CA1220998A - Granular detergent compositions containing mixed polymer additive system - Google Patents
Granular detergent compositions containing mixed polymer additive systemInfo
- Publication number
- CA1220998A CA1220998A CA000447604A CA447604A CA1220998A CA 1220998 A CA1220998 A CA 1220998A CA 000447604 A CA000447604 A CA 000447604A CA 447604 A CA447604 A CA 447604A CA 1220998 A CA1220998 A CA 1220998A
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- Prior art keywords
- weight
- ingredient
- detergent
- composition
- phosphorus
- Prior art date
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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
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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)
Abstract
GRANULAR DETERGENT COMPOSITIONS CONTAINING MIXED
POLYMER ADDITIVE SYSTEM
Abstract of the Disclosure Granular detergent compositions with no or reduced levels of phosphorus -containing builders containing a mix-ture of homopolymeric and copolymeric carboxylates. Pre-ferred homopolymeric carboxylates are polyacrylates having a molecular weight below 3000, most preferably a mixture of polymer species having molecular weights of 1000 and 2000 respectively. The preferred copolymeric ingredient contains maleic acid and (meth)-acrylic acid monomers.
POLYMER ADDITIVE SYSTEM
Abstract of the Disclosure Granular detergent compositions with no or reduced levels of phosphorus -containing builders containing a mix-ture of homopolymeric and copolymeric carboxylates. Pre-ferred homopolymeric carboxylates are polyacrylates having a molecular weight below 3000, most preferably a mixture of polymer species having molecular weights of 1000 and 2000 respectively. The preferred copolymeric ingredient contains maleic acid and (meth)-acrylic acid monomers.
Description
~2(~
GR~NULAR DETERGENT COMPOSITIONS CONTAINING MIXED
POLYMER ADDITIVE SYSTEM
This invention relates to granular detergent compo-sitions which are free of or with reduced levels of phos-phorus-containing builders containing a mixed polymer ad-ditive system. The polymer system comprises specific homo-polymeric polyacrylates and copolymeric carboxylates where-by the homopolymeric species are characterized by a molecu lar 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 poly-acrylates having molecular weights of around 1000 and 2000respectively.
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 indi-vidual polymers or mixtures of various conventional deter-gent polymers. The claimed technology is especially bene-ficial 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 polyphospha-te builder level reduction leads to performance deficiencies which cannot be cured in a fully acceptable manner with the sole aid of a conventional detergent addi-5 tive such as a polymeric carboxylate.
The individual components of the polymer additive sys-tem are well-known in detergent technology and may have found commercial application.
The copolymeric ingredient is known from European 10 Patent 0 025 551A, BASF AG, which discloses such material in an incrustation inhibitor functionality in detergent compo-sitions.
The detergent art is also possessed of combinations of the copolymeric ingredient and conventional detergent addi-15 tives. French Patent 2,388,045, July 1, 1983, The PROCTER &GAMBLE Company, is representative of this general knowledge.
It discloses detergent compositions containing surface-active agen*s, builders, and a binary system of additive levels of a polyphosphonate and a polymeric ingredient which 20 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 915C.
In detail, this reference discloses the utilization of the ~5 copolymeric ingredient in combination with detergent per-formance additives inclusive of hydrocarbon detergent suds regulants, photoactivators, amine or oxidized amine soil release agents, silicone detergent suds regulants and bleach activators/peracids.
~he detergent utilization of polyacrylates/ having a molecular weight in the range of from 1000 to 5000, is known from ~.K. Patent Application 2.097.419D, Colgate-Palmo-live. Detergent compositions are disclosed containing high levels of difficultly processable components inclusive of 35 sodium carbonate, sodium-bicarbonate, detergent zeolites, and bentonites. It is said that the polyacrylates are added ~;22~9~
in a processing aid Eunckionality to ensure uniform mixiny of -the crutcher mix component. Comparabl.e disclosures are known from U.IC. Pa-tent Application 2 095 274 E, Colgate-Palmolive. Detergent eompositions containing substantial levels of water-insoluble ingredients inclusive of zeolite builders, and bentonite.s, carbonates and bi-carbonates are processed into beads whereby physical and detergent proper-ties are controlled with the aid of polyacrylates having moleeular 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 133F, BASF AG;
German Patent Application 26 25 444G, CIBA-GEIGY AG; and Belgian Patent 881 488H, SENZORA B.V. The BASF '133 referen-ce 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 mole-cular weight polymer mixtures, namely combinations of hydroli-zed 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 unsaturatedmonomer whereby the molecular weight of the copolymeric spe-cies 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 aeid having a molecular weight in the range of from 12.~00 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 composi-tions containing no or reduced levels of conventional poly phosphate builders with the aid of carboxylates. While prior art attempts for solving the problem have yielded some benefits, fre~uently processing advantages, the claimed sys-tem procures significant textile laundry benefits and canconstitute basis for superior commercial detergent executions.
P9~8 It i.s a major object of this invention to formulate granular detergent compositions having no or reduced level of phosphorus-containing builders capable of providing te~-tile cleaning performance comparable to phosphate built com-positions.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 ln up to the boil washing operations.
BRIEF DESCRIPTION OF THE INVENTION
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 re-duced level of conventional phosphorus (P)-containing deter-gent builders. In more detail, it has been discovered thatsuch 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 additi-ves including non-phosphorus detergent builders, characte-rized 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 whereby the weight ratio of the homopolymeric ingredient to the copolymeric ingredient is in the range from 4:1 to 1:4.
In a preferred aspect of this invention, the compositions herein comprise reduced (vs. current practice) levels of ~12~
. 5 _ polyphosphate builders such as corresponding -to phosphorus levels in the range of from 2% to 5% by weight. rrhe latter P-levels, if e.g. calculated on basis of sodiumtripolyphos-phate amount to from 8% to 20% by weight.
DETAILED DESCRIPTION OF THE INVENTION
The invention herein comprises a series of essential components, namely: a granular detergent composition contain-ing conventional matrix components; and a binary polymer system containing a homopolymeric polyacryla-te 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 des-cribed in more detail hereinafter.
Unless indicated to the contrary, the "percent" indica-tions represent "percent by weight" indications.
The detergent matrix comprises a surface-active agent, a detergent builder, preferably reduced level of tripolyphos-phate, 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.
Qualitative and quantitative indications concerning suitable detergent builder materials for use herein are found in U.S.-PS 4,192,761.
The compositions herein unexpectedly provide superior laundry cleaning performance, as compared to commercial phos-~`' .~.
~z~
phate built detergen-t compositions, in the absence of or wi-th reduced level of phosphate builder, especially deter-gent compositions containing phosphate builder levels re~
presenting 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 10 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 15 phosphorus-containing detergent builder in a level, calcu~
lated 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. des-cribed in DE-AS 24 22 655K. Additional builders for use herein include nitrilotriacetic acids or the water-soluble alkali salts thereof, sodium carbonate, sodium citrate, so-dium silicates and fatty acid soaps e.g. sodlum or potassiumsoaps.
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 deter-gent component a mixture of a polyacrylic homopolymer and a copolymeric ingredient.
The polyacrylate homopolymer has a molecular weight 35 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 oE two difEerent polyacrylates, one havi.ng a molecular weight of about 2000 and a second one having a molecular weight of about 1000, whereby these spe cies are used in a weight ratio of 2:1 to 1:2, most prefer-ably 1:1. The polyacrylate component is well-known in de-tergent -technology. The molecular weight of the polyacryl-ate 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 de-tergent matrix components. Particularly relevant in this respect are variations in the qualitative and quantitative parameters of the builder system. Reduced levels of poly-phosphate e.g. between 8-12~ by weight will require a rela-tively higher level of the homopolymer as compared to whatis needed for levels of sodium tripolyphosphate in the range of from e.g. 15%-18~.
A further essential component for use herein is a copo-lymer of an unsaturated monocarboxylic acid and an unsatura-ted di-carboxylic acid. This copolymeric ingredient is used in levels from 0,5~ to 15%. The copolymeric ingredient con-sists of an ethylenically unsaturated monocarboxylic acid monomer having not more than 5, preferably 3 or 4, carbon atoms, and an ethylenically unsaturated dicaxboxylic 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 se~uestration value. These values can be measured by nephelometric titration methods (as described .~2Z~
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 contain-ing sequestrant and sodium oxalate until turbidity is produced; the tit.ra-tion is being carried out at constant pH = 10 and room temperature.
The sequestration value is expressed in mgCaC03/gram oE
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 ~:1 and preferably from 2:1 to 1:2. While the quan-titative levels of the individual homopolymer and the indi-vidual 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 de-tergent compositions containing from 2% to 5% phosphorus.
In another embodiment the detergent compositions herein pre-ferably contain from 2% to 8% of the homopolymeric ingre-dient 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 cornponents, a series of supplemen-tary substances to perfect and augment the performance bene-fits. The additional components are represented by known ingredients which have already found application in deter-gency, for their known functionality in the art established levels. Examp].es of the like components include peroxygen .~
bleaches, such as perborate mono-or tetrahydrate and perca~-bonate, oxygen bleach activators such as -tetraacetyl ethy-lene diamine, oxygen bleach regulants such as a copolymer of maleic anhydride and methylvlnylether, detergent enzymes such as proteases, amylases, lipases and mixtures thereof, and stabili~ing agents Eor the like enzymes. Other optional components include soil suspending agents such as the sodium salt of carboxymethylcellulose and the sodium salt of methyl-hydroxypropyl cellulose; through-the-wash softening smectite clays such as alkali montmorillonites, saponites and hecto-rites, having an ion-exchange capacity of at least 50m.eg./
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 187L
and 0 042 188M. Preferred soil release agents include N-hy-drogenated tallow C16-C18-N,N',N'-tri-(2-hydroxyethyl)-propylene-1,3-diamine and N-C12-CI4-coconutalkyl-N,N-dime-thyl-N-amine oxide and ~an 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 des-cribed in European Patent Application 0 011 340N.
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 ~-OS sodium salt of ~-olefin (C12_18) sUlonate 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 DT~ : Ditallow methyl a~ine CFA : C12 14 coconut fatty acid HFA : Hydrogenated C16_22 fatty acid STPP : Sodium tripolyphosphate Zeolite A : Sodium salt of zeolite 4A (avera~e particle size between 2-6 microns) NTA : Sodium salt of nitrilotriacetate Copolymer : AA JMA = 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 Silica.te 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 following granular detergent compositions were pre-pared by conventional spray-drying of a slurry of most of the individual lngredients and subsequent dry-mixing oE the ~z~
spray-dried powder with spray-drying sensitive ingredien-ts, namely perborate enzyme photoactivator and suds regulant.
COMPOSITIONS (~ by weight) EXAMPLES
I A B II C
LAS 5.05.0 5.05.0 5.0 TAS 3.03.0 3.03.0 TAE 1.01.0 1.01.0 1.0 HFA 1.01.0 1.01.0 1.0 10 STPP 18.018.0 18.018.0 18.0 Copolymer MA /AA2.0 2.04.0 1.0 1.0 Polyacrylate MW 1000 1.0 - - - -Polyacrylate MW 2000 1.0 - - 2.0 Polyacrylate MW 4500 - 2.0 - - -15 Polyacrylate MW 200 000 - - - - 2.0 P.A 0.004 0.004 0.004 0.004 0.004 CMC 1.0 1.0 1.0 1.0 1.0 Silicate 1.6 8.0 8.-0 8.0 8.0 8.0 MgSO4 0.5 0.5 0.5 0.5 0.5 20 EDTA 0.2 0.2 0.2 0.2 0.2 Perborate 24.024.0 24.0 24.0 24.0 Enzyme 0.6 0.6 0.6 0.6 0.6 Suds regulant (l) 1.0 1.0 1.0 1.0 1.0 Brightener/Perfume/Water/
25 Sodium Sulfate balance to 100 (l) Prilled suds regulant system consisting of: 77~5%
sodiumtripolyphosphate and 22,5% active consisting of:
13,5% paraffin oil; 6~ paraffin wax (m.p. 70C); and 3% amorphous hydrophobi~ silica.
The compositions of Examples l (invention?, A and B
(prior art) were compared under the following conditions.
The variations were expressed as whiteness maintenance:
~ minidrums testing apparatus;
1~ 2Q~
- 0,6~ product concen-tration in wash liquor;
- 18 grains/US ~allon water hardness (3:1 Ca/Mg ratio);
- ~eating up from 15C to 90C; ~ 20' at 90C;
- fabrics : terry tracers;
- 4 cumulative cycles;
- whiteness readinys 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 differen-ce).
The testing results were as~ follows:
Composition I vs. Composition Astandard - 1.7 Composition I vs. Composition B
standard - 0-4 These results show the significant ~erformance benefit.s derivable from inventive Composition I vs. closely related prior art compositions A and B.
The compositions of EYamples 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);
- 90C prewash + mainwash cycle;
- 8 cumulative washes.
The whi.eness maintenance results were as follows:
Composition II vs. Composition C
_.
standa rd - 1.1 13 ~ gt3 The performance superi.ority of the claimed technology vs. identical compositions containing high molecular weight polvacrylates is confirmed.
An additional cornposition of this invention --III-- and closely related prior art compositions were spray-dried/dry-mixed as described above, the sole difference being the levels of polymers as follows:
E~pr~
III D E F
10Copol~er~60/AA40 1.5 1.0 3.0 Polyacrylate MW 1000 0.75 - - 1.5 " ~ 2000 0.75 - - 1.5 " M~'4500 - 2.0 The compositions of Examples III, D, and E were compa-red for whiteness maintenance under the conditions recitedfor Examples II and C, except that the water hardness was 18 grains/~S gallon.
The results were as follows:
Composition III vs.Composition D
_ _ _ 20standard - 2.8 Composition III vs.Composition E
standard - 2.1 The inventive composition is again markedly superior over the art.
Compositions III and F were compared for soil anti-redeposition, measured as whiteness, thereby using the follo-wing testing conditions:
- tubes testing apparatus;
- 0,3~ to 1,0~ product concentrations;
GR~NULAR DETERGENT COMPOSITIONS CONTAINING MIXED
POLYMER ADDITIVE SYSTEM
This invention relates to granular detergent compo-sitions which are free of or with reduced levels of phos-phorus-containing builders containing a mixed polymer ad-ditive system. The polymer system comprises specific homo-polymeric polyacrylates and copolymeric carboxylates where-by the homopolymeric species are characterized by a molecu lar 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 poly-acrylates having molecular weights of around 1000 and 2000respectively.
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 indi-vidual polymers or mixtures of various conventional deter-gent polymers. The claimed technology is especially bene-ficial 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 polyphospha-te builder level reduction leads to performance deficiencies which cannot be cured in a fully acceptable manner with the sole aid of a conventional detergent addi-5 tive such as a polymeric carboxylate.
The individual components of the polymer additive sys-tem are well-known in detergent technology and may have found commercial application.
The copolymeric ingredient is known from European 10 Patent 0 025 551A, BASF AG, which discloses such material in an incrustation inhibitor functionality in detergent compo-sitions.
The detergent art is also possessed of combinations of the copolymeric ingredient and conventional detergent addi-15 tives. French Patent 2,388,045, July 1, 1983, The PROCTER &GAMBLE Company, is representative of this general knowledge.
It discloses detergent compositions containing surface-active agen*s, builders, and a binary system of additive levels of a polyphosphonate and a polymeric ingredient which 20 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 915C.
In detail, this reference discloses the utilization of the ~5 copolymeric ingredient in combination with detergent per-formance additives inclusive of hydrocarbon detergent suds regulants, photoactivators, amine or oxidized amine soil release agents, silicone detergent suds regulants and bleach activators/peracids.
~he detergent utilization of polyacrylates/ having a molecular weight in the range of from 1000 to 5000, is known from ~.K. Patent Application 2.097.419D, Colgate-Palmo-live. Detergent compositions are disclosed containing high levels of difficultly processable components inclusive of 35 sodium carbonate, sodium-bicarbonate, detergent zeolites, and bentonites. It is said that the polyacrylates are added ~;22~9~
in a processing aid Eunckionality to ensure uniform mixiny of -the crutcher mix component. Comparabl.e disclosures are known from U.IC. Pa-tent Application 2 095 274 E, Colgate-Palmolive. Detergent eompositions containing substantial levels of water-insoluble ingredients inclusive of zeolite builders, and bentonite.s, carbonates and bi-carbonates are processed into beads whereby physical and detergent proper-ties are controlled with the aid of polyacrylates having moleeular 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 133F, BASF AG;
German Patent Application 26 25 444G, CIBA-GEIGY AG; and Belgian Patent 881 488H, SENZORA B.V. The BASF '133 referen-ce 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 mole-cular weight polymer mixtures, namely combinations of hydroli-zed 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 unsaturatedmonomer whereby the molecular weight of the copolymeric spe-cies 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 aeid having a molecular weight in the range of from 12.~00 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 composi-tions containing no or reduced levels of conventional poly phosphate builders with the aid of carboxylates. While prior art attempts for solving the problem have yielded some benefits, fre~uently processing advantages, the claimed sys-tem procures significant textile laundry benefits and canconstitute basis for superior commercial detergent executions.
P9~8 It i.s a major object of this invention to formulate granular detergent compositions having no or reduced level of phosphorus-containing builders capable of providing te~-tile cleaning performance comparable to phosphate built com-positions.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 ln up to the boil washing operations.
BRIEF DESCRIPTION OF THE INVENTION
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 re-duced level of conventional phosphorus (P)-containing deter-gent builders. In more detail, it has been discovered thatsuch 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 additi-ves including non-phosphorus detergent builders, characte-rized 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 whereby the weight ratio of the homopolymeric ingredient to the copolymeric ingredient is in the range from 4:1 to 1:4.
In a preferred aspect of this invention, the compositions herein comprise reduced (vs. current practice) levels of ~12~
. 5 _ polyphosphate builders such as corresponding -to phosphorus levels in the range of from 2% to 5% by weight. rrhe latter P-levels, if e.g. calculated on basis of sodiumtripolyphos-phate amount to from 8% to 20% by weight.
DETAILED DESCRIPTION OF THE INVENTION
The invention herein comprises a series of essential components, namely: a granular detergent composition contain-ing conventional matrix components; and a binary polymer system containing a homopolymeric polyacryla-te 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 des-cribed in more detail hereinafter.
Unless indicated to the contrary, the "percent" indica-tions represent "percent by weight" indications.
The detergent matrix comprises a surface-active agent, a detergent builder, preferably reduced level of tripolyphos-phate, 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.
Qualitative and quantitative indications concerning suitable detergent builder materials for use herein are found in U.S.-PS 4,192,761.
The compositions herein unexpectedly provide superior laundry cleaning performance, as compared to commercial phos-~`' .~.
~z~
phate built detergen-t compositions, in the absence of or wi-th reduced level of phosphate builder, especially deter-gent compositions containing phosphate builder levels re~
presenting 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 10 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 15 phosphorus-containing detergent builder in a level, calcu~
lated 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. des-cribed in DE-AS 24 22 655K. Additional builders for use herein include nitrilotriacetic acids or the water-soluble alkali salts thereof, sodium carbonate, sodium citrate, so-dium silicates and fatty acid soaps e.g. sodlum or potassiumsoaps.
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 deter-gent component a mixture of a polyacrylic homopolymer and a copolymeric ingredient.
The polyacrylate homopolymer has a molecular weight 35 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 oE two difEerent polyacrylates, one havi.ng a molecular weight of about 2000 and a second one having a molecular weight of about 1000, whereby these spe cies are used in a weight ratio of 2:1 to 1:2, most prefer-ably 1:1. The polyacrylate component is well-known in de-tergent -technology. The molecular weight of the polyacryl-ate 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 de-tergent matrix components. Particularly relevant in this respect are variations in the qualitative and quantitative parameters of the builder system. Reduced levels of poly-phosphate e.g. between 8-12~ by weight will require a rela-tively higher level of the homopolymer as compared to whatis needed for levels of sodium tripolyphosphate in the range of from e.g. 15%-18~.
A further essential component for use herein is a copo-lymer of an unsaturated monocarboxylic acid and an unsatura-ted di-carboxylic acid. This copolymeric ingredient is used in levels from 0,5~ to 15%. The copolymeric ingredient con-sists of an ethylenically unsaturated monocarboxylic acid monomer having not more than 5, preferably 3 or 4, carbon atoms, and an ethylenically unsaturated dicaxboxylic 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 se~uestration value. These values can be measured by nephelometric titration methods (as described .~2Z~
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 contain-ing sequestrant and sodium oxalate until turbidity is produced; the tit.ra-tion is being carried out at constant pH = 10 and room temperature.
The sequestration value is expressed in mgCaC03/gram oE
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 ~:1 and preferably from 2:1 to 1:2. While the quan-titative levels of the individual homopolymer and the indi-vidual 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 de-tergent compositions containing from 2% to 5% phosphorus.
In another embodiment the detergent compositions herein pre-ferably contain from 2% to 8% of the homopolymeric ingre-dient 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 cornponents, a series of supplemen-tary substances to perfect and augment the performance bene-fits. The additional components are represented by known ingredients which have already found application in deter-gency, for their known functionality in the art established levels. Examp].es of the like components include peroxygen .~
bleaches, such as perborate mono-or tetrahydrate and perca~-bonate, oxygen bleach activators such as -tetraacetyl ethy-lene diamine, oxygen bleach regulants such as a copolymer of maleic anhydride and methylvlnylether, detergent enzymes such as proteases, amylases, lipases and mixtures thereof, and stabili~ing agents Eor the like enzymes. Other optional components include soil suspending agents such as the sodium salt of carboxymethylcellulose and the sodium salt of methyl-hydroxypropyl cellulose; through-the-wash softening smectite clays such as alkali montmorillonites, saponites and hecto-rites, having an ion-exchange capacity of at least 50m.eg./
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 187L
and 0 042 188M. Preferred soil release agents include N-hy-drogenated tallow C16-C18-N,N',N'-tri-(2-hydroxyethyl)-propylene-1,3-diamine and N-C12-CI4-coconutalkyl-N,N-dime-thyl-N-amine oxide and ~an 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 des-cribed in European Patent Application 0 011 340N.
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 ~-OS sodium salt of ~-olefin (C12_18) sUlonate 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 DT~ : Ditallow methyl a~ine CFA : C12 14 coconut fatty acid HFA : Hydrogenated C16_22 fatty acid STPP : Sodium tripolyphosphate Zeolite A : Sodium salt of zeolite 4A (avera~e particle size between 2-6 microns) NTA : Sodium salt of nitrilotriacetate Copolymer : AA JMA = 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 Silica.te 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 following granular detergent compositions were pre-pared by conventional spray-drying of a slurry of most of the individual lngredients and subsequent dry-mixing oE the ~z~
spray-dried powder with spray-drying sensitive ingredien-ts, namely perborate enzyme photoactivator and suds regulant.
COMPOSITIONS (~ by weight) EXAMPLES
I A B II C
LAS 5.05.0 5.05.0 5.0 TAS 3.03.0 3.03.0 TAE 1.01.0 1.01.0 1.0 HFA 1.01.0 1.01.0 1.0 10 STPP 18.018.0 18.018.0 18.0 Copolymer MA /AA2.0 2.04.0 1.0 1.0 Polyacrylate MW 1000 1.0 - - - -Polyacrylate MW 2000 1.0 - - 2.0 Polyacrylate MW 4500 - 2.0 - - -15 Polyacrylate MW 200 000 - - - - 2.0 P.A 0.004 0.004 0.004 0.004 0.004 CMC 1.0 1.0 1.0 1.0 1.0 Silicate 1.6 8.0 8.-0 8.0 8.0 8.0 MgSO4 0.5 0.5 0.5 0.5 0.5 20 EDTA 0.2 0.2 0.2 0.2 0.2 Perborate 24.024.0 24.0 24.0 24.0 Enzyme 0.6 0.6 0.6 0.6 0.6 Suds regulant (l) 1.0 1.0 1.0 1.0 1.0 Brightener/Perfume/Water/
25 Sodium Sulfate balance to 100 (l) Prilled suds regulant system consisting of: 77~5%
sodiumtripolyphosphate and 22,5% active consisting of:
13,5% paraffin oil; 6~ paraffin wax (m.p. 70C); and 3% amorphous hydrophobi~ silica.
The compositions of Examples l (invention?, A and B
(prior art) were compared under the following conditions.
The variations were expressed as whiteness maintenance:
~ minidrums testing apparatus;
1~ 2Q~
- 0,6~ product concen-tration in wash liquor;
- 18 grains/US ~allon water hardness (3:1 Ca/Mg ratio);
- ~eating up from 15C to 90C; ~ 20' at 90C;
- fabrics : terry tracers;
- 4 cumulative cycles;
- whiteness readinys 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 differen-ce).
The testing results were as~ follows:
Composition I vs. Composition Astandard - 1.7 Composition I vs. Composition B
standard - 0-4 These results show the significant ~erformance benefit.s derivable from inventive Composition I vs. closely related prior art compositions A and B.
The compositions of EYamples 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);
- 90C prewash + mainwash cycle;
- 8 cumulative washes.
The whi.eness maintenance results were as follows:
Composition II vs. Composition C
_.
standa rd - 1.1 13 ~ gt3 The performance superi.ority of the claimed technology vs. identical compositions containing high molecular weight polvacrylates is confirmed.
An additional cornposition of this invention --III-- and closely related prior art compositions were spray-dried/dry-mixed as described above, the sole difference being the levels of polymers as follows:
E~pr~
III D E F
10Copol~er~60/AA40 1.5 1.0 3.0 Polyacrylate MW 1000 0.75 - - 1.5 " ~ 2000 0.75 - - 1.5 " M~'4500 - 2.0 The compositions of Examples III, D, and E were compa-red for whiteness maintenance under the conditions recitedfor Examples II and C, except that the water hardness was 18 grains/~S gallon.
The results were as follows:
Composition III vs.Composition D
_ _ _ 20standard - 2.8 Composition III vs.Composition E
standard - 2.1 The inventive composition is again markedly superior over the art.
Compositions III and F were compared for soil anti-redeposition, measured as whiteness, thereby using the follo-wing testing conditions:
- tubes testing apparatus;
- 0,3~ to 1,0~ product concentrations;
- 2, grains/US galLon aater hardness (3:1 Ca/Mg ratio):
~L~2~
- heatiny up from 15C to 90C ~ 30' at 90C;
- fabrics : terry tracers.
The whiteness readings were done wi.th a Zeiss-spectro-photometer. The results were as -follows:
EX~MPLE
III F
% of soil deposition avoided at:
0.3% prod. concentration 70.3 70.4 0.4~ " 71.1 71.0 0.5% " 71.2 63.g 0.6% 'i 72.3 61.2 0.7% " 71.9 70.9 0.8% " 72.5 72.3 0.9% " 72.6 72.7 -1.0~ " 73.0 72.9 These results show that the combined utili~ation of t~e copolymeric and the homopolymeric ingredients is a requisite for obtaining the inventive benefits.
- 15 -- ~22~9~
Additional detergents of this invention ar. prepared haviny the following composition.
EXAMPLES
(~ by weight) ING~EDIENT IV V VI VII
-LAS 5.0 5.0 - 5.0 TAS 3.0 ~ 2.53.0 ~-OS - - 5.0 Coconut-trimethyl-~[uaternary ammonium chloride - 2.C - -TAEll 1.0 2.5 - 1.0 25 7 ~ - 4 0 DTMA ~ 5~5 CFA - - 4.0 HFA
STPP 20.0 20.0 16.028.0 Zeolite A - - 16.0 NTA 6.0 Na3Citrate - 5.0 20 Copolymer A~40/MA 1.5 2.0 2.01.O
Polyacrylate MW 1000 1.0 1.5 1.00.5 Polyacrylate ~IW 2000 1.0 1.5 1.00.5 CMC 0.8 - 1.0t0.8 Montmorillonite - 8.0 25 Silicate 1.6 6.0 6.0 2.0~.O
gSO4 0.5 - 0 51.0 NaOH 0.8 1.3 0.950.75 EGTA 0.2 0.2 0.30.2 Perborate 32.0 - 28.028.0 30 Suds regulant (1) 1.0 2.7 1.51.2 Enzyme (proteolytic) 0.2 0.6 0.30.2 Brightener, perfume, ~ater/
sodium sulfate b a 1 a n c e t o 100 (1) See E~ample I
~Z2~1~$~
EXAMPLES
(% by weightJ
INGREDIE~TS VIII IX X
LAS 10.0 5.0 7.0 TAS - 3.0 FAE3S 3.0 - -TAEll 1.0 1.0 2.7 HFA - 4~0 3.5 S~PP - 24.0 10.0 NTA 6.0 ~ 4,0 Na2C3 20.0 - 10.0 Copolymer MAA /~ 7.7 1.4 3.3 CMC 1.0 1.0 0.8 Polyacrylates l:l(MW1~00/2000)7.7 1.0 3.3 lS Silicate solids 1.6 4.0 3.0 8.0 MgSO4 1.0 - 0.5 NaOH 1.1 O.9 0.2 STS 1.4 -EDTA 0.2 0.3 0.3 Perborate 25.0 - 30.0 P.A. 0.007 0.003 0.002 Enzyme (proteolytic) 0.3 0.6 0.2 Brightener, perfume, ~2/
sulfate balance to IO0 ~2~ 3 EXAMPLES
(~ ~y wei~ht~
INGREDIENT XI XII XIII XIV
LAS
TAS - 2.5 - 2.5 A.O. 0.5 0.3 0.81.0 TAEll 2.7 - 2.7 FA25 7 2~.0 - 2.0 CFA - 2.0 - 2.0 STPP 4.0 24.0 16.08.0 Zeolite A - - 16.Q
NTA ~ - 4.0 - 6.0 Copolymer AA6 /MA 5.0 1.02.0 3.0 15 Polyacrylate MW 1000 2.0 1.0 1.51.0 Polyacrylate MW 2000 2.0 0.5 1.52.0 CMC 0.8 0.8 1.01.0 Silicate 1~6 5.0 5.0 2.02.0 MsSO4 - 0.5 0.51.0 20 Na2CO3 10.0 - 6.010.0 Ethylenediamine tetramethyl-phosphonate Na-salt 1.3 - 0.8 EDTA 0.2 0.3 0.30.2 Perborate 32.0 28.0 30.028.0 25 Enzyme (proteolytic) 0.2 0.2 0.30.2 Brishtener, perfume, water, sulfate balance to 100 EXAMPLES
(%~y weight) INGREDIENTS XV XVI XVlI
LAS
5 ~-OS _ _ 4.5 25E7 12.0 l0.0 6.0 CFA - 2.0 6.0 HFA 0.5 _ ~ 5 STPP 12.0 20.0 18.0 10 Zeolite A - - 20.0 Na3 Citrate - 10Ø
Copol~mer A~75/MA-5 2.0 1.O 1.3 Polyacrylates l:l mix (MW l000 and 2000) 4.0 1.0 2.5 15 CMC 0.8 1.0 0.8 Silicate l.6 6.0 6.0 2.0 ~ o4 0.5 - l.0 So~ium carbonate 5.0 5.0 NaOH 1.3 0.8 0.8 20 EDTA 0.2 0.2 0.3 Perborate 24.0 l0.0 28.0 Antioxidant 0.0l 0.0l 0.01 Silicone su~s regulant of Example I 1.6 2.1 1.3 25 Brightener, perfume, H2O, sulfate balance to 100 22~9~3 EXAMPLES
(~ by weight) INGREDIENT XVIII XIX XX XXI
~ . ~
LAS 7.0 5.0 15.0 4.0 5 TAS - 3~0 - -TAEll 2.7 - 2.5 25 7 2.0 - 12.0 C~A - 2.0 HFA 3.5 - 0.5 0.5 10 STPP 20.G 16.0 25.0 24.0 Zeolite A - 16.0 - -Copolymer AA6 /MA 2.0 2.0 1.0 1.0 Polyacrylate MW 1000 1.0 1.5 0.5 1.0 Polyacrylate MW 3000 1.0 1.5 0.5 0.5 15 CMC 0.8 1.2 1.0 1.0 Silicate solids 1.6 5.0 2.0 5.0 6.0 Silicate solids 1.0 1.0 MgSO4 0.5 l.C 0.5 1.0 Sod.ium carbonate 6.0 - 6.0 6.0 20 NaOH 0'75 0.50 0,95 1.1 TAED 3.0 2.5 4.0 2.5 Perborate 24.0 20.0 8.0 2.0 Antioxidant - - - O.01 Enzyme (proteolyLic) 0.3 0.6 0.6 0.3 25 Suds regulant silicone - 0,5 1.3 0.16 Brightener, perfume, water, su1fate bal~nce to 100
~L~2~
- heatiny up from 15C to 90C ~ 30' at 90C;
- fabrics : terry tracers.
The whiteness readings were done wi.th a Zeiss-spectro-photometer. The results were as -follows:
EX~MPLE
III F
% of soil deposition avoided at:
0.3% prod. concentration 70.3 70.4 0.4~ " 71.1 71.0 0.5% " 71.2 63.g 0.6% 'i 72.3 61.2 0.7% " 71.9 70.9 0.8% " 72.5 72.3 0.9% " 72.6 72.7 -1.0~ " 73.0 72.9 These results show that the combined utili~ation of t~e copolymeric and the homopolymeric ingredients is a requisite for obtaining the inventive benefits.
- 15 -- ~22~9~
Additional detergents of this invention ar. prepared haviny the following composition.
EXAMPLES
(~ by weight) ING~EDIENT IV V VI VII
-LAS 5.0 5.0 - 5.0 TAS 3.0 ~ 2.53.0 ~-OS - - 5.0 Coconut-trimethyl-~[uaternary ammonium chloride - 2.C - -TAEll 1.0 2.5 - 1.0 25 7 ~ - 4 0 DTMA ~ 5~5 CFA - - 4.0 HFA
STPP 20.0 20.0 16.028.0 Zeolite A - - 16.0 NTA 6.0 Na3Citrate - 5.0 20 Copolymer A~40/MA 1.5 2.0 2.01.O
Polyacrylate MW 1000 1.0 1.5 1.00.5 Polyacrylate ~IW 2000 1.0 1.5 1.00.5 CMC 0.8 - 1.0t0.8 Montmorillonite - 8.0 25 Silicate 1.6 6.0 6.0 2.0~.O
gSO4 0.5 - 0 51.0 NaOH 0.8 1.3 0.950.75 EGTA 0.2 0.2 0.30.2 Perborate 32.0 - 28.028.0 30 Suds regulant (1) 1.0 2.7 1.51.2 Enzyme (proteolytic) 0.2 0.6 0.30.2 Brightener, perfume, ~ater/
sodium sulfate b a 1 a n c e t o 100 (1) See E~ample I
~Z2~1~$~
EXAMPLES
(% by weightJ
INGREDIE~TS VIII IX X
LAS 10.0 5.0 7.0 TAS - 3.0 FAE3S 3.0 - -TAEll 1.0 1.0 2.7 HFA - 4~0 3.5 S~PP - 24.0 10.0 NTA 6.0 ~ 4,0 Na2C3 20.0 - 10.0 Copolymer MAA /~ 7.7 1.4 3.3 CMC 1.0 1.0 0.8 Polyacrylates l:l(MW1~00/2000)7.7 1.0 3.3 lS Silicate solids 1.6 4.0 3.0 8.0 MgSO4 1.0 - 0.5 NaOH 1.1 O.9 0.2 STS 1.4 -EDTA 0.2 0.3 0.3 Perborate 25.0 - 30.0 P.A. 0.007 0.003 0.002 Enzyme (proteolytic) 0.3 0.6 0.2 Brightener, perfume, ~2/
sulfate balance to IO0 ~2~ 3 EXAMPLES
(~ ~y wei~ht~
INGREDIENT XI XII XIII XIV
LAS
TAS - 2.5 - 2.5 A.O. 0.5 0.3 0.81.0 TAEll 2.7 - 2.7 FA25 7 2~.0 - 2.0 CFA - 2.0 - 2.0 STPP 4.0 24.0 16.08.0 Zeolite A - - 16.Q
NTA ~ - 4.0 - 6.0 Copolymer AA6 /MA 5.0 1.02.0 3.0 15 Polyacrylate MW 1000 2.0 1.0 1.51.0 Polyacrylate MW 2000 2.0 0.5 1.52.0 CMC 0.8 0.8 1.01.0 Silicate 1~6 5.0 5.0 2.02.0 MsSO4 - 0.5 0.51.0 20 Na2CO3 10.0 - 6.010.0 Ethylenediamine tetramethyl-phosphonate Na-salt 1.3 - 0.8 EDTA 0.2 0.3 0.30.2 Perborate 32.0 28.0 30.028.0 25 Enzyme (proteolytic) 0.2 0.2 0.30.2 Brishtener, perfume, water, sulfate balance to 100 EXAMPLES
(%~y weight) INGREDIENTS XV XVI XVlI
LAS
5 ~-OS _ _ 4.5 25E7 12.0 l0.0 6.0 CFA - 2.0 6.0 HFA 0.5 _ ~ 5 STPP 12.0 20.0 18.0 10 Zeolite A - - 20.0 Na3 Citrate - 10Ø
Copol~mer A~75/MA-5 2.0 1.O 1.3 Polyacrylates l:l mix (MW l000 and 2000) 4.0 1.0 2.5 15 CMC 0.8 1.0 0.8 Silicate l.6 6.0 6.0 2.0 ~ o4 0.5 - l.0 So~ium carbonate 5.0 5.0 NaOH 1.3 0.8 0.8 20 EDTA 0.2 0.2 0.3 Perborate 24.0 l0.0 28.0 Antioxidant 0.0l 0.0l 0.01 Silicone su~s regulant of Example I 1.6 2.1 1.3 25 Brightener, perfume, H2O, sulfate balance to 100 22~9~3 EXAMPLES
(~ by weight) INGREDIENT XVIII XIX XX XXI
~ . ~
LAS 7.0 5.0 15.0 4.0 5 TAS - 3~0 - -TAEll 2.7 - 2.5 25 7 2.0 - 12.0 C~A - 2.0 HFA 3.5 - 0.5 0.5 10 STPP 20.G 16.0 25.0 24.0 Zeolite A - 16.0 - -Copolymer AA6 /MA 2.0 2.0 1.0 1.0 Polyacrylate MW 1000 1.0 1.5 0.5 1.0 Polyacrylate MW 3000 1.0 1.5 0.5 0.5 15 CMC 0.8 1.2 1.0 1.0 Silicate solids 1.6 5.0 2.0 5.0 6.0 Silicate solids 1.0 1.0 MgSO4 0.5 l.C 0.5 1.0 Sod.ium carbonate 6.0 - 6.0 6.0 20 NaOH 0'75 0.50 0,95 1.1 TAED 3.0 2.5 4.0 2.5 Perborate 24.0 20.0 8.0 2.0 Antioxidant - - - O.01 Enzyme (proteolyLic) 0.3 0.6 0.6 0.3 25 Suds regulant silicone - 0,5 1.3 0.16 Brightener, perfume, water, su1fate bal~nce to 100
Claims (7)
1. A granular detergent composition containing no or reduced levels of phosphorus-containing builders, surface-active agents, polymeric carboxylates and, if desired, conventional detergent additives including non-phosphorus detergent builders, characterized in, that the composition contains a) from 0.5% to 15% by weight of a polyacrylate homopoly-mer having a molecular weight below 3000;
b) from 0.5% to 15% by weight of a copolymer which con-sists 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, whereby the weight ratio oE the homopolymeric ingredient to the copolymeric ingredient is in the range from 4:1 to 1:4.
b) from 0.5% to 15% by weight of a copolymer which con-sists 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, whereby the weight ratio oE the homopolymeric ingredient to the copolymeric ingredient is in the range from 4:1 to 1:4.
2. The composition in accordance with claim 1 wherein the copolymeric ingredient is comprised of (meth)-acrylic acid and maleic acid monomers.
3. The composition in accordance with claim 1 wherein, for a detergent composition containing phosphorus-builders in a level, expressed as phosphorus, of from 2% to 5% by weight, the homopolymeric ingredient represents from 0.5 to 4% by weight and the copolymeric ingredient represent from 0.5% to 4% by weight.
4. The composition in accordance with claim 1 wherein, for a detergent composition containing phosphorus-builders in a level, expressed as phosphorus, below 2% by weight, the homopolymeric ingredient represents from 2% to 8% by weight and the copolymeric ingredient from 2% to 8% by weight.
5. The composition in accordance with claims 1, 3 and 4 wherein the weight ratio of the copolymeric ingredient to the homopolymeric ingredient is from 2:1 to 1:2.
6. The composition in accordance with Claim wherein the homopolymeric ingredient is comprised of a polyacrylate having a molecular weight of 2000 and a poly-acrylate of a molecular weight of 1000 in a weight ratio of 2:1 to 1:2.
7. The detergent composition in accordance with Claims 1 and 6 wherein the homopolymer is represented by a 1:1 weight ratio mixture of polyacrylates having molecular weights of 1000 and 2000 respectively.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8309610 | 1983-04-08 | ||
| GB8309610 | 1983-04-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1220998A true CA1220998A (en) | 1987-04-28 |
Family
ID=10540835
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000447604A Expired CA1220998A (en) | 1983-04-08 | 1984-02-16 | 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) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3444960A1 (en) * | 1984-12-10 | 1986-06-12 | Henkel KGaA, 4000 Düsseldorf | GRAINY ADSORPTION |
| IN165509B (en) * | 1984-12-24 | 1989-11-04 | Colgate Palmolive Co | |
| GB8504733D0 (en) * | 1985-02-23 | 1985-03-27 | Procter & Gamble Ltd | Detergent compositions |
| DE3720806C2 (en) * | 1986-07-03 | 1997-08-21 | Clariant Finance Bvi Ltd | Use of a stabilizer in peroxide bleaching processes |
| DE3717227A1 (en) * | 1987-05-21 | 1988-12-01 | Henkel Kgaa | PHOSPHATE-FREE DETERGENT WITH REDUCED INCRUSTING TENDENCY |
| 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 (en) * | 1992-11-20 | 1994-05-26 | Basf Ag | Mixtures of polymers of monoethylenically unsaturated dicarboxylic acids and polymers of ethylenically unsaturated monocarboxylic acids and / or polyaminocarboxylic acids and their use |
| WO2010125154A1 (en) | 2009-04-30 | 2010-11-04 | Sanofi-Aventis Deutschland Gmbh | Pen-type injector with ergonomic button arrangement |
| EP2689001B1 (en) * | 2011-05-20 | 2017-09-27 | Dow Global Technologies LLC | Method of promoting soil release from fabrics |
| GB2502558A (en) * | 2012-05-30 | 2013-12-04 | Reckitt Benckiser Nv | Water softening composition |
| EP2855371B1 (en) * | 2012-05-30 | 2021-12-01 | Reckitt Benckiser Calgon BV | A water softening composition |
| JP2017149936A (en) * | 2016-02-23 | 2017-08-31 | ライオン株式会社 | Powder detergent composition for clothing |
Family Cites Families (7)
| 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 |
| NL7900849A (en) * | 1979-02-02 | 1980-08-05 | Senzora B V | DETERGENTS. |
| DE2936984A1 (en) * | 1979-09-13 | 1981-04-02 | Basf Ag, 6700 Ludwigshafen | USE OF (METH) ACRYLIC ACID-MALEIC ACID COPOLYMERISATES AS INCREDIBLE INHIBITORS IN DETERGENTS |
| IN161821B (en) * | 1981-02-26 | 1988-02-06 | Colgate Palmolive Co | |
| AU549000B2 (en) * | 1981-02-26 | 1986-01-09 | Colgate-Palmolive Pty. Ltd. | Base beads for detergent compositions |
| DE3277630D1 (en) * | 1981-05-30 | 1987-12-17 | Procter & Gamble | Detergent composition containing performance additive and copolymeric compatibilizing agent therefor |
-
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
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 |
| EP0124913A1 (en) | 1984-11-14 |
| IE840262L (en) | 1984-10-08 |
| JPH0522757B2 (en) | 1993-03-30 |
| IE56762B1 (en) | 1991-12-04 |
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