EP0124913B1 - Granular detergent compositions containing mixed polymer additive system - Google Patents

Granular detergent compositions containing mixed polymer additive system Download PDF

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Publication number
EP0124913B1
EP0124913B1 EP84200104A EP84200104A EP0124913B1 EP 0124913 B1 EP0124913 B1 EP 0124913B1 EP 84200104 A EP84200104 A EP 84200104A EP 84200104 A EP84200104 A EP 84200104A EP 0124913 B1 EP0124913 B1 EP 0124913B1
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EP
European Patent Office
Prior art keywords
weight
ingredient
detergent
composition
copolymeric
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP84200104A
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German (de)
English (en)
French (fr)
Other versions
EP0124913A1 (en
Inventor
Paolo Zini
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble European Technical Center
Procter and Gamble Co
Original Assignee
Procter and Gamble European Technical Center
Procter and Gamble Co
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Publication date
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Application filed by Procter and Gamble European Technical Center, Procter and Gamble Co filed Critical Procter and Gamble European Technical Center
Priority to AT84200104T priority Critical patent/ATE20476T1/de
Publication of EP0124913A1 publication Critical patent/EP0124913A1/en
Application granted granted Critical
Publication of EP0124913B1 publication Critical patent/EP0124913B1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • This invention relates to granular detergent compositions which are free of or with reduced levels of phosphorus -containing builders containing a mixed polymer additive system.
  • the polymer system comprises specific homopolymeric polyacrylates and copolymeric carboxylates whereby the homopolymeric species are characterized by a molecular weight below 3 000.
  • the preferred copolymeric component is prepared from an ethylenically unsaturated carboxylic acid, most preferably maleic acid. and (meth)-acrylic acid monomers.
  • Particularly preferred polyacrylates herein are represented by substantially equiponderant mixtures of polyacrylates having molecular weights of around 1 000 and 2 000 respectively.
  • the polymer additive system provides unpredictable and significant textile cleaning benefits expressed, for example, in terms of whiteness and whiteness maintenance after multiple washes as compared to identical granular detergents containing same total level of either the individual polymers or mixtures of various conventional detergent polymers.
  • the claimed technology is especially beneficial in granular detergent compositions containing reduced levels of polyphosphate builders such as from 8 % to 20 % by weight of the composition.
  • polyphosphate builder level reduction leads to performance deficiencies which cannot be cured in a fully acceptable manner with the sole aid of a conventional detergent additive such as a polymeric carboxylate.
  • the individual components of the polymer additive system are well-known in detergent technology and may have found commercial application.
  • copolymeric ingredient is known from European Patent 0025551. BASF AG, which discloses such material in an incrustation inhibitor functionality in detergent compositions.
  • the detergent art is also possessed of combinations of the copolymeric ingredient and conventional detergent additives.
  • FR-A-2 388 045 The PROCTER & GAMBLE Company, is representative of this general knowledge. It discloses detergent compositions containing surface-active agents, builders, and a binary system of additive levels of a polyphosphonate and a polymeric ingredient which latter ingredient can be represented by copolymers of (meth)-acrylic acid and maleic anhydride.
  • the detergent utilization of the copolymeric ingredient is also known from European Patent Application 0066915.
  • this reference discloses the utilization of the copolymeric ingredient in combination with detergent performance additives inclusive of hydrocarbon detergent suds regulants, photoactivators. amine or oxidized amine soil release agents, silicone detergent suds regulants and bleach activators/peracids.
  • the detergent utilization of polyacrylates having a molecular weight in the range of from 1 000 to 5000, is known from U.K. Patent Application 2.097.419, Colgate-Palmolive.
  • Detergent compositions are disclosed containing high levels of difficultly processable components inclusive of sodium carbonate, sodium bi-carbonate, detergent zeolites, and bentonites. It is said that the polyacrylates are added in a processing aid functionality to ensure uniform mixing of the crutcher mix component. Comparable disclosures are known from U.K. Patent Application 2 095 274, Colgate-Palmolive.
  • Detergent compositions containing substantial levels of water-insoluble ingredients inclusive of zeolite builders, and bentonites. carbonates and bi-carbonates are processed into beads whereby physical and detergent properties are controlled with the aid of polyacrylates having molecular weight e. g. in the range from 1 000 to 5 000.
  • the detergent utilization of mixed polymer systems is known from German Patent Application 29 10 133, BASF AG ; German Patent Application 26 25 444, CIBA-GEIGY AG ; and Belgian Patent 881 488, SENZORA B. V.
  • the BASF '133 reference relates to the utilization of detergent builder mixtures consisting of a copolymeric ingredient and polymaleic acid.
  • the CIBA-GEIGY '444 citation refers to the use of low molecular weight polymer mixtures, namely combinations of hydrolized polymaleic anhydride, having a molecular weight in the range from 300 to 5 000, in combination with a hydrolized copolymer of maleic anhydride and an ethylenically unsaturated monomer whereby the molecular weight of the copolymeric species is below 1 000.
  • the SENZORA '488 reference refers to the partial or total replacement of polyphosphate detergent builders by a ternary combination consisting of polyvalent substituted carboxylic acids, a copolymer of methyl vinyl ether and maleic anhydride ; and a polyacrylic acid having a molecular weight in the range of from 12 000 to 20 000.
  • compositions herein comprise reduced (vs. current practice) levels of polyphosphate builders such as corresponding to phosphorus levels in the range of from 2 % to 5 % by weight.
  • P-levels if e. g. calculated on basis of sodiumtripolyphosphate amount to from 8 % to 20 % by weight.
  • the invention herein comprises a granular detergent composition containing a binary polymer system containing a homopolymeric polyacrylate having a low molecular weight and a copolymeric polycarboxylate with a given monomers ratio and whereby further the weight ratio of homopolymer to copolymer can be varied within narrowly set conditions.
  • a binary polymer system containing a homopolymeric polyacrylate having a low molecular weight and a copolymeric polycarboxylate with a given monomers ratio and whereby further the weight ratio of homopolymer to copolymer can be varied within narrowly set conditions.
  • percent indications represent « percent by weight indications.
  • the detergent matrix comprises a surface-active agent, a detergent builder, preferably reduced level of tripolyphosphate, and a series of optional. but frequently desirable. components such as an oxygen- bleach component, possibly an activator therefore, a suds regulant frequently based on silicones, and further usual additives in the art established level for their known functionality.
  • compositions herein unexpectedly provide superior laundry cleaning performance, as compared to commercial phosphate built detergent compositions, in the absence of or with reduced level of phosphate builder, especially detergent compositions containing phosphate builder levels representing from 2-5 % of phosphorus.
  • the latter limit in terms of sodium tripolyphosphate, amounts to from 8 % to 20 %.
  • the detergent builder can be represented by non-phosphorus containing builders, by mixtures of such non-phosphorus containing builders and phosphorus-containing builders, or by reduced levels (vs. current levels) of P-containing builders alone, such as sodium tripolyphosphate.
  • the total level of the detergent builder ingredients can vary within broad limits well-known in the detergent art.
  • the inventive technology is particularly adapted for use in combination with a detergent composition containing a phosphorus-containing detergent builder in a level, calculated as phosphorus, from 2 % to 5 %.
  • Suitable non-phosphorus containing detergent builders can be represented by conventional species inclusive of but not limited to detergent zeolites such as zeolite A, zeolite X and zeolite P, most preferably zeolite A. having a particle size in the range from 1-10 f.Lm as e. g. described in DE-B-24 22 655.
  • Additional builders for use herein include nitrilotriacetic acids or the water-soluble alkali salts thereof, sodium carbonate, sodium citrate, sodium silicates and fatty acid soaps e. g. sodium or potassium soaps.
  • the total level of the detergent builder can vary within broad ranges.
  • the builder usually represents from 5 % to 70 %, but frequently, and depending upon the selection of the builder, is in the range from 10 % to 50 %.
  • compositions herein contain as an essential detergent component a mixture of a polyacrylic homopolymer and a copolymeric ingredient.
  • the polyacrylate homopolymer has a molecular weight below 3 000 and is utilized in levels of from 0.5 % to 15 %.
  • the homopolymeric polyacrylate is represented by a mixture of two different polyacrylates, one having a molecular weight of about 2 000 and a second one having a molecular weight of about 1 000. whereby these species are used in a weight ratio of 2 : 1 to 1 : 2, most preferably 1 : 1.
  • the polyacrylate component is well-known in detergent technology.
  • the molecular weight of the polyacrylate polymer is determined with the aid of known techniques inclusive of intrinsic viscosity measurements.
  • the level of the polyacrylate homopolymer can vary as pointed out above and depending upon the nature of the detergent matrix components. Particularly relevant in this respect are variations in the qualitative and quantitative parameters of the builder system. Reduced levels of polyphosphate e. g. between 8-12 % by weight will require a relatively higher level of the homopolymer as compared to what is needed for levels of sodium tripolyphosphate in the range of from e. g. 15 %-18 %.
  • a further essential component for use herein is a copolymer of an unsaturated monocarboxylic acid and an unsaturated di-carboxylic acid.
  • This copolymeric ingredient is used in levels from 0.5 % to 15 %.
  • the copolymeric ingredient consists of an ethylenically unsaturated monocarboxylic acid monomer having not more than 5, preferably 3 or 4. carbon atoms, and an ethylenically unsaturated dicarboxylic acid monomer having not more than 6, preferably 4 carbon atoms. whereby the molar ratio of the monomers is in the range from 1 : 4 to 4:1, most preferably 1 : 1.
  • Suitable examples of the monocarboxylic acid monomer are : acrylic acid, methacrylic acid and vinyl acetic acid. Acrylic and methacrylic acids are preferred.
  • Suitable examples of the dicarboxylic acid monomers are : maleic acid ; fumaric acid ; citraconic acid ; itaconic acid ; and mesaconic acid. Preferred dicarboxylic acids are maleic acid, citraconic acid, and itaconic acid.
  • the copolymeric ingredient can be further defined with the aid of the calcium sequestration value. These values can be measured by nephelometric titration methods (as described in literature
  • the sequestration value is expressed in mgCaC0 3 /gram of copolymeric ingredient.
  • the calcium sequestration value of the copolymeric ingredient is preferably higher than 200 mg CaC0 3 /g.
  • the weight ratio of the homopolymeric ingredient to the copolymeric ingredient is in the range from 1 : 4 to 4 : 1 and preferably from 2 : 1 to 1 : 2. While the quantitative levels of the individual homopolymer and the individual copolymer can vary from 0.5 % to 15 % provided their weight ratio is from 4 : 1 to 1 : 4, the level selection of these individual polymers will vary depending upon the major detergent matrix ingredients, particularly the detergent builder.
  • the homopolymer and copolymer are preferably used in levels of 0.5 % to 4 % each when incorporated in built detergent compositions containing from 2 % to 5 % phosphorus in another embodiment the detergent compositions herein preferably contain from 2 % to 8 % of the homopolymeric ingredient and from 2 % to 8 % of the copolymeric ingredient if the phosphorous based builder/sequestrant is present in a level, expressed as phosphorus of below 2 %.
  • the detergent compositions herein can comprise, in addition to the essential components, a series of supplementary substances to perfect and augment the performance benefits.
  • the additional components are represented by known ingredients which have already found application in detergency, for their known functionality in the art established levels.
  • the like components include peroxygen bleaches. such as perborate mono-or tetrahydrate and percarbonate, oxygen bleach activators such as tetraacetyl ethylene diamine, oxygen bleach regulants such as a copolymer of maleic anhydride and methylvinylether, detergent enzymes such as proteases, amylases, lipases and mixtures thereof, and stabilizing agents for the like enzymes.
  • soil suspending agents such as the sodium salt of carboxymethylcellulose and the sodium salt of methylhydroxypropyl cellulose ; through-the-wash softening smectite clays such as alkali montmorillonites, saponites and hectorites, having an ion-exchange capacity of at least 50 m.sq./100 g, and photoactivators, for example, sulfonated metal phthalocyanines such as zinc and aluminium phthalocyanines.
  • soil suspending agents such as the sodium salt of carboxymethylcellulose and the sodium salt of methylhydroxypropyl cellulose
  • through-the-wash softening smectite clays such as alkali montmorillonites, saponites and hectorites, having an ion-exchange capacity of at least 50 m.sq./100 g
  • photoactivators for example, sulfonated metal phthalocyanines such as zinc and aluminium phthalocyanines.
  • compositions further can comprise suds regulants e. g. those of U.S. Patent 4,192,761 and more in general suds regulants based on silicones. silica, waterinsoluble hydrocarbons, either individually or optimized mixtures thereof, and renewable textile soil release agents such as described in European Patent Applications 0.042.187 and 0.042.188.
  • Preferred soil release agents include N-hydrogenated tallow C 16 -C 18 -N,N'.N'-tri-(2-hydroxyethyl)-propylene-1,3-diamine and N-C 12 -C 14 -coconutalkyl-N,N-dimethyl-N-amine oxide and can be utilized in levels of from 0.1-1.5 %.
  • compositions also can contain brighteners, perfumes, dyes, bactericidal agents, antioxidants and fillers.
  • a preferred additive system is comprised of a combination of a tertiary amine and an impalpable smectite clay as described in European Patent Application 0011 340.
  • the following granular detergent compositions were prepared by conventional spray-drying of slurry of most of the individual ingredients and subsequent dry-mixing of the spray-dried powder with spray-drying sensitive ingredients, namely perborate enzyme photoactivator and suds regulant.
  • Prilled suds regulant system consisting of : 77.5 % sodiumtripolyphosphate and 22.5 % active consisting of : 13.5 % paraffin oil ; 6 % paraffin wax (m. p. 70 °C) ; and 3 % amorphous hydrophobic silica.
  • compositions of Examples I (invention), A and B (prior art) were compared under the following conditions.
  • the variations were expressed as whiteness maintenance :
  • compositions of Examples II and C were compared as described hereinbefore except for the following conditions.
  • compositions of Examples III. D. and E were compared for whiteness maintenance under the conditions recited for Examples II and C, except that the water hardness was 0.3 g/l (18 grains/US gallon).
  • the inventive composition is again markedly superior over the art.
  • compositions III and F were compared for soil antiredeposition, measured as whiteness, thereby using the following testing conditions :
  • Additional detergents of this invention are prepared having the following composition.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP84200104A 1983-04-08 1984-01-30 Granular detergent compositions containing mixed polymer additive system Expired EP0124913B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84200104T ATE20476T1 (de) 1983-04-08 1984-01-30 Granulierte detergenszusammensetzungen, welche ein gemischtes polymerzusatzsystem enthalten.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8309610 1983-04-08
GB8309610 1983-04-08

Publications (2)

Publication Number Publication Date
EP0124913A1 EP0124913A1 (en) 1984-11-14
EP0124913B1 true EP0124913B1 (en) 1986-06-18

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ID=10540835

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84200104A Expired EP0124913B1 (en) 1983-04-08 1984-01-30 Granular detergent compositions containing mixed polymer additive system

Country Status (8)

Country Link
EP (1) EP0124913B1 (enrdf_load_stackoverflow)
JP (1) JPS6018595A (enrdf_load_stackoverflow)
AT (1) ATE20476T1 (enrdf_load_stackoverflow)
CA (1) CA1220998A (enrdf_load_stackoverflow)
DE (1) DE3460228D1 (enrdf_load_stackoverflow)
GR (1) GR81656B (enrdf_load_stackoverflow)
IE (1) IE56762B1 (enrdf_load_stackoverflow)
MX (1) MX159427A (enrdf_load_stackoverflow)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3444960A1 (de) * 1984-12-10 1986-06-12 Henkel KGaA, 4000 Düsseldorf Koerniges adsorptionsmittel
SE466963B (sv) * 1984-12-24 1992-05-04 Colgate Palmolive Co Textilmjukgoerande hoegverkande flytande detergent med stabil viskositet
GB8504733D0 (en) * 1985-02-23 1985-03-27 Procter & Gamble Ltd Detergent compositions
DE3720806C2 (de) * 1986-07-03 1997-08-21 Clariant Finance Bvi Ltd Verwendung eines Stabilisators in Peroxydbleichverfahren
DE3717227A1 (de) * 1987-05-21 1988-12-01 Henkel Kgaa Phosphatfreies waschmittel mit reduzierter inkrustierungstendenz
AU4211889A (en) * 1989-05-02 1990-11-29 Ecolab Inc. Zero phosphorus heavy duty laundry detergent composition
GB8928320D0 (en) * 1989-12-14 1990-02-21 Unilever Plc Polymers and detergent compositions containing them
US5273675A (en) * 1990-02-16 1993-12-28 Rohm And Haas Company Phosphate-free liquid cleaning compositions containing polymer
US5401807A (en) * 1992-10-08 1995-03-28 Rohm And Haas Company Process of increasing the molecular weight of water soluble acrylate polymers by chain combination
DE4239076A1 (de) * 1992-11-20 1994-05-26 Basf Ag Mischungen aus Polymerisaten von monoethylenisch ungesättigten Dicarbonsäuren und Polymerisaten ethylenisch ungesättigter Monocarbonsäuren und/oder Polyaminocarbonsäuren und ihre Verwendung
EP2424592A1 (en) 2009-04-30 2012-03-07 Sanofi-Aventis Deutschland GmbH Pen-type injector with ergonomic button arrangement
US8912135B2 (en) * 2011-05-20 2014-12-16 Rohm And Haas Company Method of promoting soil release from fabrics
GB2502558A (en) * 2012-05-30 2013-12-04 Reckitt Benckiser Nv Water softening composition
RU2635250C2 (ru) * 2012-05-30 2017-11-09 Рекитт Бенкизер Калгон Б.В. Композиция для умягчения воды
JP2017149936A (ja) * 2016-02-23 2017-08-31 ライオン株式会社 衣料用粉末洗浄剤組成物

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3922230A (en) * 1971-08-04 1975-11-25 Lever Brothers Ltd Oligomeric polyacrylates as builders in detergent compositions
JPS5827320B2 (ja) * 1975-06-30 1983-06-08 株式会社日本触媒 センザイソセイブツ
NL7900849A (nl) * 1979-02-02 1980-08-05 Senzora B V Wasmiddelen.
DE2936984A1 (de) * 1979-09-13 1981-04-02 Basf Ag, 6700 Ludwigshafen Verwendung von (meth)acrylsaeure-maleinsaeure-copolymerisaten als inkrustierungsinhibitoren in waschmitteln
AU549000B2 (en) * 1981-02-26 1986-01-09 Colgate-Palmolive Pty. Ltd. Base beads for detergent compositions
IN161821B (enrdf_load_stackoverflow) * 1981-02-26 1988-02-06 Colgate Palmolive Co
ATE30738T1 (de) * 1981-05-30 1987-11-15 Procter & Gamble Reinigungsmittelzusammensetzung enthaltend einen wirkungsfoerdernden zusatz und ein kopolymer zum gewaehrleisten der vertraeglichkeit desselben.

Also Published As

Publication number Publication date
JPH0522757B2 (enrdf_load_stackoverflow) 1993-03-30
IE840262L (en) 1984-10-08
DE3460228D1 (en) 1986-07-24
GR81656B (enrdf_load_stackoverflow) 1984-12-12
IE56762B1 (en) 1991-12-04
ATE20476T1 (de) 1986-07-15
JPS6018595A (ja) 1985-01-30
EP0124913A1 (en) 1984-11-14
CA1220998A (en) 1987-04-28
MX159427A (es) 1989-05-29

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