EP0117569A1 - Detergent compositions containing polyacetal carboxylate detergency builders - Google Patents

Detergent compositions containing polyacetal carboxylate detergency builders Download PDF

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Publication number
EP0117569A1
EP0117569A1 EP84200054A EP84200054A EP0117569A1 EP 0117569 A1 EP0117569 A1 EP 0117569A1 EP 84200054 A EP84200054 A EP 84200054A EP 84200054 A EP84200054 A EP 84200054A EP 0117569 A1 EP0117569 A1 EP 0117569A1
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composition
alkyl
group
weight
carbon atoms
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French (fr)
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Thomas Edward Cook
William Ajalon Cilley
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Procter and Gamble Co
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Procter and Gamble Co
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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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0047—Other compounding ingredients characterised by their effect pH regulated 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3711—Polyacetal carboxylates

Definitions

  • This invention relates to detergent compositions containing polyacetal carboxylate detergency builder materials and which - - provide a pH of from about 6.0 to about 8.5 in aqueous washing solutions. These compositions deliver excellent soil removal performance relative to detergent compositions containing other types of polycarboxylate and polyphosphate detergency builder materials at said pH.
  • STP Sodium tripolyphosphate
  • Sodium tripolyphosphate (STP) has been found to be a highly efficient detergency builder and this compound has been widely used for decades in detergent formulations.
  • STP Sodium tripolyphosphate
  • the detergent industry has been looking for materials suitable for use as detergency builders which do not contain phosphorus, and which are environmentally acceptable from other standpoints such as biodegradability. It has been difficult, however, to simultaneously deliver effective cleaning performance and biodegradability from materials that contain no phosphorus.
  • At least one type of organic polycarboxylate specifically a water soluble nitrilotriacetate (NTA) such as sodium nitrilotriacetate, has proven very satisfactory from the standpoints of effectiveness as a detergency builder and biodegradability.
  • NTA water soluble nitrilotriacetate
  • detergent compositions that provide a neutral or less alkaline washing solution than pH 9 is necessary or highly recommended. This includes the washing of "fine" fabrics, such as wool and silk and of fabrics having dyes or finishes not stable at alkaline pH values.
  • Detergent compositions in which the active ingredients from a detergency standpoint are limited to surface active agents (surfactants) are typically employed in such applications.
  • surfactants surface active agents
  • soaps i.e., the water soluble salts of fatty acids
  • soaps generally provide alkaline pH values in water solution. A reduction in the pH value of a soap solution by means of addition of acidic material can cause precipitation of fatty acids and consequent loss of surface activity.
  • U.S. Patent 4,144,226, Crutchfield et al discloses ether and acetal carboxylates useful as detergent builders having the emper- ical formula wherein M is a cation, alkyl group, etc., n averages at least 4 and R 1 and R 2 are radicals which stabilize the polymer.
  • a washing solution between pH 9 and pH 10 is said to be usual.
  • U.S. Patent 4,233,422, Dryroff et ai discloses a process for making polyacetal carboxylates from an ester of glyoxylic acid and stabilization against rapid depolymerization by addition of terminal alkyl groups via dialkyl sulfate and metal hydride addition.
  • Canadian Patent 941,765, Mast discloses detergent compositions providing a solution pH of 6 to 8.5 and containing: (a) a specified non-calcium sensitive surfactant; (b) a proteolytic enzyme with activity in the pH range of 6 to 8.5; and (c) a polycarboxylate builder compound.
  • U.S. Patent 3,658,727, Mast discloses phosphorus containing builders in detergent compositions containing a proteolytic enzyme, said compositions providing a solution pH of 6 to 8.5.
  • European patent application 0 015 024, published 03.09.80 discloses detergent compositions containing a combination of polyacetal carboxylate and aluminosilicate as the builder. It is disclosed that the pH of detergent solutions is usually between 9 and 10.
  • compositions are preferably formulated so as to have a pH of at least about 7 in a laundry solution.
  • Preferred compositions are said to have the ability to maintain a pH of about 8 to 11 throughout the washing operation.
  • European patent application 0 095 205 published 30.11.83,discloses detergent compositions containing 5-40% fatty acid which provide an initial pH of 6.0 to 8.5 in the washing solution.
  • the possible use of polyacetal polycarboxylates is disclosed by incorporation by reference of U.S. Patent 4,284,532, Leikhim et at.
  • the present invention encompasses a detergent composition, which contains:
  • the detergent composition contains from about 0.005% to about 0.4% by weight of pure enzymes selected from the group consisting of proteolytic enzymes, amylolytic enzymes and mixtures thereof, said enzymes preferably having activity in the pH range of 6.0 to 8.5 than at higher pH values.
  • the detergent composition contains a peroxygen bleaching agent selected from the group consisting of peroxyacid bleaching agents and peroxyacid precursors comprising peroxy compounds in combination with a peroxygen bleach activator, said peroxyacid bleaching agent and peroxyacid, formed by the reaction of said peroxy compound and said peroxygen bleach activator, preferably having pKa values below about 8.5.
  • a peroxygen bleaching agent selected from the group consisting of peroxyacid bleaching agents and peroxyacid precursors comprising peroxy compounds in combination with a peroxygen bleach activator, said peroxyacid bleaching agent and peroxyacid, formed by the reaction of said peroxy compound and said peroxygen bleach activator, preferably having pKa values below about 8.5.
  • This invention relates to the use of an improved detergency builder for use in detergent compositions that provide washing solution pH values from about 6.0 to about 8.5.
  • the builder delivers excellent particulate soil removal performance at low pH values relative to other detergency builders and provides conditions at which certain detergent composition adjuncts can deliver their full potential benefit to the detergency process.
  • the essential materials in the detergent composition of this invention are a detergent surfactant and a polyacetal carboxylate detergency builder material.
  • the detergent surfactant represents from about 3% to about 40%, preferably from about 5% to about 30%, and more preferably from about 10% to about 20% by weight of the detergent composition.
  • Suitable surfactants are any of those generally known in the art. More specifically, the surfactant can be selected from the group consisting of anionic, nonionic, ampholytic, zwitterionic and cationic surfactants, and compatible mixtures thereof.
  • Suitable surfactants for use herein are described in U.S. Patent 3,936,537, Baskerville et at, issued February 3, 1976, the disclosure of which are incorporated herein by reference.
  • Useful anionic surfactants include the water-soluble salts, particularly the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • alkyl is the alkyl portion of aryl groups.
  • this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 8 -C 18 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 alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U. S. Patents 2,220,099 and 2,477,383.
  • Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C 11-13 LAS.
  • anionic surfactants herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 4 units of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing about 1 to about 4 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.
  • Other useful anionic surfactants herein 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 from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 4 motes of ethylene oxide; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
  • soaps Water-soluble salts of the higher fatty acids, i.e., "soaps", can be useful anionic surfactants herein, but as discussed hereinafter, are not necessarily stable throughout a pH range of from about 6 to about 8.5. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Examples of soaps are the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms.
  • ammonium or substituted ammonium soaps e.g., ethanolamine soaps
  • ammonium or substituted ammonium soaps have superior stability at the pH values of washing solutions within the invention.
  • Particularly preferred anionic surfactants are the alkali metal (especially sodium) salts of C 11-13 alkylbenzene sulfonates, C 12-18 alkyl sulfates, C 12-18 alkyl polyethoxy sulfates containing from about 1 to about 4 moles of ethylene oxide, and mixtures thereof.
  • Anionic surfactants in which the cation is magnesium can find use in the compositions of the invention.
  • the polyacetal carboxylate segments of the detergency builder will preferentially sequester calcium ions from washing solutions.
  • Nonionic surfactants can be prepared by a variety of methods well known in the art. As described hereinafter many nonionic surfactants are prepared by condensing ethylene oxide with an -OH containing hydrocarbyl moiety, e.g., an alcohol or alkyl phenol, under conditions of acidic or basic catalysis.
  • an -OH containing hydrocarbyl moiety e.g., an alcohol or alkyl phenol
  • Nonionic surfactants for use herein comprise the typical nonionic surface active agents well known in the detergency arts.
  • Useful nonionic surfactants include those described in U.S. Patent 4,075,118, issued to Gault et al on February 21, 1978, in U.S. Patent 4,079.078, issued to Collins on March 14, 1978, and in U.S. Patent 3,963,649, issued to Spadini et al on June 15, 1976, all incorporated herein by reference.
  • Suitable, water-soluble, nonionic surface-active agents useful in the detergent composition of the present invention include:
  • Alkylpolysaccharides having a hydrophobic group containing from about 8 to about 20 carbon atoms and a polysaccharide hydrophilic group containing from about 1.5 to about 10 saccharide units.
  • Preferred nonionic surfactants herein are those obtained by the condensation of from about 1 to 12 moles of ethylene oxide with a C 10 -C 20 aliphatic alcohol. Especially preferred are those obtained by the condensation of from about 5 to 8 moles of ethylene oxide with a C 12 -C 15 aliphatic alcohol.
  • An especially preferred nonionic surfactant is obtained by the condensation of about 6 to 7 moles of ethylene oxide with a C 12 -C 13 aliphatic alcohol.
  • Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be 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-solubilizing group.
  • Zwitterionic surfactants include derivatives of aliphatic, quaternary, ammonium, phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms.
  • Cationic surfactants useful in the compositions of the invention include quaternary ammonium compounds having the formula: wherein R is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain; each R 3 is selected from the group consisting of -CH 2 CH 2 -, -CH 2 CH(CH 3 )-, -CH CH-(CH 2 0H)-, -CH 2 CH 2 CH 2 -, and mixtures thereof; each R 4 is selected from the group consisting of C 1-4 alkyl, C 1-4 hydroxyalkyl, benzyl, ring structures formed by joining the two R 4 groups, -CH 2 CHOHCHOHCOR 6 CHOHCH 2 0H wherein R 6 is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0; R 5 is the same as R 4 or is an alkyl chain wherein the total number of carbon atoms of
  • alkyl quaternary ammonium surfactants especially the mono-long chain alkyl surfactants described in the above formula when R 5 is selected from the same groups as R 4 .
  • di-long chain alkyl quaternary ammonium surfactants are not compatible with anionic surfactants without physical separation as disclosed in U.S. Patent 3,936,537 issued February 3, 1976, to Baskerville et al, incorporated herein by reference.
  • the most preferred quaternary ammonium surfactants are the chloride, bromide and methylsulfate C 8-16 alkyl trimethylammonium salts, C 8-16 alkyl di(hydroxyethyl)methylammonium salts, the C 8-16 alkyl hydroxyethyldimethylammonium salts, and C 8-16 alkyloxypropyltrimethylammonium salts.
  • C 8-16 alkyl trimethylammonium methylsulfate lauryl trimethylammonium chloride, myristyl trimethylammonium bromide and coconut trimethylammonium chloride and methylsulfate are particularly preferred.
  • the C 8-10 alkyltrimethyl ammonium surfactants are particularly preferred since they have a lower Kraft boundry and, therefore, a lower crystallization temperature than the longer alkyl chain quaternary ammonium surfactants herein.
  • Cationic diquaternary ammonium surfactants useful herein are of the formula: wherein the R 2 , R 3 , R 4 , R 5 , y and X substituents are as defined above for the quaternary ammonium surfactants. These substituents are also preferably selected to provide diquaternary ammonium surfactants corresponding to the preferred quaternary ammonium surfactants. Particularly preferred are the C 8-16 alkyl pentamethylethylenediammonium chloride, bromide and methylsulfate salts.
  • Cationic amine surfactants useful herein are of the formula: wherein the R 2 , R 3 , R 4 , R and y substituents are as defined above for the quaternary ammonium surfactants. Particularly preferred are the C 12-16 alkyl dimethyl amines.
  • Cationic diamine surfactants useful herein are of the formula wherein the R 2 , R 3 , R 4 , R 5 and y substituents are as defined above. Preferred are the C 12-16 alkyl trimethylethylene diamines.
  • the disclosure and compositions of European Patent Application 0 095 205, published 30.11.1983, bv Wertz et al. are incorporated herein by reference.
  • the detergent surfactant is selected from the group consisting of cationic and nonionic surfactants, and mixtures thereof, particularly those described in U.S. published Patent Applications 4,222,905, Cockrell, filed June 26, 1978; 4,259,217, Murphy, filed June 26, 1978; and European Patent Application 0 004 121, Murphy, published September 19, 1979; the disclosures of which are incorporated herein by reference.
  • the surfactant comprises at least about 30% anionic surfactant by weight of total surfactant and any cationic surfactant does not comprise compounds with more than a single C 12-18 alkyl group.
  • the detergent compositions herein contain from about 5% to about 70%, preferably from about 10% to about 50%, by weight of a stabilized water-soluble polymer comprising polyacetal carboxylate segments having the structure wherein M is selected from the group consisting of alkali metal, ammonium, tetraalkyl, ammonium and alkanol amine groups having from 1 to about 4 carbon atoms in the alkyl and alkanol chains; n averages at least 4; and the total number of polyacetal carboxylate segments comprise at least 50% by weight of the total polymer.
  • polyacetal carboxylates can be prepared by bringing 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 carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a surfactant.
  • rapidly depolymerization in alkaline solution shall mean that in an aqueous solution of 0.5 molar sodium hydroxide containing 10 grams per liter of polyacetal carboxylate, the average chain length of the polyacetal carboxylate will be reduced by more than 50%, as determined by Proton Magnetic Resonance, after 1 hour at 20°C.
  • esters of glyoxylic acid can be used to prepare the polyacetal carboxylates of the present invention.
  • Such esters can be made by the reaction of an alcohol containing from 1 to 4 carbon atoms with glyoxylic acid hydrate under conditions known to those skilled in the art. Thereafter, the ester hemiacetal can be converted to the corresponding aldehyde ester by any number of techniques known to those skilled in the art, such as the reaction of the ester hemiacetal with phosphorus pentoxide.
  • the product of the above reaction is then polymerized by techniques known to those skilled in the art using an initiator in accordance with the following genera! equation:
  • the resulting polyacetal carboxylate ester is then reacted at its termini with a reagent which produces a chemically stable end group to stabilize the polyacetal carboxylate against rapid depolymerization.
  • the stabilized polyacetal carboxylate is then reacted with a base, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, alkanolammonium hydroxide, and the like to make the polyacetal carboxylate salt suitable for use as a builder and as a sequestrant.
  • the glyoxylic acid can be converted to the ester by reaction with any number of alcohols, such as methanol, ethanol, propanol, isopropanol, and the like. It is only necessary that the ester group does not interfere with the subsequent polymerization. Methanol is preferred.
  • Nonionic or ionic initiators provide satisfactory results. Suitable initiators include 2-hydroxypyridine -H 2 0 complex; triethyl amine; ethylvinyl ether trifluoroacetic acid, and the like. Even traces of hydroxy ion or cyanide ion will trigger the polymerization under nonaqueous conditions. Compounds such as diethylsodiomalonate or sodiomethylmalonate esters have been used with good results.
  • any number of chemically reactive groups can be added to the polyacetal carboxylate termini to stabilize the polyacetal carboxylate against rapid depolymerization.
  • the specific nature of the chemically reactive group is not important in the proper function of the polyacetal carboxylate in its intended use.
  • suitable chemically stable end groups include stable substituent moieties derived from otherwise stable compounds, such as alkanes, such as decane, dodecane, octadecane and the like; alkenes such as ethylene, propylene, butylene, decene, dodecene and the like; branched chain hydrocarbons, both saturated and unsaturated, such as 2-methyl butane, 2-methyl butene, 4-butyl-2,3-dimethyl octane and the like; aromatic hydrocarbons such as benzene, toluene, xylene and the like; cycloalkanes and cycloalkenes such as cyclohexane and cyclohexene and the like; haloalkanes such as chlorobutane, dichloropentane and the like; alcohols such as methanol, ethanol, 2-propanol, cyclohexanol and the like; polyhydric alcohols
  • chemically stable end groups that stabilize the polyacetal carboxylate against rapid depolymerization include nitrilo groups and halides such as chlorides, bromides and the like.
  • Particularly suitable end groups include alkyl groups and cyclic alkyl groups containing oxygen: such as oxyalkyl groups like methoxy, ethoxy and the like; carboxylic acids such as -CH 2 COOM, and the like; aldehydes, ethers and other oxygen-containing alkyl groups such as -OCHCH 3 OC 2 H 5 , ( ⁇ OCH 2 CH 2 O) ⁇ 1-4 OH, ( ⁇ OCH 2 CH 2 O)- 1-4 H, and the like.
  • M is alkali metal, ammonium, alkanol amine, alkyl groups having 1 to 4 carbon atoms, tetraalkyl ammonium groups and alkanol amine groups having from 1 to about 4 carbon atoms in the alkyl chain
  • R is hydrogen or alkyl group of 1 to 8 carbon atoms.
  • one end group can be a polymer, and particularly a polymer with an anionic charge, which permits one or more of the polyacetal carboxylates of the present invention to be appended to the polymer, or on the other hand, the polyacetal carboxylates of the present invention can be the part of a block copolymer having a polymer chain at each of the polyacetal carboxylate termini.
  • Preferred polymers that are anionic or can be made anionic include: polymers of cellulose acetate, cellulose propionate, cellulose acetate butyrate, polyvinyl acetate, polyvinyl alcohol and the like.
  • the polymer can be used to initiate the polymerization to form the polyacetal carboxylates wherein the polymer adds to the termini as one of the chemically stable end groups to stabilize that end of the polyacetal carboxylate against rapid depolymerization and thereafter the other end of the polyacetal carboxylate can be stabilized with a compound such as ethylene oxide or the like, as described above.
  • diethylsodiomalonate or sodiomethylmalonate is used as an initiator to form the polymer.
  • These compounds not only serve to initiate the polymerization, but also the ester adds to the termini as one of the chemically stable end groups to stabilize that end of the polyacetal carboxylate against rapid hydrolysis in an alkaline solution.
  • These compounds can be prepared from the corresponding esters using sodium hydride in a solvent, such as tetrahydrofuran, by techniques known to those skilled in the art.
  • the builder mixture contains a water-soluble polyacetal carboxylate havinq the structure; wherein M is selected from the group consisting of alkali metal, ammonium, tetraalkyl ammonium groups and alkanol amine groups having from 1 to about 4 carbon atoms in the alkyl chain; n averages at least 4; and R 1 and R 2 are individually any chemically stable group which stabilizes the polyacetal carboxylate against rapid depolymerization.
  • the number of repeating units, i.e., the value of n, in the polyacetal carboxylate is important since the effectiveness of the polyacetal carboxylate salt as a detergency builder is affected by the chain length. Even when there are as few as four repeating units (i.e., n averages 4), the polyacetal carboxylate salt shows some effectiveness as a sequestrant, chelating agent and builder. Although there is no upper limit to the desired number of repeating units, which may be as high as 400, or even higher, there does not seem to be an advantage to having more than about 200 repeating units. When the number of repeating units exceeds about 100, significant improvement in sequestration, chelating and builder properties is not observed. Thus, it is preferred that the polyacetal carboxylate contain between about 10 and about 200 units, and even more preferred that the polyacetal carboxylate contains between about 50 and about 100 repeating units.
  • the most important factors believed to control the chain length include (1) the initiator concentration, (2) the temperature of the polymerization, (3) the purity of the starting materials, and (4) the presence of solvents and their levels.
  • concentration of the initiator, solvents and their levels, and the temperature of the polymerization reaction are all interrelated and the desired chain length can easily be controlled by simple experimentation by controlling these variables.
  • the lower the temperature at the beginning of the polymerization the higher the chain length.
  • the resulting polyacetal carboxylate contained 60 repeating units as determined by Proton Magnetic Resonance (PMR).
  • PMR Proton Magnetic Resonance
  • the resulting polyacetal carboxylate had only about 20 repeating units.
  • the polyacetal carboxylate can also contain other polymer fragments, and accordingly, the polymer can be a linear homopolymer or copolymer, or it can be branched.
  • the polyacetal carboxylate segments are polymerized with any number of chain extending agents known to those skilled in the art. It is only necessary that the chain extending agent does not cause the polyacetal carboxylate to depolymerize or become insoluble in water. Either aliphatic or aromatic chain extending agents can be used, but aliphatic chain extending agents are preferred to make the polymer more environmentally acceptable, and aliphatic chain extending agents having from 1 to 4 carbon atoms, such as ethylene oxide or propylene oxide, are especially preferred.
  • a copolymer contains at least 4 repeating units (i.e., n averages at least 4) of the acetal carboxylate to insure that the copolymer will effectively sequester calcium and magnesium ions and provide builder properties. It is preferred that the copolymer contain at least 10 repeating units of acetal carboxylate, or more, say 50 or 100 repeating units, for the reasons described above.
  • acetal carboxylate esters are copolymerized with a chain extending agent
  • the amount of acetal carboxylate should be at least about 50% by weight, based on the total weight of the polymer, to insure that the polymer will effectively sequester calcium and magnesium ions and retain its builder properties. It is preferred that the amount of acetal carboxylate is 80% by weight, based on the total weight of the polymer, or even higher.
  • chain extending agents can be copolymerized with the polyacetal carboxylates of the present invention. It is only necessary that the chain extending agent will provide at least two reactive sites. Suitable chain extending agents include: polyhydric alcohols, such as ethylene glycol, propylene glycol and the like; epoxy compounds, such as ethylene oxide, propylene oxide, epihalohydrin epoxysuccinates and the like; aldehydes, such as formaldehyde, acetaldehyde, and the like. It is particularly beneficial when the chain extending agent contains substituent carboxy groups.
  • the builder mixture contains a stabilized water-soluble polymer comprising polyacetal carboxylate segments having the general formula: where Y is at least one chain extending agent, preferably alkyl or oxyalkyl having 1 to 4 carbon atoms, p averages at least 4, q is at least 1, and M is selected from the group consisting of alkali metal, ammonium, tetraalkyl ammonium groups and alkanol amine groups having from 1 to about 4 carbon atoms in the alkyl chain.
  • the polyacetal carboxylates having a chain extending agent can be stabilized by the same techniques used above using suitable reagents or polymers as described above.
  • the polyacetal carboxylate ester can be converted to the corresponding alkali metal, ammonium, tetraalkyl ammonium or alkanol amine salts by conventional saponification techniques.
  • alkali metal salts particularly the sodium salt
  • ammonium or alkanol ammonium salts may be desirable.
  • the detergent compositions of the invention provide a pH of from about 6 to about 8.5, preferably from about 6.5 to about 8, and most preferably about 7, in a 0.2% by weight water solution at 20°C. This characteristic can be provided by any suitable means including the addition of acidic material or use of anionic surfactants in a unneutralized acid form.
  • the detergent compositions of the invention are generally used in aqueous washing solutions containing from about 0.05% to about 1% of the detergent composition by weight. Use as a laundry detergent composition is a preferred embodiment, but the compositions can also be used for hard surface cleaning such as dishwashing or interior household surfaces.
  • the pure enzyme component can be incorporated in an amount of from about 0.005% to about 0.2%, preferably from about 0.02% to about 0.09%. If incorporated, the proteolytic enzyme component should give to the composition a proteolytic activity of at least about 0.003 Anson Units per liter, preferably from about 0.003 to about 0.125 Anson Units per liter of wash solution and most preferably, from about 0.016 to about 0.063 Anson Units per liter of wash solution. Above about 0.1 Anson units per titer of wash solution additional proteolytic enzyme provides only a minimal increase in performance. Other enzymes including amylolytic enzymes or amalyses can be incorporated, e.g. Rapidase (Gist-Brocades N.V.) and Termamyl (Novo Industri AS). The cleaning advantages contributed by amylolytic enzymes is particularly enhanced by the low solution pH values provided by - compositions of the invention.
  • the enzyme components are characterized by an isoelectric point of from about 6 to about 9, most preferably from about 6.5 to about 8.5.
  • Preferred enzymes have an activity at pH values of 6.0 to 8.5 than at higher pH values.
  • suitable proteolytic enzymes include many species which are known to be adapted for use in detergent compositions and, in fact, have been used in detergent compositions.
  • Sources of the enzymes include commercial enzyme preparation such as "Alcalase”, sold by Novo Industries, and “Maxatase”, sold by Gist-Brocades Delft, The Netherlands, which contain from about 10% to about 20% pure enzyme.
  • Other enzyme compositions include those commercially available under the trade names SP-72 ("Esperase"), manufactured and sold by Novo Industries, AS, Copenhagen, Denmark, and "AZ-Protease", manufactured and sold by Gist-Brocades Delft, The Netherlands.
  • Peroxygen bleaches useful in the practice of this invention are selected from the group consisting of peroxyacid bleaching agents and peroxyacid precursors comprising peroxy compounds in combination with a peroxygen bleach activator, said peroxyacid bleaching agent and peroxyacid formed by the reaction of said peroxy compound and said peroxygen bleach activator having pKa values below about 8.5.
  • a preferred peroxyacid bleaching agent is metachloroperoxybenzoic acid which has a pKa value of 7.53.
  • Other suitable peroxyacid bleaching agents are perlauric acid and diperoxydodecanedioic acid.
  • compositions of this invention can contain detergency builder materials additional to the essential polyacetal carboxylate.
  • Optional water-soluble detergency builders can be selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, polyhydroxy sulfonates, polyacetates, carboxylates, and polycarboxylates.
  • Alkali metal, especially sodium, salts are preferred for economy if product stability and solution pH considerations allow their use.
  • inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphate.
  • polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane l-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane, 1,1,2-triphosphonic acid.
  • Other phosphorus builder compounds are disclosed in U.S. Patents 3,159,581, 3,213,030; 3,422,021; 3,422,137; 3,400,176; and 3,400,148, incorporated herein by reference.
  • nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicates having a weight ratio of Si0 2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4.
  • Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates.
  • polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
  • Polymeric polycarboxylate builders are set forth in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, incorporated herein by reference. Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
  • Other useful builders herein are sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclo- hexanehexacarboxylate, cis-cyclopentanetetracarboxylate, phloro- glucinol trisulfonate, and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.
  • Additional detergency builders useful herein are water- insoluble crystalline or amorphous aluminosilicate ion exchange materials.
  • Crystalline material useful herein is of the formula 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 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 CaC0 3 hardness per gram of anhydrous 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 aiumi- nosilicate 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 0.01 micron.
  • Preferred ion exchange materials have a particle size diameter of from about 0.2 micron to about 4 microns.
  • particle size diameter herein represents the average 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 mg equivalent of CaC0 3 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from about 300 mg eq./g to about 352 mg eq./g.
  • aluminosilicate ion exchange materials herein are still further characterized by their calcium ion exchange rate which is at least about 2 grains/gallon/minute/gram/gallon of aluminosilicate (anhydrous basis), and generally lies within the range of from about 2 to 6 grains/gallon/minute/gram/gallon, based on calcium ion hardness.
  • Optimum aluminosilicate for builder purposes exhibit a calcium ion exchange rate of at least about 4 grains/gallon/minute/gram/gallon.
  • the amorphous aluminosilicate ion exchange materials usually have a Mg ++ exchange capacity of at least about 50 mg. eq. CaC0 3 /g (12 mg Mg ++ /g) and a Mg ++ exchange rate of at least about 1 grain/gallon/minutelgram/gallon. Amorphous materials do not exhibit an observable diffraction pattern when examined by Cu radiation (1.54 Angstrom Units).
  • Aluminosilicate ion exchange materials useful in the practice of 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.
  • a method for producing aluminosilicate ion exchange materials is discussed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976, incorporated herein by reference.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, and Zeolite X.
  • the crystalline aluminosilicate ion exchange material has the formula wherein x is from about 20 to about 30, especially about 27.
  • fatty acids containing from about 12 to about 18 carbon atoms are utilized as detergency builders. Such fatty acids are useful to control washing solution pH to within the desired range and act as fatty soil solvents when applied to fabrics in an undiluted form.
  • detergent compositions of the present invention include other detergency builders, antistatic and fabric-softening agents, color speckles, suds boosters or suds suppressors, anti-tarnish and anticorrosion agents, soil suspending agents, soil release agents, dyes, fillers, optical brighteners, germicides, hydrotropes, perfumes, and other optional detergent compounds.
  • a liquid detergent having the following composition was prepared:
  • the detergent compositions A, B & C were tested as follows.
  • Identical clay-soiled polyester/cotton swatches were washed in aqueous solutions having dissolved therein 920 parts per million of the detergent compositions described. Washing solution pH was adjusted by addition of NaOH or HCI as necessary. The swatches were washed for 10 minutes in a miniature washing machine containing 1-1/2 gallons of washing liquor at 100°F and artificial water hardness (molar equivalents of 2 moles Ca to 1 mole Mg ++ ) at a level of 4 grains of CaCO 3 equivalent per gallon. The swatches comprised approximately 4% by weight of the washing liquor.
  • the swatches were spun dry and rinsed with 1-1/2 gallons of water, at 100°F, having the same water hardness as that of the water they were washed in. The swatches were then dried in a miniature electric dryer. A Hunter Reflectometer was used to obtain a reflectance reading (in Hunter Whiteness Units) for each of the laundered swatches. A higher reflectance reading indicates greater cleaning effectiveness. The results were as follows:
  • Composition C containing the polymeric acetal carboxylate has a cleaning advantage at pH values below 9 relative to Composition B containing a nitrilotriacetate.
  • a liquid detergent having the following composition was prepared:
  • Example 1 The testing procedure of Example 1 was repeated except for product usage of 1770 ppm with the following results:
  • Composition C containing the polymeric acetal carboxylate has a cleaning advantage at pH values below 9 relative to Composition B containing a nitrilotriacetate.
  • Stained fabrics were prepared using white denim cotton and two natural stains - tea and grape juice.
  • Stain removal evaluations were conducted using the washing procedure and pH adjustments described in Example I. Added levels of polymeric acetal carboxylate (as in Example 1), sodium tripolyphosphate and metachloroperoxybenzoic acid bleach are tabulated below. Percent stain removal is calculated as follows.
  • a laundry load consisting of one set of the stained fabrics , four clean terry cloth towels and one terry cloth towel soiled with 1.5 grams of a mixture of artificial body soil and vacuum cleaner soil was placed in the miniature wash system described in Example
  • each of the stained fabrics was visually graded by comparing it to its unwashed counterpart.
  • a grading scale of 0 to 5 was used, with 0 indicating no stain removal and 5 indicating 100% stain removal.
  • Each fabric was graded by three graders and the average grade for each fabric was calculated. This average was then scaled from 0 to 100, with 100 being 100% stain removal. Also, the mean for the set of fabrics was calculated.
  • composition is prepared by the agglomeration of dry materials with sufficient water to hydrate anhydrous salts.
  • compositions (a) and (b) at a 0.2% level by weight are prepared and adjusted to a pH of 7 by the addition of H 2 S0 4 .
  • the detergency of the two solutions is compared following the procedure of Example I.
  • Composition (b) containing a polymeric acetal carboxylate has a detergency advantage over Composition (a) containing sodium nitrilotriacetate at a wash solution pH of 7.
  • a calcium ion electrode was used to measure calcium ion sequestration of detergency builder materials. Calcium concentration standards were prepared and used to establish a plot of millivolt values that correspond to a range of calcium ion concentrations with the particular calcium ion electrode.
  • Sodium nitrilotriacetate has an sequestration advantage over the polymeric acetal carboxylate at pH 9.5 when compared at theoretical sequestration equivalence (carboxylate molar basis).
  • the polymeric acetal carboxylate has an advantage at pH 7.5.
  • Polyplymaleic acid is poorer at both pH values.
  • the polymeric acetal carboxylate has a cleaning advantage over nitrilotriacetate and polymaleate builder materials.
  • the relative advantage is greater at pH 7.5 than at pH 9.5.

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EP84200054A 1983-01-28 1984-01-18 Detergent compositions containing polyacetal carboxylate detergency builders Withdrawn EP0117569A1 (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2159529A (en) * 1984-06-01 1985-12-04 Colgate Palmolive Co Built synthetic detergent composition
GB2159531A (en) * 1984-06-01 1985-12-04 Colgate Palmolive Co Particulate built nonionic detergent composition
FR2565245A1 (fr) * 1984-06-01 1985-12-06 Colgate Palmolive Co Composition detergente synthetique blanchissante et procede d'elimination des taches
FR2574088A1 (fr) * 1984-12-03 1986-06-06 Colgate Palmolive Co Composition detergente organique synthetique antistatique a adjuvant de detergence et ses procedes de preparation et d'utilisation
FR2586424A1 (fr) * 1985-08-20 1987-02-27 Colgate Palmolive Co Compositions detergentes liquides non aqueuses de blanchissage et procedes pour nettoyer des tissus salis les utilisant
US4655954A (en) * 1985-08-20 1987-04-07 Colgate-Palmolive Company Low phosphate or phosphate free nonaqueous liquid nonionic laundry detergent composition and method of use
AU581437B2 (en) * 1984-06-01 1989-02-23 Colgate-Palmolive Company, The Particulate built nonionic synthetic detergent composition.
AU581436B2 (en) * 1984-06-01 1989-02-23 Colgate-Palmolive Company, The Particulate built nonionic synthetic organic detergent composition
US4847005A (en) * 1987-10-22 1989-07-11 Monsanto Company Solutions of hydrolytically stable polymeric acetal carboxylate salts and stable liquid detergent compositions containing such salts

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Publication number Priority date Publication date Assignee Title
ZA853572B (en) * 1984-06-01 1986-12-30 Colgate Palmolive Co Antistatic synthetic organic detergent composition
JPH0668113B2 (ja) * 1985-11-13 1994-08-31 花王株式会社 洗浄剤組成物
JPH0668112B2 (ja) * 1985-11-13 1994-08-31 花王株式会社 洗浄剤組成物

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US4146495A (en) * 1977-08-22 1979-03-27 Monsanto Company Detergent compositions comprising polyacetal carboxylates
US4204052A (en) * 1977-08-22 1980-05-20 Monsanto Company Copolymers of acetal carboxylates
EP0015024A1 (en) * 1979-02-16 1980-09-03 THE PROCTER & GAMBLE COMPANY Detergent compositions containing binary builder system
US4315092A (en) * 1977-08-22 1982-02-09 Monsanto Company Polyacetal carboxylates

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Publication number Priority date Publication date Assignee Title
US4146495A (en) * 1977-08-22 1979-03-27 Monsanto Company Detergent compositions comprising polyacetal carboxylates
US4204052A (en) * 1977-08-22 1980-05-20 Monsanto Company Copolymers of acetal carboxylates
US4315092A (en) * 1977-08-22 1982-02-09 Monsanto Company Polyacetal carboxylates
EP0015024A1 (en) * 1979-02-16 1980-09-03 THE PROCTER & GAMBLE COMPANY Detergent compositions containing binary builder system

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2192405A (en) * 1984-06-01 1988-01-13 Colgate Palmolive Co Particulate built nonionic detergent composition
AU583270B2 (en) * 1984-06-01 1989-04-27 Colgate-Palmolive Company, The Particulate built nonionic detergent composition
FR2565245A1 (fr) * 1984-06-01 1985-12-06 Colgate Palmolive Co Composition detergente synthetique blanchissante et procede d'elimination des taches
FR2565240A1 (fr) * 1984-06-01 1985-12-06 Colgate Palmolive Co Composition detergente synthetique renforcee par un adjuvant de detergence et procede de lavage
GB2160217A (en) * 1984-06-01 1985-12-18 Colgate Palmolive Co Bleaching synthetic detergent composition
AU581436B2 (en) * 1984-06-01 1989-02-23 Colgate-Palmolive Company, The Particulate built nonionic synthetic organic detergent composition
AU581437B2 (en) * 1984-06-01 1989-02-23 Colgate-Palmolive Company, The Particulate built nonionic synthetic detergent composition.
GB2159529A (en) * 1984-06-01 1985-12-04 Colgate Palmolive Co Built synthetic detergent composition
GB2159531A (en) * 1984-06-01 1985-12-04 Colgate Palmolive Co Particulate built nonionic detergent composition
GB2168073A (en) * 1984-12-03 1986-06-11 Colgate Palmolive Co Antistatic built synthetic organic detergent composition
FR2574088A1 (fr) * 1984-12-03 1986-06-06 Colgate Palmolive Co Composition detergente organique synthetique antistatique a adjuvant de detergence et ses procedes de preparation et d'utilisation
US4655954A (en) * 1985-08-20 1987-04-07 Colgate-Palmolive Company Low phosphate or phosphate free nonaqueous liquid nonionic laundry detergent composition and method of use
FR2586424A1 (fr) * 1985-08-20 1987-02-27 Colgate Palmolive Co Compositions detergentes liquides non aqueuses de blanchissage et procedes pour nettoyer des tissus salis les utilisant
US4847005A (en) * 1987-10-22 1989-07-11 Monsanto Company Solutions of hydrolytically stable polymeric acetal carboxylate salts and stable liquid detergent compositions containing such salts

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