Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/128—Aluminium silicates, e.g. zeolites
• • 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, as an improved builder system, a combination of polyacetal carboxylate builder materials and aluminosilicate materials. These compositions deliver excellent particulate soil removal performance and greasy/oily soil removal benefits.
• this builder system is incorporated into detergent compositions cotaining nonionic, and more preferably cationic/nonionic, surfactants.
• STP sodium tripolyphosphate
• the present invention encompasses a detergent composition, which contains from 0 to about 25% phosphate materials, comprising:
• the above-described builder mixture is incorporated into a detergent composition containing a nonionic surfactant, and; more preferably, a cationic/nonionic surfactant mixture, as hereinafter described.
• This invention comprises the discovery of an improved builder system for use in detergent compositions.
• the builder system a combination of polyacetal carboxylate builder materials and aluminosilicate materials, delivers excellent particulate soil removal performance and greasy/ oily soil removal benefits.
• the detergent compositions are especially good in 10-40°C water, especially when the particle size diameter of the aluminosilicate material is from about 0.5 to about 2 microns.
• the essential elements in the detergent composition of this invention are: a detergent surfactant, a polyacetal carboxylate builder material, and an aluminosilicate material.
• the detergent surfactant represents from about 1% to about 95%, preferably from about 10% to about 50%, 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, cationic, monionic, ampholytic, and zwitterionic surfactants, and mixtures thereof.
• Suitable surfactants for use herein are described in U.S. Patent 3,936,537, Baskerville et al, issued February 3, 1976, the disclosures of which 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 Japanese patent application 79-39411, Cockrell, published March 26, 1979; Japanese patent application 79-39412, Murphy, published March 26, 1979; and European published application 0 004 121, Murphy, published September 19, 1979, the disclosures of which are incorporated herein by reference.
• a particularly preferred surfactant mixture consists essentially of:
• the surfactant for use herein is a nonionic surfactant, and preferably is a biodegradable nonionic surfactant having the formula R(OC 2 H 4 ) n OH wherein R is a primary or secondary alkyl chain of from about 8 to about 22 carbon atoms and n is an average of from about 2 to about 12, having an HLB of from about 5 to about 17.
• the detergent compositions herein contain from about 5% to about 99%, preferably from about 20% to about 60%, by weight of a detergency builder mixture.
• the builder mixture consists essentially of:
• the aluminosilicate materials for use herein are those commonly known as hydrated zeolites A, X, and P(B).
• the zeolites should have a particle size diameter of from about 0.1 microns to about 100 microns, preferably from about 0.1. microns to about 10 microns.
• Aluminosilicate materials are more fully described in U.S. Patent 4,096,081, Phenicie et al, issued June 20, 1978; copending Japanese patent appli cation 77-115554, Ohren, published September 28, 1977; and copending Japanese patent application 75-53404, Corkill et al, published May 12, 1975; the disclosures of which are incorporated herein by reference.
• polyacetal carboxylates for use herein are more fully described in the copending U.S. Patents of Crutchfield et al, No. 4,144,226, for Polymeric Acetal Carboxylates, issued March 13, 1979, and No. 4,146,495, for Detergent Compositions Comprising Polyacetal Carboxylates, issued March 27, 1979, the disclosures of which are incorporated herein by reference.
• 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.
• 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 t.o 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 general 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 in alkaline solution.
• 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.
• initiators can be used for the polymerization.
• Suitable initiators include 2-hydroxy pyridine -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 diethylsodio- m alonate 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 in an alkaline solution. It is only necessary that the chemically reactive group stabilizes the polyacetal carboxylate against rapid depolymerization in an alkaline solution, and the specific nature of the chemically reactive group is not important in the proper function of the polyacetal carboxy-' late in its intended use.
• suitable chemically stable end groups include stable substituent moieties derived from otherwise stable compounds, such as alkanes, such as methane, ethane, propane, butane and higher 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 cyeloalkenes such as cyclohexane and cyclohexene and the like; haloalkanes such as chlorobutane, dichloropentane and the like; alcohols such as methanol
• chemically stable end groups that stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution 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 ) ⁇ 1-4 OH, ( ⁇ CH 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 in an alkaline solution, 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.
• diethylsodjo- malonate 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 thcse skilled in the art.
• the builder mixture contains a water-soluble polyacetal carboxylate having 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 in alkaline solution.
• 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, chelation 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).
• one mole percent 2-hydroxy pyridine -H 2 0 complex was used at about 20°C, 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 rapidly depolymerize in alkaline solution, 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 and does not cause the polyacetal carboxylates to depolymerize in alkaline solution.
• 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 against rapid depolymerization in alkaline solution 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, and such salts are especially useful as a builder in detergent formulations. Since the pH of a detergent solution is usually between pH 9 and pH 10, the polyacetal carboxylate salt will not depolymerize rapidly when used as a detergent builder in aqueous solution at normal use concentrations (1 cup/washer), temperatures (10°-60°C); and times (i.e., about 15 minutes) typical of United States home laundry practices. Generally, the use of the alkali metal salts, particularly the sodium salt, is preferred. However, in some formulations where greater builder solubility is required, the use of ammonium or alkanol ammonium salts may be desirable.
• alkali, ammonium, or alkanol ammonium salts of the present invention when used as builders, they will be used generally in an alkaline medium.
• the compositions of the present invention are used at a pH of 7 or below, some of the preferred the polymer salts will depolymerize.
• the compositions of the present invention are effective cleaning agents, but when an aqueous solution containing the composition is discharged into a sewer or other waste water system, these preferred polyacetal carboxylate salts will soon depolymerize - into small fragments which are readily biodegradable.
• detergent compositions of the present invention can be included in the detergent compositions of the present invention.
• these components include other detergency builders, antistatic and fabric-softening agents, color speckles, bleaching agents and bleach activators, suds boosters or suds suppressors, anti-tarnish and anti-corrosion agents, soil suspending agents, soil release agents, dyes, fillers, optical brighteners, germicides, pH adjusting agents, alkalinity sources, hydrotropes, enzymes, enzyme-stabilizing agents, perfumes, alkyl polyethoxylate nonionic surfactants, and other optional detergent compounds.
• composition delivered excellent particulate soil removal performance, as demonstrated hereinafter in Example III. Further, the composition provided greasy/oily soil removal benefits.
• Identical clay-soiled cotton, polyester/cotton, and polyester swatches were washed in aqueous solutions having dissolved therein 500 parts per million of the detergent compositions described in Examples I and II.
• the swatches were washed for 10 minutes in a miniature agitator containing 1-1/2 gallons of washing liquor at 100°F and artificial water hardness (2 parts Ca ++ to 1 part Mg ++ ) at levels of 2, 7 and 12 grains 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:
• Substantially similar cleaning performance is obtained when the surfactant for use in Composition A is selected from the group consisting of anionic, cationic, nonionic, ampholytic, and zwitterionic surfactants, and mixtures thereof; and especially when the surfactant is selected from the group consisting of cationic and nonionic surfactants, and mixtures thereof.
• Similar cleaning is obtained when the surfactant is a biodegradable nonionic surfactant having the formula R(OC 2 H 4 ) n OH wherein R is a primary or secondary alkyl chain of from about 8 to about 22 carbon atoms and n is an average of from about 2 to about 12, having an HLB of from about 5 to about 17.
• the surfactant is any mixture consisting essentially of a biodegradable nonionic surfactant having the formula R(OC 2 H 4 ) n OH wherein R is a primary or secondary alkyl chain of from about 8 to about 22 carbon atoms and n is an average of from about 2 to about 12, having an HLB of from about 5 to about 17, and a cationic surfactant, free of hydrazinium groups, having the formula as defined herein.
• aluminosilicate material is any hydrated zeolite A, X or P(B), having a particle size diameter of from about 0.1 microns to about 100 microns, especially from about 0.1 microns to about 10 microns, especially about 1 micron.
• Substantially similar cleaning performance is obtained when the number of polyacetal carboxylate segments averages at least 4, but especially when n averages between 10 and 200.
• the following detergent composition is produced: Hydrated sodium Zeolite X 10 (3 micron diameter) Sodium sulfate, H 2 O, and minors Balance

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• 1980
  • 1980-02-07 EP EP80200102A patent/EP0015024A1/fr not_active Withdrawn
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