[0001] 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.
[0002] 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.
[0003] The individual components of the polymer additive system are well-known in detergent
technology and may have found commercial application.
[0004] 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.
[0005] 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.
[0006] 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.
[0007] 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.
[0008] 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.
[0009] 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.
[0010] 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.
[0011] 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.
BRIEF DESCRIPTION OF THE INVENTION
[0012] 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:
.
[0013]
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 -H4.
[0014] 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.
DETAILED DESCRIPTION OF THE INVENTION
[0015] 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.
[0016] Unless indicated to the contrary, the "percent" indications represent "percent by
weight" indications.
[0017] 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.
[0018] 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.
[0019] 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.
[0020] 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%.
[0021] 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.
[0022] 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%.
[0023] The compositions herein contain as an essential detergent component a mixture of
a polyacrylic homopolymer and a copolymeric ingredient.
[0024] The polyacrylate homopolymer has a molecular weight below 3000 and is utilized in
levels of from 0,5% to 15%.
[0025] 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.
[0026] 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%.
[0027] 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.
[0028] 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.
[0029] The sequestration value is expressed in mgCaC0
3/gram of copolymeric ingredient.
[0030] The calcium sequestration value of the copolymeric ingredient is preferably higher
than 200 mg CaC0
3/g.
[0031] 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%.
[0032] 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.
[0033] 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 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%.
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.
[0034] The following examples illustrate the invention and highlight the benefits derivable
therefrom.
[0035] 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)
[0036] 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.
![](https://data.epo.org/publication-server/image?imagePath=1984/46/DOC/EPNWA1/EP84200104NWA1/imgb0001)
[0037] 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).
[0038] The testing results were as follows:
![](https://data.epo.org/publication-server/image?imagePath=1984/46/DOC/EPNWA1/EP84200104NWA1/imgb0002)
[0039] These results show the significant performance benefits derivable from inventive
Composition I vs. closely related prior art compositions A and B.
[0040] The compositions of Examples II and C were compared as described hereinbefore except
for the following conditions.
[0041]
- 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.
[0042] The whiteness maintenance results were as follows:
![](https://data.epo.org/publication-server/image?imagePath=1984/46/DOC/EPNWA1/EP84200104NWA1/imgb0003)
[0043] The performance superiority of the claimed technology vs. identical compositions
containing high molecular weight polyacrylates is confirmed.
[0044] An additional composition 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:
![](https://data.epo.org/publication-server/image?imagePath=1984/46/DOC/EPNWA1/EP84200104NWA1/imgb0004)
[0045] 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.
[0046] The results were as follows:
![](https://data.epo.org/publication-server/image?imagePath=1984/46/DOC/EPNWA1/EP84200104NWA1/imgb0005)
[0047] The inventive composition is again markedly superior over the art.
[0048] 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.
[0049] The whiteness readings were done with a Zeiss-spectrophotometer. The results were
as follows:
![](https://data.epo.org/publication-server/image?imagePath=1984/46/DOC/EPNWA1/EP84200104NWA1/imgb0006)
[0050] These results show that the combined utilization of the copolymeric and the homopolymeric
ingredients is a requisite for obtaining the inventive benefits.
1. A granular detergent composition 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 composition contains
a) from 0.5% to 15% by weight of a polyacrylate homopolymer having a molecular weight
below 3000;
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.
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 P-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 P-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 1 wherein the homopolymeric ingredient
is comprised of a polyacrylate having a molecular weight of 2000 and a polyacrylate
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.