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Claims  |
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What is claimed is:
1. A solid automatic dishwashing detergent composition, comprising by
weight:
(A) from about 15% to about 80% of a detergency builder selected from the
group consisting of water soluble, alkali metal, ammonium, or substituted
ammonium phosphates, polyphosphates, citrates, and mixtures thereof;
(B) from about 0.1% to about 10% modified polyacrylate copolymer having a
molecular weight of from about 1,000 to about 5,000, said modified
polyacrylate copolymer comprising from about 90% to 10% acrylic acid
monomer or its salts and from about 10% to about 90% of a substituted
acrylic monomer, said substituted acrylic monomer having the formula:
##STR5##
wherein at least one of said R.sub.1 -R.sub.3 is a C.sub.1 -C.sub.4 alkyl
or hydroxyalkyl, R.sub.1 -R.sub.2 may be hydrogen and R.sub.3 may be
hydrogen or alkali metal salt;
(C) from about 0.001% to about 5% detersive enzyme; and
(D) from about 0.01% to about 40% alkali metal silicate.
2. An automatic dishwashing detergent composition according to claim 1
wherein said detersive enzyme is selected from the group consisting of
protease, amylase, lipase and mixtures thereof.
3. An automatic dishwashing detergent composition according to claim 2
wherein said polyacrylate copolymer is from about 80% to about 20% by
weight acrylic acid monomer or its salts and from about 20% to about 80%
by weight of a substituted acrylic monomer having the general formula:
##STR6##
wherein at least one of the substituents R.sub.1, R.sub.2, or R.sub.3 is a
1 to 4 carbon alkyl or hydroxyalkyl group.
4. An automatic dishwashing detergent composition according to claim 3
further comprising from about 0.01% to about 40% low foaming detergent
surfactant.
5. An automatic dishwashing detergent composition according to claim 1
wherein said detergency builder further comprises a builder selected from
the group consisting of carbonate, bicarbonate, polyacetate, carboxylates,
polycarboxylates and mixtures thereof.
6. An automatic dishwashing detergent composition according to claim 1
wherein said detergency builder further includes ethane 1-hydroxy-1, 1
diphosphonic acid or its alkali metal salts, present at a level of from
about 0.01% to about 20% by weight of the composition.
7. An automatic dishwashing detergent composition according to claim 5
further comprising a bleach component sufficient to provide from about
0.1% to about 5.0% by weight available oxygen.
8. An automatic dishwashing detergent composition according to claim 6
wherein said low foaming detergent is a nonionic surfactant.
9. An automatic dishwashing detergent composition according to claim 7
comprising from about 0.005 to about 3% by weight protease or amylase.
10. An automatic dishwashing detergent composition according to claim 9
wherein said bleach is percarbonate.
11. An automatic dishwashing detergent composition according to claim 9
wherein said polyacrylate copolymer has a molecular weight of 3500 and is
about 70% by weight acrylic acid and about 30% by weight methylacrylic
acid.
12. A granular automatic dishwashing detergent composition according to
claim 11 wherein said composition is agglomerated with from about 4% to
about 25% by weight of a liquid binder selected from the group consisting
of water, aqueous solution(s) of alklai metal salts of a polycarboxylic
acid, nonionic surfactant and mixtures thereof.
13. A granular automatic dishwashing detergent composition according to
claim 9 further comprising from about 0.01% to about 6% by weight chlorine
bleach scavengers.
14. A liquid automatic dishwashing detergent composition, comprising by
weight:
(A) from about 15% to about 80% of a detergency builder selected from the
group consisting of water soluble, alkali metal, ammonium, or substituted
ammonium phosphates, polyphosphates, citrates, and mixtures thereof;
(B) from about 0.1% to about 10% modified polyacrylate copolymer having a
molecular weight of from about 1,000 to about 5,000, said modified
polyacrylate copolymer comprising from about 90% to 10% acrylic acid
monomer or its salts and from about 10% to about 90% of a substituted
acrylic monomer, said substituted acrylic monomer having the formula:
##STR7##
wherein at least one of said R.sub.1 -R.sub.3 is a C.sub.1 -C.sub.4 alkyl
or hydroxyalkyl, R.sub.1 -R.sub.2 may be hydrogen, and R.sub.3 may be
hydrogen or alkali metal salt;
(C) from about 0.001% to about 5% detersive enzyme;
(D) from about 0.01% to about 40% alkali metal silicate; and
(E) the balance comprising a liquid carrier selected from the group
consisting of water, primary alcohols, secondary alcohols, monohyric
alcohols, polyols, and mixtures thereof.
15. A liquid automatic dishwashing detergent according to claim 14 further
comprising from about 0.001% to about 10% of an enzyme stabilizing system.
16. A liquid automatic dishwashing detergent composition according to claim
15 further comprising from about 0.1% to about 10% of thixotropic
thickening agent.
17. A liquid automatic dishwashing detergent composition according to claim
16 wherein said thixotropic thickening agent is a polymer with a molecular
weight from about 500,000 to about 10,000,000.
18. A liquid automatic dishwashing detergent composition according to claim
17 wherein said enzyme stabilizing system is selected from the group
consisting of calcium ion, boric acid, propylene glycol, short chain
carboxylic acid, boronic acid, polyhydroxyl compounds and mixtures
thereof.
19. A solid automatic dishwashing detergent composition, comprising by
weight:
(A) from about 15% to about 80% of a detergency builder selected from the
group consisting of carbonate, bicarbonate, polyacetate, carboxylates,
polycarboxylates and mixtures thereof;
(B) from about 0.1% to about 10% modified polyacrylate copolymer having a
molecular weight of from about 1,000 to about 5,000, and comprising about
70% by weight acrylic acid and about 30% by weight methacrylic acid;
(C) from about 0.005% to about 3% protease, amylase, or mixtures;
(D) from about 0.01% to about 40% low foaming nonionic surfactant;
(E) from about 4% to about 25% alkali metal silicate; and
(F) a sufficient amount of perborate to provide from about 0.1% to about
20% by weight available oxygen.
20. The composition of claim 18 wherein said composition is agglomerated
with from about 4% to about 25% by weight of a liquid binder selected from
the group consisting of water, aqueous solutions of alkali metal salts of
polycarboxylic acid, nonionic surfactant, and mixtures thereof.
21. A liquid automatic dishwashing detergent composition, comprising by
weight:
(A) from about 15% to about 80% of a detergency builder selected from the
group consisting of carbonate, bicarbonate, polyacetate, carboxylates,
polycarboxylates and mixtures thereof;
(B) from about 0.1% to about 10% modified polyacrylate copolymer having a
molecular weight of from about 1,000 to about 5,000, and comprising about
70% by weight acrylic acid and about 30% by weight methacrylic acid;
(C) from about 0.005% to about 3% protease, amylase, or mixtures;
(D) from about 0.1% to about 10% of thixotropic thickening agent;
(E) from about 0.001% to about 10% of an enzyme stabilizing system selected
from the group consisting of calcium ion, boric acid, propylene glycol,
short chain carboxylic acid, boronic acid, polyhydroxyl compounds and
mixtures thereof; and
(F) the balance comprising a liquid carrier selected from the group
consisting of water, primary alcohols, secondary alcohols, monohyric
alcohols, polyols, and mixtures thereof. |
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Claims |
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Description |
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TECHNICAL FIELD
This invention is in the field of liquid and granular automatic dishwashing
compositions. More specifically, the invention relates to compositions
containing builder (i.e. citrate, carbonate and/or phosphate), low
molecular weight modified polyacrylate copolymers, and enzyme.
BACKGROUND OF THE INVENTION
Liquid and granular automatic dishwashing detergent components while
necessary for various cleaning benefits, often can create other problems.
For example, carbonate, and phosphate, conventional detergent ingredients,
are known to contribute to formation of hard water film on glasses.
Organic dispersants can overcome the problem of unsightly films which form
on china, especially on glassware, due to calcium- or
magnesium-hardness-induced precipitation of pH-adjusting agents. However
not all dispersants work as well on the various types of precipitation.
Although conventional low molecular weight polyacrylate homopolymers are
satisfactory in the dispersion of insoluble calcium carbonate in automatic
dishwashing detergent compositions, it has recently been found that low
molecular weight modified polyacrylate copolymers enhance filming
performance in automatic dishwashing detergent compositions.
In addition, not only do the low molecular weight modified polyacrylates of
the present invention prevent hard water filming due to precipitation but
it has been surprisingly found that these modified polyacrylate copolymers
show improved enzyme performance (i.e. bulk food removal) in enzyme
containing automatic dishwashing detergent compositions.
SUMMARY OF THE INVENTION
The present invention encompasses a liquid or granular automatic
dishwashing detergent composition comprising:
(a) from about 0.01% to about 90% detergency builder;
(b) from about 0.1% to about 20% modified polyacrylate copolymer having a
molecular weight of less than about 15,000; and
(c) from about 0.001% to about 5% detersive enzyme.
A preferred liquid or granular automatic dishwashing detergent composition
herein comprises carbonate.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is a liquid or granular automatic dishwashing
detergent composition comprising:
(a) from about 0.01% to about 90% detergency builder;
(b) from about 0.1% to about 20% modified polyacrylate copolymer having a
molecular weight less than about 15,000; and
(c) from about 0.001% to about 5% detersive enzyme.
Compositions of the invention exhibit enhanced hard water filming
performance and improved enzyme performance by the presence of low
molecular weight modified polyacrylate copolymers.
Detergency Builder
The detergency builders used can be any of the detergency builders known in
the art, which include the various water-soluble, alkali metal, ammonium
or substituted ammonium phosphates, polyphosphates, phosphonates,
polyphosphonates, carbonates, bicarbonates, borates,
polyhydroxysulfonates, polyacetates, carboxylates (e.g. citrates), and
polycarboxylates. Preferred are the alkali metal, especially sodium, salts
of the above and mixtures thereof.
The amount of builder is from about 0.01% to about 90%, preferably from
about 15% to about 80%, most preferably from about 15% to about 75% by
weight of the automatic dishwashing detergent composition.
Specific examples of inorganic phosphate builders are sodium and potassium
tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree
of polymerization of from about 6 to 21, and orthophosphate. Examples of
polyphosphonate builders are the sodium and potassium salts of ethylene
diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-1,
1-diphosphonic acid and the sodium and potassium salts of ethane,
1,1,2-triphosphonic acid. A particularly preferred polyphosphonate builder
component is ethane 1-hydroxy-1, 1 diphosphonic acid or its alkali metal
salts, which demonstrates calcium carbonate crystal growth inhibition
properties, present at a level of from about 0.01% to about 20%,
preferably from about 0.1% to about 10%, most preferably from about 0.2%
to about 5% by weight of the compositions. Other phosphorus builder
compounds are disclosed in U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021;
3,422,137, 3,400,176 and 3,400,148, incorporated herein by reference.
Examples of non-phosphorus, inorganic builders are sodium and potassium
carbonate, bicarbonate, sesquicarbonate and hydroxide.
Water-soluble, non-phosphorus organic builders useful herein include the
various alkali metal, ammonium and substituted ammonium polyacetates,
carboxylates, polycarboxylates and polyhydroxysulfonates. Examples of
polyacetate and polycarboxylate builders are the sodium, potassium,
lithium, ammonium and substituted ammonium salts of ethylene diamine
tetraacetic acid, nitrilotriacetic acid, tartrate monosuccinic acid,
tartrate disuccinic acid, oxydisuccinic acid, carboxy methyloxysuccinic
acid, mellitic acid, benzene polycarboxylic acids, and citric acid. The
acidic forms of these builders can also be used, preferably citric acid.
Preferred detergency builders have the ability to remove metal ions other
than alkali metal ions from washing solutions by sequestration, which as
defined herein includes chelation, or by precipitation reactions. Sodium
tripolyphosphate is typically a particularly preferred detergency builder
material because of its sequestering ability. Sodium citrate is also a
particularly preferred detergency builder, particularly when it is
desirable to reduce or eliminate the total phosphorus level of the
compositions of the invention.
Particularly preferred automatic dishwashing detergent compositions of the
invention contain, by weight of the automatic dishwashing detergent
composition, from about 5% to about 40%, preferably from about 10% to
about 30%, most preferably from about 15% to about 20%, of sodium
carbonate. Particularly preferred as a replacement for the phosphate
builder is sodium citrate with levels from about 5% to about 40%,
preferably from about 7% to 35%, most preferably from about 8% to about
30%, by weight of the automatic dishwashing detergent composition.
Low Molecular Weight Modified Polyacrylates
The present invention can contain from about 0.1% to about 20%, preferably
from about 1% to about 10%, most preferably from about 3% to about 8%, by
weight of the automatic dishwashing detergent composition, of low
molecular weight modified polyacrylate copolymers.
The term modified polyacrylate is defined as a copolymer which contains as
monomer units: a) from about 90% to about 10%, preferably from about 80%
to about 20% by weight acrylic acid or its salts and b) from about 10% to
about 90%, preferably from about 20% to about 80% by weight of a
substituted acrylic monomer or its salts having the general formula:
##STR1##
wherein at least one of the substituents R.sub.1, R.sub.2 or R.sub.3,
preferably R.sub.1 or R.sub.2 is a 1 to 4 carbon alkyl or hydroxyalkyl
group, R.sub.1 or R.sub.2 can be a hydrogen and R.sub.3 can be a hydrogen
or alkali metal salt. Most preferred is a substituted acrylic monomer
wherein R.sub.1 is methyl, R.sub.2 is hydrogen and R.sub.3 is sodium.
The low molecular weight polyacrylate preferably has a molecular weight of
less than about 15,000, preferably from about 500 to about 10,000, most
preferably from about 1,000 to about 5,000. The most preferred
polyacrylate copolymer has a molecular weight of 3500 and is about 70% by
weight acrylic acid and about 30% by weight methyl acrylic acid.
Suitable modified polyacrylate copolymers include the low molecular weight
copolymers of unsaturated aliphatic carboxylic acids as disclosed in U.S.
Pat. Nos. 4,530,766, and 5,084,535, both of which are incorporated herein
by reference.
Detersive Enzyme
The compositions of this invention may contain from about 0.001% to about
5%, more preferably from about 0.003% to about 4%, most preferably from
about 0.005% to about 3%, by weight, of active detersive enzyme. The
preferred detersive enzyme is selected from the group consisting of
protease, amylase, lipase and mixtures thereof. Most preferred are
protease or amylase or mixtures thereof.
The proteolytic enzyme can be of animal, vegetable or microorganism
(preferred) origin. More preferred is serine proteolytic enzyme of
bacterial origin. Purified or nonpurified forms of this enzyme may be
used. Proteolytic enzymes produced by chemically or genetically modified
mutants are included by definition, as are close structural enzyme
variants. Particularly preferred is bacterial serine proteolytic enzyme
obtained from Bacillus, Bacillus subtilis and/or Bacillus licheniformis.
Suitable proteolytic enzymes include Alcalase.RTM., Esperase.RTM.,
Durazym.RTM., Savinase.RTM.(preferred); Maxatase.RTM., Maxacal.RTM.
(preferred), and Maxapem.RTM. 15 (protein engineered Maxacal);
Purafect.RTM. (preferred) and subtilisin BPN and BPN'; which are
commercially available. Preferred proteolytic enzymes are also modified
bacterial serine proteases, such as those described in European Patent
Application Serial Number 87 303761.8, filed Apr. 28, 1987 (particularly
pages 17, 24 and 98), and which is called herein "Protease B", and in
European Patent Application 199,404, Venegas, published Oct. 29, 1986,
which refers to a modified bacterial serine proteolytic enzyme which is
called "Protease A" herein. Preferred proteolytic enzymes, then, are
selected from the group consisting of Savinase.RTM., Esperase.RTM.,
Maxacal.RTM., Purafect.RTM., BPN', Protease A and Protease B, and mixtures
thereof. Savinase.RTM. is most preferred.
Suitable lipases for use herein include those of bacterial, animal, and
fungal origin, including those from chemically or genetically modified
mutants.
Suitable bacterial lipases include those produced by Pseduomonas, such as
Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent
1,372,034, incorporated herein by reference. Suitable lipases include
those which show a positive immunological cross-reaction with the antibody
of the lipase produced from the microorganism Pseudomonas fluorescens IAM
1057. This lipase and a method for its purification have been described in
Japanese Patent Application 53-20487, laid open on Feb. 24, 1978, which is
incorporated herein by reference. This lipase is available under the trade
name Lipas P "Amano," hereinafter referred to as "Amano-P." Such lipases
should show a positive immunological cross reaction with the Amano-P
antibody, using the standard and well-known immunodiffusion procedure
according to Oucheterlon (Acta. Med. Scan., 133, pages 76-79 (1950)).
These lipases, and a method for their immunological cross-reaction with
Amano-P, are also described in U.S. Pat. No. 4,707,291, Thom et al.,
issued Nov. 17, 1987, incorporated herein by reference. Typical examples
thereof are the Amano-P lipase, the lipase ex Pseudomonas fragi FERM P
1339 (available under the trade name Amano-B), lipase ex Pseudomonas
nitroreducens var. lipolyticum FERM P 1338 (available under the trade name
Amano-CES), lipases ex Chromobacter viscosum var. lipolyticum NRR1b 3673,
and further Chromobacter viscousm lipases, and lipases ex Pseudomonas
gladioli. A preferred lipase is derived from Pseudomonas
pseudoalcaligenes, which is described in Granted European Patent,
EP-B-0218272. Other lipases of interest are Amano AKG and Bacillis Sp
lipase (e.g. Solvay enzymes).
Other lipases which are of interest where they are compatible with the
composition are those described in EP A 0 339 681, published Nov. 28,
1990, EP A 0 385 401, published Sep. 5, 1990, EO A 0 218 272, published
Apr. 15, 1987, and PCT/DK 88/00177, published May 18, 1989, all
incorporated herein by reference.
Suitable fungal lipases include those produced by Humicola lanuginosa and
Thermomyces lanuginosus. Most preferred is lipase obtained by cloning the
gene from Humicola lanuginosa and expressing the gene in Aspergillus
oryzae as described in European Patent Application 0 258 068, incorporated
herein by reference, commercially available under the trade name
Lipolase.RTM. from Novo-Nordisk.
Any amylase suitable for use in a dishwashing detergent composition can be
used in these compositions. Amylases include for example, .alpha.-amylases
obtained from a special strain of B. licheniforms, described in more
detail in British Patent Specification No. 1,296,839. Amylolytic enzymes
include, for example, Rapidase.TM., Maxamyl.TM., Termamyl.TM. and BAN.TM..
In a preferred embodiment, from about 0.001% to about 5%, preferably 0.005%
to about 3%, by weight of active amylase can be used. Preferably from
about 0.005% to about 3% by weight of active protease can be used.
Preferrably the amylase is Maxamyl.TM. and/or Termamyl.TM. and the
protease is Savinase.RTM. and/or protease B.
Detergent Surfactants
The compositions of this invention can contain from about 0.01% to about
40%, preferably from about 0.1% to about 30% of a detergent surfactant. In
the preferred automatic dishwashing detergent compositions of the
invention the detergent surfactant is most preferably low foaming by
itself or in combination with other components (i.e. suds suppressors) is
low foaming.
Compositions which are chlorine bleach free do not require the surfactant
to be bleach stable. However, since these compositions contain enzymes,
the surfactant employed is preferably enzyme stable (enzyme compatible)
and free of enzymatically reactive species. For example, when proteases
and amylases are employed, the surfactant should be free of peptide or
glycosidic bonds.
Desirable detergent surfactants include nonionic, anionic, amphoteric and
zwitterionic detergent surfactants, and mixtures thereof.
Examples of nonionic surfactants include:
(1) The condensation product of 1 mole of a saturated or unsaturated,
straight or branched chain, alcohol or fatty acid containing from about 10
to about 20 carbon atoms with from about 4 to about 40 moles of ethylene
oxide. Particularly preferred is the condensation product of a fatty
alcohol containing from 17 to 19 carbon atoms, with from about 6 to about
15 moles, preferably 7 to 12 moles, most preferably 9 moles, of ethylene
oxide provides superior spotting and filming performance. More
particularly, it is desirable that the fatty alcohol contain 18 carbon
atoms and be condensed with from about 7.5 to about 12, preferably about 9
moles of ethylene oxide. These various specific C.sub.17 -C.sub.19
ethoxylates give extremely good performance even at lower levels (e.g.,
2.5%-3%). At the higher levels (less than 5%), they are sufficiently low
sudsing, especially when capped with a low molecular weight (C.sub.1-5)
acid or alcohol moiety, so as to minimize or eliminate the need for a
suds-suppressing agent. Suds-suppressing agents in general tend to act as
a load on the composition and to hurt long term spotting and filming
characteristics.
(2) Polyethylene glycols or polypropylene glycols having molecular weight
of from about 1,400 to about 30,000, e.g., 20,000; 9,500; 7,500; 7,500;
6,000; 4,500; 3,400; and 1,450. All of these materials are wax-like solids
which melt between 110.degree. F. (43.degree. C.) and 200.degree. F.
(93.degree. C.).
(3) The condensation products of 1 mole of alkyl phenol wherein the alkyl
chain contains from about 8 to about 18 carbon atoms and from about 4 to
about 50 moles of ethylene oxide.
(4) Polyoxypropylene, polyoxyethylene condensates having the formula
HO(C.sub.2 H.sub.6 O).sub.x (C.sub.3 H.sub.6 O).sub.x H or HO(C.sub.3
H.sub.6 O).sub.y (C.sub.2 H.sub.4 O).sub.x (C.sub.3 H.sub.6 O).sub.y H
where total y equals at least 15 and total (C.sub.2 H.sub.4 O) equals 20%
to 90% of the total weight of the compound and the molecular weight is
from about 2,000 to about 10,000, preferably from about 3,000 to about
6,000. These materials are, for example, the PLURONICS.RTM. from BASF
which are well known in the art.
(5) the compounds of (1) and (4) which are capped with propylene oxide,
butylene oxide and/or short chain alcohols and/or short chain fatty acids,
e.g., those containing from 1 to about 5 carbon atoms, and mixtures
thereof.
Useful surfactants in detergent compositions are those having the formula
RO--(C.sub.2 H.sub.4 O).sub.x R.sup.1 wherein R is an alkyl or alkylene
group containing from 17 to 19 carbon atoms, x is a number from about 6 to
about 15, preferably from about 7 to about 12, and R.sub.1 is selected
from the group consisting of: hydrogen, C.sub.1-5 alkyl groups, C.sub.2-5
acyl groups and groups having the formula --(C.sub.y H.sub.2y O).sub.n H
wherein y is 3 or 4 and n is a number from one to about 4.
Particularly suitable surfactants are the low-sudsing compounds of (4), the
other compounds of (5), and the C.sub.17 -C.sub.19 materials of (1) which
have a narrow ethoxy distribution. Certain of the block co-polymer
surfactant compounds designated PLURONIC.RTM., PLURAFAC.RTM. and
TETRONIC.RTM. by the BASF Corp., Parsippany, N.J. are suitable as the
surfactant for use herein. A particularly preferred embodiment contains
from about 40% to about 70% of a polyoxypropylene, polyoxethylene block
polymer blend comprising about 75%, by weight of the blend, of | | |
