrylic acid.
  • Other useful monomers will include crotonic acid, itaconic acid, as well as vinyl acetic acid.
  • Examples of the oxyalkylated monomer would be compounds that have a poly erizable olefinic moiety with at least one acidic hydrogen and are capable of undergoing addition reaction with alkylene ox- ides. It is also possible to include monomers with at least one acidic hydrogen that are polymerized first, and then subsequently oxyalkylated to yield the desired product.
  • allyl al ⁇ cohol is especially preferred since it represents a mono- functional initiator with a polymerizable olefinic moiety having an acidic hydrogen on the oxygen, and is capable of adding to alkylene oxide.
  • diallylamine represents another mono- functional initiator with polymerizable olefinic moieties, having an acidic hydrogen on the nitrogen, and is capable of adding to alkylene oxide.
  • Other examples of the oxyalkylated monomer of the copolymer will include reaction products of either acrylic acid, methacrylic acid, maleic acid, or 3-allyloxy-l,2-propanediol with alkylene oxide, preferably ethylene oxide.
  • the oxyethylated moiety represents the side chain of this mono ⁇ mer.
  • the side chain is hydrophilic in nature, that is, the side chain when isolated from its linkage to the backbone carbon atom is completely soluble in water.
  • the monomer unit containing the hydrophilic side chain also has similar solubility characteristics as the side chain.
  • the side chain when isolated from its linkage to the backbone will have'a solu ⁇ bility in water of at least about 700 grams/liter, and even more preferably about 1000 grams/liter, or more.
  • the entire side chain is hydrophilic in nature by virtue of its extensive solubility in water.
  • hydrophilic copolymer as part of the invention may be pre ⁇ pared by the skilled artisan according to the process below, in which the ethylene oxide adduct of allyl alcohol is copolymerized with acrylic acid by way of a non-limiting example.
  • the addition was halted and allowed to react at 145°C for 30 minutes.
  • the vessel was slowly vented to a 0 psig and repadded to 34 psig with nitrogen.
  • the addition was continued at 140 - 150°C and ⁇ 90 psig pressure.
  • the ma ⁇ terial was held at 145°C for 1 hour. It was then cooled to 900 and 2.9 grams of 85% phosphoric acid was added.
  • the material was mixed for 30 minutes and then vacuum stripped at 100°C for 1 hour.
  • the batch was cooled to 70°C and discharged into a holding tank.
  • the product was found to have a number average molecular weight of 4095 g/mol by phthalic anhydride esterification in pyridine.
  • the sodium bisulfite solution and monomer blend feeds are added over 4 hours while the sodium persulfate solution is added over 4.25 hours.
  • the three feeds are added via TEFLON • 1/8 inch tubing lines connected to rotating piston pumps. Appropriately sized glass reservoirs attached to the pumps hold the monomer blend and initiator feeds on balances accurate to 0.1 gram to precisely maintain feed rates.
  • the system is cooled to 80°C. At this temperature, 25.3 grams of a 2.4% 2,2'-Azobis(N,N'-dimethyleneisobutylramidine)dihydrochloride solution is added to the system over 0.5 hours as a postpolymer- izer.
  • the system When addition is complete the system is reacted for 2 hours at 80°C. After reaction, the system is cooled to 60°C and the solution pH is adjusted to about 7 with the addition of 658 grams of 50% sodium hydroxide solution. The resultant neutral polymer solution has an approximate solids content of about 40%.
  • the oxyalkylated monomer which is a propylene oxide and ethylene oxide adduct of allyl alcohol.
  • This monomer has a molecular weight of about 3800, and R 4 is a propyle ⁇ neoxy group represented by the formula -CH 2 -CH(CH 3 )-0 and R5 is -CH 2 -CH 2 -0.
  • Ri H
  • R 2 COOM
  • R 3 CH - 0,
  • y 0, M is sodium in this monomer as well.
  • the weight ratio of R 4 : R 5 in the oxyalkylated monomer is prefer ⁇ ably about 1:4 (this ratio may vary considerably, so long as the solubility criteria of at least about 500 grams/liter is met).
  • the molecular weight of the oxyalkylated monomer according to the various embodiments of the invention will be within the range of- about 200 to 30,000, more preferably about 500 to 15,000, and more preferably about 1000 to 5000.
  • the oxyalkylated moiety represents the side chain of this mono ⁇ mer.
  • the side chain is hydrophilic in nature, that is, the side chain when isolated from its linkage to the backbone carbon atom has extensive solubility in water.
  • the monomer unit containing the hydrophilic side chain also has similar solubility characteristics as the side chain.
  • the side chain when isolated from its linkage to the backbone will have a solu ⁇ bility in water of at least about 500 grams/liter, and even more preferably about 700 grams/liter, or more.
  • the entire side chain is hydrophilic in nature by virtue of its extensive solubility in water.
  • hydrophilic copolymer as part of the invention may be pre ⁇ pared by the skilled artisan according to the process below, in which the alkylene oxide adduct of allyl alcohol is copolymerized with acrylic acid by way of a non-limiting example.
  • the addition was halted and allowed to react at 145°C for 30 minutes.
  • the vessel was slowly vented to 0 psig and re- padded to 34 psig with nitrogen.
  • the addition was continued at 140-150°C and ⁇ 90 psig pressure.
  • the sodium bisulfite solution and monomer blend feeds are added over 4 hours while the sodium persulfate solution is added over 4.25 hours.
  • the three feeds are added via teflon 1/8 inch tubing lines con ⁇ nected to rotating piston pumps. Appropriately sized glass reser ⁇ voirs attached to the pumps hold the monomer blend and initiator feeds on balances accurate to 0.1 gram to precisely maintain feed rates.
  • the additions are complete, the system is cooled to 80 degrees centigrade. At 80 degrees centigrade, 25.3 grams of a 2.4% 2,2'-Azobis (N,N'-dimethyleneisobutyramidine) dihydro- chloride solution is added to the system over 0.5 hours as a postpolymerizer.
  • the resultant neutral polymer solution has an approximate solids content of 40%.
  • the hydrophilic copolymer of the invention is added to detergent compositions, hereinafter described, to impart stability thereto.
  • stable detergent compositions are those that do not give more than about a 2% phase separation upon storage at room temperature for a period of one month (30 days) from the time of preparation.
  • the phase separation is within the range of about 0 - 2%, and even more preferably less than about 1%.
  • the volume fraction of the separated aqueous phase is measured as a function of the total volume of the sample. For example, if the total volume of the sample is 100 ml, then a 2% separation would correspond to 2 ml.
  • the hydrophilic copolymer will therefore comprise about 0.01 to 5% by weight of the liquid detergent composition.
  • the copolymer of the invention will make up about 0.5 to 4% of a typ- ical laundry formulation, even more preferably about 1 to 2%. (Unless otherwise stated, all weight percentages are based upon the weight of the total laundry formulation) .
  • the laundry formulation will contain about 5 to 70% of detergent active matter, more preferably about 15 to 40%, and even more de ⁇ sirably greater than about 25 and up to about 35%.
  • the detergent active matter may be selected from the group of anionic, nonionic, cationic, amphoteric and zwitterionic surfactants known to the skilled artisan. Examples of these surfactants may be found in NcCutcheon, Detergents and Emulsifi- ers 1993, incorporated herein by reference. Examples of nonionic surfactants will include commonly utilized nonionic surfactants which are either linear or branched and have an HLB of from about 6 to 18, preferably from about 10 to 14. Examples of such non ⁇ ionic detergents are alkylphenol oxyalkylates (preferably oxye- thylates) and alcohol oxyethylates.
  • alkylphenol oxyalkylates examples include C 6 -Ci 8 -alkylphenols with about 1 - 15 moles of ethylene oxide or propylene oxide or mixtures of both.
  • Exam ⁇ ples of alcohol oxyalkylates include Cs - Ci ⁇ alcohols with about 1 - 15 moles of ethylene oxide or propylene oxide or mixtures of both.
  • Some of these types of nonionic surfactants are available from BASF Corp. under the trademark PLURAFAC.
  • Other types of non- ionic surfactants are available from Shell under the trademark NEODOL.
  • a C 12 - C 15 alcohol with an average of 7 moles of ethylene oxide under the trademark NEODOL® 25-7 is espe ⁇ cially useful in preparing the laundry detergent compositions useful in the invention.
  • nonionic surfactants include products made by condensation of ethylene oxide and propylene oxide with ethylene diamine (BASF, TETRONIC® and TE- TRONIC® R) . Also included are condensation products of ethylene oxide and propylene oxide with ethylene glycol and propylene gly- col (BASF, PLURONIC® and PLUR0NIC®R) .
  • Other nonionic surface active agents also include alkylpolyglycosides, long chain aliphatic tertiary amine oxides and phosphine oxides.
  • anionic surfactants used in the detergency art include the synthetically derived water-soluble alkali metal salts of organic sulphates and sulphonates having about 6 to 22 carbon atoms.
  • the commonly used anionic surf actants are sodium alkyl- benzene sulphonates, sodium alkylsulphates and sodium alk lether sulphates.
  • Other examples include reaction products of fatty acids with isethionic acid and neutralized with sodium hydroxide, sulphate esters of higher alcohols derived from tallow or coconut oil, and alpha—methylestersulfonates.
  • amphoylitic detergents include straight or branched aliphatic derivatives of heterocyclic secondary or tertiary amines.
  • zwitterionic detergents include de- rivatives of straight or branched aliphatic quaternary ammonium, phosphoniu or sulfonium compounds.
  • the laundry detergent formulation will also contain one or more electrolytes.
  • Electrolytes defined herein are any ionic water- soluble material. The presence of the electrolyte is often re ⁇ quired to bring about the structuring of the detergent active ma ⁇ terial, although lamellar dispersions are reported to be formed with detergent active material alone in the absence of a suitable electrolyte. Electrolytes typically comprise from about 1 to 60% by weight, and more preferably about 25 to 35% of a laundry de ⁇ tergent formulation.
  • Suitable electrolytes include compounds capable of providing sufficient ionic strength to the aqueous detergent com- position. These compounds would include alkali metal salts of citric acid, alkali metal carbonates, and alkali metal hydrox ⁇ ides. Of these, sodium citrate, sodium carbonate and sodium hy ⁇ droxide are preferred. Potassium salts can also be incorporated to promote better solubility, other examples of suitable electro- lytes will include the phosphate salts such as sodium or potas ⁇ sium tripolyphosphate, and alkali metal silicates.
  • the electrolyte utilized will also serve as the builder for enhancing detergency.
  • the builder material sequesters the free calcium or magnesium ions in water and promote better detergency. Additional benefits provided by the builder are in ⁇ creased alkalinity and soil suspending properties.
  • the most commonly used non-phosphate builders are the alkali metal ci- trates, carbonates, bicarbonates and silicates. All of these compounds are water—soluble.
  • Water-insoluble builders which re ⁇ move hardness ions from water by an ion-exchange mechanism are the crystalline or amorphous aluminosilicates referred to as zeo ⁇ lites.
  • electrolytes or builders can also be employed.
  • the amount of electrolyte used in laundry detergent compositions according to the invention will be well above the solubility limit of the electrolyte.
  • Secondary builders such as the alkali metals of ethylene diamine tetraacetic acid, nitrilotriacetic acid can also be uti ⁇ lized in the laundry formulations of the invention.
  • Other second- ary builders known to those skilled in the art may also be uti ⁇ lized.
  • the laundry detergent formulations heretofore described may also contain additional ingredients such as enzymes, antiredeposition agents, optical brighteners, as well as dyes and perfumes known to those skilled in the art.
  • additional ingredients such as enzymes, antiredeposition agents, optical brighteners, as well as dyes and perfumes known to those skilled in the art.
  • other optional ingredients may in ⁇ clude fabric softeners, foam suppressants, and oxygen or chlorine releasing bleaching agents.
  • the nonionic surfactant used in the formulations shown in the Tables is NEODOL® 25-7, a product of Shell.
  • the linear alkylben- zene sulfonic acid, sodium salt (LAS) was obtained from Vista un ⁇ der the name Vista C-560 slurry.
  • the zeolite was "ZEOLITE A", also known as VALFOR® 100, available from the PQ Corp of Valley Forge, PA.
  • the polymer used in the formulations was a copolymer of acrylic acid with an oxyalkylated allyl alcohol, within the scope of the invention. In case of
  • Monomer A the ratio of acrylic acid to oxyethylated allyl alcohol was 90:10 by weight, while the molar ratio was about 503:1.
  • the molecular weight of the oxyethylated monomer was about 3800.
  • M equals sodium in the oxyethylated monomer.
  • Tables 1 and 2 demonstrate the flexibility of formulating concen ⁇ trated aqueous liquid detergents that allow the incorporation of major amounts of builders such as sodium citrate, sodium carbonate, and zeolite in the formulation. Furthermore, these compositions were pourable, stable compositions.
  • Example 9 in Table 3 shows that water-soluble poly ⁇ carboxylates can be successfully incorporated in concentrated liquid detergent formulations that contain relatively small amounts of a copolymer according to one or more embodiments of the invention.
  • Table 3 also illustrates several examples of de ⁇ tergent formulations that lack stability despite the inclusion of hydrophobically modified polymers.
  • Nonionic Surfactant 7 6.6 7.1 7 6.6
  • Sokalan® CP5 1.3
  • Sokalan® PA30C1 Sokalan® PA30C1 1.3
  • Lipolase, Savinase and Termamyl are laundry enzymes - Novo Nodisk Biolndustrials, Inc., Danbury, CT.
  • Tables 4, 5 and 7 demonstrate the flexibility of formulating con ⁇ centrated aqueous liquid detergents that allow the incorporation of major amounts of builders such as sodium citrate, sodium carbonate, and zeolite in the formulation. Furthermore, these compositions were pourable, stable compositions.
  • Example 22 in Table 6 shows that water-soluble poly- carboxylates can be successfully incorporated in concentrated liquid detergent formulations that contain relatively small amounts of a copolymer according to one or more embodiments of the invention.
  • Table 6 also illustrates several examples of de ⁇ tergent formulations that lack stability despite the inclusion of hydrophobically modified polymers.
  • Nonionic Surfactant 7 6.6 7.1 7 6.6
  • Sokalan® CP5 1.3
  • Sokalan® PA30C1 Sokalan® PA30C1 1.3
  • Lipolase, Savinase and Termamyl are laundry enzymes - Novo Nodisk Biolndustrials, Inc., Danbury, CT.

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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention concerne une composition détergente liquide contenant des tensioactifs, des électrolytes ainsi que 0,01 à 5 % d'au moins un copolymère hydrophile représenté par la formule (I) ou (II). Dans la formule (I), x, y, z, a et b représentent des nombres entiers et N un métal alcalin, ou hydrogène, et les motifs monomères sont dans un ordre aléatoire. (x+y):z est compris entre environ 5:1 et 1000:1, et y peut être égal à toute valeur comprise entre zéro et la valeur maximale de x; R1 représente H ou CH3; R2 représente COOM, OCH3, SO3M, O-CO-CH3, CO-NH2; R3 représente CH2-O, CH2-N-, COO-, -O-, (i), CO-NH-; R4 représente -CH2-CH2-O; R5 représente un groupe alcylène-oxy, de préférence des groupes propylène-oxy ou butylène-oxy, à condition que, si b est différent de zéro, les valeurs de a et b dans la chaîne latérale soient telles que les poids combinés de R4 et R5 soient tels que le monomère présente une solubilité d'au moins 500 g/l dans l'eau; dans la formule (II) R6 représente (a) ou (b), ou des mélanges des deux; x, y, z, a et b représentent des nombres entiers et M un métal alcalin tel que le sodium ou l'hydrogène, et les motifs monomères sont dans un ordre aléatoire, (x+y):z est compris entre environ 5:1 et 1000:1, et y peut être égal à toute valeur comprise entre zéro et la valeur maximale de x, et b peut être égal à zéro; et R1 représente H ou CH3; R2 représente COOM, OCH3, SO3M, O-CO-CH3, CO-NH2; R4 représente éthylène-oxy; R5 représente alcylène-oxy, de préférence propylène-oxy ou butylène-oxy, à condition que, si b est différent de zéro, les valeurs de a et b dans la chaîne latérale soient telles que les poids combinés de R4 et R5 soient tels que le monomère présente une solubilité d'au moins 500 g/l dans l'eau. L'eau représente le reste de la formulation de ce détergent pour lessive.
PCT/EP1995/002597 1994-07-14 1995-07-05 Compositions detergentes liquides concentrees aqueuses stables, contenant des copolymeres hydrophiles WO1996002622A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP95925829A EP0770122B1 (fr) 1994-07-14 1995-07-05 Compositions detergentes liquides concentrees aqueuses stables, contenant des copolymeres hydrophiles
JP8504639A JPH10502694A (ja) 1994-07-14 1995-07-05 親水性コポリマーを含有する、安定な水性濃厚液体洗剤組成物
DE69506551T DE69506551T2 (de) 1994-07-14 1995-07-05 Stabile wässrige konzentrierte flüssigwaschmittel enthaltend hydrophile copolymere
AU29814/95A AU2981495A (en) 1994-07-14 1995-07-05 Stable, aqueous concentrated liquid detergent compositions containing hydrophilic copolymers

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US08/274,948 US5536440A (en) 1994-07-14 1994-07-14 Stable, aqueous concentrated liquid detergent compositions containing hydrophilic copolymers
US08/274,948 1994-07-14
US08/274,938 US5534183A (en) 1994-07-14 1994-07-14 Stable, aqueous concentrated liquid detergent compositions containing hydrophilic copolymers
US08/274,938 1994-07-14

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AU (1) AU2981495A (fr)
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WO (1) WO1996002622A1 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996037597A1 (fr) * 1995-05-23 1996-11-28 Basf Corporation Formulations de detergents
WO1998055576A1 (fr) * 1997-06-06 1998-12-10 Unilever N.V. Materiaux polymeres
WO1999027057A1 (fr) * 1997-11-21 1999-06-03 The Procter & Gamble Company Compositions detergentes liquides comprenant des activateurs polymeres de mousse
EP0778340A3 (fr) * 1995-12-06 1999-10-27 Basf Corporation Compositions exemptes de phosphate pour le lavage en lave-vaisselle contenant des copolymères à base de produits d'addition d'oxyde d'alkylène d'alcool allylique et d'acide acrylique
EP0870822A3 (fr) * 1997-04-07 2000-01-26 Basf Corporation Détergents liquides concentrés contenant du "builder" et un additif inhibiteur du tranfert de colorant
US6207631B1 (en) 1997-11-21 2001-03-27 The Procter & Gamble Company Detergent compositions comprising polymeric suds volume and suds duration enhancers and methods for washing with same
US6376631B1 (en) 2000-09-27 2002-04-23 Rhodia, Inc. Processes to control the residual monomer level of copolymers of tertiary amino monomer with a vinyl-functional monomer
US6528476B1 (en) 1999-05-26 2003-03-04 The Procter & Gamble Company Liquid detergent compositions comprising block polymeric suds enhancers
US6573234B1 (en) 1999-05-26 2003-06-03 The Procter & Gamble Company Liquid detergent compositions comprising polymeric suds enhancers
US6589926B1 (en) 1998-06-02 2003-07-08 Procter & Gamble Company Dishwashing detergent compositions containing organic diamines
US6864314B1 (en) 1999-05-26 2005-03-08 Dominic Wai-Kwing Yeung Block polymers, compositions and methods of use for foams, laundry detergents, shower rinses and coagulants
US7241729B2 (en) 1999-05-26 2007-07-10 Rhodia Inc. Compositions and methods for using polymeric suds enhancers
US8907033B2 (en) 1999-05-26 2014-12-09 Solvay Usa Inc. Polymers, compositions and methods of use for foams, laundry detergents, shower rinses and coagulants

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JP3264837B2 (ja) * 1996-08-23 2002-03-11 花王株式会社 濃厚系液体洗浄剤組成物
JP4626927B2 (ja) * 2001-05-08 2011-02-09 花王株式会社 液体洗浄剤組成物
JP4626926B2 (ja) * 2001-05-08 2011-02-09 花王株式会社 液体洗浄剤組成物
JP4489422B2 (ja) * 2003-12-26 2010-06-23 花王株式会社 液体洗浄剤組成物
US7951768B2 (en) * 2007-06-29 2011-05-31 The Procter & Gamble Company Laundry detergent compositions comprising amphiphilic graft polymers based on polyalkylene oxides and vinyl esters
JP2009185294A (ja) * 2009-03-31 2009-08-20 Nippon Shokubai Co Ltd 液体洗剤用ビルダーおよび液体洗剤組成物
WO2020065399A1 (fr) 2018-09-25 2020-04-02 Pro Med Instruments Gmbh Dispositif de stabilisation de tête avec broches non uniformes

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Cited By (17)

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WO1996037597A1 (fr) * 1995-05-23 1996-11-28 Basf Corporation Formulations de detergents
EP0778340A3 (fr) * 1995-12-06 1999-10-27 Basf Corporation Compositions exemptes de phosphate pour le lavage en lave-vaisselle contenant des copolymères à base de produits d'addition d'oxyde d'alkylène d'alcool allylique et d'acide acrylique
EP0870822A3 (fr) * 1997-04-07 2000-01-26 Basf Corporation Détergents liquides concentrés contenant du "builder" et un additif inhibiteur du tranfert de colorant
WO1998055576A1 (fr) * 1997-06-06 1998-12-10 Unilever N.V. Materiaux polymeres
WO1999027057A1 (fr) * 1997-11-21 1999-06-03 The Procter & Gamble Company Compositions detergentes liquides comprenant des activateurs polymeres de mousse
US6207631B1 (en) 1997-11-21 2001-03-27 The Procter & Gamble Company Detergent compositions comprising polymeric suds volume and suds duration enhancers and methods for washing with same
US6369012B1 (en) 1997-11-21 2002-04-09 The Procter & Gamble Company Detergent compositions comprising polymeric suds volume and suds enhancers and methods of washing with same
US6372708B1 (en) 1997-11-21 2002-04-16 The Procter & Gamble Company Liquid detergent compositions comprising polymeric suds enhancers
US6589926B1 (en) 1998-06-02 2003-07-08 Procter & Gamble Company Dishwashing detergent compositions containing organic diamines
US6864314B1 (en) 1999-05-26 2005-03-08 Dominic Wai-Kwing Yeung Block polymers, compositions and methods of use for foams, laundry detergents, shower rinses and coagulants
US6573234B1 (en) 1999-05-26 2003-06-03 The Procter & Gamble Company Liquid detergent compositions comprising polymeric suds enhancers
US6528476B1 (en) 1999-05-26 2003-03-04 The Procter & Gamble Company Liquid detergent compositions comprising block polymeric suds enhancers
US7241729B2 (en) 1999-05-26 2007-07-10 Rhodia Inc. Compositions and methods for using polymeric suds enhancers
US7335700B2 (en) 1999-05-26 2008-02-26 Rhodia Inc. Block polymers, compositions and methods of use for foams, laundry detergents, shower rinses and coagulants
US8907033B2 (en) 1999-05-26 2014-12-09 Solvay Usa Inc. Polymers, compositions and methods of use for foams, laundry detergents, shower rinses and coagulants
US9044413B2 (en) 1999-05-26 2015-06-02 Solvay Usa Inc. Block polymers, compositions and methods for use for foams, laundry detergents, and shower rinses and coagulants
US6376631B1 (en) 2000-09-27 2002-04-23 Rhodia, Inc. Processes to control the residual monomer level of copolymers of tertiary amino monomer with a vinyl-functional monomer

Also Published As

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DE69506551D1 (de) 1999-01-21
EP0770122B1 (fr) 1998-12-09
EP0770122A1 (fr) 1997-05-02
JPH10502694A (ja) 1998-03-10
DE69506551T2 (de) 1999-05-06
AU2981495A (en) 1996-02-16

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