EP0124913A1 - Granular detergent compositions containing mixed polymer additive system - Google Patents
Granular detergent compositions containing mixed polymer additive system Download PDFInfo
- 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
Links
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.
Landscapes
- 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)
Abstract
Description
- 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. As is well-known, the 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.
- The 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. In detail, 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.
- The total prior art is consistently and unequivocally confirmatory of a standing desire for improving and enhancing textile laundry performance of granular detergent compositions containing no or reduced levels of conventional polyphosphate builders with the aid of carboxylates. While prior art attempts for solving the problem have yielded some benefits, frequently processing advantages, the claimed sys- tem procures significant textile laundry benefits and can constitute basis for superior commercial detergent executions.
- It is a major object of this invention to formulate granular detergent compositions having no or reduced level of phosphorus-containing builders capable of providing textile cleaning performance comparable to phosphate built compositions.
- It is a further object of this invention to formulate granular detergent compositions capable of providing superior textile cleaning benefits over a broad range of laundry conditions particularly in up to the boil washing operations.
- It has now been discovered that significantly enhanced textile cleaning can be obtained from the use of granular detergent compositions which do not contain or contain reduced level of conventional phosphorus (P)-containihg detergent builders. In more detail, it has been discovered that such benefits are derived from the utilization of granular detergent compositions containing no or reduced levels of P-containing builders, surface-active agents, polymeric carboxylates and, if desired, conventional detergent additives including non-phosphorus detergent builders, characterized in, that the compositions contain: .
-
- a) from 0.5% to 15% by weight of a polyacrylate homopolymer having a molecular weight below 3000; and
- b) from 0.5% to 15% by weight of a copolymer which consists of an ethylenically unsaturated monocarboxylic acid monomer having not more than 5 carbon atoms, and an ethylenically unsaturated dicarboxylic acid monomer having not more than 6 carbon atoms, whereby the molar ratio of the monomers is from 1:4 to 4:1; and
- In a preferred aspect of this invention, the 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. The latter 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. The major parameters of the invention are described in more detail hereinafter.
- Unless indicated to the contrary, the "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.
- Qualitatively and quantitatively suitable surface-active agents for use herein are disclosed in U.S.-PS 4,192,761, column 3, line 49 to column 5, line 42, this passage being incorporated herein by reference.
- Qualitative and quantitative indications concerning suitable detergent builder materials for use herein are found in U.S.-PS 4,192,761, column 8, line 56 to column 9, line 68, this passage being also incorporated herein by reference.
- The 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. Importantly, 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%.
- The 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%.
- In a preferred execution, 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
- - S. Chaberek and A.E. Martell, Organic Sequestering Agents, Wiley, New York, 1959;
- - R.L. Smith, The Sequestration of Metals, Chapman and Hall, London, 1959):
- a calcium nitrate solution is added to a solution containing sequestrant and sodium oxalate until turbidity is produced; the titration is being carried out at constant pH = 10 and room temperature.
- The sequestration value is expressed in mgCaC03/gram of copolymeric ingredient.
- The calcium sequestration value of the copolymeric ingredient is preferably higher than 200 mg CaC03/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 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. Examples of 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. Other optional components include 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.
- The subject 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 C16-C18-N,N'-N'-tri-(2-hydroxyethyl)-propylene-1,3-diamine and N-C12-C14-coconutalkyl-N,N-dimethyl-N-amine oxide and can be utilized in levels of from 0.1%-1,5%. The claimed 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 examples illustrate the invention and highlight the benefits derivable therefrom.
- The abbreviations for the individual ingredients have the following meaning:
- LAS : Sodium salt of linear dodecyl benzene sulfonate
- TAS : Sodium salt of tallow alcohol sulfate
- α-OS : Sodium salt of α-olefin (C12-18) sulfonate
- FAE3S : Sodium salt of fatty alcohol (C12-18) (ethoxy)3 sulfate
- AO : C12-14 alkyl dimethylamine oxide
- TAE11 : Tallow alcohol ethoxylated with about 11 moles of ethylene oxide
- FA25EX : Fatty alcohol (C12-C15) ethoxylated with X moles of ethylene oxide
- DTMA : Ditallow methyl amine
- CFA : C12-14 coconut fatty acid
- HFA : Hydrogenated C16-22 fatty acid
- STPP : Sodium tripolyphosphate
- Zeolite A : Sodium salt of zeolite 4A (average particle size between 2-6 microns)
- NTA : Sodium salt of nitrilotriacetate
- Copolymer : AA40/MA60 = copolymer of acrylic acid 40% mol.% and maleic acid 60% mol.%
- CMC : Sodium salt of carboxymethyl cellulose
- Clay : Sodium montmorillonite
- Silicate 1.6 : Sodium silicate SiO2/Na2O = 1.6
- Silicate 1.0 : Sodium metasilicate
- STS : Sodium salt of toluene sulfonate
- EDTA : Sodium salt of ethylene diamine tetra-acetate
- Perborate : NaBO2·H2O2·3H2O
- P.A. : Photoactivator sulfonated Zn phthalocyanine
- Antioxidant : 4,4'-thiobis(6-tertiary butyl-3-m-cresol)
-
- The compositions of Examples I (invention), A and B (prior art) were compared under the following conditions. The variations were expressed as whiteness maintenance:
- - minidrums testing apparatus;
- - 0,6% product concentration in wash liquor;
- - 18 grains/US gallon water hardness (3:1 Ca/Mg ratio);
- - heating up from 15°C to 90°C; + 20' at 90°C;
- - fabrics : terry tracers;
- - 4 cumulative cycles;
- - whiteness-readings under standard daylight: visual grading by two judges working independently. O to 4 scale (0 = no difference, 1 = probable difference, 2 = consistent small difference, 3 = clear difference, 4 = big difference).
-
- These results show the significant performance benefits derivable from inventive Composition I vs. closely related prior art compositions A and B.
- The compositions of Examples II and C were compared as described hereinbefore except for the following conditions.
-
- - commercial washing machine;
- - 1% product concentration;
- - 12 grains/US gallon water hardness (3:1 Ca/Mg ratio);
- - 90°C prewash + mainwash cycle;
- - 8 cumulative washes.
-
- The performance superiority of the claimed technology vs. identical compositions containing high molecular weight polyacrylates is confirmed.
-
- The 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:
- - tubes testing apparatus;
- - 0,3% to 1,0% product concentrations;
- - 25 grains/US gallon water hardness (3:1 Ca/Mg ratio);
- - heating up from 15°C to 90°C + 30' at 90°C;
- - fabrics : terry tracers.
-
- These results show that the combined utilization of the copolymeric and the homopolymeric ingredients is a requisite for obtaining the inventive benefits.
-
Claims (7)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT84200104T ATE20476T1 (en) | 1983-04-08 | 1984-01-30 | GRANULATED DETERGENT COMPOSITIONS CONTAINING A MIXED POLYMER ADDITIVE SYSTEM. |
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 (en) | 1984-11-14 |
EP0124913B1 EP0124913B1 (en) | 1986-06-18 |
Family
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 (en) |
JP (1) | JPS6018595A (en) |
AT (1) | ATE20476T1 (en) |
CA (1) | CA1220998A (en) |
DE (1) | DE3460228D1 (en) |
GR (1) | GR81656B (en) |
IE (1) | IE56762B1 (en) |
MX (1) | MX159427A (en) |
Cited By (13)
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 (en) * | 1985-02-23 | 1986-09-03 | The Procter & Gamble Company | Detergent compositions |
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 (en) * | 1986-07-03 | 1990-11-13 | Sandoz Sa | STABILIZATION OF PEROXIDE-BASED BLEACHING AGENTS. |
WO1990013622A1 (en) * | 1989-05-02 | 1990-11-15 | Ecolab Inc. | Zero phosphorus heavy duty laundry detergent composition |
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 (en) * | 1992-10-08 | 1994-06-08 | Rohm And Haas Company | Method for preparing low molecular, crosslinked, water soluble polymers and their use as detergent builder, scale inhibitor or dispersant |
WO1994012571A2 (en) * | 1992-11-20 | 1994-06-09 | Basf Aktiengesellschaft | Mixtures of unsaturated carboxylic acid polymerizates and use |
GB2502558A (en) * | 2012-05-30 | 2013-12-04 | Reckitt Benckiser Nv | Water softening composition |
WO2013178990A2 (en) * | 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)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2689001B1 (en) * | 2011-05-20 | 2017-09-27 | Dow Global Technologies LLC | Method of promoting soil release from fabrics |
JP2017149936A (en) * | 2016-02-23 | 2017-08-31 | ライオン株式会社 | Powder detergent composition for clothing |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3002710A1 (en) * | 1979-02-02 | 1980-09-04 | Senzora B V | Low-phosphate detergent compsns. - contg. poly:carboxylate and carboxylic polymer salts |
EP0025551A1 (en) * | 1979-09-13 | 1981-03-25 | BASF Aktiengesellschaft | Use of (meth)acrylic acid and maleic acid copolymers as incrustation inhibitors in detergents |
FR2500475A1 (en) * | 1981-02-26 | 1982-08-27 | Colgate Palmolive Co | BASE PEARLS FOR THE MANUFACTURE OF DETERGENT COMPOSITIONS, PROCESS AND MIXTURES FOR THEIR MANUFACTURE AND DETERGENT COMPOSITIONS CONTAINING SAME |
EP0066915A2 (en) * | 1981-05-30 | 1982-12-15 | THE PROCTER & GAMBLE COMPANY | Detergent composition containing performance additive and copolymeric compatibilizing agent therefor |
Family Cites Families (3)
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 (en) * | 1975-06-30 | 1983-06-08 | 株式会社日本触媒 | Senzai Sosabutsu |
IN161821B (en) * | 1981-02-26 | 1988-02-06 | Colgate Palmolive Co |
-
1984
- 1984-01-30 EP EP84200104A patent/EP0124913B1/en not_active Expired
- 1984-01-30 AT AT84200104T patent/ATE20476T1/en not_active IP Right Cessation
- 1984-01-30 DE DE8484200104T patent/DE3460228D1/en not_active Expired
- 1984-02-03 IE IE262/84A patent/IE56762B1/en not_active IP Right Cessation
- 1984-02-16 CA CA000447604A patent/CA1220998A/en not_active Expired
- 1984-02-20 GR GR73845A patent/GR81656B/el unknown
- 1984-02-27 MX MX200467A patent/MX159427A/en unknown
- 1984-03-13 JP JP59048006A patent/JPS6018595A/en active Granted
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3002710A1 (en) * | 1979-02-02 | 1980-09-04 | Senzora B V | Low-phosphate detergent compsns. - contg. poly:carboxylate and carboxylic polymer salts |
EP0025551A1 (en) * | 1979-09-13 | 1981-03-25 | BASF Aktiengesellschaft | Use of (meth)acrylic acid and maleic acid copolymers as incrustation inhibitors in detergents |
FR2500475A1 (en) * | 1981-02-26 | 1982-08-27 | Colgate Palmolive Co | BASE PEARLS FOR THE MANUFACTURE OF DETERGENT COMPOSITIONS, PROCESS AND MIXTURES FOR THEIR MANUFACTURE AND DETERGENT COMPOSITIONS CONTAINING SAME |
EP0066915A2 (en) * | 1981-05-30 | 1982-12-15 | THE PROCTER & GAMBLE COMPANY | Detergent composition containing performance additive and copolymeric compatibilizing agent therefor |
Cited By (19)
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 (en) * | 1985-02-23 | 1986-09-03 | The Procter & Gamble Company | Detergent compositions |
EP0193360A3 (en) * | 1985-02-23 | 1987-07-01 | The Procter & Gamble Company | Detergent compositions |
BE1002261A5 (en) * | 1986-07-03 | 1990-11-13 | Sandoz Sa | STABILIZATION OF PEROXIDE-BASED BLEACHING AGENTS. |
US4919845A (en) * | 1987-05-21 | 1990-04-24 | Henkel Kommanditgesellschaft Auf Aktien | Phosphate-free detergent having a reduced tendency towards incrustation |
WO1990013622A1 (en) * | 1989-05-02 | 1990-11-15 | Ecolab Inc. | Zero phosphorus heavy duty laundry detergent composition |
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 (en) * | 1992-10-08 | 1994-06-08 | Rohm And Haas Company | Method for preparing low molecular, crosslinked, water soluble polymers and their use as detergent builder, scale inhibitor or dispersant |
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 (en) * | 1992-11-20 | 1994-06-09 | Basf Aktiengesellschaft | Mixtures of unsaturated carboxylic acid polymerizates and use |
WO1994012571A3 (en) * | 1992-11-20 | 1994-08-04 | Basf Ag | Mixtures of unsaturated carboxylic acid polymerizates and use |
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 (en) * | 2012-05-30 | 2013-12-05 | Reckitt Benckiser N.V. | Composition |
WO2013178990A3 (en) * | 2012-05-30 | 2014-01-30 | Reckitt Benckiser N.V. | A water softening composition |
RU2635250C2 (en) * | 2012-05-30 | 2017-11-09 | Рекитт Бенкизер Калгон Б.В. | Composition for water softening |
Also Published As
Publication number | Publication date |
---|---|
EP0124913B1 (en) | 1986-06-18 |
DE3460228D1 (en) | 1986-07-24 |
JPS6018595A (en) | 1985-01-30 |
ATE20476T1 (en) | 1986-07-15 |
MX159427A (en) | 1989-05-29 |
GR81656B (en) | 1984-12-12 |
CA1220998A (en) | 1987-04-28 |
IE840262L (en) | 1984-10-08 |
JPH0522757B2 (en) | 1993-03-30 |
IE56762B1 (en) | 1991-12-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0066915B1 (en) | Detergent composition containing performance additive and copolymeric compatibilizing agent therefor | |
EP0126551B1 (en) | Detergent compositions | |
EP0068721B1 (en) | Fabric washing process and detergent composition for use therein | |
EP0124913B1 (en) | Granular detergent compositions containing mixed polymer additive system | |
US4695284A (en) | Cool water fabric washing process using a particulate detergent containing a nonionic and a fatty acid builder salt | |
US4919845A (en) | Phosphate-free detergent having a reduced tendency towards incrustation | |
EP0137669B1 (en) | Detergent compositions | |
EP0221777B1 (en) | Detergent compositions | |
JPS61246299A (en) | Detergent composition | |
US4988454A (en) | Low phosphorus containing detergent powders and process for preparing them: surfactant, aluminosilicate, sodium silicate and polyacrylate | |
AU620381B2 (en) | Detergent powders and process for preparing them | |
CA1314188C (en) | Detergent compositions | |
US4325829A (en) | Detergent compositions | |
EP0419036A2 (en) | Detergency builder additive and detergent system containing it | |
GB2109398A (en) | Detergent composition for washing fabrics | |
EP0042188B1 (en) | Detergent composition containing low levels of amine oxides | |
EP0182411B1 (en) | Detergent compositions containing polymers | |
GB2138439A (en) | Detergent composition | |
EP0492679B1 (en) | Detergent powders | |
JPH05132696A (en) | Composition and method for preventing sticking of textile | |
JPH01161098A (en) | Phosphorus free washing and bleaching composition | |
EP0075347B1 (en) | Low phosphate detergent composition | |
IE60527B1 (en) | Detergent compositions | |
JPH05132697A (en) | Composition and method for preventing sticking of textile | |
JPH1121597A (en) | Powdery laundry detergent composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19840309 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
REF | Corresponds to: |
Ref document number: 20476 Country of ref document: AT Date of ref document: 19860715 Kind code of ref document: T |
|
ITF | It: translation for a ep patent filed |
Owner name: ING. C. GREGORJ S.P.A. |
|
REF | Corresponds to: |
Ref document number: 3460228 Country of ref document: DE Date of ref document: 19860724 |
|
ET | Fr: translation filed | ||
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
26 | Opposition filed |
Opponent name: UNILEVER PLC / UNILEVER N.V. Effective date: 19870310 |
|
NLR1 | Nl: opposition has been filed with the epo |
Opponent name: UNILEVER PLC / UNILEVER N.V. |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
R26 | Opposition filed (corrected) |
Opponent name: UNILEVER PLC / UNILEVER N.V. Effective date: 19870310 |
|
PLBN | Opposition rejected |
Free format text: ORIGINAL CODE: 0009273 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: OPPOSITION REJECTED |
|
27O | Opposition rejected |
Effective date: 19890717 |
|
NLR2 | Nl: decision of opposition | ||
ITTA | It: last paid annual fee | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19950110 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 19950111 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19950118 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19950120 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19950121 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19950125 Year of fee payment: 12 |
|
EAL | Se: european patent in force in sweden |
Ref document number: 84200104.2 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19950131 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19950302 Year of fee payment: 12 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19960130 Ref country code: AT Effective date: 19960130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19960131 Ref country code: LI Effective date: 19960131 Ref country code: CH Effective date: 19960131 Ref country code: BE Effective date: 19960131 |
|
BERE | Be: lapsed |
Owner name: PROCTER & GAMBLE EUROPEAN TECHNICAL CENTER Effective date: 19960131 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19960801 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19960130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Effective date: 19960930 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 19960801 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19961001 |
|
EUG | Se: european patent has lapsed |
Ref document number: 84200104.2 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |