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EP0124913A1 - Compositions détergentes granulées contenant un systéme mélangé d'additifs polymères - Google Patents

Compositions détergentes granulées contenant un systéme mélangé d'additifs polymères Download PDF

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Publication number
EP0124913A1
EP0124913A1 EP84200104A EP84200104A EP0124913A1 EP 0124913 A1 EP0124913 A1 EP 0124913A1 EP 84200104 A EP84200104 A EP 84200104A EP 84200104 A EP84200104 A EP 84200104A EP 0124913 A1 EP0124913 A1 EP 0124913A1
Authority
EP
European Patent Office
Prior art keywords
weight
ingredient
detergent
copolymeric
homopolymeric
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.)
Granted
Application number
EP84200104A
Other languages
German (de)
English (en)
Other versions
EP0124913B1 (fr
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
Priority date (The priority date 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 date listed.)
Filing date
Publication date
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=10540835&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0124913(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
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/fr
Application granted granted Critical
Publication of EP0124913B1 publication Critical patent/EP0124913B1/fr
Expired legal-status Critical Current

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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 3000.
  • 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 1000 and 2000 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 0 025 551, 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.
  • French Patent Application 78-11917 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 0 066 915.
  • 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 1000 to 5000, is known from U.K. Patent Application 2.097.419, Colgate-Palmo- live.
  • 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 1000 to 5000.
  • 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 5000, in combination with a hydrolized co ⁇ polymer of maleic anhydride and an ethylenically unsaturated monomer whereby the molecular weight of the copolymeric species is below 1000.
  • 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 sodiumtripolyphos- phate amount to from 8% to 20% by weight.
  • the invention herein comprises a series of essential components, namely: a granular detergent composition containing conventional matrix components; and 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 granular detergent composition containing conventional matrix components
  • 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 microns as e.g. described in DE-AS 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 3000 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 2000 and a second one having a molecular weight of about 1000, 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 normally 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
  • 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 hecto- rites, having an ion-exchange capacity of at least 50m.eq./ 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 hecto- rites, having an ion-exchange capacity of at least 50m.eq./ 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, water-insoluble 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 0 011 340, incoporated herein by reference.
  • the following granular detergent compositions were prepared by conventional spray-drying of a 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.
  • 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 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 Compositions détergentes granulées contenant un systéme mélangé d'additifs polymères Expired EP0124913B1 (fr)

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 true EP0124913A1 (fr) 1984-11-14
EP0124913B1 EP0124913B1 (fr) 1986-06-18

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ID=10540835

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84200104A Expired EP0124913B1 (fr) 1983-04-08 1984-01-30 Compositions détergentes granulées contenant un systéme mélangé d'additifs polymères

Country Status (8)

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

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2168717A (en) * 1984-12-24 1986-06-25 Colgate Palmolive Co Controlling viscosity of fabric softening heavy duty liquid detergent containing bentonite
EP0193360A2 (fr) * 1985-02-23 1986-09-03 The Procter & Gamble Company Compositions détergentes
US4707290A (en) * 1984-12-10 1987-11-17 Henkel Kommanditgesellschaft Auf Aktien Granular adsorbent
US4919845A (en) * 1987-05-21 1990-04-24 Henkel Kommanditgesellschaft Auf Aktien Phosphate-free detergent having a reduced tendency towards incrustation
BE1002261A5 (fr) * 1986-07-03 1990-11-13 Sandoz Sa Stabilisation des agents de blanchiment a base de peroxydes.
WO1990013622A1 (fr) * 1989-05-02 1990-11-15 Ecolab Inc. Composition detergente de lessive a teneur en phosphore nulle pour lavage industriel
US5159041A (en) * 1989-12-14 1992-10-27 Lever Brothers Company 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
EP0600592A1 (fr) * 1992-10-08 1994-06-08 Rohm And Haas Company Procédé de préparation de polymères réticulés à bas poids moléculaire, solubles dans l'eau et leur utilisation comme agents de renforcement pour détergents, dispersants ou inhibiteur de tartre
WO1994012571A2 (fr) * 1992-11-20 1994-06-09 Basf Aktiengesellschaft Melanges de polymerisats d'acide carboxyliques insatures et utilisation
GB2502558A (en) * 2012-05-30 2013-12-04 Reckitt Benckiser Nv Water softening composition
WO2013178990A2 (fr) * 2012-05-30 2013-12-05 Reckitt Benckiser N.V. Composition
US9227009B2 (en) 2009-04-30 2016-01-05 Sanofi-Aventis Deutschland Gmbh Pen-type injector with ergonomic button arrangement

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103562369B (zh) * 2011-05-20 2016-04-20 陶氏环球技术有限责任公司 促进污物从织物释放的方法
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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3002710A1 (de) * 1979-02-02 1980-09-04 Senzora B V Verfahren zum waschen von textilien, sowie die dazu dienenden waschmittel
EP0025551A1 (fr) * 1979-09-13 1981-03-25 BASF Aktiengesellschaft Utilisation de copolymères d'acide (méth)acrylique et d'acide maléique comme inhibiteurs d'incrustation dans des produits de lavage
FR2500475A1 (fr) * 1981-02-26 1982-08-27 Colgate Palmolive Co Perles de base destinees a la fabrication de compositions detergentes, procede et melanges pour leur fabrication et compositions detergentes les contenant
EP0066915A2 (fr) * 1981-05-30 1982-12-15 THE PROCTER & GAMBLE COMPANY Composition détergente contenant un additif augmentant la performance et un copolymère pour assurer la compatibilité de cet additif

Family Cites Families (3)

* 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
IN161821B (fr) * 1981-02-26 1988-02-06 Colgate Palmolive Co

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3002710A1 (de) * 1979-02-02 1980-09-04 Senzora B V Verfahren zum waschen von textilien, sowie die dazu dienenden waschmittel
EP0025551A1 (fr) * 1979-09-13 1981-03-25 BASF Aktiengesellschaft Utilisation de copolymères d'acide (méth)acrylique et d'acide maléique comme inhibiteurs d'incrustation dans des produits de lavage
FR2500475A1 (fr) * 1981-02-26 1982-08-27 Colgate Palmolive Co Perles de base destinees a la fabrication de compositions detergentes, procede et melanges pour leur fabrication et compositions detergentes les contenant
EP0066915A2 (fr) * 1981-05-30 1982-12-15 THE PROCTER & GAMBLE COMPANY Composition détergente contenant un additif augmentant la performance et un copolymère pour assurer la compatibilité de cet additif

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4707290A (en) * 1984-12-10 1987-11-17 Henkel Kommanditgesellschaft Auf Aktien Granular adsorbent
GB2168717A (en) * 1984-12-24 1986-06-25 Colgate Palmolive Co Controlling viscosity of fabric softening heavy duty liquid detergent containing bentonite
EP0193360A2 (fr) * 1985-02-23 1986-09-03 The Procter & Gamble Company Compositions détergentes
EP0193360A3 (en) * 1985-02-23 1987-07-01 The Procter & Gamble Company Detergent compositions
BE1002261A5 (fr) * 1986-07-03 1990-11-13 Sandoz Sa Stabilisation des agents de blanchiment a base de peroxydes.
US4919845A (en) * 1987-05-21 1990-04-24 Henkel Kommanditgesellschaft Auf Aktien Phosphate-free detergent having a reduced tendency towards incrustation
WO1990013622A1 (fr) * 1989-05-02 1990-11-15 Ecolab Inc. Composition detergente de lessive a teneur en phosphore nulle pour lavage industriel
US5159041A (en) * 1989-12-14 1992-10-27 Lever Brothers Company 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
EP0600592A1 (fr) * 1992-10-08 1994-06-08 Rohm And Haas Company Procédé de préparation de polymères réticulés à bas poids moléculaire, solubles dans l'eau et leur utilisation comme agents de renforcement pour détergents, dispersants ou inhibiteur de tartre
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
WO1994012571A2 (fr) * 1992-11-20 1994-06-09 Basf Aktiengesellschaft Melanges de polymerisats d'acide carboxyliques insatures et utilisation
WO1994012571A3 (fr) * 1992-11-20 1994-08-04 Basf Ag Melanges de polymerisats d'acide carboxyliques insatures et utilisation
AU672851B2 (en) * 1992-11-20 1996-10-17 Basf Aktiengesellschaft Mixtures of polymers of monoethylenically unsaturated dicarboxylic acids and polymers of ethylenically unsaturatedmonocarboxylic acids and/or polyaminocarboxylic acids, and the use of such mixtures
US9227009B2 (en) 2009-04-30 2016-01-05 Sanofi-Aventis Deutschland Gmbh Pen-type injector with ergonomic button arrangement
GB2502558A (en) * 2012-05-30 2013-12-04 Reckitt Benckiser Nv Water softening composition
WO2013178990A2 (fr) * 2012-05-30 2013-12-05 Reckitt Benckiser N.V. Composition
WO2013178990A3 (fr) * 2012-05-30 2014-01-30 Reckitt Benckiser N.V. Composition
RU2635250C2 (ru) * 2012-05-30 2017-11-09 Рекитт Бенкизер Калгон Б.В. Композиция для умягчения воды

Also Published As

Publication number Publication date
MX159427A (es) 1989-05-29
IE840262L (en) 1984-10-08
JPS6018595A (ja) 1985-01-30
DE3460228D1 (en) 1986-07-24
ATE20476T1 (de) 1986-07-15
EP0124913B1 (fr) 1986-06-18
CA1220998A (fr) 1987-04-28
GR81656B (fr) 1984-12-12
IE56762B1 (en) 1991-12-04
JPH0522757B2 (fr) 1993-03-30

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