+

WO1996037597A1 - Formulations de detergents - Google Patents

Formulations de detergents Download PDF

Info

Publication number
WO1996037597A1
WO1996037597A1 PCT/EP1996/002112 EP9602112W WO9637597A1 WO 1996037597 A1 WO1996037597 A1 WO 1996037597A1 EP 9602112 W EP9602112 W EP 9602112W WO 9637597 A1 WO9637597 A1 WO 9637597A1
Authority
WO
WIPO (PCT)
Prior art keywords
copolymer
composition
monomer
detergent
weight
Prior art date
Application number
PCT/EP1996/002112
Other languages
English (en)
Inventor
Sridhar Gopalkrishnan
Kathleen M. Guiney
John V. Sherman
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 US08/447,513 external-priority patent/US5618782A/en
Priority claimed from US08/448,283 external-priority patent/US5733861A/en
Priority claimed from US08/448,281 external-priority patent/US5595968A/en
Application filed by Basf Corporation, Basf Aktiengesellschaft filed Critical Basf Corporation
Priority to AU58980/96A priority Critical patent/AU5898096A/en
Priority to EP96916104A priority patent/EP0850294A1/fr
Priority to JP8535351A priority patent/JPH11505867A/ja
Publication of WO1996037597A1 publication Critical patent/WO1996037597A1/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
    • C11D3/3746—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
    • 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
    • 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

Definitions

  • the present invention relates to detergent crutcher slurry com ⁇ positions that contain hydrophilic copolymers which permit the reduction of viscosity of such slurries and facilitate their pro ⁇ cessing during the manufacture of commercial powder detergents, as well as to laundry detergent formulations containing said copolymers and showing improved anti-redeposition properties.
  • Spray-drying is a typical method of manufacturing powder laundry detergents and involves combining inorganic builder mixtures such as alkali metal bicarbonate, alkali metal carbonate, alkali metal silicate or water-insoluble builders such as zeolite, with water, to form a concentrated slurry.
  • inorganic builder mixtures such as alkali metal bicarbonate, alkali metal carbonate, alkali metal silicate or water-insoluble builders such as zeolite
  • surfactants which are usually anionic in nature, such as linear alkylbenzene sulfonate, alcohol ether sulfates, alcohol sulfates, secondary alkane sulfonates, alphaolefin sulfonates etc.
  • Non- ionic surfactants although not normally included in the crutcher, can be incorporated in the crutcher in small amounts; however, particular attention needs to be devoted to environmen ⁇ tal concerns related to "pluming" associated with the spray dry ⁇ ing of such slurries.
  • a crutcher composition typically consti ⁇ tutes about 45 % - 60 % solids although it is possible to have a solids content greater than 60 % in the crutcher.
  • Powder detergent compositions typically involve the addition of substantial amounts of alkali metal carbonates, such as sodium carbonate, to the crutcher mix.
  • Alkali metal carbonates in par ⁇ ticular sodium carbonate, can constitute a substantial percentage of the powder detergent formulation, and are added primarily to remove hardness ions such as calcium, via an ion exchange mecha ⁇ nism, and also to provide alkalinity to the wash liquor.
  • the crutcher mix is processed through a spray tower at very high temperatures to form dry beads. If the detergent formulation contains nonionic surfactants or heat-sensitive ingredients, these additives are sprayed on and absorbed into the dried beads.
  • crutcher slurries that contain significant amounts of alkali metal carbonates is their tendency to gel, particularly in the presence of anionic surfactants. This gelling significantly increases the viscosity of the crutcher slurry and makes the crutcher slurry very difficult to process.
  • polymeric dispersants have been added to the crutcher mix.
  • polycarboxylate polymers such as acrylic polymers and acrylic/maleic copolymers which are added in small amounts, typically about 5 % based on the weight of the de ⁇ tergent composition.
  • the addition of polycarboxylates results in the dispersion of solids in the crutcher and thereby reduces the viscosity of the crutcher slurry.
  • U.S. Patent No. 4,368,134 teaches the use of water-soluble citric acid salts along with magnesium sulphate to reduce the viscosity of aqueous detergent slurries.
  • U.S. Patent No. 4,362,640 teaches a method for reducing the viscosity of carbonate based crutcher slurries during the addition of aqueous sodium silicate by adding CO 2 with the silicate solution.
  • U.S. Patent No. 4,311,606 teaches a method of reducing the viscosity of carbonate based crutcher slurries through the addition of sodium sesquicarbonate along with citric acid.
  • the additives listed in the prior art described above function merely as dispersants and the viscosity reduction achieved via these methods ist modest.
  • Cellulosic polymers such as hydroxypropyl methylcellulose offer good anti-redeposition advantages for oil- type soil, but also do not offer significant anti-redeposition benefits for particulate soil removal, specifically clay soil.
  • said copolymers should be useful in reducing the viscosity of aqueous detergent slurries, in particular of concentrated, optionally soda ash based, deter ⁇ gent slurries.
  • copolymers with improved anti-redeposi ⁇ tion properties for incorporation into laundry detergents should be provided for the purpose of minimizing redeposition of par ⁇ ticulate soils, such als clay soil, during the laundering pro- cess.
  • a second object is to provide a method of reducing the viscosity of aqueous detergent slurries.
  • a third object is to provide a method of reducing the viscosity of aqueous soda ash based detergent slurries.
  • a fourth object of the invention is to provide a method of pre ⁇ venting redeposition of particulate soils, such as clay soil, during the laundering process.
  • hydrophilic copolymers when incorporated in small amounts in the crutcher slurry com ⁇ position give a substantial decrease in the viscosity of the slurry compared to the viscosity reducers known in the art.
  • the viscosity decrease with the hydrophilic polymers may be two to three orders of magnitude lower than the viscosity achieved with- out the polymer in the slurry.
  • a second embodiment refers to an aqueous detergent slurry com ⁇ position with reduced viscosity which contains about 5 - 60 % of inorganic builder salts, about 5 - 70 % of detergent active mat ⁇ ter selected from the group consisting of anionic, nonionic, cationic, amphoteric and zwitterionic surfactants, and about 0.01 - 10 % of said hydrophilic copolymer comprising said unsaturated hydrophilic monomer copolymerized with an oxyalkylated monomer.
  • a third embodiment of the invention refers to an aqueous soda ash based detergent slurry composition with reduced viscosity which contains about 5 - 65 % of inorganic builder salt comprising soda ash, and about 0.01 - 20 % of said copolymer comprising an unsat ⁇ urated hydrophilic monomer copolymerized with an oxyalkylated monome .
  • a fourth embodiment of the invention refers to a laundry deter ⁇ gent composition comprising 0.01 to 10 % by weight of said copolymer comprising a hydrophilic monomer and an oxyalkylated monomer, which provides superior anti-redeposition benefits compared to conventional polycarboxylate polymers used in laundry detergents.
  • Also provided as part of the invention is a method of reducing the viscosity of aqueous detergent slurries which comprises ad- ding thereto about 0.01 - 10 % of at least one of the herein de ⁇ fined hydrophilic copolymer as well as a method of reducing the viscosity of aqueous soda ash based detergent slurries which com ⁇ prises adding thereto about 0.01 - 20 % of at least one of the herein defined copolymers.
  • a further embodiment of the invention concerns a method of pre ⁇ venting soil redeposition, comprising adding to a laundry deter ⁇ gent 0.01 to 10 % by weight of at least one of the herein defined copolymers.
  • hydrophilic copolymer of the present invention is preferably of the formula (I)
  • x, y, and z are integers, (x + y):z is from about 5:1 to about 1000:1, and y can be any value ranging from zero up to the value of x;
  • M is an alkali metal or hydrogen
  • R l is H or CH 3 ;
  • R 2 is -COOM, -OCH 3 -S0 3 M, -O-CO-CH 3 , -CO-NH 2 ;
  • W is selected from residues of formula (II), (III) or (IV)
  • Ri is as defined above;
  • R 3 is -CH 2 -0-, -CH 2 -N-, -COO-, -0-, -CH 2 -0-CH 2 -CH-0-, -CO-NH-;
  • M is as defined above a is an integer from 0 to about 516 b is an integer from 0 to about 680 with the proviso that the sum of a + b cannot be 0; R 4 is a C 3 -C alkyleneoxy group; R5 is -CH 2 -CH 2 -0-; and G and G 1 are end groups.
  • Figure 1 shows the ability of the copolymers of the invention to reduce the viscosity of aqueous sodium carbonate slurries.
  • the performance of the polymers of this invention is compared to com ⁇ dismissally available polymers that are typically added to deter- 0 gent slurries during the commercial manufacture of powder laundry detergents.
  • Figures 2 and 3 illustrate the soil anti-redeposition properties of the copolymers of the invention as against known anti-rede- 5 position additives.
  • the hydrophilic copolymer of the present invention is preferably 0 a compound of the formula (I)
  • x, y, and z are integers, (x + y):z is from about 5:1 to about 30 1000:1, preferably about 50:1 to 800:1, and more preferably about 100:1 to about 500:1, as for example 125:1, and y can be any value ranging from zero up to the value of x, preferably zero;
  • M is hydrogen or an alkali metal, preferably sodium or potassium. 35
  • Ri is H or CH 3 ; preferably H;
  • R 2 is -COOM, -OCH 3 , -SO 3 M, -O-CO-CH3, -CO-NH 2 , preferably -COOM;
  • W is selected from residues of formula (II), (III) or (IV) 40
  • Ri is as defined above;
  • R 3 is -CH 2 -0-, -CH 2 -N-, -COO-, -0-, -CH 2 -0-CH 2 -CH-0-, -CO-NH-;
  • R 3 is linked to the polymer backbone via the left-hand free chemical bond
  • M is as defined above a is an integer from 0 to about 516 b is an integer from 0 to about 680 with the proviso that the sum of a + b cannot be 0;
  • R is a C 3 -C 4 alkyleneoxy group
  • R 5 is -CH 2 -CH -0-
  • G and G 1 are end groups such as OH, SH, SR 7 , SO 3 M, OR 7 or H, R 7 being alkyl or aryl. G and G 1 may have the same meaning.
  • a copolymer of formula (I) is provided wherein a is 0 and b is an integer from about 3 to about 680; preferably from about 8 to about 225, more preferably from about 12 to about 135, most preferably about 15.
  • the ratio of a : b is from about 5:95 to about 100:0 and preferably from about 20:80 to about 80:20.
  • copolymers wherein a:b is from about 1:4 to about 1:99, preferably from about 1:5 to about 1:20 and in par ⁇ ticular about 1:5.
  • 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 oxalkylated monomer has a solubility of at least about 500 grams/liter in water, preferably at least about 700 grams/liter.
  • R 4 and R 5 may be interchangeable or randomly distributed in the sidechain.
  • the total molecular weight of the copolmer should be within the range of about 500 to 500,000, as determined by gel permeation chromatography. Preferably, the molecular weight falls within the range of about 1,000 to 100,000; more preferably within the range of about 1,000 to 20,000 (weight average molecular weight - WAMW; unless otherwise specified, molecular weights herein are given in terms of WAMW) .
  • the hydrophilic copolymer of the present invention is prepared by copolymerizing at least two different kinds of monomers, an un- saturated hydrophilic monomer and an oxyalkylated monomer. These monomers may be randomly distributed in polymerized form as monomer units within the polymer backbone.
  • unsaturated hydrophilic monomers useful in the pres- ent invention include acrylic acid, maleic acid, maleic anhydride, methacrylic acid, methacrylate esters and substituted methacrylate esters, vinyl acetate, vinyl acetate copolymerized with said oxyalkylated monomer and hydrolyzed to polyvinyl alco ⁇ hol, vinyl alcohol, polyvinyl alcohol, methylvinyl ether, cro- tonic acid, itaconic acid, vinyl acetic acid, and vinylsulpho- nate.
  • the unsaturated hydrophilic monomer component of the hydrophilic copolymer in formula I is acrylic acid.
  • Examples of the oxyalkylated monomer include compounds that have a polymerizable olefinic moiety with at least one acidic hydrogen and are capable of undergoing addition reaction with alkylene ox ⁇ ide. 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 pxoduct.
  • 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 include reaction products of either acrylic acid, meth ⁇ acrylic acid, maleic acid, or 3-allyloxy-l,2-propanediol with alkylene oxide.
  • the molecular weight of the oxalkylated monomer according to the various embodiments of the invention should be within the range of about 200 to 30,000, preferably about 300 to 15,000, and more preferably about 600 to 5000.
  • This monomer has a molec ⁇ ular weight of about 700, and R 4 is a oxyethylene group repre ⁇ sented by the formula -CH 2 -CH 2 -0.
  • Another preferred oxyalkylated monomer is a propylene oxide and ethylene oxide adduct of allyl alcohol.
  • This monomer has a molec ⁇ ular weight of about 3800, and R is a propyleneoxy group repre ⁇ sented by the formula -CH 2 -CH(CH 3 )-0 and R 5 is -CH 2 -CH 2 -0.
  • Ri H
  • R 2 COOM
  • R 3 CH 2 - 0,
  • y 0.
  • the weight ratio percent of a:b in the oxyalkylated monomer is preferably about 20:80.
  • Preferred oxyalkylated monomer is also a propylene oxide and ethylene oxide adduct of allyl alcohol.
  • This monomer has a molec- ular weight of about 700, and R 4 is a propylene group and R 5 is -CH 2 -CH -0.
  • Ri H
  • R 2 COOM
  • the weight ratio recent of a:b in the oxalkylated monomer is preferably about 80:20.
  • Still another preferred oxyalkylated monomer is a propylene oxide and ethylene oxide adduct of allyl alcohol having a molecular weight of about 1500 to 3800.
  • Ri H
  • R 2 COOM
  • R 3 CH 2 - O
  • y - 0 the ratio of a:b is about 1:5.
  • the oxyalkylated moiety represents the side chain of this oxyal- kylated monomer.
  • 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 copolymers are added to detergent compositions, hereinafter described, preferably to reduce viscos ⁇ ity of the detergent slurry or to improve the anti-redeposition properties of the detergent.
  • a first preferred aqueous detergent slurry composition of the in ⁇ vention comprises
  • the copolymer of the invention make up about 0.5 to 7 % of a typical laundry formulation, even more prefe ⁇ rably about 1 to 5 %. (Unless otherwise stated, all weight percentages are based upon the weight of the total detergent formulation) .
  • this composition comprises at least one copolymer of one of the following formulas:
  • Ri, R2, R3 R5, M, G, G 1 , x, y, and z are as defined above;
  • R ⁇ is a residue of the above formulas (III) or (IV) or a mixture thereof, wherein Q is as defined Pbove, provided that a is 0 and R 5 and M are as defined jove; and b is an integer from about 3 to about 680.
  • this composition may comprise at least one copolymer of one of the following formulas:
  • R ⁇ 2»
  • Re is a residue of the above formulas (III) or (IV) or a mixture thereof; and
  • a:b is from about 1:4 to about 1:99.
  • composition of the invention is an aqueous soda ash based detergent slurry composition
  • aqueous soda ash based detergent slurry composition comprising
  • inorganic builder salt comprising soda ash (i.e. sodium carbonate) and
  • the copolymer of the invention is about 1 % to 14 % of a slurry composition; more preferably about 2 % to 5 % of the slurry composition. (Unless otherwise stated, all weight-percent ⁇ ages are based upon the weight of the total solids in the slurry composition) .
  • the slurry composition may contain about 0 - 20 %, preferably about 10 - 15 %, of inorganic builder salts other than sodium carbonate, such that the total amount of inorganic builder salt including sodium carbonate is as defined above.
  • the aqueous soda ash slurry composition can also optionally con ⁇ tain small amounts of surfactants or detergent active matter, that are conventionally employed in cleaning compositions.
  • soda ash based compositions preferably comprise at least one copolymer of one of the following formulas:
  • Ri, R 2 , R 3 , M, G, G 1 , x, y, and z are as defined above;
  • Re is a residue of the above formulas (III) or (IV) or a mixture thereof,
  • a:b is from about 5:95 to about 100:0
  • Still another preferred composition is a laundry detergent com- position comprising about 0.01 to 10 %, preferably about 0.5 to 6 % and more preferably about 2 % by weight, of an anti-redeposi ⁇ tion additive comprising a copolymer of a hydrophilic monomer and an oxyalkylated monomer.
  • this laundry composition comprises a copolymer having the following formula:
  • R 2 , R 3 , R 4 , R 5 , M, G, G l , x, y, z, a, and b are as defined above.
  • the inorganic builder salts as used in the compositions of the invention may be selected from the group consisting of alkali metal carbonates, alkali metal bicarbonates, alkali metal sili ⁇ cates, alkali metal phosphates, and zeolites.
  • the de ⁇ tergent slurry composition contains major amounts of alkali metal carbonates such as sodium or potassium carbonate as for example about 15 - 45 %, preferably about 25 - 35 %.
  • the builder material sequesters the free calcium or magnesium ions in water and pro ⁇ motes better detergency. Additional benefits provided by the builder are increased alkalinity and soil suspending properties.
  • Water-insoluble builders which remove hardness ions from water by an ion-exchange mechanism are the crystalline or amorphous alumi- nosilicates referred to as zeolites.
  • Typical zeolites are univa- lent cation-exchanging compounds and examples of such crystalline types of zeolites are Zeolite A, Zeolite X or Zeolite Y.
  • the above-mentioned zeolites are typically used as builders in deter ⁇ gent ocmpositions. A more detailed description of such types of zeolites can be found in the Zeolite Molecular Sieves (1984) au ⁇ thored by D.W. Breck.
  • Secondary builders such as the alkali metal salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid can also be utilized in the detergent compositions of the inven ⁇ tion. Other secondary builders known to those skilled in the art may also be utilized.
  • the detergent active matter as used in the compositions of the invention 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 McCutcheon, Detergents and Emulsifiers (1993), incorporated herein by reference. Examples of nonionic surfactants will in ⁇ clude commonly utilized nonionic surfactants which are either linear or branched and have an HLB of from about 6 to 18, prefer- ably from about 10 to 14. Examples of such nonionic detergents are alk lphenol oxyalkylates (preferably oxyethylates) and alco ⁇ hol oxyethylates.
  • alkylphenol oxyalkylates in- elude C6 - Ci8 alkylphenols, preferably C to CQ , with about 1 - 15 moles of ethylene oxide or propylene oxide or mixtures of both.
  • alcohol oxyalkylates include Cg - Cie alcohols with about 1 - 15 moles of ethylene oxide or propylene oxide or mixtures of both.
  • nonionic surfactants include products made by condensation of ethylene ox ⁇ ide and propylene oxide with ethylene diamine (BASF, TETRONIC ® AND TETRONIC ® R) . Also included are condensation products of ethylene oxide and propylene oxide with ethylene glycol and propylene glycol (BASF, PLURONIC ® and PLURONIC ® R) .
  • non ⁇ ionic 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, preferably 12 to 15 carbon atoms.
  • the commonly used anionic surfactants are sodium alkylbenzene sulphonates, sodium alkylsulphates and sodium alkylether sulphates.
  • Other examples include N-alkylglucosamides, reaction products of fatty acids with isethionic acid neutralized with sodium hydroxide, sulphate esters of higher alcohols derived from tallow or coconut oil, and alpha-methylestersulfonates.
  • ampholytic detergents include straight or branched aliphatic derivatives of heterocyclic secondary or tertiary amines.
  • the aliphatic portion of the molecule typically contains about 8 to 20 carbon atoms, preferably 12 to 15 carbon atoms.
  • Zwitterionic detergents include derivatives of straight or branched aliphatic quaternary ammonium, phosphonium or sulfonium compounds.
  • the detergent slurry compositions heretofore described may be used to manufacture detergent compositions.
  • the slurry can be spray dried and additional ingredients such as enzymes, anti-re ⁇ deposition agents, optical brighteners, as well as dyes and per ⁇ fumes known to those skilled in the art can be added.
  • Other op ⁇ tional ingredients may include fabric softeners, foam suppres- sants, and oxygen or chlorine releasing bleaching agents.
  • the hydophilic copolymer as part of the invention may be prepared 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 sodium bisulfite solution and monomer blend feeds were added over 4 hours while the sodium persulfate solution was added over 4.25 hours.
  • the three feeds were 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 additions were complete, the system was 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 was added to the system over 0.5 hours as a postpolymerizer.
  • Example 2 When addition was complete, the system was reacted for 2 hours at 80 degrees centigrade. After reaction, the system was cooled to 60 degrees centigrade and the solution pH was adjusted to about 7 with the addition of 658 grams of 50 % sodium hydroxide solution. The resultant neutral polymer solution had an approximate solids content of 40 %.
  • Example 2 Example 2:
  • the sodium bisulfite solution and monomer blend feeds were added over 4 hours while the sodium persulfate solution was added over 4.25 hours.
  • the three feeds were 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 grams to precisely maintain feed rates.
  • the examples describe the viscosity reducing properties of the hydrophilic copolymers of this invention when added in small amounts to aqueous detergent slurry compositions.
  • the numbers in each column in Table 1 refer to the active weight percentage of each component in the detergent formulation.
  • the viscosity values reported in Table 1 are Brookfield viscosities measured with a Brookfield Viscometer (RVT Model) using spindle # 4 at 20 rpm. All viscosity measurements were immediately measured after sample preparation at 25°C.
  • the viscosity reducing properties of the hy- drophilic copolymers of this invention were evaluated in a con ⁇ centrated aqueous detergent composition built with different builders such as sodium silicate, sodium carbonate, alkali metal phosphate, and zeolite.
  • the performance of Polymers C & D, copolymers that fall within the scope of the invention are compared to conventional polycarboxylates (Polymers A & B) that are widely used in detergent formulations.
  • the nonionic surfactant used in the formulations shown in the Table 1 is NEODOL ® 25-7, a product of Shell.
  • the linear alkyl- benzene sulfonic acid, sodium salt (LAS) was obtained from Vista under 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 sodium carbonate was obtained from the FMC corpo ⁇ ration under the name "FMC Grade 100".
  • the sodium citrate used was sodium citrate dihydrate obtained from Mallinckrodt Specialty Chemicals Company. Tetrapotassiu pyrophosphate was obtained from the Stauffer Chemical Company. Polymers A and B shown in Table 1 are used for comparative purposes.
  • Polymer A is a sodium salt copolymer of acrylic acid with maleic acid with a weight average molecular weight of 70,000 available from BASF Corporation under the tradename SOKALAN CP5.
  • Polymer B is a sodium salt homopolymer of acrylic acid with a weight average molecular weight of 8000, available from the BASF Corporation under the tradename SOKALAN PA39CL.
  • Polymer C shown in Table 1 is a copolymer of acrylic acid with an oxyalkylated allyl alcohol, within the scope of the invention and is prepared according to Example 2 ratio by weight of acrylic acid to the oxyalkylated allyl alcohol was 90:10 by weight, while the molar ratio was about 474:1.
  • the oxyalkylated monomer compo ⁇ nent had a molecular weight of about 3800.
  • Ri H
  • R 2 COONa
  • R 3 CH 2 - O
  • R 4 -CH 2 -CH(CH 3 ) -0
  • R 5 -CH 2 -CH 2 -0
  • y 0.
  • the ratio of a:b was about 1:5.
  • the average molecular weight of Polymer C is about 16000.
  • Polymer D shown in Table 1 is a copolymer of acrylic acid with an oxyalkylated allyl alcohol, within the scope of the invention and is prepared according to Example 1 except that the ratio of acrylic acid to the oxyalkylated allyl alcohol was 85:15 by weight, while the molar ratio was about 123:1.
  • R 2 COONa
  • R 3 CH 2 - 0,
  • R 4 -CH 2 -CH(CH 3 )-0,
  • R 5 -CH -CH -0 and
  • y 0.
  • the ratio of a:b was about 1:5.
  • the average molecular weight of Polymer D was 9280.
  • Table 1 illustrates that the copolymers of this invention are able to reduce the viscosity of aqueous detergent slurries con ⁇ taining surfactants and inorganic builders by several orders of magnitude compared to conventional polycarboxylates such as
  • Sokalan CP5 polymer and Sokalan PA30C1 polymer typically used as dispersants for reducing the viscosity of crutcher slurries.
  • the viscosity reducing properties of Polymers C and D of this inven ⁇ tion are also compared to the viscosity of detergent slurried that do not contain a polymer.
  • the sodium carbonate was obtained from the FMC corporation under the name "FMC Grade 100".
  • Polymer E shown in Figure 1 is a copolymer of acrylic acid with an oxyalkylated allyl alcohol, of Formula I within the scope of the invention and is prepared ac ⁇ cording to Example 2 except that the ratio of acrylic acid to the oxyalkylated allyl alcohol was 90:10 by weight, while the molar ratio was about 474:1.
  • the oxyalkylated monomer component had a molecular weight of about 3800, and R was a propyleneoxy group represented by the formula -CH 2 -CH(CH 3 )-0 and R 5 was -CH 2 -CH 2 -0.
  • Ri H
  • R 2 COONa
  • Polymer F shown in Figure 1 is a copolymer of acrylic acid with an oxyalkylated allyl alcohol, of Formula I within the scope of the invention and is prepared according to Example 1 except that the ratio of acrylic acid to the oxyalkylated allyl alcohol was 93:7, while the molar ratio was about 123:1.
  • the oxyalkylated monomer component had a molecular weight of about 700.
  • Q is of the structure such that R 5 is bonded directly to R 3 ; R was a pro ⁇ pyleneoxy group represented by the formula -CH 2 -CH(CH 3 )-0 and R 5 was -CH 2 -CH 2 -0.
  • the ratio of a:b was 80:20 by weight.
  • Sokalan® PA30C1 polymer used in Figure 1 is a polyacrylic, sodium salt sold with a molecular weight of 8000, commercially by BASF Corporation. Sokalan® PA75 polymer is also a polyacrylic acid so ⁇ dium salt with a molecular weight of 90,000 available commer- cially from the BASF Corporation. Sokalan® CP5 polymer is a copolymer of acrylic acid and maleic acid with a molecular weight of 70000, also available from BASF Corporation.
  • Figure 1 shows the ability of the copolymers of this invention to reduce the viscosity of aqueous sodium carbonate slurries.
  • the performance of the polymers of this invention is compared to com ⁇ dismissally available polymers that are typically added to deter ⁇ gent slurries during the commercial manufacture of powder laundry detergents.
  • the dispersing properties of the copolymers of this invention was evaluated as follows: To a one liter stainless bea ⁇ ker, was added 600 grams of FMC Grade 100 soda ash followed by 400 grams of tap water. The resulting slurry was mixed using a Lightnin"® mixer equipped with a digital read out of the rota ⁇ tional speed of the impeller as well as the torque.
  • the torque read out reflects the power in watts required to stir the slurry at a fixed rpm.
  • the rpm in this example was set at 1200.
  • the initial torque in the absence of the polymer is noted.
  • the polymer additive is added in small incre ⁇ ments ranging from 0.5 % to 3.8 % by weight of the solids in the slurry, to the stirred slurry and the torque readout is then noted.
  • all polymer additives shown in Figure-1 had the same active polymer content. All evaluations were done at 25°C.
  • Figure 1 shows the performance of three commercial polymers available from BASF Corporation under the SOKALAN trade name.
  • Figure-1 also shows the superior dispersing properties of two copolymers of this invention.
  • the anti-redeposition performance of the copolymers of this invention were measured over three wash and rinse cycles, using six clean cotton swatches in the first cycle. These swatches are carried over through three wash and rinse cycles. After each wash and rinse cycle, the clay soiled cotton swatches used to provide the clay soil load to the wash liquor were discarded and a fresh set of nine clay swatches were added at the beginning of each wash cycle. At the end of the third rinse cycle, the cotton swatches were dried in a Whirlpool dryer for 90 minutes. The reflectance of the dried swatches were then measured using a Hunter calorimeter. The difference in the re ⁇ flectance values between the initial clean cotton swatch and the reflectance value of the cotton swatch after three wash and rinse cycles are reported in Figures 2 and 3.
  • the nonionic surfactant used in the formulation is NEODOL ® 25-7, a product of Shell.
  • the linear alkylbenzene sulfonic acid, sodium salt (LAS) was obtained from Vista under 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 sodium carbonate was obtained from the FMC Corporation under the name "FMC Grade 100".
  • the sodium silicate used was sodium silicate pentahydrate obtained from Mayo Products.
  • SOKALAN ® PA30C1 Poly ⁇ acrylic acid, sodium salt
  • SOKALAN ® HP 22 nonionic graft copolymer
  • Polymer G is a copolymer of acrylic acid with an oxyalkylated al- lyl alcohol, within the scope of the invention and is prepared according to Example 1 exept that the ratio of acrylic acid to the oxyalkylated allyl alcohol was 85:15 by weight, while the mo ⁇ lar ratio was about 123:1.
  • the oxyalkylated monomer component had a molecular weight of about 1500, and R 4 was a propyleneoxy group represented by the formula -CH 2 -CH(CH 3 )-O and R 5 was -CH 2 -CH 2 -O.
  • the percent ratio of a:b was 20:80.
  • Ri H
  • R 2 COONa
  • R 3 CH 2 - O
  • y 0.
  • Polymer H is a copolymer of acrylic acid with an oxyethylated al- lyl alcohol, within the scope of the invention and prepared ac ⁇ cording to Example 2 except that the ratio of acrylic acid to the oxyethylated allyl alcohol was 70:30 by weight, while the molar ratio was about 131:1.
  • Polymer E is a copolymer of acrylic acid with an oxyalkylated al ⁇ lyl alcohol, within the scope of the invention and prepared ac ⁇ cording to Example 1 except that the ratio of acrylic acid to the oxyalkylated allyl alcohol was 90:10 by weight, while the molar ratio was about 474:1.
  • the oxyalkylated monomer component had a molecular weight of about 3800, and R was a propyleneoxy group represented by the formula -CH 2 -CH(CH 3 )-0 and R 5 was -CH 2 -CH 2 -0.
  • Ri H
  • R 2 COONa
  • the percent ratio of a:b is 20:80.
  • Polymer F is a copolymer of acrylic acid with an oxyalkylated al ⁇ lyl alcohol, within the scope of the invention and prepared ac ⁇ cording to Example 1 except that the ratio of acrylic acid to the oxyalkylated allyl alcohol was 93:7, while the molar ratio was about 123:1.
  • the oxyalkylated monomer component had a molecular weight of about 700.
  • Q is of the structure such that R 5 is bonded directly to R 3 ; R 4 is a propyleneoxy group represented by the for ⁇ mula -CH 2 -CH(CH 3 )-0 and R 5 was -CH -CH 2 -0.
  • the percent ratio of a:b is 80:20.
  • Ri H
  • R 2 COONa
  • Polymer J is a copolymer of acrylic acid with an oxyethylated al ⁇ lyl alcohol, within the scope of the invention and prepared ac ⁇ cording to Example 1 except that the ratio of acrylic acid to the oxyethylated allyl alcohol was 92.3:7.7 by weight, while the mo- lar ratio was about 116:1.
  • Figures 2 and 3 show the anti-redeposition performance of commer- cial polymers such as Sokalan PA30C1 and Sokalan HP22 polymers as well as polymers of the invention, in anionic and nonionic based detergent formulas. Both of these charts demonstrate the signif ⁇ icant anti-redeposition benefits provided by the polymers of this invention when compared to conventional anti-redeposition polymers used in detergent formulations.
  • Example 6 shows the signif ⁇ icant anti-redeposition benefits provided by the polymers of this invention when compared to conventional anti-redeposition polymers used in detergent formulations.
  • the following example describes the viscosity reducing properties of the hydrophilic copolymers of the invention when added to aqueous detergent slurry compositions.
  • the numbers in each column in Table 2 refer to the active weight percentage of each compo- nent in the detergent formulation.
  • the viscosity values reported in Table 2 are measured with a Brookfield Viscometer (RVT Model) using spindle # 4 at 20 rpm. All viscosity measurements were im ⁇ mediately measured after sample preparation at 25°C.
  • the viscosity reducing properties of the hydrophilic copolymers of this inven- tion were evaluated in a concentrated aqueous detergent composi ⁇ tion built with different builders such as sodium silicate, so ⁇ dium carbonate, alkali metal phosphate, and zeolite.
  • the nonionic surfactant used in the formulations shown in the Table 2 is NEO ⁇ DOL ® 25-7, a product of Shell.
  • the linear alkylbenzene sulfonic acid, sodium salt (LAS) was obtained from Vista under the name Vista C-560 slurry.
  • the zeolite was "ZEOLITE A", also known als VALFOR ® 100, available from the PQ Corp of Valley Forge, PA.
  • the sodium carbonate was obtained from the FMC corporation under the name "FMC Grade 100".
  • the sodium silicate used was sodium meta- silicate pentahydrate obtained from Mayo Products Company. Tetra- potassium pyrophosphate was obtained from the Stauffer Chemical Company.
  • Polymers A & B that are widely used in detergent formulations.
  • Polymer A is a sodium salt copolymer of acrylic acid with maleic acid with a weight average molecular weight of 70,000, available from BASF Corporation under the tradename SOKALAN CP5.
  • Polymer B is a sodium salt homopolymer of acrylic acid with a weight aver ⁇ age molecular weight of 8000, available from the BASF Corporation under the tradename SOKLAN PA30CL.
  • Polymer J shown in Table 2 is a copolymer of acrylic acid with an oxyethylated allyl alcohol, within the scope of the invention.
  • the weight ratio of acrylic acid to the oxyethylated allyl alco ⁇ hol was 92.3:7.7, while the molar ratio was about 116:1.
  • the ox ⁇ yethylated monomer component had a molecular weight of about 700, and 5 was -CH 2 -CH 2 -O.
  • Ri H
  • R 2 COONa
  • R 3 CH 2 - 0,
  • y 0.
  • the weight average molecular weight of Polymer J is about 17,000.
  • Table 2 illustrates that the copolymers of this invention are able to reduce the viscosity of aqueous detergent slurries con ⁇ taining surfactants and inorganic builders by several orders of magnitude compared to conventional polycarboxylates such as Sokalan CP5 polymer and Sokalan PA30C1 polymer typically used as dispersants for reducing the viscosity of crutcher slurries.
  • the viscosity reducing properties of Polymer C of this invention are also compared to the viscosity of detergent slurries that do not contain a polymer.

Landscapes

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

Abstract

La présente invention concerne des compositions de détergents contenant des copolymères hydrophiles de la formule (I), dans laquelle x, y et z représentent des nombres entiers, le rapport (x + y):z étant d'environ 5:1 à environ 1000:1, y pouvant avoir n'importe quelle valeur comprise entre 0 et la valeur de x; M représente un métal alcalin ou hydrogène; R1 représente H ou CH3; R2 représente -COOM, -OCH3, -SO3M, -O-CO-CH3, -CO-NH2; W est choisi parmi des restes des formules (II), (III) ou (IV), ou des mélanges des groupes des formules (III) et (IV), groupes dans lesquels R1 correspond à la définition donnée ci-dessus; R3 représente -CH2-O-, -CH2-N-, -COO-, -O- (1), -CO-NH-; Q représente (2), (3) ou (4), où M correspond à la définition donnée ci-dessus; a représente un nombre entier compris entre 0 et environ 516; b représente un nombre entier compris entre 0 et environ 680; cela à condition que la somme de a + b ne soit pas égale à 0; R4 représente un groupe alkylenoxy C3-C4; et R5 représente -CH2-CH2-O-, G et G1 étant des groupes terminaux.
PCT/EP1996/002112 1995-05-23 1996-05-17 Formulations de detergents WO1996037597A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU58980/96A AU5898096A (en) 1995-05-23 1996-05-17 Detergent formulations
EP96916104A EP0850294A1 (fr) 1995-05-23 1996-05-17 Formulations de detergents
JP8535351A JPH11505867A (ja) 1995-05-23 1996-05-17 洗剤調製物

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US44820795A 1995-05-23 1995-05-23
US08/447,513 US5618782A (en) 1995-05-23 1995-05-23 Hydrophilic copolymers for reducing the viscosity of detergent slurries
US08/448,283 US5733861A (en) 1995-05-23 1995-05-23 Hydrophilic copolymers for reducing the viscosity of detergent slurries
US08/447,513 1995-05-23
US08/448,207 1995-05-23
US08/448,283 1995-05-23
US08/448,281 US5595968A (en) 1995-05-23 1995-05-23 Polymeric dispersants for soda ash based detergent slurries
US08/448,281 1995-05-23

Publications (1)

Publication Number Publication Date
WO1996037597A1 true WO1996037597A1 (fr) 1996-11-28

Family

ID=27503946

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/002112 WO1996037597A1 (fr) 1995-05-23 1996-05-17 Formulations de detergents

Country Status (4)

Country Link
EP (1) EP0850294A1 (fr)
JP (1) JPH11505867A (fr)
AU (1) AU5898096A (fr)
WO (1) WO1996037597A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
WO2000071651A3 (fr) * 1999-05-26 2001-08-23 Rhodia Polymeres, compositions et procedes a utiliser pour des mousses, des lessives, des produits de rinçage sous la douche et des 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
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
US7939601B1 (en) 1999-05-26 2011-05-10 Rhodia Inc. Polymers, compositions and methods of use for foams, laundry detergents, shower rinses, and coagulants

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004031040A1 (de) * 2004-06-25 2006-01-12 Basf Ag Verfahren zur Herstellung von granulären oder pulverförmigen Waschmittelzusammensetzungen
DE102005041349A1 (de) * 2005-08-31 2007-03-01 Basf Ag Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophil modifizierte Polycarboxylate

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS587415A (ja) * 1981-07-07 1983-01-17 Nippon Shokubai Kagaku Kogyo Co Ltd 新規水溶性共重合体及びその製造方法
US4676921A (en) * 1982-12-23 1987-06-30 The Procter & Gamble Company Detergent compositions containing ethoxylated amine polymers having clay soil removal/anti-redeposition properties
WO1996002622A1 (fr) * 1994-07-14 1996-02-01 Basf Corporation Compositions detergentes liquides concentrees aqueuses stables, contenant des copolymeres hydrophiles

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS587415A (ja) * 1981-07-07 1983-01-17 Nippon Shokubai Kagaku Kogyo Co Ltd 新規水溶性共重合体及びその製造方法
US4676921A (en) * 1982-12-23 1987-06-30 The Procter & Gamble Company Detergent compositions containing ethoxylated amine polymers having clay soil removal/anti-redeposition properties
WO1996002622A1 (fr) * 1994-07-14 1996-02-01 Basf Corporation Compositions detergentes liquides concentrees aqueuses stables, contenant des copolymeres hydrophiles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8308, Derwent World Patents Index; Class A14, AN 83-18780K, XP002011127 *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
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
WO2000071651A3 (fr) * 1999-05-26 2001-08-23 Rhodia Polymeres, compositions et procedes a utiliser pour des mousses, des lessives, des produits de rinçage sous la douche et des coagulants
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
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
US7915212B2 (en) 1999-05-26 2011-03-29 Rhodia Inc. Block polymers, compositions and methods of use for foams, laundry detergents, shower rinses and coagulants
US7939601B1 (en) 1999-05-26 2011-05-10 Rhodia Inc. 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

Publication number Publication date
AU5898096A (en) 1996-12-11
EP0850294A1 (fr) 1998-07-01
JPH11505867A (ja) 1999-05-25

Similar Documents

Publication Publication Date Title
JP2542035B2 (ja) ポリアルキレンオキシドを基礎とするグラフト重合体を有効成分とする洗濯用灰色化防止剤
JP2541617B2 (ja) ポリアルキレンオキシドを基礎とするグラフト重合体を有効成分とする洗濯用灰色化防止剤
JP2541616B2 (ja) ポリアルキレンオキシドを基礎とするグラフト重合体を有効成分とする洗濯用灰色化防止剤
JP2608949B2 (ja) 洗剤組成物のビルダー／分散剤としてのアミノ官能性化合物
WO1996037597A1 (fr) Formulations de detergents
NZ248033A (en) Detergent compositions containing polysuccinimide
US5536440A (en) Stable, aqueous concentrated liquid detergent compositions containing hydrophilic copolymers
EP0697422A1 (fr) Améliorations dans ou en relation à des polymères
CA2213090A1 (fr) Compositions liquides de nettoyage, a usage industriel et des collectivites, contenant des tensioactifs de polyglycoside d'alkyle
US6054424A (en) Process for the production of a liquid laundry detergent composition of desired viscosity containing nonionic and anionic surfactants
EP0770122B1 (fr) Compositions detergentes liquides concentrees aqueuses stables, contenant des copolymeres hydrophiles
US5534183A (en) Stable, aqueous concentrated liquid detergent compositions containing hydrophilic copolymers
US5618782A (en) Hydrophilic copolymers for reducing the viscosity of detergent slurries
US20030162679A1 (en) Hydrophobically modified polymer formulations
US6034045A (en) Liquid laundry detergent composition containing a completely or partially neutralized carboxylic acid-containing polymer
JPH02127500A (ja) 洗剤組成物
US5496495A (en) Detergent formulations free of phosphates, zeolites and crystalline layered silicates
JP7224340B2 (ja) 分散剤ポリマーを含む自動食器洗浄用組成物
CN107075425B (zh) 用于在自动餐具洗涤体系中减少污渍的添加剂
JP2003336095A (ja) 液体洗浄剤
US6180589B1 (en) Polyether hydroxycarboxylate copolymers
EP0636687A2 (fr) Perfectionnements apportés aux hydrotropes
US5595968A (en) Polymeric dispersants for soda ash based detergent slurries
US6511952B1 (en) Use of 2-methyl-1, 3-propanediol and polycarboxylate builders in laundry detergents
US5733861A (en) Hydrophilic copolymers for reducing the viscosity of detergent slurries

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU JP

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

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
WWE Wipo information: entry into national phase

Ref document number: 1996916104

Country of ref document: EP

ENP Entry into the national phase

Ref country code: JP

Ref document number: 1996 535351

Kind code of ref document: A

Format of ref document f/p: F

WWP Wipo information: published in national office

Ref document number: 1996916104

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1996916104

Country of ref document: EP

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载