CA1229285A - Detergents containing polyacrylate polymer - Google Patents
Detergents containing polyacrylate polymerInfo
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- CA1229285A CA1229285A CA000457671A CA457671A CA1229285A CA 1229285 A CA1229285 A CA 1229285A CA 000457671 A CA000457671 A CA 000457671A CA 457671 A CA457671 A CA 457671A CA 1229285 A CA1229285 A CA 1229285A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—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
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- 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
DETERGENTS CONTAINING
POLYACRYLATE POLYMER
Abstract of the Disclosure Detergents containing organic surfactant, non-phosphorus detergent builder and polyacrylate polymer having a weight average molecular weight of from about 2,000 to about 10,000 are disclosed.
POLYACRYLATE POLYMER
Abstract of the Disclosure Detergents containing organic surfactant, non-phosphorus detergent builder and polyacrylate polymer having a weight average molecular weight of from about 2,000 to about 10,000 are disclosed.
Description
US
DETERGENTS CONTAINING POLYACRYLATE POLYMER
Antoinette L. Larrabee Gianfranco Logy Spading Technical Field The present invention relates to detergent compositions containing organic surfactant, non-phosphate detergent builder, preferably an alkali metal silicate, and polyacrylate polymer having a weight average molecular weight of from about 2,000 to about 10, 000 -sack round Art US. Patent 4,072,621, Rose, issued Feb. 7, 1978, discloses the addition of a water-soluble copolymer of a vinyl compound and malefic android to granular detergents containing aluminosilicate builders.
- British Patent 2,048,841, Burzlo, published Deco 17~ 1980, discloses the use of polymeric acrylamid~s to stabilize aqueous suspensions of zealots. The suspensions are said to be suitable for spray-drying to obtain detergent compositions.
US. Patent 3,933,673, Davies issued Jan. 20, 1976, describes the use of partial alkali metal salts of home- or copolymers of unsaturated aliphatic moo- or polycarboxyl~c acids as builders which provide improved storage properties.
US. Patent 3,794,605, Doyle, issued Feb. 26, 1974, relates to the use of from 0.1% to 20% of a mixture of salts of cellulose sulfate esters and copolymers of a vinyl compound with malefic android to provide whiteness maintenance benefits to detergent compositions.
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DETERGENTS CONTAINING POLYACRYLATE POLYMER
Antoinette L. Larrabee Gianfranco Logy Spading Technical Field The present invention relates to detergent compositions containing organic surfactant, non-phosphate detergent builder, preferably an alkali metal silicate, and polyacrylate polymer having a weight average molecular weight of from about 2,000 to about 10, 000 -sack round Art US. Patent 4,072,621, Rose, issued Feb. 7, 1978, discloses the addition of a water-soluble copolymer of a vinyl compound and malefic android to granular detergents containing aluminosilicate builders.
- British Patent 2,048,841, Burzlo, published Deco 17~ 1980, discloses the use of polymeric acrylamid~s to stabilize aqueous suspensions of zealots. The suspensions are said to be suitable for spray-drying to obtain detergent compositions.
US. Patent 3,933,673, Davies issued Jan. 20, 1976, describes the use of partial alkali metal salts of home- or copolymers of unsaturated aliphatic moo- or polycarboxyl~c acids as builders which provide improved storage properties.
US. Patent 3,794,605, Doyle, issued Feb. 26, 1974, relates to the use of from 0.1% to 20% of a mixture of salts of cellulose sulfate esters and copolymers of a vinyl compound with malefic android to provide whiteness maintenance benefits to detergent compositions.
L {
- 2 - I
US. Potent 3/922,230, Lamberti et at, issued November 25, 1975, discloses detergent compositions con-twining oligomeric polyacrylates.
US. Patent 4,031,022, Volt et at, issued June 21, 1977, discloses detergent compositions containing copolymers of alphahydroxyacrylic acid and acrylic acid.
US. Patent 4,379,080, Murphy, issued April 5, 1983~ discloses low levels of film forming polymers for improving detergent granules' structure.
British Patent Application AYE, published November 3, 1982, discloses "base beadle come positions containing low levels of low molecular weight especially 1,000-2,000, polyacrylate for structure reasons.
British Patent 1,333,915, published Oct. 17, 1973, discloses that polyacrylic acids of molecular weight greater than 1000 and having from 5-55% of its carboxyl groups neutralized as the sodium salt are free-flowing powders useful as detergent builders.
British Patent 1,330,402, Pritchard et at, published Jan. 15,1975, relates to the addition of low levels of reactive and non-reactive polymers to provide free-flowing granular detergents containing non ionic surfactants.
Summary of the Invention The present invention encompasses a spray dried deterrent composition comprising:
(a) from about 5% to about 50% by weight of organic surfacta~t selected from the group consisting of anionic, non ionic, zwitterionic, ampholytic and cat ionic surfactants, and mixtures thereof;
(by from about So to about 80% by weight of a non phosphorus detergent builder;
(c) from about 0.3% to about I by weight of so .
a polyacr~late polymer soluble in an aqueous slurry comprising the above components and having a weight average molecular weight of from about 2,000 to about 10, 000.
Detailed Description of the Invention The detergent compositions of the present invention contain organic surfactant, water-soluble non-phosphorus detergent builder, and a polyacrylate polymer of selected molecular weight at a low level. The polyp acrylate polymers herein provide a surprising boost to the removal of clay soils even at these low levels which do not provide substantial builder capacity The compositions of the present invention can be prepared by drying an aqueous slurry comprising the components, by agglomeration or by mixing the various ingredients, either dry or in liquid form, either aqueous or an hydrous. The effect is obtained regardless of the method of preparation. It is believed that the effect is obtained by some kind of surface modification.
Organic Surfactant The detergent compositions herein contain from about 5% to about 50% by weight of an organic surfactant selected from the group consisting of anionic, non ionic, ~witterionic, ampholytic and cat ionic surfactants, and mixtures thereof. The surfactant preferably represents from about 10% to about 30% by weight of the detergent composition. Surfactants useful herein are listed in US. Patent 3,664,961/ Norris, issued May 23, 1972, and 30 in US. Patent 3,919,578, Laughlin, et at, issued December 30, 1975. Useful cat ionic surfactants also include those descried in US. Patent 4,222,905~ Cockrell, issued September 16, 1980, and in US. Patent 4,239,659, Murphy, issued December 16, 1980.
Water-soluble salts of the higher fatty acids, _ 4 _ I
i.e., "soaps", aye useful anionic surfactants in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and substituted ammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms and preferably from about 12 to about 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or the neutralization of free fatty acids. Particularly useful are -the sodium and potassium salts ox the mixtures of fatty acids derived from coconut oil and tallow, ire., sodium or potassium tallow and coconut soap Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal, ammonium and substituted ammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyd group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyd" is the alkyd portion of azalea groups.) Examples of this group of synthetic suractants are the sodium and potassium alkyd sulfates, especially those obtained by sulfating the higher alcohols (C8-C18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyd group contains from about 9 to about lo carbon atoms, in straight chain or branched chain configuration, e.g., those of the type descried in US. Patents 2,220,099 and 2,477,383.
Especially valuable are linear straight chain alkyd-Bunsen sealants in which the average number ox carbon~toms in the alkali group is from about 11 to 13t abbreviated as Cll_l3LAS.
Other anionic surfactants herein are the sodium alkyd glycerol ether sulfonates, especially those ethers of higher alcohols derived from tallow ''"!
and coconut Gil; sodium coconut oil Tao acid monogl~ceride sulfonates an sulfates; sodium or potassium sulks of alkyd phenol ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and from about 8 to about 12 carbon atoms in thy alkyd group; and sodium or potassium salts of alkyd ethylene oxide ether sulfates containing about 1 to about 10 units of ethylene oxide per molecule and from about 10 to about 20 carbon atoms in the alkyd group.
Other useful anionic sur~actants include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-l-sulfonic acids containing prom about 2 to 9 carbon atoms in the azalea group and from about 9 to about 23 carbon atoms in the Al Kane moiety; alkyd ether sulfates containing from about 10 to 20 carbon atoms in the alkyd group and from about 1 to 30 moles of ethylene oxide;
I water-soluble salts of oleEin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy Al Kane sulfonates containing from about 1 to 3 carbon atoms in the alkyd group and from about 8 to 20 carbon atoms in the Al Kane moiety.
Water-soluble non ionic surfactants are also useful in the compositions of the invention. Such non ionic materials include compounds produced by the condensation of alky~ene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic pa or allele aromatic in nature. The length of the polyp oxyalkylene group Which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-solublé compound having the desired degree of balance between hydrophilic and hydrophobic elements.
Suitable non ionic surfactants include the ....
polyethylene oxide condensates of alkali phenols, e.g., the condensation products of alkyd phenols having an alkyd group containing from about 6 to 15 carbon atoms, in either a straight chain or branched chain_configura-lion, with from about 3 to 12 moles of ethylene oxide per mole of alkyd phenol.
Preferred nonionics are the water-soluble condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 3 to 12 moles of ethylene oxide per mole of alcohol. Particularly pro-furred are the condensation products of alcohols having an alkyd group containing from about 9 to 15 carbon atoms with from about 4 to 8 moles of ethylene oxide per mole of alcohol.
Semi-polar non ionic surfactants useful herein include water-soluble amine oxides containing one alkyd moiety of from about 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyd groups and hydroxyalkyl groups containing from 1 to 3 carton atoms; water-soluble phosphine oxides containing one alkyd moiety of about 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyd groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyd moiety of from about it to 18 carbon atoms and a moiety selected from the group consisting of alkyd and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
Ampholytic surfactants include derivatives of aliphatic or aliph.atic derivatives of heterocyclic secondary and tertiary amine in which the aliphatic moiety can ye straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubiliz~ng group, Z~itterionic surfactants include dirts of aliphatic qua ternary ammonium, phosphDnium, and sulfonium compounds in which one ox the aliph~tic substituents contains from about 8 to 18 carbon atoms Particularly preferred surfactants herein do not comprise staunchly amounts of non ionic detergent sur~actants and, preferably, are anionic surfactants, especially those selected from the group consisting ox the alkali metal salts of C11 13 alkylbenzene sulfonates, C14_18 alkyd sulfates, C14_18 alkyd linear polyethoxy sulfates containing from about 1 to about 4 moles of ethylene oxide, and mixtures thereof.
The Non-Phos~horus Deterrent Builder The compositions of the present invention also contain from about I to about 80%, preferably from about 10% to about 70%, and most preferably from about 15~ to about 60%, by weight of a non phosphorus detergent builder. The non-phosphorus detergent builder can be either organic or inorganic in nature. They function as detergency builder materials in the laundering solution.
Non-phosphorus detergent builders are generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium carbonates, silicates, carboxylates, and polycarboxylates other than the polyp acrylates as defined hereinafter, especially non-polymeric polycarboxylates. Preferred are the alkali metal, especially sodium, salts of the above. However, the present compositions preferably contain less than about I more preferably less than about 4%, by weigh* of silicate materials for optimum granule volubility.
pacific examples of non-phosphorus, inorganic builders-are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, ",, I
and silicate having a molar ratio ox ion to alkali metal oxide of from about 0.5 to about 4,0, preferably from about 1.0 to about 2.4 An especially preferred detergency builder is crystalline aluminosilicate Jon exchange material of the formula .
Naz[(AlO2)~SiO2)y~xH2O
wherein z and y are at least about 6, the molar ratio of z to y is from about 1.0 to about 0~5 and x is from about 10 to about 264. Amorphous hydrated aluminosilicate materials useful herein have the empirical formula MZ(ZAlO2-YSiO2) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2 and y is 1, said material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of Cook hardness per gram of an hydrous aluminosilicate.
The aluminosilicate ion exchange builder materials herein are in hydrated form and contain from about 10% to about 28% of water by weight if crystalline, and potentially even higher amounts of water if amorphous.
Highly preferred crystalline aluminosilicate ion exchange materials contain from about 18% to about 22% water in their crystal matrix. The crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 10 microns. Amorphous materials are often smaller, e.g., down to less than about Q.01 micron. Preferred ion exchange materials have a particle size diameter of from about 0.2 micron to about 4 microns The term "particle size diameter" herein represents the average _ 9 _ particle size diameter of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope. The crystalline aluminosilicate ion exchange materials herein are usually further characterized by their calcium ion exchange capacity, which is at least about 200 my. equivalent of Cook water hardness/g. of aluminosilicate, calculated on an an hydrous basis, and which generally is in the 10 range of from about 300 my. erg to about 352 my.
erg The aluminosilicate ion exchange materials herein are still further characterized by their calcium ion exchange rate which is at least about 2 grains Cay gallon/minute/gram/gallon ox aluminosilicate (an hydrous basis), and generally lies within the range of from about 2 grains/gallon/minute/gram/gallon to about grains/gallon/mlnute/gram/gallon, based on calcium ion hardness Optimum aluminosilicate for builder purposes exhibit a calcium ion exchange rate of at least about grains/gallon/minute/~ram/gallon.
The amorphous aluminosilicate ion exchange materials usually have a My + exchange capacity of at least about 50 my. en. CaCO3/g. (12 my. My go and a My++ exchange rate of at least about 1 gxain/gallon/
minute/gram/gallon. Amorphous materials do not exhibit an observable diffraction pattern when examined by Cut radiation (1.54 Angstrom Units).
A~uminosilicate ion exchange materials useful in the pretty ox this invention are commercially available. The aluminosilicates useful in this invention can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. method for producing aluminosilicate ion exchange materials is discussed in US. Patent 3,985,669, 35 Cromwell et at, issued October 12, 1976.
`'~,:`' i ,, Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zealot A, Zealot B, and elite X.
In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material is Zealot A and has the formula Allah (Sulks wherein x is prom about 20 to about 30, especially about 27.
Water-solu~le, non-phosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium, carboxylates, polycarbo~ylates and polyhydroxysulfonates. Examples of non-polymeric polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, Bunsen polycarboxylic acids, and citric acid. the compositions of this in-mention only contain the limited amount of polyacrylate defined hereinafter.
Other useful builders herein are sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate, cis-cyclopentanetetra-carboxylate, and phloroglucinol trisulfonate~
Other suitable polycarboxylates are top polyacetal carboxylates described in US. Patent 4,144,226, issued March 13, 1979 to Crutch field, et at., and US.
Patent 4,246~495, issued March 27, 1979 to Crutch field, et at.
These poly~cetal caxboxylates can be prepared by bring together under polymerization conditions an ester of glyoxylic acid and a polymerization initiator.
The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carbox~late against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a surfactant.
Other detergency builder materials useful herein are the "seeded builder" compositions disclosed in Belgian Patent No. 798,856, issued October 29, 1973.
Specific examples of sun seeded builder mixtures are:
US. Potent 3/922,230, Lamberti et at, issued November 25, 1975, discloses detergent compositions con-twining oligomeric polyacrylates.
US. Patent 4,031,022, Volt et at, issued June 21, 1977, discloses detergent compositions containing copolymers of alphahydroxyacrylic acid and acrylic acid.
US. Patent 4,379,080, Murphy, issued April 5, 1983~ discloses low levels of film forming polymers for improving detergent granules' structure.
British Patent Application AYE, published November 3, 1982, discloses "base beadle come positions containing low levels of low molecular weight especially 1,000-2,000, polyacrylate for structure reasons.
British Patent 1,333,915, published Oct. 17, 1973, discloses that polyacrylic acids of molecular weight greater than 1000 and having from 5-55% of its carboxyl groups neutralized as the sodium salt are free-flowing powders useful as detergent builders.
British Patent 1,330,402, Pritchard et at, published Jan. 15,1975, relates to the addition of low levels of reactive and non-reactive polymers to provide free-flowing granular detergents containing non ionic surfactants.
Summary of the Invention The present invention encompasses a spray dried deterrent composition comprising:
(a) from about 5% to about 50% by weight of organic surfacta~t selected from the group consisting of anionic, non ionic, zwitterionic, ampholytic and cat ionic surfactants, and mixtures thereof;
(by from about So to about 80% by weight of a non phosphorus detergent builder;
(c) from about 0.3% to about I by weight of so .
a polyacr~late polymer soluble in an aqueous slurry comprising the above components and having a weight average molecular weight of from about 2,000 to about 10, 000.
Detailed Description of the Invention The detergent compositions of the present invention contain organic surfactant, water-soluble non-phosphorus detergent builder, and a polyacrylate polymer of selected molecular weight at a low level. The polyp acrylate polymers herein provide a surprising boost to the removal of clay soils even at these low levels which do not provide substantial builder capacity The compositions of the present invention can be prepared by drying an aqueous slurry comprising the components, by agglomeration or by mixing the various ingredients, either dry or in liquid form, either aqueous or an hydrous. The effect is obtained regardless of the method of preparation. It is believed that the effect is obtained by some kind of surface modification.
Organic Surfactant The detergent compositions herein contain from about 5% to about 50% by weight of an organic surfactant selected from the group consisting of anionic, non ionic, ~witterionic, ampholytic and cat ionic surfactants, and mixtures thereof. The surfactant preferably represents from about 10% to about 30% by weight of the detergent composition. Surfactants useful herein are listed in US. Patent 3,664,961/ Norris, issued May 23, 1972, and 30 in US. Patent 3,919,578, Laughlin, et at, issued December 30, 1975. Useful cat ionic surfactants also include those descried in US. Patent 4,222,905~ Cockrell, issued September 16, 1980, and in US. Patent 4,239,659, Murphy, issued December 16, 1980.
Water-soluble salts of the higher fatty acids, _ 4 _ I
i.e., "soaps", aye useful anionic surfactants in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and substituted ammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms and preferably from about 12 to about 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or the neutralization of free fatty acids. Particularly useful are -the sodium and potassium salts ox the mixtures of fatty acids derived from coconut oil and tallow, ire., sodium or potassium tallow and coconut soap Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal, ammonium and substituted ammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyd group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyd" is the alkyd portion of azalea groups.) Examples of this group of synthetic suractants are the sodium and potassium alkyd sulfates, especially those obtained by sulfating the higher alcohols (C8-C18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyd group contains from about 9 to about lo carbon atoms, in straight chain or branched chain configuration, e.g., those of the type descried in US. Patents 2,220,099 and 2,477,383.
Especially valuable are linear straight chain alkyd-Bunsen sealants in which the average number ox carbon~toms in the alkali group is from about 11 to 13t abbreviated as Cll_l3LAS.
Other anionic surfactants herein are the sodium alkyd glycerol ether sulfonates, especially those ethers of higher alcohols derived from tallow ''"!
and coconut Gil; sodium coconut oil Tao acid monogl~ceride sulfonates an sulfates; sodium or potassium sulks of alkyd phenol ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and from about 8 to about 12 carbon atoms in thy alkyd group; and sodium or potassium salts of alkyd ethylene oxide ether sulfates containing about 1 to about 10 units of ethylene oxide per molecule and from about 10 to about 20 carbon atoms in the alkyd group.
Other useful anionic sur~actants include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-l-sulfonic acids containing prom about 2 to 9 carbon atoms in the azalea group and from about 9 to about 23 carbon atoms in the Al Kane moiety; alkyd ether sulfates containing from about 10 to 20 carbon atoms in the alkyd group and from about 1 to 30 moles of ethylene oxide;
I water-soluble salts of oleEin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy Al Kane sulfonates containing from about 1 to 3 carbon atoms in the alkyd group and from about 8 to 20 carbon atoms in the Al Kane moiety.
Water-soluble non ionic surfactants are also useful in the compositions of the invention. Such non ionic materials include compounds produced by the condensation of alky~ene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic pa or allele aromatic in nature. The length of the polyp oxyalkylene group Which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-solublé compound having the desired degree of balance between hydrophilic and hydrophobic elements.
Suitable non ionic surfactants include the ....
polyethylene oxide condensates of alkali phenols, e.g., the condensation products of alkyd phenols having an alkyd group containing from about 6 to 15 carbon atoms, in either a straight chain or branched chain_configura-lion, with from about 3 to 12 moles of ethylene oxide per mole of alkyd phenol.
Preferred nonionics are the water-soluble condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 3 to 12 moles of ethylene oxide per mole of alcohol. Particularly pro-furred are the condensation products of alcohols having an alkyd group containing from about 9 to 15 carbon atoms with from about 4 to 8 moles of ethylene oxide per mole of alcohol.
Semi-polar non ionic surfactants useful herein include water-soluble amine oxides containing one alkyd moiety of from about 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyd groups and hydroxyalkyl groups containing from 1 to 3 carton atoms; water-soluble phosphine oxides containing one alkyd moiety of about 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyd groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyd moiety of from about it to 18 carbon atoms and a moiety selected from the group consisting of alkyd and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
Ampholytic surfactants include derivatives of aliphatic or aliph.atic derivatives of heterocyclic secondary and tertiary amine in which the aliphatic moiety can ye straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubiliz~ng group, Z~itterionic surfactants include dirts of aliphatic qua ternary ammonium, phosphDnium, and sulfonium compounds in which one ox the aliph~tic substituents contains from about 8 to 18 carbon atoms Particularly preferred surfactants herein do not comprise staunchly amounts of non ionic detergent sur~actants and, preferably, are anionic surfactants, especially those selected from the group consisting ox the alkali metal salts of C11 13 alkylbenzene sulfonates, C14_18 alkyd sulfates, C14_18 alkyd linear polyethoxy sulfates containing from about 1 to about 4 moles of ethylene oxide, and mixtures thereof.
The Non-Phos~horus Deterrent Builder The compositions of the present invention also contain from about I to about 80%, preferably from about 10% to about 70%, and most preferably from about 15~ to about 60%, by weight of a non phosphorus detergent builder. The non-phosphorus detergent builder can be either organic or inorganic in nature. They function as detergency builder materials in the laundering solution.
Non-phosphorus detergent builders are generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium carbonates, silicates, carboxylates, and polycarboxylates other than the polyp acrylates as defined hereinafter, especially non-polymeric polycarboxylates. Preferred are the alkali metal, especially sodium, salts of the above. However, the present compositions preferably contain less than about I more preferably less than about 4%, by weigh* of silicate materials for optimum granule volubility.
pacific examples of non-phosphorus, inorganic builders-are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, ",, I
and silicate having a molar ratio ox ion to alkali metal oxide of from about 0.5 to about 4,0, preferably from about 1.0 to about 2.4 An especially preferred detergency builder is crystalline aluminosilicate Jon exchange material of the formula .
Naz[(AlO2)~SiO2)y~xH2O
wherein z and y are at least about 6, the molar ratio of z to y is from about 1.0 to about 0~5 and x is from about 10 to about 264. Amorphous hydrated aluminosilicate materials useful herein have the empirical formula MZ(ZAlO2-YSiO2) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2 and y is 1, said material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of Cook hardness per gram of an hydrous aluminosilicate.
The aluminosilicate ion exchange builder materials herein are in hydrated form and contain from about 10% to about 28% of water by weight if crystalline, and potentially even higher amounts of water if amorphous.
Highly preferred crystalline aluminosilicate ion exchange materials contain from about 18% to about 22% water in their crystal matrix. The crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 10 microns. Amorphous materials are often smaller, e.g., down to less than about Q.01 micron. Preferred ion exchange materials have a particle size diameter of from about 0.2 micron to about 4 microns The term "particle size diameter" herein represents the average _ 9 _ particle size diameter of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope. The crystalline aluminosilicate ion exchange materials herein are usually further characterized by their calcium ion exchange capacity, which is at least about 200 my. equivalent of Cook water hardness/g. of aluminosilicate, calculated on an an hydrous basis, and which generally is in the 10 range of from about 300 my. erg to about 352 my.
erg The aluminosilicate ion exchange materials herein are still further characterized by their calcium ion exchange rate which is at least about 2 grains Cay gallon/minute/gram/gallon ox aluminosilicate (an hydrous basis), and generally lies within the range of from about 2 grains/gallon/minute/gram/gallon to about grains/gallon/mlnute/gram/gallon, based on calcium ion hardness Optimum aluminosilicate for builder purposes exhibit a calcium ion exchange rate of at least about grains/gallon/minute/~ram/gallon.
The amorphous aluminosilicate ion exchange materials usually have a My + exchange capacity of at least about 50 my. en. CaCO3/g. (12 my. My go and a My++ exchange rate of at least about 1 gxain/gallon/
minute/gram/gallon. Amorphous materials do not exhibit an observable diffraction pattern when examined by Cut radiation (1.54 Angstrom Units).
A~uminosilicate ion exchange materials useful in the pretty ox this invention are commercially available. The aluminosilicates useful in this invention can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. method for producing aluminosilicate ion exchange materials is discussed in US. Patent 3,985,669, 35 Cromwell et at, issued October 12, 1976.
`'~,:`' i ,, Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zealot A, Zealot B, and elite X.
In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material is Zealot A and has the formula Allah (Sulks wherein x is prom about 20 to about 30, especially about 27.
Water-solu~le, non-phosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium, carboxylates, polycarbo~ylates and polyhydroxysulfonates. Examples of non-polymeric polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, Bunsen polycarboxylic acids, and citric acid. the compositions of this in-mention only contain the limited amount of polyacrylate defined hereinafter.
Other useful builders herein are sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate, cis-cyclopentanetetra-carboxylate, and phloroglucinol trisulfonate~
Other suitable polycarboxylates are top polyacetal carboxylates described in US. Patent 4,144,226, issued March 13, 1979 to Crutch field, et at., and US.
Patent 4,246~495, issued March 27, 1979 to Crutch field, et at.
These poly~cetal caxboxylates can be prepared by bring together under polymerization conditions an ester of glyoxylic acid and a polymerization initiator.
The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carbox~late against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a surfactant.
Other detergency builder materials useful herein are the "seeded builder" compositions disclosed in Belgian Patent No. 798,856, issued October 29, 1973.
Specific examples of sun seeded builder mixtures are:
3:1 wt. mixtures of sodium carbonate and calcium carbonate having 5 micron particle diameter; 2.7:1 wt. mixtures of sodium sesquicarbonate and calcium carbonate having a particle diameter of 0.5 microns; 20:1 wt. mixtures of sodium sesquicaxbonate and calcium hydroxide having a particle diameter of 0.01 micron; and a 3:3:1 wt.
mixture of sodium carbonate, sodium acuminate and calcium oxide having a particle diameter of 5 microns.
Preferably the builder is selected from the group consisting ox zealots, especially Zealot A;
carbonates, especially sodium carbonate; and citrates, especially sodium citrate.
Soaps, as described herein before, can also act as builders depending upon the pi of the wash solution, the insolubility of the calcium and/or magnesium soaps, and the presence of other builders and soap dispersants.
The compositions herein preferably contain from about 0% to about 6%, preferably from about 0.5% to about I and most preferably from about I to about I by weight of an alkali metal silicate having a molar ratio of Sue to alkali metal oxide of prom about 1.0 to about 30 3.2, preferably from about 1.6 to about 2.4. Sodium silicate, particularly one having a molar ratio of from about 1.8 to about 2.2, is preferred.
The alkali metal silicates can be purchased in either liquid or granular Norm. Silicate slurries can conveniently be used to avoid having to dissolve the dried form in the aqueous slurry (eye, crutches mix of the components herein.
Polyacrylate Polymer The compositions of the present invention contain from about 0.3~ to about 5%, preferably from about 1.0~ to about I and more preferably from about 1.5~ to about 2%, by weight of a polyacrylate polymer having a molecular weight of from about 2,000 to about 10,000, preferably from about 3,000 to about 8,000, and 10 more preferably from about 3,000 to about 6,0Q0.
Optimum volubility of the polymer is obtained when it is in the form of an at least partially neutralized alkali metal, ammonium or substituted ammonium (erg , moo-, dip or triethanol ammonium) salt. Thy alkali metal, especially sodium, salts are most preferred.
Lower levels of polyacrylate are preferred for cost reasons and there is less chance of an adverse effect on other detergent properties, e.g., cleaning of other soils, performance by minor ingredients such as enzymes or brighteners, etc.
Suitable polymers herein are the at least partially neutralized salts of polymers of acrylic acid. One can also use copolymers formed with small amounts of other copolymerisable monomers. The percentage by weight of the polymer units which is derived from acrylic acid is preferably greater than about 80%.
Suitable copolymerisable monomers include, fox example, methacrylic acid, hydroxyacrylic acid, vinyl chloride, vinyl alcohol, foreign acrylonitrile, methacrylonitrile, vinyl acetate, methyl acrylate, methyl methacrylate, styrenes al~ha-methylst~rene, vinyl methyl ether, vinyl ethyl ether, vinyl propel ether, acrylamide, ethylene, propylene and botanic acid.
Preferred copolymers of the above group contain at least about 90% by weight of units derived . i , prom the acrylic acid. Preferably essentially all of the polymer is derived from acrylic acid. Particularly preferred is sodium polyacrylate, especially when it has an average molecular weight of prom about 3,00~ to about 6,000.
Optional Components Tune compositions of the invention preferably contain from about 0.3% to about 6.0%, preferably from about 0.5~ to about 4.0%, and more preferably from about 0.7% to about 3.0% by weight of a water soluble polymeric material, or mixtures thereof, containing at least about 50~ ethylene oxide by weight, said polymer or mixtures thereof having a melting point not less than about 35~C, Preferably the polymeric material will have a melting point not less than about 45C, more preferably not less than about 50C and most preferably not less than about 55C. Because the polymeric materials useful in the practice of the invention are generally mixtures representing a range of molecular weights, the materials tend to soften and begin to become liquid over a range of temperatures of from about 3C to about 7C above their melting point. Mixtures of two or more polymeric materials can have an even wider range.
Preferred polymers contain at least about 70% ethylene oxide by weight and more preferred polymers contain at least about 80% ethylene oxide by weight.
Polyethylene glycol which can be said to contain essentially 100% ethylene oxide by weight is particularly preferred.
Preferred polyethylene glycols have an average molecular weight at least about 1000, and more preferably from about 2~00 to about 20,000 and most preferably Rome about 3000 to about`l0,000~
Other suitable polymeric materials are the 35 condensation products of Clue alcohols or C8_18 alkyd aye phenols with sufficient ethylene oxide, not less than about 50% by weight of the polymer, so that the resultant product has a melting point above about 35C.
Block and heteric polymers based on ethylene oxide and propylene oxide addition to a low molecular weight organic compound containing one or more active hydrogen atoms are suitable in the practice of the invent lion. Polymers based on the addition of ethylene oxide and propylene oxide to propylene glycol, ethylenediamine, and trimethylolpropane are commercially available under the trademarks "Pluronics'~ "Pluronic"~R, "Tetronics'~
and "Pluradots'~ from the BASS Wyandotte Corporation of Wyandotte, Michigan. Corresponding nonproprietary names of the first three trademarks are poloxamer, meroxapol and poloxamine, respectively.
Preferably these ethylene oxide polymers are incorporated into the detergent crutches and dried with a major portion of the detergent composition when forming granular compositions.
Other ingredients commonly used in detergent compositions can be included in the compositions of the present invention. These include solvents, delineates, sources of ionic strength, color speckles, bleaching agents and bleach activators, suds boosters or suds suppressors, anti-tarnish and anti-corrosion agents, soil release agents, dyes, fillers, optical brighteners, germicides, non-builder alkalinity sources, enzymes, enzyme-stabilizing agents, and perfumes.
ye following non-limiting examples illustrate I the detergent compositions of the present invention -11 percentages, parts, and ratios used herein are by weight unless otherwise specified ..
. .
Component it %
A B
No C13 alkylbenzene sulfonate (CLAUS 7.3 9.25 No Clue 15 alkyd sulfate (Clue ASSAY) 7.3 9.25 Clue 13 alkylpolyethoxylate (6.5) stripped to remove unexthoxylated alcohol and monoethoxylated alcohol (C12_13 En 5) 2.0 C12 alkyltrimethylammonium chloride I _ No Zealot A, hydrated ~2-3~) 23.8 23.8 10 Nikko 13.1 13.1 No silicate (1.6r) 1.0 1.0 Nazi, water, minors, No polyacrylate as indicated etc. ----Balance----The above compositions with the indicated amounts of the indicated sodium polyacrylates were tested in automatic mini washers with assorted soils and stains present including the particulate soil (clay) that defines the "Cleaning Index". The "Cleaning Index" is obtained by finding the panel score grades for each product using a scale in which 0 means "There is no difference."; 1 means "I think 1 see a difference."; 2 means "I see a difference."; and 3 means "I see a big difference.". The control product contains no polyacrylate and the best performing product is set at 100 with all other grades being ranked as a percent of the difference.
Test 1 Conditions; 95F; indicated water hardness;
Product A with different molecular weight sodium polyp acrylates at the 1.5~ level.
,., I
Polyac~ylate molecular weight Cleaning as indicated Index LSD
Polycotton Fabric, 12 grains per gallon none Q 30 Cotton Fabric, 12 grains per gallon none 0 30 Polyester and Cotton Fabric (Polycotton~, 5 grains per gallon none 0 30 ~500 100 30 Test 2 Conditions: 95~F, indicated hardness, Product B with 1.5~ of sodium polyacrylate with the indicated molecular weight.
Cleaning Index LSD
Cotton Fabric (12 gig) none 50 15,000 0 50 60, on -167 50 Polycotton Fabric (5 gig none , 0 40 guy 100 40 15,000 ' 46 40 60,000 -31 I
,` lo Cleaning Cotton Fabric (5 gig) Index LSD
none 0 30 15,000 -20 30 60,000 -2Q0 30 As can be seen from the above, there is essentially no benefit from using a polyacrylate with a molecular weight above about 10,000 and for a consistent meaningful benefit, the molecular weight should be less than about 8,000. For optimum performance, the molecular weight should not exceed about 6,000. Polymers containing less than 100%, e.g., 80%, acrylate monomers can be used 5 with substantially equivalent results.
Test 3 Conditions: 95F; under built, and Product A
containing the indicated amounts of No Zealot A and No Polyacrylate (MOW. 4500).
Cleaning Index LSD
Polycotton solute Cotton Fabric Fabric none 23 0 0 25 1.5 23 100 I 25 9.6 18 85 100 25 11.8 none 72 59 25 As can be seen from the above, the clay imp provement is essentially independent of the amount of other detergent builder present and there is essentially pa no advantage in using more than about 5% of the polyp acrylate.
-Component %
us 'Conlponent - %
No Zealot I, hydrated (yo-yo) 24.4 Nay C3 5 No silicate (1.6r) 2 No sulfosuccinate 2 Polyethylene glycol (MOW. -SEIKO 1.5 Minors including protozoa and aimless, Nazi and water Balance The above composition was prepared as a spray-dried granule and tested with (control) and without 1.5%
added sodium polyacrylate (MOW. 4500). The temperature was 95F., the water had 10 grains/gal. hardness and the results in panel score grade units difference were as follows for clay removal.
Clay on cotton fabric: 0.9 LSD=0.51 Clay on polycotton fabric: 1.0 LSD=0.41 Based on these results, it is clear that a small amount of a low molecular weight polyacrylate provides a substantial cleaning boost or clay removal.
Preferred compositions are (1) spray-dried detergent granules wherein at least the surfactant and, preferably, the detergent builder are both in the deter-gent crutches mix prior to spray drying and (~) liquid compositions.
I,
mixture of sodium carbonate, sodium acuminate and calcium oxide having a particle diameter of 5 microns.
Preferably the builder is selected from the group consisting ox zealots, especially Zealot A;
carbonates, especially sodium carbonate; and citrates, especially sodium citrate.
Soaps, as described herein before, can also act as builders depending upon the pi of the wash solution, the insolubility of the calcium and/or magnesium soaps, and the presence of other builders and soap dispersants.
The compositions herein preferably contain from about 0% to about 6%, preferably from about 0.5% to about I and most preferably from about I to about I by weight of an alkali metal silicate having a molar ratio of Sue to alkali metal oxide of prom about 1.0 to about 30 3.2, preferably from about 1.6 to about 2.4. Sodium silicate, particularly one having a molar ratio of from about 1.8 to about 2.2, is preferred.
The alkali metal silicates can be purchased in either liquid or granular Norm. Silicate slurries can conveniently be used to avoid having to dissolve the dried form in the aqueous slurry (eye, crutches mix of the components herein.
Polyacrylate Polymer The compositions of the present invention contain from about 0.3~ to about 5%, preferably from about 1.0~ to about I and more preferably from about 1.5~ to about 2%, by weight of a polyacrylate polymer having a molecular weight of from about 2,000 to about 10,000, preferably from about 3,000 to about 8,000, and 10 more preferably from about 3,000 to about 6,0Q0.
Optimum volubility of the polymer is obtained when it is in the form of an at least partially neutralized alkali metal, ammonium or substituted ammonium (erg , moo-, dip or triethanol ammonium) salt. Thy alkali metal, especially sodium, salts are most preferred.
Lower levels of polyacrylate are preferred for cost reasons and there is less chance of an adverse effect on other detergent properties, e.g., cleaning of other soils, performance by minor ingredients such as enzymes or brighteners, etc.
Suitable polymers herein are the at least partially neutralized salts of polymers of acrylic acid. One can also use copolymers formed with small amounts of other copolymerisable monomers. The percentage by weight of the polymer units which is derived from acrylic acid is preferably greater than about 80%.
Suitable copolymerisable monomers include, fox example, methacrylic acid, hydroxyacrylic acid, vinyl chloride, vinyl alcohol, foreign acrylonitrile, methacrylonitrile, vinyl acetate, methyl acrylate, methyl methacrylate, styrenes al~ha-methylst~rene, vinyl methyl ether, vinyl ethyl ether, vinyl propel ether, acrylamide, ethylene, propylene and botanic acid.
Preferred copolymers of the above group contain at least about 90% by weight of units derived . i , prom the acrylic acid. Preferably essentially all of the polymer is derived from acrylic acid. Particularly preferred is sodium polyacrylate, especially when it has an average molecular weight of prom about 3,00~ to about 6,000.
Optional Components Tune compositions of the invention preferably contain from about 0.3% to about 6.0%, preferably from about 0.5~ to about 4.0%, and more preferably from about 0.7% to about 3.0% by weight of a water soluble polymeric material, or mixtures thereof, containing at least about 50~ ethylene oxide by weight, said polymer or mixtures thereof having a melting point not less than about 35~C, Preferably the polymeric material will have a melting point not less than about 45C, more preferably not less than about 50C and most preferably not less than about 55C. Because the polymeric materials useful in the practice of the invention are generally mixtures representing a range of molecular weights, the materials tend to soften and begin to become liquid over a range of temperatures of from about 3C to about 7C above their melting point. Mixtures of two or more polymeric materials can have an even wider range.
Preferred polymers contain at least about 70% ethylene oxide by weight and more preferred polymers contain at least about 80% ethylene oxide by weight.
Polyethylene glycol which can be said to contain essentially 100% ethylene oxide by weight is particularly preferred.
Preferred polyethylene glycols have an average molecular weight at least about 1000, and more preferably from about 2~00 to about 20,000 and most preferably Rome about 3000 to about`l0,000~
Other suitable polymeric materials are the 35 condensation products of Clue alcohols or C8_18 alkyd aye phenols with sufficient ethylene oxide, not less than about 50% by weight of the polymer, so that the resultant product has a melting point above about 35C.
Block and heteric polymers based on ethylene oxide and propylene oxide addition to a low molecular weight organic compound containing one or more active hydrogen atoms are suitable in the practice of the invent lion. Polymers based on the addition of ethylene oxide and propylene oxide to propylene glycol, ethylenediamine, and trimethylolpropane are commercially available under the trademarks "Pluronics'~ "Pluronic"~R, "Tetronics'~
and "Pluradots'~ from the BASS Wyandotte Corporation of Wyandotte, Michigan. Corresponding nonproprietary names of the first three trademarks are poloxamer, meroxapol and poloxamine, respectively.
Preferably these ethylene oxide polymers are incorporated into the detergent crutches and dried with a major portion of the detergent composition when forming granular compositions.
Other ingredients commonly used in detergent compositions can be included in the compositions of the present invention. These include solvents, delineates, sources of ionic strength, color speckles, bleaching agents and bleach activators, suds boosters or suds suppressors, anti-tarnish and anti-corrosion agents, soil release agents, dyes, fillers, optical brighteners, germicides, non-builder alkalinity sources, enzymes, enzyme-stabilizing agents, and perfumes.
ye following non-limiting examples illustrate I the detergent compositions of the present invention -11 percentages, parts, and ratios used herein are by weight unless otherwise specified ..
. .
Component it %
A B
No C13 alkylbenzene sulfonate (CLAUS 7.3 9.25 No Clue 15 alkyd sulfate (Clue ASSAY) 7.3 9.25 Clue 13 alkylpolyethoxylate (6.5) stripped to remove unexthoxylated alcohol and monoethoxylated alcohol (C12_13 En 5) 2.0 C12 alkyltrimethylammonium chloride I _ No Zealot A, hydrated ~2-3~) 23.8 23.8 10 Nikko 13.1 13.1 No silicate (1.6r) 1.0 1.0 Nazi, water, minors, No polyacrylate as indicated etc. ----Balance----The above compositions with the indicated amounts of the indicated sodium polyacrylates were tested in automatic mini washers with assorted soils and stains present including the particulate soil (clay) that defines the "Cleaning Index". The "Cleaning Index" is obtained by finding the panel score grades for each product using a scale in which 0 means "There is no difference."; 1 means "I think 1 see a difference."; 2 means "I see a difference."; and 3 means "I see a big difference.". The control product contains no polyacrylate and the best performing product is set at 100 with all other grades being ranked as a percent of the difference.
Test 1 Conditions; 95F; indicated water hardness;
Product A with different molecular weight sodium polyp acrylates at the 1.5~ level.
,., I
Polyac~ylate molecular weight Cleaning as indicated Index LSD
Polycotton Fabric, 12 grains per gallon none Q 30 Cotton Fabric, 12 grains per gallon none 0 30 Polyester and Cotton Fabric (Polycotton~, 5 grains per gallon none 0 30 ~500 100 30 Test 2 Conditions: 95~F, indicated hardness, Product B with 1.5~ of sodium polyacrylate with the indicated molecular weight.
Cleaning Index LSD
Cotton Fabric (12 gig) none 50 15,000 0 50 60, on -167 50 Polycotton Fabric (5 gig none , 0 40 guy 100 40 15,000 ' 46 40 60,000 -31 I
,` lo Cleaning Cotton Fabric (5 gig) Index LSD
none 0 30 15,000 -20 30 60,000 -2Q0 30 As can be seen from the above, there is essentially no benefit from using a polyacrylate with a molecular weight above about 10,000 and for a consistent meaningful benefit, the molecular weight should be less than about 8,000. For optimum performance, the molecular weight should not exceed about 6,000. Polymers containing less than 100%, e.g., 80%, acrylate monomers can be used 5 with substantially equivalent results.
Test 3 Conditions: 95F; under built, and Product A
containing the indicated amounts of No Zealot A and No Polyacrylate (MOW. 4500).
Cleaning Index LSD
Polycotton solute Cotton Fabric Fabric none 23 0 0 25 1.5 23 100 I 25 9.6 18 85 100 25 11.8 none 72 59 25 As can be seen from the above, the clay imp provement is essentially independent of the amount of other detergent builder present and there is essentially pa no advantage in using more than about 5% of the polyp acrylate.
-Component %
us 'Conlponent - %
No Zealot I, hydrated (yo-yo) 24.4 Nay C3 5 No silicate (1.6r) 2 No sulfosuccinate 2 Polyethylene glycol (MOW. -SEIKO 1.5 Minors including protozoa and aimless, Nazi and water Balance The above composition was prepared as a spray-dried granule and tested with (control) and without 1.5%
added sodium polyacrylate (MOW. 4500). The temperature was 95F., the water had 10 grains/gal. hardness and the results in panel score grade units difference were as follows for clay removal.
Clay on cotton fabric: 0.9 LSD=0.51 Clay on polycotton fabric: 1.0 LSD=0.41 Based on these results, it is clear that a small amount of a low molecular weight polyacrylate provides a substantial cleaning boost or clay removal.
Preferred compositions are (1) spray-dried detergent granules wherein at least the surfactant and, preferably, the detergent builder are both in the deter-gent crutches mix prior to spray drying and (~) liquid compositions.
I,
Claims (16)
1. A spray dried detergent composition comprising:
(a) from about 5% to about 50% by weight of an organic detergent surfactant selected from the group consisting of anionic, zwitterionic, ampholytic and cationic surfactants, and mixtures thereof;
(b) from about 5% to about 80% by weight of a non-phosphorus detergent builder;
(c) from about 0.3% to about 5% by weight of a polyacrylate polymer soluble in an aqueous slurry comprising the above com-ponents and having a weight average molecular weight of from about 3,000 to about 6,000.
(a) from about 5% to about 50% by weight of an organic detergent surfactant selected from the group consisting of anionic, zwitterionic, ampholytic and cationic surfactants, and mixtures thereof;
(b) from about 5% to about 80% by weight of a non-phosphorus detergent builder;
(c) from about 0.3% to about 5% by weight of a polyacrylate polymer soluble in an aqueous slurry comprising the above com-ponents and having a weight average molecular weight of from about 3,000 to about 6,000.
2. The composition of Claim 1 wherein the organic surfactant comprises an anionic surfactant selected from the group consisting of alkali metal salts of C11-13 alkylbenzene sulfonates, C14-18 alkyl sulfates, C14-18 alkyl polyethoxy sulfates containing from about 1 to about 4 moles of ethylene oxide, and mixtures thereof.
3. The composition of Claim 1 wherein the non- phosphorus detergent builder comprises a zeolite, a carbonate or mixtures thereof.
4. The composition of Claim 1 comprising from about 1% to about 4% by weight of an alkali metal silicate having a molar ratio of from about 1.6 to about 2.4.
5. The composition of Claim 1 wherein the polyacrylate is a salt of a homopolymer of acrylic acid, hydroxyacrylic acid or methacrylic acid, or a copolymer thereof containing at least about 80% by weight of units derived from said acids and the remainder of said units being derived from the group consisting of vinyl chloride, vinyl alcohol, furan, acrylonitrile, methacrylonitrile, vinyl acetate, methyl acrylate, methyl methacrylate, styrene, alpha-methylstyrene, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, ethylene, propylene, 3-butenoic acid, and mixtures thereof.
6. The composition of claim 5 wherein the polymer is sodium polyacrylate.
7. The composition of claim 2 comprising from about 10% to about 30% by weight of the organic surfactant; from about 15% to about 60% by weight of a non-phosphate detergent builder salt comprising hydrated sodium Zeolite A, carbonate, nitrilotriacetate, or mixtures thereof.
8. The composition' of claim 7 comprising from about 1% to about 3% by weight of sodium polyacrylate, having a weight average molecular weight of from about 3,000 to about 8,000.
9. The composition of claim 8 comprising from about 10% to about 30% by weight of aluminosilicate ion exchange material of the formula Na12[(A102)12].(SiO2)12].x H2O, wherein x is from about 20 to about 30.
10. The composition of claim 1 which is substantially free of nonionic detergent surfactant.
11. The composition of claim 10 wherein the non-phosphate detergent builder comprises a zeolite, a carbonate, or mixtures thereof.
12. The composition of claim 10 comprising from about 1% to about 4% by weight of an alkali metal silicate having a molar ratio of from about 1.6 to about 2.4.
13. The composition of claim 10 wherein the polyacrylate is a salt of a homopolymer of acrylic acid, hydroxyacrylic acid or methacrylic acid, or a copolymer thereof containing at least about 80% by weight of units derived from said acids.
14. The composition of claim 10 wherein the polymer is sodium polyacrylate.
15. A detergent composition comprising:
(a) from about 5% to about 50% by weight of an organic detergent surfactant selected from the group consisting of anionic, zwitterionic, ampholytic, and cationic surfactants, and mixtures thereof;
(b) from about 5% to about 80% by weight of a non-phosphorus detergent builder;
(c) from about 0.3% to about 5% by weight of a polyacrylate polymer soluble in an aqueous slurry comprising the above components and having a weight average molecular weight of from about 3,000 to about 6,000, said detergent composition being in the form of a liquid.
(a) from about 5% to about 50% by weight of an organic detergent surfactant selected from the group consisting of anionic, zwitterionic, ampholytic, and cationic surfactants, and mixtures thereof;
(b) from about 5% to about 80% by weight of a non-phosphorus detergent builder;
(c) from about 0.3% to about 5% by weight of a polyacrylate polymer soluble in an aqueous slurry comprising the above components and having a weight average molecular weight of from about 3,000 to about 6,000, said detergent composition being in the form of a liquid.
16. The composition of claim 15 which is in the form of an aqueous liquid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US50988583A | 1983-06-30 | 1983-06-30 | |
| US509,885 | 1983-06-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1229285A true CA1229285A (en) | 1987-11-17 |
Family
ID=24028492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000457671A Expired CA1229285A (en) | 1983-06-30 | 1984-06-28 | Detergents containing polyacrylate polymer |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0130640A1 (en) |
| JP (1) | JPS6021000A (en) |
| CA (1) | CA1229285A (en) |
| GR (1) | GR79977B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU620140B2 (en) * | 1988-09-07 | 1992-02-13 | Unilever Plc | Detergent compositions |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0665720B2 (en) * | 1985-04-03 | 1994-08-24 | 花王株式会社 | Concentrated powder detergent composition |
| JPS61264099A (en) * | 1985-05-17 | 1986-11-21 | 花王株式会社 | Detergent for dyeing machinery |
| CA1297376C (en) * | 1985-11-01 | 1992-03-17 | David Philip Jones | Detergent compositions, components therefor, and processes for theirpreparation |
| GB8526999D0 (en) * | 1985-11-01 | 1985-12-04 | Unilever Plc | Detergent compositions |
| CA1286563C (en) * | 1986-04-04 | 1991-07-23 | Jan Hendrik Eertink | Detergent powders and processes for preparing them |
| DE3614779A1 (en) * | 1986-05-02 | 1987-11-05 | Henkel Kgaa | GRANULAR, PHOSPHATE-FREE WATER SOFTENER |
| JPH0633399B2 (en) * | 1986-07-16 | 1994-05-02 | 花王株式会社 | Cleaning composition |
| JPH0633400B2 (en) * | 1986-07-16 | 1994-05-02 | 花王株式会社 | Cleaning composition |
| GB8710291D0 (en) * | 1987-04-30 | 1987-06-03 | Unilever Plc | Preparation of granular detergent composition |
| GB8710290D0 (en) * | 1987-04-30 | 1987-06-03 | Unilever Plc | Preparation of granular detergent composition |
| JP2682014B2 (en) * | 1988-06-10 | 1997-11-26 | 石川島播磨重工業株式会社 | Hydraulic drive speaker |
| GB8918984D0 (en) * | 1989-08-21 | 1989-10-04 | Unilever Plc | Detergent compositions |
| DE19858888A1 (en) * | 1998-12-19 | 2000-06-21 | Henkel Kgaa | Use of low molecular weight homopolymeric polyacrylates in water softeners and in preventing deposits on heating rods during machine washing of textiles |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3922230A (en) * | 1971-08-04 | 1975-11-25 | Lever Brothers Ltd | Oligomeric polyacrylates as builders in detergent compositions |
| US4031022A (en) * | 1973-05-28 | 1977-06-21 | Hoechst Aktiengesellschaft | Builders for detergent and cleaning compositions |
| DE3271441D1 (en) * | 1981-11-16 | 1986-07-03 | Procter & Gamble | Process for preparing granular detergent compositions containing an intimately admixed anionic surfactant and an anionic polymer |
-
1984
- 1984-06-01 GR GR74897A patent/GR79977B/el unknown
- 1984-06-18 EP EP84200874A patent/EP0130640A1/en not_active Withdrawn
- 1984-06-28 JP JP13217984A patent/JPS6021000A/en active Pending
- 1984-06-28 CA CA000457671A patent/CA1229285A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU620140B2 (en) * | 1988-09-07 | 1992-02-13 | Unilever Plc | Detergent compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6021000A (en) | 1985-02-02 |
| GR79977B (en) | 1984-10-31 |
| EP0130640A1 (en) | 1985-01-09 |
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