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Publication numberUS3558499 A
Publication typeGrant
Publication dateJan 26, 1971
Filing dateJul 1, 1969
Priority dateJul 1, 1969
Publication numberUS 3558499 A, US 3558499A, US-A-3558499, US3558499 A, US3558499A
InventorsGalvin Thomas J, Hughes Francis A
Original AssigneeAtlas Chem Ind
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Anti-redeposition agents
US 3558499 A
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Description  (OCR text may contain errors)

United States Patent US. Cl. 252-137 8 Claims ABSTRACT OF THE DISCLOSURE Built detergent compositions containing an anti-redeposition agent selected from the group consisting of graft copolymers of a polymerizable monomer and a water soluble or water dispersible polymeric material or a physical blend of a polymerized monomer and a water soluble or water dispersible polymeric material.

This is a continuation of Ser. No. 528,835, filed Feb. 21, 1966, now abandoned.

The present invention relates to detergent compositions and more particularly to built detergent compositions which contain a graft copolymer of a polymerizable vinyl monomer and a water soluble or water dispersible polymeric material as an anti-redeposition agent. Alternatively, the detergent compositions of this invention may contain a physical blend of a polymerized vinyl monomer and a water soluble or water dispersible polymeric material as an anti-redeposition agent.

Most modern detergent compositions contain not only a detergent compound but varying amounts of builders, optical brighteners, perfumes and what are known as anti-redeposition agents. It is generally known that detergent compounds as such are effective in removing dirt from cloth but they do not have the colloidal character which acts to prevent redeposition of the dirt onto the cloth resulting in a dull, gray appearance. Therefore, in order to utilize the detergent materials effectively it is necessary to incorporate an anti-redeposition agent into the detergent composition along with the detergent compound, and builders in order to produce a satisfactory composition for washing purposes.

When incorporated in a detergent composition, the anti-redeposition agents act to keep the dirt, which is removed from the cloth during washing by the detergent compound, suspended in the wash water. By doing so, the suspended dirt will not become redeposited upon the washed cloth.

It is an object of this invention to provide a detergent composition which possesses anti-redeposition properties.

It is another object of this invention to provide a built detergent composition containing a graft copolymer of a polymerizable vinyl monomer and a water soluble or water dispersible polymeric material as an anti-redeposition agent.

It is a further object of this invention to provide a built detergent composition containing a blend of a polymerized vinyl monomer and a water soluble or water dispersible polymeric material as an anti-redeposition agent.

Other objects of the present invention will become apparent from the following description.

In accordance with the present invention graft copolymers of a polymerizable vinyl monomer and a water soluble or water dispersible polymeric material or a physical blend of a polymerized vinyl monomer and a water soluble or water dispersible polymeric material are incorporated in detergent compositions to impart antiredeposition qualities therein. By the term polymerizable 3,558,499 Patented Jan. 26, 1971 ICC vinyl monomer as used herein is included vinyl monomers capable of free radical catalyzed polymerization.

In general, and in accordance with the present invention built detergent compositions contain (1) from about 10% to about 25% of a suitable detergent compound, (2) from about 60% to about 89.9% of builders and (3) from about 0.10% to about of an anti-redeposition agent. As set forth above, such formulations may also contain minor amounts of perfume, and other suitable modifiers.

In the built detergent compositions of the present in vention the detergent component may be anionic or nonionic. Among the anionic detergents that may be used are the sodium alkyl sulfonates, sodium alkyl sulfates, sodium alkyl aryl sulfonates, sodium salts of sulfated and sulfonated alkyl amides, sodium salts of sulfated and sulfonated esters, and the sodium salts of esters of polyhydric alcohol-sulfonates; however, any suitable anionic detergent may be used in the present composition. EX- amples of suitable anionic detergents are sodium longchain hydrocarbon sulfonate (Alkanol 189-8, Du Pont, Wilmington, Del.), sodium lauryl sulfate (Dupanol C, Du Pont, Wilmington, Del.), sodium dodecylbenzene su1 fonate (Ultrawet K, Atlantic Refining Co., Philadelphia, Pa.), sulfonated fatty amide (Pyrotex, .Standard Chemical Products, Inc., Hoboken, N.J.), sulfonated fatty ester (Nopco 2272-R, Nopso Chemical Co., Newark, N.J.), sodium 1-(N-methyl-N-oleoyl-amino) ethyl sulfonate (Igepon T, General Aniline and Film Corp., New York, N.Y.).

Any suitable nonionic detergent may also be used in the present invention. Among the nonionic detergents that may be used in the present detergent compositions are condensation products of lower alkylene oxides, for example, ethylene oxide, propylene oxide, butylene oxides, and mixtures thereof, with compounds having at least one active hydrogen atom such as fatty acids, rosin acids, tall oil acids, alcohols, phenols, and alkyl phenols. Generally, these condensation products: will have a mole ratio of alkylene oxide to the active hydrogen component of from about 8 to about 25 respectively. Examples of suitable nonionic detergents are dodecylphenol condensed with 15 moles of ethylene oxide; oleyl alcohol condensed with 15 moles of ethylene oxide, rosin acids condensed with 20 moles ethylene oxide, dod-ecanol condensed with 4 moles of propylene oxide plus 8 moles of ethylene oxide. Examples of commercially available nonionic detergents suitable for use according to the present invention are Renex 679 and Renex 690 (Atlas Chemical Industries, Inc., Wilmington, Del.), Tergitol 15-8-9 (Union Carbide Co.) and Standamul 18 (Standard Chemical Products).

Other types of nonionic detergents wherein the hydroph-ilic portion of the compound is supplied by polyhydric alcohols such as glycerol, sorbitol, mannitol, ethylene glycol, propylene glycol, erythritol and mixtures thereof may also be used in the present detergent composition.

The builders which are incorporated in the detergent compositions of this invention may be any of those which are generally used in known built detergent products. Builders as used in detergent compositions are used to enhance the activity of the detergent component. For example, borax, sodium carbonate, sodium tripolyphosphate, sodium metasilicate, sodium bicarbonate, sodium phosphate and tetrasodium pyrophosphate are commonly used as detergent builders and are suitable for inclusion in the products of the present invention.

The graft copolymers of a water soluble or water dispersible polymeric material and a polymerizable vinyl monomer which are utilized as anti-redeposition agents according to the present invention may be prepared by several different processes. Preferred processes are disclosed in US. patent application Ser. No. 258,119, filed Feb. 13, 1963, now abandoned and US. patent application Ser. No. 33, 614, filed June 3, 1960, now abandoned and the entire disclosures thereof are hereby incorporated by reference. The process of application Ser. No. 258,119 comprises (1) contacting oxygen with a water-dispersible acid and other suitable water dispersible or water soluble polymeric materials. The graft copolymers as used in this invention also include blends of grafts with sufiicient water dispersible or water soluble polymeric materials to dilute the copolymer graft to the desired polypolymeric substrate While it is being irradiated whereby a acrylic id content,

hydroperoxide groups are introduced into the said polymer It h b n determined that physical blends (110 and then contacting the PerOXidiZed Polymeric grafted) of polymerized vinyl monomers and suitable Strete with an aqueous dispersion of a v y 111011011161 water soluble or Water dispersible polymeric material capable of free radical induced polymerization in the such as corn starch, potato starch, tapioca starch, amylose presence of a catalyst capable of producing free radicals casein, sorghum, polyvinyl alcohol, methylcellulose, polyby reaction with hydroperoxides. The process disclosed vinyl yrrolidone and polyvinyl glycol may also be used inaPP1iCati0n,Sef-N0- 33,614 Comprises moistening Starch as an anti-redeposition agent; however, such blends are with Water and then contacting the starch with a vinyl not as effective as the grafted copolymer products. Such monomer in fluid form and then subjecting the resulting physical blends have a polyacrylic acid content in the mixture to high energy radiation. However, other methsame percentage range as the present polyacrylic acidods may be used to prepare suitable copolymers of a starch grafts. water soluble or water dispersible polymeric material and The grafted copolymer anti-redeposition agents of this a polymerizable vinyl monomer such as those described invention may also be used in the form of their salts. 1n Great Britain Patent No. 869,329 and US. Pat. Nos. For example, the sodium, ammonium and potassium salts 2,999,056 and of polyacrylic acid-starch grafts copolymers are much Among the starch products from which the copolymer more soluble in water than the polyacrylic acid-starch antr-redeposition agents of this invention may be made graft in its acid form and hence dissolved more rapidly are, for example, corn starch, tapioca starch, casein, in water than the acid form of the polyacrylic acid-starch amylose and sorghum. Additionally, any water soluble graft copolymer. The salt of the polyacrylic acid-starch or water dispersible natural, modified natural products grafts can be readily prepared in several ways, for exor synthetic polymers that can be radiation grafted by ample, by adding sodium hydroxide, potassium hydroxide reactive monomers may be used. For example, casein, or ammonium hydroxide to an aqueous slurry of the alginates, dextrin, dextran, polyvinyl alcohol polyvinylpolyacrylic acid starch graft copolymer until a pH of 7 pyrrolidone, polyethylene glycol and methylcellulose may is obtained and then precipitating the salt of the acid graft be used in preparing the anti-redeposition agents as used copolymer by pouring the neutralized solution into a lower in the present invention. alcohol such as methanol, ethanol or isopropanol.

The polymerizable vinyl monomers suitable for use In general, it has been found that from about 0.1% in preparing the present graft copolymers may be suitably to about 10% of the subject anti-redeposition agents on acrylic acid itself or methacrylic acid. The polyacrylic the weight of a built detergent composit1on produce deteracid component of the anti-redeposition agent comprisn Products Whleh exhlblt excellent Washing qualifiesing a physical blend of a polymerized vinyl monomer and It 15 usually Preferred f use P} about 010% to abolft a water soluble or water dispersible polymeric material 5% 0f e Present antl'redepesftlon agents 011 the 133515 as used in the present invention may be polyacrylic acid of the bullt detefgenll eomposltlofl l t0 economy and it lf or l th li id I general, i h b 0 excellent results obtained. Concentrations less than 0.1% found that polyacrylic acid and polymethacrylic acid havy be usedfiut i entlredepositlon q y 0f e detering a molecular weight in the range from about 5,000 to gent C({IIIPOSIUOII 15 generally feducedi Whereas yylth C011- about 500,000 are suitable for use in the subject comcentretlons gfeatef than 10% n0 slgnlfieallt p positiorm ment in anti-redeposltion is obtained.

It has been determined that a polyacryli a idt h The anti-redeposition agents as disclosed in this invengraft copolymer suitable for use in the present invention P may be Incorporated! 111 y Sultable anlonle 0f will contain from about 1% to about of a polylonle detergel'ft eomposltlonacrylic acid. However, it has been found that in most in- The folloyvmg e p of detergent eomposltlons 0f stances, l li id Starch ft h i fr about the present invention as set forth in Tables I and II Will 5% to abo t 40% of a polyacrylic id content are 50 provide a further understanding of the products of this ferred in view of excellent results obtained and economy. invention but iS not itative of the scope thereof. Un- The above same concentrations are also applicable to less otherwise indicated all parts and percentages indipresent anti-redeposition agents made from an acrylic cated are by weight.

TABLE I Anti-redeposition agent composition qdmm Sod um mitt Percent of tripolymetasih- Sodlum Reucx Ultrawct IMAA-PS rcdeposition anti re- Example phosphate eate carbonate 690 K-Sott FAA-PS3 grait Potato agent deposition Number percent percent percent; percent percent percent percent starch percent agent 34. 82 9. 95 39. 81 75 34. 9. 90 39. i8 918% 34. 47 9. 86 10 1. 50 34. 92 9. 9s 40 .25 34. 92 9. 95 40 0. 50 34. 9. 40 1. 00 34. 65 9. 90 10 1.00 34. 92 9. 08 40 0. 25 34. 82 9. 40 5Q 34. 65 9. 90 40 1. 00 24. 65 9.90 10 1.0 34. 65 9. 90 4 1.0 34. 82 9. 95 40 0. 50 34.65 9. 90 40 1.0 34. 92 9. 9s 40 0. 25 34. a2 9. 95 49 0. 50 34. 95 9. 99 40 1. on

lfl-polyoxyethylcnc nonylphenol (Atlas Chemical Industries, 1110.).

2 Sodium dotlccylbcuzcncsullouate (Atlantic Refining 00.).

3 Polyacrylic Acid-potato starch graft. 4 lolymethacryhc acid-potato starch graft.

TABLE II Percent Sodium tri- Sodium Sodium Renex Ultrawet Antianti-re- Example phate metasilicate carbonate 690 l K-Soft 2 redcposition deposi- Numbcr percent percent percent percent percent agent tion agent 35 10 39. 5 15 PAA 3 0.5 35 10 39.0 15 PA 1.0 35 10 39. 5 15 IAA-PVA 0. 5 35 10 39. 15 PAA-PVA. 1.0 35 10 39.5 15 FAA-MC 0.5 35 39.0 P A-MC-. 1.0 35 10 39. 15 PAA/75PS 1.0 10 30. 15 25PAA/75PS 0.5 35 10 39. 1. 0 35 1O 39. 1. 0 35 10 0.5 35 10 15 10PAA/90PS 1, 0

1 ld-Polyoxyethylene nonylphenol (Atlas Chemical Industries, Inc.).

2 Sodium dodecylbenzenesulfonate (Atlantic Refining 00.).

3 Polyacrylic acid, added in form of 25% aqueous solution (Acrysol A-3, Rohm and Haas, Washington Square) 4 Polyacrylic acid, polyvinyl alcohol graft polyacrylic acid content) 5 Polyacrylic acid, methylecllulose graft (40% polyacrylic acid content).

Physical blend of 75% potato starch and 25% polyacrylic acid (added in form of Acrysol A-3).

1 Physical blend of 90% potato starch and 10% polyacrylic acid (added in form of Acrysol A-3).

The detergent compositions illustrated in Examples TABLE I I.C0ntinued 129 above were tested for washing effectiveness and 20 Percent the results obtained are set forth in Table III below. A fi g g f of t zgf iger r 0.25% concentration of each of the detergent composireflectance M composfiion tions of Examples 1-29 and suitable control compositions soiled cloth based on D t were p p m 1000 mlof 300 pp hardness water, e ergent e\ample number after washin control of 100% calculated as calcium carbonate of which the ratio of 25 Group C1 calcium to magnesium is 60/40. These detergent solutions 1010ntrol if); were then used to wash four standard dirty cloths ob- 126 104 tained from American Conditioning House, Boston, 37 100 Massachusetts. A Baker Terg-O-Tometer (Baker Instru- 3 13% ment Company, Orange, NJ.) was used for the tests. The- Terg-O-Tometer was operated at 60 r.p.m. with the dei8? tergent bath water adjusted to 120 F. Each of the stand- 133 105 ard cloths were washed ten minutes, twice rinsed three 134 107 minutes with 300 p.p.m. hardness water, (60/40 as 81 100 Ca/Mg ratio calculated as CaCO dried one hour at 3% %8% 185 F. and conditioned overnight at 75 C. at 40 rela- 88 109 tively humidity and then measured for changes in re- 79 100 fiectance by the Hunter Multi-Purpose Reflectometer 88 111 (Henry A. Gardner Laboratory, Inc., Washington, DC). 2? i3; The results obtained are expressed as percent increase in reflection of cloth after washing and percent efliciency g? {22 of detergent composition based on a control as being 8 109 100%. Separate controls were run for each group of de- 83 tergent compositions which were run at different times. 85 100 Each control composition used in Group A, B, F, G and 32 H was composed of the following detergent compositions 90 105 Percent ReneX 690 15 What we claim is: Sodium tripolyphosphate 35 1. A detergent composition consisting essentially of: Sodium metasilicate 10 (1) from about 10% to about 25% of organic syn Sodium carbonate 40 thetic detergent selected from the group consisting The control compositions used in Groups C, D, E and I of a Synthetic anionic detergents and Orgamc were composed of: synthet1c noniomc detergents,

Percent (2) from about to about 89.9% of inorganic Ultrawet K 15 detergent builders, and Sodium tripolyphosphate 35 (3) from about to about 10% of an anti-redepo- Sodium Carbonate 10 sition agent which is a graft copolymer selected from sodium metasflicate 40 the group consisting of graft copolymers of starch 60 with acrylic acid, graft copolymers of starch with TABLE III methacrylic acid, and the sodium, potassium and Percent Egg? ammonium salts of the graft copolymers of starch increasein ofdetergerg with either acrylic acid or methacrylic acid, wherein gfig gg g s g g the polymerized acrylic acid or methacrylic acid has Detergent example number after was hiiig control Ei IlOO W molecular Weight from about 5000 to SOOIOOO and Group 1 is present, by weight of copolymer, in an amount of contgol 72 100 from about 1% to 50%.

S3 2. A detergent composition of claim 1 wherein the go 124 polymerizable monomer is acrylic acid. 33 3. A detergent composition of claim 1 wherein the 125 polymerizable monomer is methacrylic acid. (310811131 4. A detergent composition of claim 1 wherein the ontrol. 80 7 91 114 polymenzable monomer is a sodium, potassium, or amg 2; i monium salt of acrylic or methacrylic acid.

10 so lit 75 5. A detergent composition of claim 1 wherein the anti- 8 redeposition agent is a graft copolymer of potato starch and said graft copolymer containing from about 1% and acrylic acid. to about 50% by weight of polymerized acrylic acid.

6. A detergent composition of claim 1 wherein the antiredeposition agent is a graft copolymer of potato References Cited starch and methacrylic acid. UNITED STATES P ATENTS 7. A detergent composition of claim 1 wherein the 3 211660 /1965 Marion et a1 252 137 detergent builders are selected from the group consisting 3254028 5/1966 Wixon of sodium tripolyphosphate, sodium metasilicate, sodium 3284364 11/1966 Sic 1 2 ge e 8289X carbonate, borax, sodium bicarbonate, sodlum phosphate, 3,377,290 4/1968 Stein et a1 252 137X i dgt e rg gni ggfiss iiiz rf consisting essentially of 10 3393154 7/1968 Treitler 252 137 (1) from about 10% to about by weight of or- 3441526 4/1969 Zllkha et 260874X ganic synthitic detergent selected from tle group FOREIGN PATENTS consisting 0 an organic synthetic anionic etergent and an organic synthetic nonionic detergent, 15 9 35,733 9/1963 England S011 suspendmg (2) from about to about 89.9% by Weight of inorganic detergent builders selectcd from the group OTHER REFERENCES consisting of sodium tripolyphosphate, sodium meta- Schwartz & Perry, Surface Actlve Agents, 1949 silicate, sodium carbonate, borax, sodium bicarbo- P- 379, 2 P- nate, sodium hos hate, and tetrasodium ro hosphate, and P P W p 20 LEON D. ROSDOL, Primary Examiner (3) from about 0.1% to about 10% by weight of an L HALPERN, Assistant Examiner anti-redeposition agent which is a graft copolymer of potato starch and acrylic acid, said graft copoly- U.S. Cl. X.R. mer containing polymerized acrylic acid having a 2 252-89, 152 molecular weight from about 5,000 to about 500,000

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4617139 *Oct 21, 1985Oct 14, 1986Lever Brothers CompanyAcrylic acid derivative polymers modified with phosphorous containing compounds
US4657693 *Dec 23, 1985Apr 14, 1987The Procter & Gamble CompanySpray-dried granular detergent compositions containing tripolyphosphate detergent builder, polyethylene glycol and polyacrylate
US5207941 *May 10, 1991May 4, 1993Basf AktiengesellschaftUse of water-soluble or water-dispersible grafted proteins as detergent additives
US5223171 *Jun 26, 1991Jun 29, 1993Rhone Poulenc ChimieDetergent composition containing a biodegradable graft polysaccharide
US5227446 *Feb 1, 1991Jul 13, 1993Basf AktiengesellschaftGraft copolymers of monosaccharides, oligosaccharides, polysaccharides and modified polysaccharides, the preparation thereof, and their use
US5296470 *Jun 26, 1991Mar 22, 1994Rhone-Poulenc ChimiePolydextrose backbone with grafted water soluble unsaturated monomer
US5409571 *Feb 1, 1994Apr 25, 1995Hakuto Co., Ltd.A pulping antiscaling agent comprising a terpolymers of maleic acid, acrylic acid, hypophosphorous acid
US6764992May 9, 2001Jul 20, 2004Unilever Home & Personal Care Usa, Division Of Conopco, Inc.Anionic, hydrophobic polysaccharide which is a graft copolymer of a polysaccharide having anionic substituents with an ethylenically unsaturated monomer
CN100448970CMay 1, 2001Jan 7, 2009荷兰联合利华有限公司Soil release polymers and laundry detergent compositions containing them
DE2657517A1 *Dec 18, 1976Jul 7, 1977Procter & GambleWasch- und reinigungsmittel
EP0441197A2 *Jan 25, 1991Aug 14, 1991BASF AktiengesellschaftGraftcopolymer of monosaccharides, oligosaccharides, polysaccharides and modified polysaccharides, process of preparing same and its application
EP0457205A2 *May 10, 1991Nov 21, 1991BASF AktiengesellschaftUse of water-soluble or water-dispersible grafted proteins as detergent and cleaning agent additives
EP0465287A1 *Jun 17, 1991Jan 8, 1992Rhone-Poulenc ChimieDetergent composition containing a biodegradable grafted polysaccharide
WO2001088075A1 *May 1, 2001Nov 22, 2001Lever Hindustan LtdSoil release polymers and laundry detergent compositions containing them
Classifications
U.S. Classification510/345, 510/356, 510/472, 510/359, 510/361, 510/471
International ClassificationC11D3/37
Cooperative ClassificationC11D3/3788
European ClassificationC11D3/37E