WO1991013145A1 - Procedes et compositions en polymeres ionisables de nettoyage de taches - Google Patents

Procedes et compositions en polymeres ionisables de nettoyage de taches Download PDF

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Publication number
WO1991013145A1
WO1991013145A1 PCT/US1991/001178 US9101178W WO9113145A1 WO 1991013145 A1 WO1991013145 A1 WO 1991013145A1 US 9101178 W US9101178 W US 9101178W WO 9113145 A1 WO9113145 A1 WO 9113145A1
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Prior art keywords
cleaning
cleaning composition
ionizable polymer
composition
percent
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PCT/US1991/001178
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English (en)
Inventor
Dale M. Pickelman
Gene D. Rose
John G. Lenhart
David G. Long
Donald L. Schmidt
John Klier
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The Dow Chemical Company
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Priority to BR919104647A priority Critical patent/BR9104647A/pt
Priority to CA002055432A priority patent/CA2055432A1/fr
Publication of WO1991013145A1 publication Critical patent/WO1991013145A1/fr

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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43Solvents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions

Definitions

  • This invention is directed to cleaning compositions and methods useful in removing stains, particularly those of oil and grease or those of oil and grease containing particulates from surfaces or fabric.
  • Prior art cleaning compositions have not performed as well as desired in removing stains, especially hydrophobia oily ones containing particulates, from surfaces and fabrics. Problems have included insufficient lipophilic compatibility of the cleaning compositions with the stains; lack of wettability sufficient to overcome the work of adhesion at the substrate-stain interface; insufficient stabilization of the stain removed from the surface or fabric; and variability of cleaning efficiency with pH and ionic content of the washing media.
  • Lipophilic compatibility of prior art cleaning compositions with stains is a problem because such compositions are typically highly aqueous, and, thus, very hydrophilic. Stains which are difficult to clean are either hydrophobic or amphiphilic. Still more difficult to clean are hydrophobic stains containing particulates. Prior art compositions are typically too hydrophilic to clean these stains. Though the inclusion of conventional surfactants and organic solvents may reduce the hydrophilicity of the compositions, the compositions nonetheless are typically still too hydrophilic to remove the stains.
  • Cleaning efficiency of prior art compositions may vary according to pH or ionic content due to their effect upon the chemical composition of prior art anionic surfactants. Soaps are subject to formation of insoluble lime salts or loss of anionic charge. Such side reactions and ionic variations have necessitated the use of buffering agents, builders and lime soap dispersing aids.
  • an improved cleaning composition which offers superior cleaning of stains, especially those of oil and grease and those of oil and grease containing particulates; an improved cleaning composition which is more compatible with hydrophobic and nonhydrophilic stains; an improved cleaning composition which offers superior wetting and stabilization of stains and compatibility therewith; and an improved cleaning composition that offers superior cleaning regardless of: composition; pH; or foreign ionic content, of the washing media.
  • the cleaning composition would offer superior cleaning without the use of buffering, antiredeposition, chelating, or sequestering agents.
  • such improved cleaning compositions would be available in a concentrated form such as in a solid stick as well as a solution or liquid. The concentrated form not only imparts synergistic cleaning but also imparts greater efficiency for use in a pretreatment function.
  • the present invention includes an improved method of cleaning a stain from a surface or fabric characterized by contacting the stain with a cleaning composition characterized by an ionizable polymer and a nonionic surfactant.
  • a cleaning composition characterized by an ionizable polymer and a nonionic surfactant.
  • the nonionic surfactant and ionizable polymer are present in a weight ratio range of 1000:1 to 1:4 respectively. More preferably, the ratio of nonionic surfactant to ionizable polymer will be 200:1 to 1:1. Most preferably, the ratio of nonionic surfactant to ionizable polymer will be 100:1 to 1.5:1.
  • the present invention also includes an improved method of cleaning a stain from a surface or fabric characterized by contacting the stain with a cleaning composition characterized by an ionizable polymer and a solvent or mixture of solvents.
  • the present invention also includes an improved method of cleaning a stain from a surface or fabric which is characterized by contacting the stain with a cleaning composition characterized by an ionizable polymer, a nonionic surfactant and a solvent or mixture of solvent(s).
  • a cleaning composition characterized by an ionizable polymer, a nonionic surfactant and a solvent or mixture of solvent(s).
  • the solvent or solvent mixture contains water, the water is present at
  • the organic solvent can be present up to or equal to 90 -c weight percent of the cleaning composition.
  • the present invention includes an improved method of cleaning a stain from a surface or
  • ,.,-• fabric characterized by contacting the stain with a cleaning composition characterized by a pH independent ionizable polymer and a nonionic surfactant.
  • a cleaning composition characterized by a pH independent ionizable polymer and a nonionic surfactant.
  • the nonionic surfactant and pH independent ionizable polymer are present in a weight ratio range of
  • the present invention also includes an improved method of cleaning a stain from a surface or fabric characterized by contacting the stain with a cleaning composition characterized by a pH independent ionizable polymer and a solvent or mixture of solvents.
  • the present invention also includes an improved method of cleaning a stain from a surface or fabric which is characterized by contacting the stain with a cleaning composition characterized by a pH independent ionizable polymer, a nonionic surfactant and a solvent or mixture of solvent(s).
  • a cleaning composition characterized by a pH independent ionizable polymer, a nonionic surfactant and a solvent or mixture of solvent(s).
  • the solvent or solvent mixture contains water
  • the water is present at equal to or less than 60 more preferably less than 40 weight percent of the cleaning composition
  • the solvent or solvent mixture contains organic solvent
  • the organic solvent can be present up to or equal to 90 weight percent of the cleaning composition.
  • the present invention also includes an improved method of pretreating a stain on a surface such as a fabric characterized by contacting the stain with the cleaning composition and washing the surface in water or aqueous solution.
  • the present invention also includes a method of cleaning a stain from a surface or fabric which comprises contacting the stain with a composition characterized by a pH independent ionizable polymer containing a nonionic hydrophobic monomer, a nonionic surfactant and a solvent which comprises greater than 10 weight percent of the composition.
  • the present invention also includes a method of cleaning a stain from a surface or fabric which comprises contacting the stain with a composition which comprises a pH independent ionizable polymer containing more than 60 weight percent of a nonionic hydrophobic monomer and a solvent.
  • the present invention also includes a method of cleaning a stain from a surface or fabric which comprises contacting the stain with a composition which comprises a pH independent ionizable polymer containing more than 40 weight percent of a nonionic
  • hydrophobic monomer 10 hydrophobic monomer, a nonionic surfactant, 0 to 10 weight percent of an organic solvent, and 0 to 25 weight percent of water.
  • the ionizable polymer is present at 1 to 40 weight percent based upon the total weight of the x r- ionizable polymer and the surfactant, and the weight percents of the solvent are based upon the weight of the composition.
  • the present invention also includes 0 a method of cleaning a stain from a surface or fabric which comprises contacting the stain with a composition which comprises a pH independent ionizable polymer containing more than 40 weight percent of a nonionic hydrophobic monomer and a nonionic surfactant.
  • the present invention also includes a method of pretreating a stain on a fabric comprises contacting the stain with a cleaning composition and washing the fabric in water or aqueous detergent 30 solution.
  • the cleaning composition comprises a pH independent ionizable polymer containing a nonionic hydrophobic monomer and a solvent wherein the organic solvent comprises greater than 10 weight percent of the composition.
  • the cleaning composition may comprise a pH independent ionizable polymer containing a nonionic hydrophobic monomer and a nonionic surfactant.
  • the present invention also includes a cleaning composition
  • a cleaning composition comprises a pH independent ionizable polymer containing a nonionic hydrophobic monomer, a nonionic surfactant, and a solvent.
  • the ionizable polymer is present at 1 to 40 weight percent based upon the total weight of the ionizable polymer and the surfactant, and the organic solvent comprises greater than 10 weight percent of the composition.
  • the present invention also includes a cleaning composition characterized by a pH independent ionizable polymer containing more than 40 weight percent of a nonionic hydrophobic monomer and a nonionic surfactant.
  • the general class of ionizable polymers useful in the cleaning compositions and methods of the present invention include the class of ionizable polymers represented by Formula I:
  • a and F are terminal groups and B,C,D, and E represent types of internally covalently bonded groups described herein below that can be covalently bound in any variety of sequences.
  • the subscripts b,c,d, and e are positive numbers that represent the mole fraction of the types of internally covalently bonded groups. Any one kind of internally covalently bonded group type car. occur in a greater number than any other kind of internally covalently bonded group type or not at all for example to impart a homopolymer. More than one kind of each type of any covalently bonded group can occur in any copolymer of this invention.
  • the copolymer may contain (Di), (D2)...(D ⁇ ) where n is a positive integer and the sum of the subscripts, b+c+d * ⁇ +d2 etc. is equal to one.
  • These internally covalently bonded groups may also occur in any polymer form.
  • they may be combined in the form of di-or tri-block or linear polymers, or in the form of branched polymers, or in the form of grafted polymers, or in the form of macromers (such as those taught by Yamashita, et al, J. Polymer Sci: Part A: Polymer Chemistry, Vol 27, 1099-114 (1989)) or in the form of blends of one or more polymers, or in the form of core/shell structures such as those taught in United States Patent No. 4,427,819.
  • the ionizable polymer typically has a number average molecular weight from 1500 to 10,000,000; preferably from 5000 to 4,000,000.
  • One class of ionizable polymers represented by Formula I is prepared by free radical polymerization of ethylenically unsaturated monomers wherein B, C, D, and E in Formula I, are selected from ethylenically unsaturated monomers described below and A and F represent chain initiator or terminating groups.
  • Ethylenically unsaturated monomers representative of B in Formula I contain at least one ionizable group that upon ionization is not sensitive to the pH of the medium.
  • examples of such monomers include, but are not limited to, acrylic or methacrylic esters of alkyl or aryl sulfonates, such as 2- sulfoethylmethacrylate and sulfopropyl methacrylate; acrylamido alkyl or aryl sulfonates. such as acrylamido- 2-methylpropanesulfonic acid; sulfonated aromatic monomers, such as styrene sulfonic acid or vinyl sulfonic acid; and the like.
  • the salts of these monomers may also be useful.
  • the value of b may vary from 0 to 1.0 with the restriction that either monomer B or C must be present in a quantity such that final charge to mass of the ionizable polymer will be at least 0.1 meq/g. If the ionizable polymer is part of a blend of polymers or a core/shell structure, the final charge of the mass of the blend or core/shell structure
  • Ethylenically unsaturated monomers representative of C in Formula I contain at least one ionizable group that upon ionization is sensitive to the
  • Such monomers include, but are not limited to, monocarboxylate containing monomers, such as acrylic acid and methacrylic acid; dicarboxylate containing monomers, such as itaconic acid, maleic anhydride; and the like.
  • monocarboxylate containing monomers such as acrylic acid and methacrylic acid
  • dicarboxylate containing monomers such as itaconic acid, maleic anhydride
  • These monomer 0 units can either be added as monomers or can be formed during the polymerization process by the hydrolysis of various esters of these monomers, or their polymers.
  • the value of c may vary from 0 to 1.0 with the restriction that either monomer B or C must be present 5 in a quantity such that final charge to mass of the ionizable polymer will be at least 0.1 meq/g. If the ionizable polymer is part of a blend of polymers or a core/shell structure, the final charge of the mass of 0 the blend or core/shell structure will be at least
  • Ethylenically unsaturated monomers representative of D -in Formula I do not contain any ionizable groups and are characterized by having nonionic. hydrophobic units.
  • hydrophobic unit or group is taken to mean those monomers, which when in the form of an amorphous homopolymer, would have a solubility in water of less than 0.1 wt% at 20°C.
  • Examples of such monomer include, but are not limited to acrylic and methacrylic acid alkyl and aryl esters, such as methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate, n-butylmethacrylate, t- butylmethacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, phenyl methacrylate, etc; aromatic monomers such as styrene, vinyl toluene, t-butyl styrene, etc; alkyl and aryl esters of dicarboxylate containing monomers, such as itaconic acid, maleic anhydride; ⁇ -olefin(s); and the like.
  • the minimum value of d is zero. The maximum value of d will depend on the formula weight of the monomers chosen and will be such that at least 0.1 meq of ionizable charge per gram of final polymer will
  • Ethylenically unsaturated monomers representative of E in Formula I do not contain any ionizable groups and are characterized by having some water solubility or amphiphilic character.
  • examples of such monomers include, but are not limited to, acrylic and methacrylic acid alkyl and arylesters of groups that confer water solubility, such as 2-hydroxyethylacrylate, 2-hydroxyethylmethacrylate, or that are surfactants, such as nonylphenyl polyoxyethylene [10] methacrylate; or acrylamide; and the like.
  • Other examples of such monomers are monomers that are cationic by nature. These can either be sensitive to pH such as the N,N- dimethylaminoethyl methacrylate, or insensitive to pH.
  • cationic or potentially cationic monomers such as N,N,N-trimethylaminoethyl methacrylate/dimethyl sulfate (Sipomer ® Q5. Alcoiac): and the like.
  • the mole fraction of this monomer will be less than that of the anionic or potentially anionic monomers B and C, respectively.
  • the minimum value of e is zero.
  • the maximum value of e will depend on the formula weight of the monomers chosen and will be chosen such that at least 0.1 meq of ionizable charge per gram of final polymer will be present.
  • the ionizable polymer is not chosen from polyalkylene glycol monoacrylate, (such as polyethylene glycol monomethacrylate) , polyalkylene glycol alkyl or aryl ether monoacrylate in the molecular
  • -j- weight range of 2,000 to 200,000 when to be used in combination with an acrylamido sulfonic acid (such as 2- acylamido-2-methyl propane sulfonic acid) at a concentration of greater than 5 preferably 10 weight, more preferably 20 percent based on the total weight of 0 the composition.
  • an acrylamido sulfonic acid such as 2- acylamido-2-methyl propane sulfonic acid
  • the optimal monomers to prepare the ionizable polymer are chosen to effectuate compatibility of the cleaning compositions with the stains and surfaces from 5 which the stain is to be removed. Selection can be made on the basis of a typical formulation scheme employing, e.g., known solubility parameters.
  • Compositions according to the present invention 0 may employ mixtures of two or more polymers. Such mixtures will contain at least one ionizable polymer and may contain one or more unionizable polymers.
  • the unionizable polymer may be formed from the hydrophilic and hydrophobic monomer combinations described previously, but will be predominantly hydrophobic in character.
  • Vinyl epoxides such as glycidyl methacrylate and allyl glycidyl ether may be copolymerized with the hydrophilic and hydrophobic monomers to form the hydrophobic polymer.
  • Such hydrophobic polymers however, may be formed with or without a vinyl epoxide.
  • the ionizable polymer and nonionic surfactant are selected to compatibilize the nonionic hydrophobic polymer.
  • polymers that have been made independently can be combined in a medium that will dissolve both of the polymers or other appropriate conditions that will give a uniform mixture.
  • These mixtures could also be formed by polymerizing monomers in the presence of an already formed ionizable polymer to form what is hereinafter referred to as an interpolymer.
  • interpolymer These polymerizations could take place in a solvent for both the ionizable polymer and the resulting interpolymer or they could take place in a manner that would lead to the formation of a latex stabilized by the ionizable polymer in water hereinafter referred to as a polymeric colloid.
  • These interpolymers may be chemically bound (grafted) to the original polymer.
  • compositions according to the present invention may include a nonionic surfactant.
  • the nonionic surfactant and ionizable polymer are present in a weight ratio range of 1000:1 to 1:4 respectively. More preferably, the ratio of nonionic surfactant and ionizable polymer will be 200:1 to 1:1. Most preferably, the ratio of nonionic surfactant and ionizable polymer will be 100:1 to 1.5:1.
  • Nonionic surfactants suitable for inclusion in the present cleaning compositions and methods are chosen to impart compatibility between the cleaning composition, the stain and the surface from which the stain is to be removed.
  • the nonionic surfactant is chosen to impart compatibility of the formulation with the stain and the surface from which the stain is to be removed.
  • the nonionic surfactants and methods include but are not limited to ethylene oxide adducts of alcohols, alkylphenols, fatty acids, fatty acid amides, and fatty acid esters.
  • the surfactant may be monomeric or polymeric.
  • Suitable nonionic surfactants include those taught in The Encyclopedia of Chemical Technology 3rd Ed., Vol. 22, pp. 360-377, which is incorporated herein by reference.
  • Preferred surfactants are ethylene oxide adducts of alcohols and alkyl phenols.
  • Preferred nonionic surfactants selected for inclusion in compositions containing an ionizable polymer will preferably have a hydrophilie-lipophilic balance (HLB) value in the range of from 8 to 15 and more preferably 8 to 13- most preferably 9 to 13.
  • HLB hydrophilie-lipophilic balance
  • the preferred nonionic surfactant is water-immiscible, water-insoluble or water-dispersible at room temperature.
  • Nonionic surfactants selected for inclusion in a composition containing an ionizable polymer which has charge density of greater than 2 meq/g may require a nonionic surfactant that is more hydrophobic (ones with a lower HLB).
  • Compositions and methods according to the present invention may further include a conventional anionic or amphoteric surfactant, including hydrotropes, with or without the above-described nonionic surfactant(s) .
  • Suitable anionic surfactants include. but are not limited to linear alkylbenzene sulfonates, alpha olefin sulfonates, alkyl sulfonates, alkyl ether sulfates, alkyl sulfosuccinates, and sulfonate derivatives of nonionic surfactants.
  • Suitable anionic surfactants include those taught in The Encyclopedia of Chemical Technology 3rd Ed., Vol. 22, pp. 347-360, which is incorporated herein by reference.
  • Preferred anionic surfactants are alkylbenzene sulfonates, and a most preferred one is dodecyl benzene sulfonic acid and para- toluene sulfonic acid and the like.
  • compositions according to the present invention may take the form of a liquid, emulsion, dispersion or solution, semi-solid, or a soft solid or stick.
  • Solid stick compositions may be formed by dispersing the various disclosed compositions into a semi-hard carrier medium. Solid stick prespotting and stain removing compositions and methods for making and using are seen in United States 4,842,762, United States 4,396,521, and United States 3,664,962, all of which are incorporated herein by reference.
  • An example of a semi-hard carrier medium is stearic acid.
  • Cleaning compositions of the present invention may contain one or more solvents.
  • water is a desirable solvent. If the solvent or solvent mixture contains water, the water is present at equal to or less than 60 preferably less than 40 weight percent of the cleaning composition, if the solvent or solvent mixture contains organic solvent(s). the organic solvent(s) can be present up to or equal to 90 weight percent of the cleaning composition.
  • the compositions will preferably incorporate an organic solvent such as d-limonene to provide greater hydrophobicity.
  • the composition may comprise greater than 10 weight percent organic solvent based upon the weight of the composition. The use of two or more different organic solvents may be efficacious in providing enhanced cleaning over that of the use of one organic solvent.
  • Preferred organic solvents include terpenes such as d-limonene, nonodorous petroleum distillates, diols, and etherated diols such as dipropylene glycol monomethyl ether as well as methyl laurate, cotton seed oil, dodecyl benzene, dibasic
  • the nonionic surfactant is not considered an organic solvent because of its surface activity.
  • compositions according to the present invention may be formed with a nonionic surfactant in lieu of or in combination with an organic solvent.
  • a nonionic surfactant in lieu of or in combination with an organic solvent, the composition will preferably comprise greater than 10 weight percent 0 nonionic surfactant.
  • a specific class of ionizable polymers of the present invention include pH independent ionizable polymers. 5
  • pH independent ionizable polymers useful in the cleaning compositions and methods of the present invention can include some of the cationic ionizable backbone polymers described in United States Patents 0 4,337,185 and the anionic ionizable backbone polymers described in 4,427,819. both of which are incorporated herein by reference.
  • the pH independent ionizable polymers may contain both pH dependent and independent groups, but are preferably pH independent in overall character. That is, the mole fraction of all B monomers of Formula I minus the mole fractions of all cationic E monomers must be greater than the mole fraction of all the C monomers.
  • Such pH independent ionizable polymers preferably have monomeric hydrophobic units and/or side- chain forming hydrophobic units, thus, forming a polymer with surface activity.
  • the pH independent ionizable polymer preferably has a net anionic charge upon ionization, and is selected to optimize stabilization of nonionic hydrophobic mixtures of monomerics, polymerics and particulates in water.
  • Such ionizable polymer comprises a combination of pH independent anionic monomers and nonionic monomers, for example groups B and D in Formula I herein above.
  • Preferred anionic monomers include sulfonated monomers such as 2-sulfoethyl methacrylate (2-SEM), styrene sulfonic acid, 2-acrylamido-2-methyl propane sulfonic acid (AMPS ® ) , and ethylene sulfonic acid.
  • such ionizable polymer comprises combinations of anionic monomers and nonionic hydrophobic and hydrophilic monomers.
  • Such ionizable polymers may include pH dependent ionizable monomers such as carboxylated monomers, for example from group C in Formula I, but will contain a greater proportion of pH independent ionizable monomers such that the pH independent character of the polymer is maintained. That is, the mole fraction of all B monomers of Formula I minus the mole fractions of all cationic E monomers must be greater than the mole fraction of all the C monomers.
  • such ionizable polymer is further formed by the copolymerization of ethylenically unsaturated monomers.
  • such ionizable polymers comprise greater than 40, more preferably greater than 60, and most preferably greater than 70 weight percent hydrophobic monomer.
  • the pH independent ionizable polymer may have a charge density up to 10.
  • the pH independent ionizable 5 polymer preferably has a charge density of between 0.1 to 5.0 and more preferably 0.15 to 2.0 milliequivalents per gram.
  • the pH independent ionizable polymer may have a
  • the pH independent ionizable polymer is preferably between 2000 to 400,000 weight average molecular weight, more preferably from 5000 to 50,000 weight average molecular weight.
  • Nonionic, hydrophobic units suitable for incorporation and copolymerization into the pH independent ionizable polymer include those derived from any copolymerizable ethylenically unsaturated monomer
  • Nonionic hydrophobic units include, but are not limited to styrene, t-butyi styrene, vinyl p r- toluene, methyl methacrylate, n-butyl methacrylate. lauryl methacrylate and 2-ethylhexyl acrylate.
  • pH independent ionizable polymer backbone examples include those derived from ethylenically unsaturated monomers that contain various hydrophobe containing side chains and are represented by group E in Formula I. These monomers can be described by the formula:
  • H 2 C C-ZWR ' where R is either H or -CH ; Z is a suitable linking
  • W is a
  • -C-0- hydrophilic extending group such as a - CH2CH2-0- ⁇ * n , with n typically less than 100 and preferably no more than 40; and R' is the hydrophobic group, such as •> -C 12 H 25
  • monomers of this type are behenyl poly (oxyethylene)[25] methacrylate and nonylphenoxy poly(oxyethylene)[10]methacrylate.
  • Nonionic, hydrophobic monomers useful in the copolymerization of pH independent ionizable polymers include but are not limited to styrenics, acrylates, methacrylates, isoprene, butadiene, ethylene, vinyl chloride, and vinylidene chloride.
  • styrenics acrylates, methacrylates, isoprene, butadiene, ethylene, vinyl chloride, and vinylidene chloride.
  • Preferred nonionic hydrophilic monomers are those which form water-swellable or water compatible homopolymers.
  • Low concentrations of monomers with weak acid (Group C in Formula I) or weak base groups (Group E in Formula I) and salts thereof may also be used provided that the pH independence of the ionizable polymer 5 backbone is maintained, e.g., a minor amount of a vinyl monomer such as acrylic acid or aminoethyl methacrylate (or the hydrochloride salt thereof) could be included to promote adhesion, serve as reactive sites and the like.
  • Q Compositions according to the pH independent ionizable polymer may employ mixtures of two or more polymers as similarly described herein above for ionizable polymers.
  • compositions according to the present invention utilizing a pH independent ionizable polymer may include a nonionic surfactant as described herein above for ionizable polymers.
  • the nonionic surfactant is present in such an amount that the ionizable polymer is preferably from about 1 to about 40, more preferably from about 20 to about 30, and most preferably about 25 weight percent based upon the total weight of the ionizable polymer and the nonionic cosurfactant.
  • Compositions and methods according to the present invention utilizing a pH independent ionizable polymer may further include a conventional anionic or amphoteric surfactant as discussed herein above.
  • compositions according to the present invention utilizing a pH independent ionizable polymer may take the form of a liquid, emulsion, dispersion or solution, semi-solid, or a soft solid or stick as discussed herein above.
  • Cleaning compositions of the present invention utilizing pH independent polymers may contain one or more solvents as discussed herein above.
  • the compositions will preferably comprise up to about 40, more preferably about 25 or less, and most preferably about 15 or less weight percent water based upon the weight of the composition.
  • compositions according to the present invention utilizing pH independent polymers as variously taught herein may be formed with a nonionic surfactant in lieu of or in combination with an organic solvent as herein described above.
  • Methods for cleaning a stain on a surface or fabric are characterized by contacting the stain with any of the cleaning compositions of the present invention described herein above. Contacting the stain with the cleaning composition may mean contacting the area of the surface or fabric where the stain resides in addition to directly upon the stain itself.
  • stain includes any substance which is embedded or not embedded, solid or liquid, wet or dry, and at or beneath the surface or fabric, and is not to be construed as limiting.
  • the stain may be removed by wiping with a substrate such as a wet cloth or sponge, or by contacting the stain with water such as by washing with a substantially aqueous media.
  • a substrate such as a wet cloth or sponge
  • the composition-treated stain is preferably laundered with water and more preferably with an aqueous solution of mostly water and a conventional laundry detergent.
  • a cleaning composition offering superior cleaning in accordance with the present invention without the inclusion of prior art sequestering or chelating agents such as EDTA, phosphates, nitriloacetates, and aminopolycarboxylic acids.
  • prior art agents such as EDTA, phosphates, nitriloacetates, and aminopolycarboxylic acids.
  • inclusion of such prior art agents may however, be appropriate in use as a cosequestrant, as a sequestrant for substances not efficiently sequestrable by the present compositions, or as an agent for some other purpose.
  • compositions and methods according to the present invention may be utilized effectively to clean soils and oily stains such as motor oil. cooking oil. bacon grease and mayonnaise and oily particulate stains such as lipstick and liquid makeup. Such compositions and methods may also be effectively utilized on oily stains having particulates of carbon or dirt such as dirty motor or diesel oil. Such compositions and methods may also be utilized effectively to clean stains of lesser hydrophobicity than oil and grease such as grass, blood, and carbohydrates such as starch on surfaces and fabrics. 0 Compositions and methods according to the present invention may be effectively utilized in laundry pretreating, stain removing, industrial and household degreasing, metal cleaning, paint stripping, and general -- purpose industrial and household cleaning.
  • test the cleaning effectiveness of various test compositions comprising an ionizable polymer with and without hydrophobic polymer, - and/or nonionic surfactants as a pretreat stain remover on fabric using varying conditions in a subsequent laundry cycle.
  • Various types of ionizable polymers, hydrophobic polymers, and nonionic surfactants are utilized.
  • Fabrics utilized in the following examples include 100 percent polyester, a 65/35 percent polyester-cotton (polycotton) blend, and 100 percent cotton. Prior to staining, the fabrics are laundered three times with a commercial laundry detergent to remove any finish applied to the fabric at the manufacturer. The fabrics are cut into ' 3X4 inch swatches, and stained with 7 drops (about 0.2 grams) of dirty motor oil. The oil is obtained from a diesel engine crankcase. The oil contains particulate carbon and dirt. The stain is allowed to sit overnight.
  • each of the test compositions is placed in the form of a thin layer on the stain.
  • the swatches are placed in a Terg-0-TometerTM United States Testing Company Model 7243S for about 15 minutes (unless otherwise specified) at 100 rpm.
  • the swatches are laundered with an aqueous solution of a heavy duty commercial laundry detergent (hereinafter referred to in the Examples as "detergent") or with water only.
  • the temperature of laundering is around 50°C unless otherwise indicated.
  • the water is tap water from the City of Midland, Michigan or deionized water unless otherwise indicated. Where detergent solution is utilized, the detergent concentration is about 1.0 gm/liter of water.
  • the swatches were analyzed along with unstained swatches on a Hunter Labscan 45°/0° D25-PC2 Colorimeter of Hunter Associates Laboratory, Inc. using the CIE 1931 standard source illuminant C.
  • CIE 1931 standard source illuminant C Alternatively on a MiniScanTM Spectrocolorimeter version MS450CL with a 45°/0° geometry and large viewing area option using the CIE XYZ Scale, CIE 1931 2° standard observer and CIE 1931 standard source illuminant C.
  • the Labscan is first calibrated using a black tile and then a white tile.
  • the swatches are read with an oval template which has axes of lengths of 35 mm and 45 mm to reduce the area analyzed to a uniform shape.
  • the MiniScan is first calibrated using a factory issued white tile; the black standard is internal. The swatches are read by setting the one inch diameter
  • An ionizable copolymer comprising 97.6 percent MMA, 2.4 percent 2-SEM (2-sulfoethyl methacrylate) by weight is prepared according to the following procedure.
  • the 2-SEM will provide a charge of 0.125 meq/g of this polymer.
  • the polymerization is achieved by adding 133•33 parts of methyl ethyl ketone (MEK) to a stirred
  • the final product is a clear amber solution.
  • a test composition is prepared by adding 3 parts of NIS-5 (nonionic surfactant with an average of 5 ethylene
  • An ionizable copolymer comprising 90.5 percent MMA, 9.5 percent 2-SEM by weight is prepared according to the procedure above. The 2-SEM will provide a charge of 0.488 meq/g of this polymer.
  • a test composition is formed from the same charged polymer and NIS-5 according 0 to the procedure above. Solids content is determined to be 98.0 percent. Stained fabrics utilizing the test composition are laundered at 50°C for 15 minutes as indicated with the detergent solution. Percent cleaning on cotton is 85.0, and percent cleaning on polycotton is 66.2.
  • An ionizable copolymer is prepared by free radical polymerization of 82.4 percent MMA, and 17.6 acrylamido-2-methylpropanesulfonic acid (AMPS ® ) by weight similarly to Example 1A except 33 grams of water is added to each of the MEK or MEK solutions.
  • the AMPS ® will provide a charge of 0.851 meq/g of this polymer.
  • a test composition if formed from the same charged polymer and NIS-5 according to the procedure of Example 1A. Solids content is determined to be 99 percent. Stained fabrics utilizing the test composition are laundered at 50°C for 15 minutes as indicated with the detergent solution. Percent cleaning on cotton is 53.0, and percent cleaning on polycotton is 36.0.
  • test compositions indicated in the following Tables are laundered at 50°C for 15 minutes as indicated with the water and/or detergent solution. These test compositions are 0 prepared by combining the indicated ionizable copolymers and NIS-5 in an amount required to give the weight percent solids of the ionizable polymer based on the ionizable copolymer plus NIS-5 shown in the Tables. In J - some cases the ionizable copolymers are added to the
  • NIS-5 in the form of a solution in some solvent, such as chloroform, or methyl ethyl ketone, or water.
  • solvents are removed by rotoevaporation at 50°C under at least 29 inches of vacuum for two hours.
  • water is initially present in the formulations they are additionally heated at 8 ⁇ °C for one hour to assure removal of the water.
  • the resulting percent cleaning on cotton and on polycotton are given in the Tables indicated that a wide variety of ionizable homopolymers and copolymers are capable of providing improved cleaning of fabrics. These include:
  • Poly(Acrylic Acid) with weight average molecular weight between 1800 and 4,000,000 and concentrations between 0.5 and 50 wt%.
  • Poly(Acrylic Acid) mixture with sulfonic acid (either dodecylbenzene sulfonic acid or toluene sulfonic acid monohydrate) with a polymer weight average molecular weight between 1800 and 450,000 and concentrations between 0.5 wt% and 17 wt% and sulfonic acid concentrations between 1.5 and 50 wt*.
  • Miscellaneous polymers with concentrations from 4.4 to 24.3 tjt including methyl cellulose (M0C), chondroitin sulfate, dextran sulfate, sulfoethyl cellulose, and polymethacrylic acid).
  • AD Aqueous Detergent
  • ⁇ n DBS dodecylbenzene sulfonic acid.
  • MOC 15 methyl cellulose with 2% aqueous solution having a viscosity of 15 centipoise. 5
  • MOC 25 methyl cellulose with 2% aqueous solution having a viscosity of 25 centipoise.
  • MOC 400 methyl cellulose with 2% aqueous solution 0 having a viscosity of 400 centipoise.
  • Sulfonated poly(styrene) 6500 was c converted from the sodium to hydrogen ion form by passing an aqueous solution through DOWEX 50W strong acid ion exchange resin.
  • a charged polymer comprising 82.0 percent MMA and 18.0 percent 2-SEM by weight is prepared according to the procedure of Example 1A.
  • the 2-SEM will provide a charge of 0.925 meq/g of the copolymer.
  • a test composition is formed from the same charged polymer and a variety of nonylphenol ethoxylate (Igepal' E nonionic surfactants from GAF Chemicals and Tergitol' 1 surfactants from Union Carbide) and alcohol ethoxylate nonionic surfactants (Neodol ® nonionic surfactants from Shell) according to the procedure of Example 1A. Stained fabrics utilizing the test compositions are laundered at 50°C for 15 minutes as indicated with the detergent solution.
  • Percent cleaning on cotton and percent cleaning on polycotton are given in Table V. These data show that good cleaning can be obtained with both the nonylphenol ethoxylates (e.g., Igepal ® C0-520) and the linear alcohol ethoxylates (e.g., Neodol ® 23.5). These data also show that the cleaning for a given formulation will depend on the HLB of the nonionic surfactant used in the formulation.
  • the nonionic surfactant blends in Table V were prepared by combining various ratios of other Neodol ® surfactants.
  • Blend 1 contains 77 percent of Neodol ® 25-3 and 23 percent of Neodol ® 25-9
  • blend 2 contains 50 percent of Neodol ® 23-3 and 50 percent of Neodol ® 23-6.5
  • blend 3 contains 32 percent of Neodol ® 25-3 and 68 percent of Neodol ® 25-9.
  • An ionizable polymer is prepared by adding 920 parts of deionized water and 1167 parts of isopropanol to a stirred reactor provided with a nitrogen atmosphere and maintained at 50°C while continuously adding reactants from five separate sources with proportionate feeds over 120 minutes and the resulting polymerization is allowed to continue for an additional 2 hours.
  • Feed compositions are as follows:
  • the devolatilized polymers solution measures 17.8 0 percent solids and 2.4 meq of strong and weak acid per gram of polymer solids.
  • Example 1E The solution of Example 1E is used as the water based stabilizer for the emulsion polymerization of hydrophobic monomers styrene and 2-ethylhexyl acrylate. 225 parts of each of the monomers were added to 2,528 parts of the water based stabilizer (450 parts ionizable 0 copolymer) and diluted with 526 parts deionized water. This mixture is heated to and maintained at about 50°C under a nitrogen atmosphere while adding proportionately from separate feed systems of 0.90 parts t-butyl hydroperoxide in 48 parts of water and 0.68 parts sodium formaldehyde sulfoxylate in 48 parts water over about 30 minutes. After completing the additions, heating is continued for another 2 hours. An aliquot reveals (a)
  • Example 1G Preparation of a Composition of an Ionizable Polymer Colloid and Nonionic Surfactants
  • Example 1F The final liquid-solid mixture of Example 1F is blended with nonionic surfactants in a quantity to produce test compositions comprising 75 parts by weight nonionic surfactant to 25 parts of the polymeric colloid.
  • the water content is reduced to about 5 percent by vacuum distillation at 80°C.
  • the nonionic surfactants used are either nonyl phenol with 5 moles of ethylene oxide adduct (NIS-5) or a 14 to 15 carbon alcohol with 7 moles of ethylene oxide adduct (45-7).
  • Example 1G are laundered in detergent solution for 15 minutes at 50°C. Percent cleaning on cotton for the combinations with NIS-5 and 45-7 is 82 and 70 respectively. Percent cleaning on polycotton with the
  • Example 1Ha Preparation of Compositions of an Ionizable Detergent Polymer and Nonionic Surfactants
  • nonionic surfactant 20 parts by weight of nonionic surfactant and 25 parts polymer solids.
  • the water content is reduced to about 5 percent by vacuum distillation at 80°C.
  • the nonionic surfactants are nonyl phenol with 4 or 5 or 6 ethylene oxide adducts or Neodol ® 45-7 (product by Shell Chemical
  • nonyl phenol surfactants are designated NIS-4, NIS-5 or NIS-6 based on the respective levels of ethylene oxide, and the 14 to 15 carbon alcohol with 7 moles ethylene oxide adduct
  • the resulting polymeric solids are about 50 percent QR-1265 charged polymer and about 25 percent styrene and 25 x r- percent 2-ethylhexyl acrylate.
  • Example IHd Preparation of a Ionizable .Colloid and Nonionic Surfactants
  • Example 1Hc 0 hydrophobic modification of water soluble detergent polymer blended with different nonionic surfactants in a quantity for testing 75 parts by weight of nonionic surfactant and 25 parts polymer solids.
  • the water r content is reduced to about 5 percent by vacuum distillation at 80°C.
  • the nonionic surfactants are nonyl phenol with 5 ethylene oxide adducts or Neodol ® 45-7 (product from Shell Chemical Company) depending on example.
  • the nonyl phenol 5 moles ethylene oxide 0 surfactant is designated as NIS-5 and the 14 to 15 carbon alcohol with 7 moles ethylene oxide as 45-7.
  • Example 1He Example 1He :
  • Example d Stained fabrics utilizing test compositions of Example d are laundered in detergent solution for 15 minutes at 50°C. Percent cleaning on cotton for the combinations with NIS-5 and 45-7 is 62 and 75. Percent cleaning on polycotton with the same order of nonionic combinations is 39 and 38.
  • Example 2A Preparation of a pH Independent Ionizable Polymer
  • An ionizable polymer is prepared by adding 1000 parts of isopropanol and 650 parts of deionized water to a stirred reactor provided with a nitrogen atmosphere and maintained at 50°C while continuously adding reactants from five separate sources with proportionate feeds over 120 minutes and the resulting polymerization is allowed to continue for an additional 2 hours.
  • Feed compositions are as follows:
  • DMAEMA Dimethylaminoethy1 methacrylate
  • Example 2B Preparation of a Solution of an Ionizable Polymer and Glycidyl Methacrylate
  • Example 2B The solution formed in Example 2B is added to 2500 parts deionized water followed by devolatilization of 1700 parts.
  • the devolatized solution of ionizable polymer is mixed with 56.3 parts of glycidyl j- methacrylate (GMA) while heating for two hours at 50°C.
  • the solution of ionizable polymer and glycidyl methacrylate has a solids content of 22.1 percent, a specific gravity of 1.05 g/cc at 25°C, pH of about 2, and a viscosity of 15 cp at 25°C.
  • the ionizable polymer 0 has a total acid content of about 1.9 meq/g and an average molecular weight of less than 40,000.
  • Example 3B Preparation of Hydrophobic Copolymers
  • Example 2B The solution of Example 2B is used as the water based stabilizer for the emulsion polymerization of hydrophobic copolymers.
  • Hydrophobic styrene/2-ethyl hexyl acrylate copolymers are prepared by copolymerization in the presence a portion of the ionizable polymer-glycidyl methacrylate solution.
  • 100 parts each of styrene (S) and of 2-ethyl hexyl acrylate (2-EHA) are stirred together in an aqueous solution of 1448 parts of deionized water, 10 parts of isopropanol and 909 parts of the ionizable polymer-glycidyl methacrylate solution of Example 2B (22 percent solids by material balance).
  • This mixture is heated to and maintained at 50°C under a nitrogen atmosphere while adding proportionately from separate feed systems of 0.40 part t-butyl hydroperoxide in 50 parts of water and 0.30 parts sodium formaldehyde sulfoxylate in 50 parts water over about 30 minutes. After completing the additions, heating is continued for another 3 hours.
  • An aliquot reveals (a) a 15 percent solids content indicating the reaction to be complete, (b) approximately a 0.9 milliequivalent total acid content per gram solids and (c) a very small particle size, about 450 Angstroms as indicated by its translucent, bluish appearance.
  • the resulting polymeric solids are about 50 weight percent of MMA/2-SEM/DMAEMA ionizable polymer and about 50 weight percent of GMA/S/2-EHA hydrophobic polymer.
  • Example 4B Preparation of a Composition of an Ionizable Polymer and Nonionic Surfactant
  • Example 3B The final liquid-solids mixture of Example 3B is blended with a nonionic surfactant in a quantity sufficient to produce test compositions comprising 75 parts by weight of a nonionic surfactant to 25 parts of the ionizable polymer system.
  • the water content is lowered by vacuum distillation at 80°C to about 5 percent.
  • the nonionic surfactant is a nonyl phenol with 5 or 9 ethylene oxide adducts depending upon the example.
  • the nonionic surfactant with an average of 5 ethylene oxide adducts is designated as NIS-5, and the one with 9 as NIS-9.
  • the following examples test the cleaning effectiveness of various test compositions of the ionizable polymer with and without hydrophobic polymer, and/or nonionic surfactants as a pretreat stain remover on fabric using varying conditions in a subsequent laundry cycle.
  • Various types of ionizable polymers, hydrophobic polymers, and nonionic surfactants are utilized.
  • Example 5B Stained fabrics not utilizing a test composition (control) are laundered in the detergent solution for 15 minutes at 50°C. Percent cleaning on cotton is 32, and percent cleaning on polycotton is 12, Fabrics of the same manufacture were used in Examples 5B-9B.
  • Example 5B Stained fabrics not utilizing a test composition (control) are laundered in the detergent solution for 15 minutes at 50°C. Percent cleaning on cotton is 32, and percent cleaning on polycotton is 12, Fabrics of the same manufacture were used in Examples 5B-9B.
  • Example 5B Stained fabrics not utilizing a test composition (control) are laundered in the detergent solution for 15 minutes at 50°C. Percent cleaning on cotton is 32, and percent cleaning on polycotton is 12, Fabrics of the same manufacture were used in Examples 5B-9B.
  • Example 5B Stained fabrics not utilizing a test composition (control) are laundered in the detergent solution for 15 minutes at 50°C. Percent cleaning on cotton is 32, and percent cleaning on polycotton is 12, Fabrics of the same manufacture were
  • Example 4B having NIS-5 Stained fabrics utilizing the test composition of Example 4B having NIS-5 are laundered as indicated with the detergent solution.
  • Percent cleaning on polyester is 86.8 at 8 minutes of laundering and 89.5 at 15 minutes of laundering.
  • Percent cleaning on polycotton is 29.0 at 8 minutes and 33• 1 at 15 minutes.
  • Percent cleaning of cotton is 47.9 at 8 minutes and 47.0 at 15 minutes.
  • Example 4B Stained fabrics utilizing the test compositi .o.n of Example 4B having NIS-9 are laundered as indicated with water only. Percent cleaning efficiency on polyester is 60.8 at 8 minutes of laundering and 67.6 at 15 minutes of laundering. Percent cleaning on polycotton is 17.4 at 8 minutes and 20.5 at 15 minutes. Percent cleaning on cotton is 30.0 at 8 minutes and 31.8 at 15 minutes.
  • Example 8B Stained fabrics utilizing the test composition of Example 4B having NIS-5 are laundered for 15 minutes as indicated with the detergent solution at various temperatures. Percent cleaning on cotton is 47.0, 39.6, and 36.9 at laundering temperatures of 50, 26.7, and 12.8°C respectively. Percent cleaning on polycotton is 20.5, 18.0, and 10.9 at laundering temperatures of 50, 26.7, and 12.8°C respectively.
  • Example 8B Stained fabrics utilizing the test composition of Example 4B having NIS-5 are laundered for 15 minutes as indicated with the detergent solution at various temperatures. Percent cleaning on cotton is 47.0, 39.6, and 36.9 at laundering temperatures of 50, 26.7, and 12.8°C respectively. Percent cleaning on polycotton is 20.5, 18.0, and 10.9 at laundering temperatures of 50, 26.7, and 12.8°C respectively.
  • Example 8B Stained fabrics utilizing the test composition of Example 4B having NIS-5 are laundered for 15 minutes as indicated with the detergent solution at various temperatures. Percent cleaning on cotton is 47.0, 39.6,
  • Percent cleaning on cotton is 31.8, 23.0, and
  • Example 4 having NIS-5 Stained fabrics utilizing the test composition of Example 4 having NIS-5 are laundered at 50°C for 15 minutes as indicated with hard water prepared by adding 15 300 ppm of a CaCO ⁇ /MgCO- ⁇ mixture (2/1 weight ratio) to tap water. Percent cleaning on cotton is 36.9, and percent cleaning on polycotton is 29.4.
  • An ionizable polymer comprising MMA/2- SEM/DMAEMA in weight proportions of 55.3/38.2/6.5 is prepared in accordance with Example 2B.
  • a hydrophobic copolymer comprising GMA/S/2-EHA in weight proportions pc - of 5.3/83.0/11.7 is polymerized in the presence of the ionizable polymer as in Example 3B.
  • the polymer mixture contains equal proportions by weight of the ionizable polymer and the hydrophobic copolymer.
  • the polymer mixture is blended with a nonionic surfactant, and
  • the test composition is prepared by adding to the polymer mixture a nonionic surfactant, Neodol ® 45-7 (marketed by The Shell Chemical Company), in a 3:1 ratio by weight based on the weight of the surfactant to the solid components of the polymer mixture to form a surfactant-polymer mixture.
  • a nonionic surfactant Neodol ® 45-7 (marketed by The Shell Chemical Company)
  • D-limonene and Isopar ® M (marketed by Exxon Corp.) are further added to the surfactant-polymer mixture as organic solvents.
  • the test composition comprises (surfactant-polymer)/d- limonene/Isopar ® M in weight proportions of 40/20/40.
  • Stained fabrics utilizing the test composition of Example 10B are laundered at 50°C for 15 minutes with a commercial laundry detergent. Percent cleaning on cotton is 100, and percent cleaning on polycotton is 92. When laundered at 50°C for 15 minutes with water, percent cleaning on cotton is 99.8, and percent cleaning on polycotton is 92.4.
  • Example 12B Preparation of an Ionizable Polymer and a Composition of Said Ionizable Polymer and a Nonionic Surfactant
  • An ionizable polymer with a weight average molecular weight of about 10,000 is prepared by free radical polymerization of methyl methacrylate (MMA) and 2- sulfoethyl methacrylate (2-SEM). It is polymerized by adding 133.33 parts of methyl ethyl ketone (MEK) to a stirred reactor provided with a nitrogen atmosphere, a condenser, and inlets for monomer and initiator addition. The reactor is purged with nitrogen and heated to 80°C by a constant temperature water bath. Two solutions are prepared for addition to this reaction flask: A solution of monomers is prepared by adding 23.26 parts of 2-SEM and 102.08 parts of MMA to 133-33
  • An initiator solution is prepared by adding 2.5 parts of VAZO ® 64 initiator (marketed by E. I. duPont deNemours & Co.) to 133-33 parts of MEK. These two solutions are added by syringe to the heated MEK in the reaction flask in 18 equal volumes once every
  • a test composition is prepared by adding 3 parts of NIS-5 to a copolymer solution containing 1 part of the copolymer. The MEK solvent is removed from this
  • Example 12B Stained fabrics utilizing the test composition of Example 12B are laundered at 50°C for 15 minutes as indicated with the detergent solution. Percent cleaning on cotton is 75.2, and percent cleaning on polycotton is 45.8.
  • MMA, 12 percent 2-SEM, and 10.5 percent lauryl methacrylate (LMA) by weight is prepared according to the procedure of Example 12B.
  • the 2-SEM will provide a charge of 0.948 meg/gram of this copolymer.
  • a test composition is formed from the same ionizable polymer and NIS-5 according to the procedure of Example 12B. Solids content is determined to be 98.1 percent. Stained fabrics utilizing the test composition are laundered at 50°C for 15 minutes as indicated with the detergent solution. Percent cleaning on cotton is 67.8, and percent cleaning on polycotton is 48.1.
  • MMA, 16.5 percent 2-SEM, and 9.7 percent nonylphenoxypoly([10] oxyethylene) methacrylate (NP10MA) by weight is prepared according to the procedure of Example 12B.
  • the 2-SEM will provide a charge of 0.933 meg/gram of this copolymer.
  • a test composition is formed from the same ionizable polymer and NIS-5 according to the procedure of Example 12B. Solids content is determined to be 99.6 percent. Stained fabrics utilizing the test composition are laundered at 50°C for 15 minutes as indicated with the detergent solution. Percent cleaning on cotton is 70, and percent cleaning on polycotton is 44.5.
  • An ionizable polymer comprising 91.0 percent styrene, 9.0 percent 2-SEM by weight is prepared according to the procedure of Example 12B.
  • the 2-SEM will provide a charge of 0.804 meg/gram of this copolymer.
  • a test composition is formed from the same ionizable polymer and NIS-5 according to the procedure of Example 12B. Solids content is determined to be 97.7 percent. Stained fabrics utilizing the test composition are laundered at 50°C for 15 minutes as indicated with the detergent solution. Percent cleaning on cotton is 58.7, and percent cleaning on polycotton is 47.6.
  • Example 12B An ionizable polymer comprising 89.5 percent methylmethacrylate, 10.5 percent 2-SEM by weight is prepared according to the procedure of Example 12B.
  • the 2-SEM will provide a charge of 0.956 meg/gram of this copolymer.
  • the test composition is formed by substituting the nonionic surfactant with Dowanol ® DPM (marketed by The Dow Chemical Company) brand dipropylene glycol monomethyl ether.
  • the Dowanol ® DPM comprises 75.1 percent by weight of the test composition. Stained fabrics utilizing the test composition are laundered at 50°C for 15 minutes as indicated with the detergent solution. Percent cleaning on cotton is 34.5, and percent cleaning on polycotton is 37.9.
  • Example 18B Example 18B
  • Example 17B The test composition of Example 17B is again utilized except that the fabrics are laundered with water only. Percent cleaning on cotton is 25.0, and percent cleaning on polycotton is 28.0.
  • a solid stick composition utilizing a test composition of the ionizable polymer composition of Example 3B and NIS-5, as made in Example 4B in the same 5 proportions, is formulated in a stick form in the following manner:
  • Example 20 The ionizable polymer MMA/2-SEM/DMAEMA and hydrophobic copolymer GMA/S/2-EHA of Example 3B is mixed with NIS-5 according to the method of Example 4B to form a first mixture.
  • the first mixture and d-Limonene were mixed together and heated to 60°C to form a second
  • Examples 20B-22B utilized the same fabrics as in Comparative Example 1B. Methodology is consistent with previous examples.
  • Example 19B Stained fabrics utilizing the test composition of Example 19B are laundered for 15 minutes at 50°C in water only. Percent cleaning on cotton is 67, and percent cleaning on polycotton is 53.
  • Example 19B Stained fabrics utilizing the test composition of Example 19B are laundered in detergent solution for 15 minutes at 50°C. Percent cleaning on cotton is 76 and percent cleaning on polycotton is 72.
  • Example 19B Stained fabrics utilizing the test composition of Example 19B are laundered in hard water for 15 minutes at 50°C.
  • the hard water prepared by adding 300 ppm of a CaCO*3/MgC ⁇ 3 mixture (2/1 weight ratio) to tap water. Percent cleaning on cotton is 77.8, and percent cleaning on polycotton is 65.0.
  • DMO DIESEL
  • Example 2B The solution of Example 2B is used as the water based ionic copolymer for surface modification of a hydrophobic rubber latex.
  • Preparation of the core-shell latex involves grafting the ionic copolymer of Example 2B with shell monomers of styrene plus methyl methacrylate onto a monodispersed sub-micron crosslinked rubber latex having an average particle diameter of 119 nm as measured by a Brice-Phoenix Universal Light Scattering Photometer.
  • the extent of crosslinking of the core rubber can be estimated from a determination of percent gel (90 percent non-extractable polymer) and swell index (15 s.i., measure of imbibition of solvent by test polymer).
  • a method for determining the present gel and swelling index is disclosed in United States Patent 4,146,589.
  • the rubber latex particles are styrene-butadiene copolymer (7 percent styrene, 93 percent butadiene) and stabilized by 3 percent sodium dodecylbenzene sulfonate soap (based on polymer).
  • the grafting procedure includes a two stage addition and temperature change.
  • Example 24B Preparation of Compositions of an Ionizable Polymer and Nonionic Surfactants
  • Example 23A The final liquid-solids colloid of Example 23A is blended individually with different nonionic surfactants in a quantity for testing comprising 75 parts by weight of nonionic surfactant and 25 parts polymer solids.
  • the water content is reduced to about 5 percent by vacuum distillation at 80°C.
  • the nonionic surfactants are nonyl phenol with 5 or 6 ethylene oxide adducts or Neodol ® 45-7 (product by Shell Chemical Company) depending on the example.
  • the nonionic surfactant with an average of 5 ethylene oxide adducts is designated as NIS-5, similarly NIS-6, and the 14 to 15 carbon alcohol with 7 moles ethylene oxide adduct as 45-7. Comparative Example:
  • Example 24B Stained fabrics utilizing test compositions of Example 24B are laundered in detergent solution for 15 minutes at 50°C. Percent cleaning on cotton for the combinations with NIS-5, NIS-6, and 45-7 is 47, 53, and 63 respectively. Percent cleaning on polycotton with the same order of nonionic combinations is 36, 49, and 54.
  • Example 24B Stained fabrics utilizing test compositions of Example 24B are laundered in water only for 15 minutes at 50°C. Percent cleaning on cotton for the combinations with NIS-5, NIS-6, and 45-7 is 29, 39, and 54 respectively. Percent cleaning on polycotton with the same order of nonionic combinations is 16, 36, and 54.
  • a copolymer comprising 33-6 percent by weight styrene (S), 61.0 percent by weight 2-ethylhexyl acrylate (EHA) and 5.4 per-cent by weight 2,3- dihydroxypropyl methacrylate (HPMA) is prepared according to the procedure of Example 12B.
  • a test composition if formed by combining 1 part of the copolymer prepared in this example with 3 parts of NIS-5. The MEK solvent is removed from this solution by rotoevaporation at 80 °C to obtain a mixture that has 98.3 percent solids. These solids consist of the nonionic surfactant and the hydrophobic, non- ionizable copolymer in a 3 to 1 weight ratio, respectively.
  • Stained fabrics utilizing the test composition are laundered at 50°C for 15 minutes as indicated with the detergent solution. Percent cleaning on cotton is 38.7, and percent cleaning on polycotton is 25.5
  • a test composition is formed by combining 0.5 parts of the hydrophobic, non-ionizable copolymer prepared in this example plus 0.5 parts of the polymer prepared in Example 12B and 3 parts of NIS-5.
  • the MEK solvent is removed from this solution by rotoevaporation at 80 °C to obtain a mixture that has 100 percent solids. These solids consist of the nonionic surfactant and the copolymer in a 3 to 1 weight ratio, respectively.
  • Stained fabrics utilizing the test composition are laundered at 50°C for 15 minutes as indicated with the detergent solution. Percent cleaning on cotton is 69.5, and percent cleaning on polycotton is 68.4.
  • a test composition is formed by combining 1 part of the copolymer prepared in Example 12B and 3 parts of NIS-5.
  • the MEK solvent is removed from this solution by rotoevaporation at 80 °C to obtain a mixture that has 100 percent solids.
  • These solids consist of the nonionic surfactant and the copolymer in a 3 to 1 weight ratio, respectively.
  • Stained fabrics utilizing the test composition are laundered at 50°C for 15 minutes as indicated with the detergent solution. Percent cleaning on cotton is 63.1, and percent cleaning on polycotton is 52.2.
  • This example illustrates that a hydrophobic, non-ionizable copolymer, such as that prepared in this example, will improve the cleaning performance of nonionic surfactants. It further illustrates that a blend of this hydrophobic non-ionizable copolymer with an ionizable copolymer improves the better cleaning performance of nonionic surfactants to an even greater extent than the hydrophobic, non-ionizable hydrophobic copolymer in combination with the nonionic surfactant.
  • the following illustration demonstrates the synergy of the nonionic surfactant and polymer interaction as a function of diluent concentration.
  • the graph shows the improved cleaning efficacy to occur when the water concentration is less than 80 weight percent of the total cleaning composition. Greater improvement in cleaning occurs at less than 60 percent water and continues to increase as the water concentration decreases to about 20 percent.
  • Curve represents mixtures of "A” with deionized water, plotting cleaning versus water content
  • Curve represents mixtures of "B” with deionized water, plotting cleaning versus water content

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Abstract

Des compositions de nettoyage utiles pour éliminer des taches d'huile et de graisse comprennent généralement un polymère ionisable et un agent tensio-actif non ionique et/ou des solvants. Notamment, on considère l'utilisation d'une classe spécifique de polymères ionisables, c'est-à-dire des polymères ionisables indépendants du pH associés à un agent tensio-actif non ionique et/ou à un solvant organique. Des procédés permettent de nettoyer des taches d'une surface ou d'un tissu par mise en contact de la surface ou du tissu avec ces diverses compositions de nettoyage. En outre, des procédés de prétraitement de taches de tissus impliquent la mise en contact de la tache avec la composition et le lavage du tissu dans une solution aqueuse d'un produit de lessive.
PCT/US1991/001178 1990-02-28 1991-02-22 Procedes et compositions en polymeres ionisables de nettoyage de taches WO1991013145A1 (fr)

Priority Applications (2)

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BR919104647A BR9104647A (pt) 1990-02-28 1991-02-22 Composicoes de limpeza de polimero ionizavel,e metodos para a limpeza de manchas
CA002055432A CA2055432A1 (fr) 1990-02-28 1991-02-22 Compositions nettoyantes a base de polymeres ionisables, et methodes pour l'enlevement des taches

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US46670890A 1990-02-28 1990-02-28
US466,708 1990-02-28

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JP (1) JPH05502909A (fr)
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US5762648A (en) * 1997-01-17 1998-06-09 The Procter & Gamble Company Fabric treatment in venting bag
US5789368A (en) * 1996-01-26 1998-08-04 The Procter & Gamble Company Fabric care bag
US5840675A (en) * 1996-02-28 1998-11-24 The Procter And Gamble Company Controlled released fabric care article
US5849039A (en) * 1997-01-17 1998-12-15 The Procter & Gamble Company Spot removal process
US5872090A (en) * 1996-10-25 1999-02-16 The Procter & Gamble Company Stain removal with bleach
US5891197A (en) * 1996-08-02 1999-04-06 The Proctor & Gamble Company Stain receiver for dry cleaning process
WO1999031213A1 (fr) * 1997-12-17 1999-06-24 Kao Corporation Composition de detergent
EP0786514A3 (fr) * 1996-01-25 1999-08-18 Unilever N.V. Compositions de prétraitement
US5942484A (en) * 1995-03-30 1999-08-24 The Procter & Gamble Company Phase-stable liquid fabric refreshment composition
US6063723A (en) * 1990-03-02 2000-05-16 Chevron U.S.A. Inc. Sulfur tolerant zeolite catalyst
US6233771B1 (en) 1996-01-26 2001-05-22 The Procter & Gamble Company Stain removal device
WO2019086273A1 (fr) * 2017-11-03 2019-05-09 Unilever Plc Composition
US11376209B2 (en) 2017-11-03 2022-07-05 Conopco, Inc. Antidandruff composition and method of use
US11382844B2 (en) 2017-11-03 2022-07-12 Conopco, Inc. Shampoo composition and method of use

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Publication number Priority date Publication date Assignee Title
US6063723A (en) * 1990-03-02 2000-05-16 Chevron U.S.A. Inc. Sulfur tolerant zeolite catalyst
US5942484A (en) * 1995-03-30 1999-08-24 The Procter & Gamble Company Phase-stable liquid fabric refreshment composition
US5681355A (en) * 1995-08-11 1997-10-28 The Procter & Gamble Company Heat resistant dry cleaning bag
EP0786514A3 (fr) * 1996-01-25 1999-08-18 Unilever N.V. Compositions de prétraitement
US6233771B1 (en) 1996-01-26 2001-05-22 The Procter & Gamble Company Stain removal device
US5789368A (en) * 1996-01-26 1998-08-04 The Procter & Gamble Company Fabric care bag
US5840675A (en) * 1996-02-28 1998-11-24 The Procter And Gamble Company Controlled released fabric care article
US5891197A (en) * 1996-08-02 1999-04-06 The Proctor & Gamble Company Stain receiver for dry cleaning process
US5872090A (en) * 1996-10-25 1999-02-16 The Procter & Gamble Company Stain removal with bleach
US5849039A (en) * 1997-01-17 1998-12-15 The Procter & Gamble Company Spot removal process
US5762648A (en) * 1997-01-17 1998-06-09 The Procter & Gamble Company Fabric treatment in venting bag
WO1999031213A1 (fr) * 1997-12-17 1999-06-24 Kao Corporation Composition de detergent
WO2019086273A1 (fr) * 2017-11-03 2019-05-09 Unilever Plc Composition
US11376209B2 (en) 2017-11-03 2022-07-05 Conopco, Inc. Antidandruff composition and method of use
US11382844B2 (en) 2017-11-03 2022-07-12 Conopco, Inc. Shampoo composition and method of use

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CA2055432A1 (fr) 1991-08-29
JPH05502909A (ja) 1993-05-20
EP0473757A1 (fr) 1992-03-11

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