Note: Descriptions are shown in the official language in which they were submitted.
CA 0221461~ 1997-09-03
C 6a~;2 (-V)
,.. .
Machine Dishwashinq Compo~ition ContAi n; n~ Am~hoteric
PolYmers
Field of Invention
The invention relates to detergent compositions containing
amphoteric polymers to control the deposition of lime soap,
particularly machine dishwashing compositions containing
lipolytic enzymes.
Backqround of the Invention
A critical criteria for an effective machine dishwashing
composition is the appearance of both the washed glassware
and plastic articles to the consumer. Spotting and filming
of such tableware, when washed with commercial products,
generally results from mineral deposition during the
evaporation of undrained wash solution in the drying step.
The deposited minerals are from many sources, including
salts of ingredients in the product formulations, calcium
carbonate from temporary water hardness, and suspended
20 soil.
The deposition on the surfaces of the washed articles make
them look dull due to the presence of spots, streaks or
surface covering film. The most intense spotting problems
are related to the deposition of hydrophobic soil
fragments. In the final rinse stage, this hydrophobic soil
is thought to break-up the water film, leaving droplets
~ehind on the tableware which result in mineral deposits
observed as white spots upon evaporation of the water
component.
A prior art solution to the removal of these white mineral
spots has been the addition of a rinse aid composition to
the rinsing water of the machine cycle. Although the visual
appearance of the washed tableware is improved, some
CA 0221461~ 1997-09-03
C 6-~62 ~v)
spotting, but especially mineral film formation has still
been observed even with the use of this additional product.
Moreover, use of a rinse aid is inconvenient to the
consumer.
The major fraction of the hydrophobic soil fragments that
are present on washed tableware is believed to be
triglyceride and fatty ester soil. Consequently, machine
dishwashing and rinse aid compositions incorporating
lipolytic enzymes which assist in breaking down these soiIs
have been described in
EP-A-346,136 and EP-A-271,155. Although lipolytic enzymes
can reduce the formation of mineral spots due to
hydrophobic soil fragments, the enzymes can also cause a
different type of white deposits to build up on hydrophobic
surfaces such as plastics. These fatty deposits are due to
precipitation of lime soaps which are formed from the
mixture of calcium and magnesium ions in the wash water
with fatty acids, which are liberated from the triglyceride
and fatty ester soils by the action of the lipolytic
enzymes. The higher the level of fatty soil present in the
dishwasher, the worse the problem of lime soap deposition.
Prior art solutions to these problems include formulations
of machine dishwashing compositions incorporating certain
lime soap dispersants with lipolytic enzymes as described
in
W0-94/07984 and W0-94/07985 (Proctor & Gamble). Tableware
washed with compositions containing lipases and these lime
soap dispersants have been observed to have low lime soap
film scores (i.e. little to no filming is observed).
However, a large number of white mineral spots on the
washed articles have been observed. It is thus believed
that the lime soap dispersants described in these
publications actually inhibit the action of the lipase.
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C 6-~62 (.V)
Hydrophobically modified copolymers, of especially acrylic
acid, have been described in copending Gordon et al.; U.S.
Serial No. 08/457,690 for incorporation in machine
dishwashing compositions. Calcium soap deposition is
reduced by the presence of these polymers.
US-A-4,891,149 describes polymeric lime soap dispersants
which consist of copolymers and water soluble salts of
copolymers of acrylic acid, methacrylic acid and mixtures
thereof and acrylamide, alkyl or alkylol substituted
acrylamide, or mixture of said acrylamides. Optionally,
enzymes may also be added to the formulations.
US-A-5,308,532 (Rohm & Haas) describes aminoacryloyl -
containing terpolymers which are useful for reducing
mineral spotting and filming of tableware. Thus, the
detergent formulation acts by preventing hydrophobic
deposits on glassware and does not address the issue of
preventing lime soap deposition. The use of lipolytic
enzymes in combination with such terpolymers to control the
deposition of lime soaps is neither taught nor suggested.
It is therefore an object of the present invention to
provide machine dishwashing compositions and methods of
using them to prevent lime soap deposition on washed
tableware.
Another object of the invention is to selectively combine
lipolytic enzymes with particular amphoteric polymers in a
detergent composition to control lime soap deposition and
virtually prevent spotting and lime soap filming on cleaned
tableware.
Summary of the Invention
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C 6.362 (V)
Accordingly, the present invention provides a machine
washing composition comprising:
(a) an effective amount of a amphoteric polymer wherein in
a 1~ aqueous wash liquor having a pH of about 7 or
greater, positive charges on the polymer comprise
between 1~ and 50~, preferably between 2~ and 20~,
most preferably between 5 and 15~ of the total charges
on the polymer having a formula selected from:
i) AXByCz where in a 1~ aqueous wash liquor pH
A is an anionic moiety, B is a cationic moiety
and C is an anionic, cationic, amphoteric or
uncharged moiety and mixtures thereof, x, y,
and z refer to mole percentages, x is 50-99~,
preferably 80-98~, most preferably 85-95~, and
y is 1-50~, preferably 2-20~, most preferably
5-15~ and z is 0 to 25~, preferably 0 to 18~;
or
ii) DdEf where at the wash pH D is an amphoteric
moiety, E is an anionic, cationic, or uncharged
moiety and mixture thereof, d and f refer to
mole percentages, and d is 1-100~ and f is 0-
99~ provided the above stated charge
distribution is satisfied;
(b) 0.01~ to about 4 wt. ~ of a lipolytic enzyme; and
(c) about 1 to about 75~ by wt. of a builder material.
A bleaching agent is optionally included.
Detailed DescriPtion of Preferred Embodiments
The amphoteric polymers incorporated in the compositions of
the invention are present in an effective amount,
preferably about 0.1 to about 25~, more preferably from
CA 022l46l~ l997-09-03
C 6362 (V)
about 1 to about 15~, most preferably from about 2 to about
10~ by wt.
Wash pH is defined as the measured pH of a 1~ aqueous
solution of dishwasher water in the main wash cycle after
addition and dissolution of the detergent composition. At a
wash pH preferably between about 7 and about 12, most
preferably between about 8 and about 11, positive charges
on the polymer comprise between 1~ and 50~, preferably
between 2~ and 20~, most preferably between 5 and 15~ of
the total charges on the polymer.
The amphoteric polymers are addition polymers which may be
prepared by (1) copolymerizing selected monomers which are
anionic at the wash pH with selected monomers which are
cationic at the wash pH, or (2) by polymerizing selected
amphoteric monomers.
A first means of preparing the amphoteric polymers which
are useful in the invention consists of copolymerizing from
about 50 to about 99~ , preferably from about 80 to about
98~, most preferably from about 85 to about 98% by wt. of
the anionic monomer (A) with about 1 to about 50~,
preferably from about 2 to about 20~, most preferably from
about 2 to about 15~ by wt. of the cationic monomer.
Optionally, a charged or uncharged moiety (C) is also
copolymerized.
The monomers (A) used to prepare the amphoteric polymers
are substituted vinyl compounds which have anionic
character at wash pH. Preferred monomers are substituted
vinyl compounds of formula l
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C 6 ~62 (V)
H R3
(I)
Rl R2
wherein R1, R2, and R3 are independently a hydrogen, C1 to C3
alkyl, a carboxylate group or a carboxylate group
substituted with a C1 to C30 straight or branched alkyl,
aromatic heterocycle or a polyalkylamine oxide with the
requirement that at least one of R1, R2, or R3 must be a
carboxylate or substituted carboxylate;
Preferred monomers include acrylic acid, methacrylic acid,
maleic acid, ~-ethacrylic acid, ~,~,-dimethacrylic acid,
methylenemalonic acid, vinylacetic acid, allylacetic acid,
ethylidineacetic acid, propylidineacitic acid, crotonic
acid, fumaric acid, itaconic acid, citraconic acid,
mesaconic acid and the like. Most preferred monomers
include acrylic acid, methacrylic acid, and maleic acid.
The monomers (B) used to form the amphoteric polymers of
the invention which have cationic character at wash pH are
substituted vinyl compounds of formula ll
R5
I I ~)
R4 Q
wherein R4 is a hydrogen, aromatic, heterocycle or a
polyalkylamine oxide; Rs is a hydrogen or a Cl to C30
straight or branched alkyl; and Q i8 a nitrogen-containing
organic radical, said radical having a pKa value of ~ 7.
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C 6~62 (~)
methacrylate, dialkylaminoalkyl acrylate, dialkylaminoalkyl
methacrylamide and dialkylaminoalkyl acrylamide.
The monomers of formula II are preferably quaternized
wherein Q is preferably selected from the group consisting
of formula 111
--CH2N (CH3)~,CH2CH=CH2 X (III)
wherein X~ is any suitable counterion such as halogen,
hydroxide, sulfate, hydrosulfate, phosphate, formate and
lS acetate or,
a compound of formula lV
-Z-CH2-CR6R7(CH2)mN ' R8R9R'0 (IV)
wherein Z is selected from the group consisting of O, COO
and CONR11 in which R11 is a hydrogen or a C1 to C3 alkyl
group; R6 and R7 are each independently selected from the
group consisting of hydrogen, C1 to C4 alkyl or R6 and R7
taken together form a C3 to C7 aliphatic heterocycle; m is
0 to 2 provided that when m is 0 a C-N bond is present in
lieu of the (CH2)m group and R8, R9, and R10are each
independently selected from a group consisting of hydrogen
or a Cl to C~ alkyl; or R8 and R9 are taken together with
the nitrogen to which they are attached to form a 3 to 7
membered non-aromatic nitrogen heterocycle; and X is any
suitable counterion such as a halogen, hydroxide, sulfate,
hydrosulfate, phosphate, formate and acetate.
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C 6362 (V.)
Preferred examples of the quaternized monomers are (3-
acrylamidopropyl) trimethylammonium chloride (APTAC), (3-
methacrylamidopropyl) trimethylammonium
chloride (MAPTAC), and dimethyldiallylammonium chloride
(DMDAC). Other suitable examples include such materials
as vinylbenzyltrialkylammonium salts and the like.
Monomers (C) which are anionic or cationic are selected
from compounds of formula I or II, respectively.
Amphoteric monomers (C) may be selected from compounds of
formula V described below.
/ IRl3 \ IRl~ 1~l
t R ~ Rl6 Y
wherein, Rl2 is a C3 to C6 monoethylenically unsaturated
carboxylate; Rl3 and Rl~ each independently represent
hydrogen or a Cl to C3 alkyl; Rls and Rl6 each independently
represent a hydrogen or a Cl to C3 alkyl; x is 1 to 3; and
y is 1 to 3.
Suitable carboxylates represented by Rl2 include, but are
not limited to, acrylic acid, methacrylic acid, ~-
ethacrylic acid, ~,~,-dimethacrylic acid, methylenemalonic
acid, vinylacetic acid, allylacetic acid, ethylidineacetic
acid, propylidineacitic acid, crotonic acid, maleic acid,
fumaric acid, itaconic acid, citraconic acid, mesaconic
acid, and alkali metal and ammonium salts thereof.
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C 6362 (V)
Preferably, the unsaturated carboxylic acid is acrylic or
methacrylic acid.
Uncharged monomers (C) are selected from C1-Cs alkyl esters
of acrylic acid, methacrylic acid, and itaconic acid; C1C4
hydroxyalkyl esters of acrylic acid, methacrylic acid, and
itaconic acid, alkylene oxide esters of acrylic acid,
methacrylic acid, and itaconic acid having 1-20 alkylene
oxide repeat units; and Cl-C20 EO1-EO20 ethoxyalkyl esters
of acrylic acid, methacrylic acid, and itaconic acid;
styrene; vinyl alcohol; vinyl acetate; methyl vinyl ether;
and allyl alcohols. Preferably the uncharged monomer is C1-
C4 alkyl ester of acrylic acid, methacrylic acid, or
itaconic acid, C1-C4 hydroxyalkyl ester of acrylic acid,
methacrylic acid, or itaconic acid, or C1-C20 EO1-EO20
ethoxyalkyl ester of acrylilc acid, methacrylic acid, or
itaconic acid.
If these optional monomers (C) are present they should be
present only in an amount of less than 25~ of the total
monomer distribution.
Preferably the amphoteric polymers (AXByCz wherein z is 0)
produced from the monomers of formulas l and ll are formed
of monomers of acrylic acid polymerized with quaternized
basic monomers.
A second means of obtaining amphoteric polymers useful in
the invention is the polymerization of an amphoteric
monomer (D) having a formula (V) as described above.
The amphoteric monomers of formula (V) may be
homopolymerized or copolymerized with non-amphoteric
polymerizable monomers (E) in an amount from about 0 to
about 99~ by wt., preferably from 0 to about 75~ by wt.,
3 5 with the requirement that the previously defined polymer
charge distribution be satisfied.
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C 6362 (~)
Suitable anionic, and cationic monomers from which the
moiety E is selected are represented by formulas I and II.
Uncharged monomers are selected from C1-C4 alkyl esters of
acrylic acid, methacrylic acid, and itaconic acid; C1-C4
hydroxyalkyl esters of acrylic acid, methacrylic acid, and
itaconic acid, alkylene oxide esters of acrylic acid,
methacrylic acid, and itaconic acid having 1-20 alkylene
oxide repeat units; and Cl-C20 EO1-EO20 ethoxyalkyl esters
of acrylic acid, methacrylic acid, and itaconic acid;
styrene; vinyl alcohol; vinyl acetate; methyl vinyl ether;
and allyl alcohols. Preferably the uncharged monomer is C1-
C4 alkyl ester of acrylic acid, methacrylic acid, or
itaconic acid, C1-C4 hydroxyalkyl ester of acrylic acid,
methacrylic acid, or itaconic acid, or C1-C20 EO1-EO20
ethoxyalkyl ester of acrylilc acid, methacrylic acid, or
itaconic acid.
Suitable examples of amphoteric polymers include, but are
not limited to, a copolymer of acrylic acid and 3-
acrylamidopropyl trimethylammonium chloride as described inEP-A- 560, 519 Rohm and Haas, and EXP-2072 and EXP-2075
(terpolymers of acrylic acid, dimethyldiallylammonium
chloride and C14-20 EO 20 itaconate ester available from
Alco). Preferably, the polymers are the copolymers of
acrylic acid and 3-acrylamido-propyl trimethylammonium
chloride.
LiPolYtic EnzYmes
Li~olytic enzymes are an essential component of the machine
washing compositions of the invention. They are present at
levels of active enzyme of from 0.01 to 4% by wt.,
preferably 0.01~ to 3% by wt., most preferably from 0.05%
to 1.5% by wt. of the composition, based on lipolytic
activity of 100 LU/mg. Lipolytic activity is commonly
defined by the amount of titratable fatty acid liberated
from triglyceride under specified conditions. One lipase
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C 6362 (v)
11
unit (LU) of activity is equivalent to liberation of one
micromole of butyric acid per minute from an emulsion of
tributyrin and gum arabic in the presence of Ca++ and NaCl
at 30 Deg. C and pH 7.
Lipases facilitate the degradation or alteration of soils
and stains comprising triglycerides or fatty esters.
Lipases suitable for use herein include those of animal,
plant and microbiological origin. Suitable lipases are
also found in many strains of bacteria and fungi. For
example, lipases suitable for use herein can be obtained
from Pseudomonas, Aspergillus, Staphylococcus, Toxins,
Mycobacterium Tuberculosis, Mycotorula Lipolytica and
Sclerotinia microorganisms. Lipases from chemically or
genetically modified mutants are also included herein.
Mixtures of lipase from various strains are also included
herein.
Suitable animal lipases are found in the body fluids and
organs of many species. A preferred class of animal lipase
herein are the pancreatic lipases.
A preferred lipase herein is obtained by cloning the gene
from Humicola lanuginosa and expressing the gene in
Aspergillus oryza, as host, as described in EP-A-0258068,
which is commercially available from Novo Industri A/S,
Denmark, under the tradename Lipolase.
Tradenames of other suitable lipases are Lipomax, ex. Gist
Brocades (now Genencor), the Netherlands and Lipase G-1000,
ex. Solvay Enzymes, USA.
Hypohalite Bleachinq Aqent
Hypohalite may be used as long as the bleach is added to
avoid deactivation of the enzymes of the formulation. A
preferred method of preventing enzyme deactivation is
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~ .
12
encapsulation of the bleach is described in-US-A-5,200,236,
herein incorporated by reference. In the patented method,
the bleaching agent is encapsulated as a core in a paraffin
wax material having a melting point from about 40~C to
50~C. The wax coating has a thickness of from 100 to 1500
mlcrons .
Suitable reactive chlorine or bromine oxidizing materials
are chloro and bromo amides such as trichloroisocyanuric,
tribromoisocyanuric, dibromoisocyanuric and
dichloroisocyanuric acids, and salts thereof with water
solubilizing cations such as potassium and sodium.
Hydantoin compounds such as 1,3-dichloro-5,5-
dimethylhydantoin are also quite suitable.
PeroxY Bleachinq Aqents
The oxygen bleaching agents of the compositions include
organic peroxy acids and diacylperoxides. Typical
monoperoxy acids useful herein include alkyl peroxy acids
and aryl peroxy acids such as:
i) peroxybenzoic acid and ring-substituted peroxybenzoic
acids, e.g., peroxy-alpha-naphthoic acid, and magnesium
monoperoxyphthalate
ii) aliphatic and substituted aliphatic monoperoxy acids,
e.g., peroxylauric acid, epsilon-phthalimido-peroxyhexanoic
acid and o-carboxybenzamido peroxyhexanoic acid, N-
nonylamidoperadipic acid and N-nonylamidopersuccinic acid.
iii) Cationic peroxyacids such as those described in US-A-
5,422,028, US-A-5,294,362; and US-A-5,292,447, Atty. Docket
No. 95-0394-UNI; Case 7392, Oakes et al.; and U.S. S/N
08/210, 973, Oakes et al., herein incorporated by reference.
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C 6362 (V)
iv) Sulfonyl peroxyacids such as compounds described in
US-A-5,039,447 (Monsanto Co.), herein incorporated by
reference.
Typical diperoxy acids useful herein include alkyl diperoxy
acids and aryl diperoxy acids, such as:
v) 1,12-diperoxydodecanedioic acid
vi) 1,9-diperoxyazelaic acid
vii) diperoxybrassylic acid; diperoxysecacic acid and
diperoxy-isophthalic acid
viii) 2-decyldiperoxybutan-1,4-dioic acid
ix) N,N1-terephthaloyl-di(6-aminopercaproic acid).
A typical diacylperoxide useful herein includes
dibenzoylperoxide.
Inorganic peroxygen compounds are also suitable for the
present invention. Examples of these materials useful in
the invention are salts of monopersulfate, perborate
monohydrate, perborate tetrahydrate, and percarbonate.
Preferred oxygen bleaching agents include epsilon-
phthalimido-peroxyhexanoic acid, o-
carboxybenzaminoperoxyhexanoic acid, and mixtures thereof.
Most preferred bleaching agents include perborate
monohydrate and percarbonate.
The oxygen bleaching agent is present in the composition in
an amount from about of 1 to 20 weight percent, preferably
1 to 15 weight percent.
The oxygen bleaching agent may be incorporated directly
into the formulation or may be encapsulated by any number
of encapsulation techniques known in the art to produce
stable capsules in alkaline liquid formulations.
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14
Bleach Precursors
Suitable peroxygen peracid precursors for peroxy bleach
compounds have been amply described in the literature,
including GB Nos. 836,988; 855,735; 907,356; 907;358;
907,950; 1,003,310 and 1,246,339; US-A-3,332,882 and US-A-
4,128,494.
Typical examples of precursors are polyacylated alkylene
diamines, such as N,N,N1,N1-tetraacetylethylene diamine
(TAED) and N,N,N1,N1-tetraacetylmethylene diamine (TAMD);
acylated glycolurils, such as tetraacetylglycoluril (TAGU);
triacetylcyanurate, sodium sulfophenyl ethyl carbonic acid
ester, sodium acetyloxybenene sulfonate (SABS), sodium
nonanoyloxy benzene sulfonate (SNOBS) and choline
sulfophenyl carbonate. Peroxybenzoic acid precursors are
known in the art, e.g., as described in GB-A-836,988.
Examples of suitable precursors are phenylbenzoate; phenyl
p-nitrobenzoate; o-nitrophenyl benzoate; o-carboxyphenyl
benzoate; p-bromophenylbenzoate; sodium or potassium
benzoyloxy benzene-sulfonate; and benzoic anhydride.
Preferred peroxygen bleach precursors are sodium p-
benzoyloxybenzene sulfonate, N,N,N1,N1-tetraacetylethylene
diamine, sodium nonanoyloxybenzene sulfonate and choline
sulfophenyl carbonate.
Bleach catalysts which may also be used in the detergent
compositions include maganese catalysts such as those
described in US-A-5,246,621.
Deter~ent Builder Materials
The compositions of this invention contains either organic
builders, particularly carboxylates, or inorganic builders,
particularly phosphorous containing compounds.
Phosphorus Cont~; n; n~ Builders
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C 6362 (V)
Examples of phosphorus-containing inorganic builders
include the water-soluble salts, especially alkali metal
pyrophosphates, orthophosphates and polyphosphates,
particularly ammonium and alkanol ammonium salts, and
phosphonates. Particularly preferred phosphate builders
include sodium and potassium tripolyphosphates,
pyrophosphates, hexametaphosphates and trimetaphosphates.
When phosphate builders are incorporated into the formula,
they are present in an amount of about 10 to about 75~ by
wt., most preferably 15 to about 60 wt. ~.
NonPhosPhorus Inor~anic BuilderR
Non-phosphorus-containing inorganic builders may be
additionally used such as water-soluble alkali metal
carbonates, bicarbonates, sesquicarbonates, borates,
silicates, layered silicates such as SKS-6 ex Hoechst,
metasilicates, phytic acid, borate and crystalline and
amorphous aluminosilicates. Specific examples include
sodium carbonate (with or without calcite seeds), potassium
carbonate, sodium and potassium bicarbonates, silicates,
including layered silicates and zeolites.
Orqanic Builders
Organic detergent builders useful in the present invention
include a variety of polycarboxylate compounds. As used
herein "polycarboxylate" refers to compounds having a
plurality of carboxylate groups, preferably at least three
(3) carboxylates. Monomeric or polymeric carboxylates are
preferred. Examples of organic builders include alkali
metal citrates, succinates, malonates, fatty acid
sulfonates, fatty acid carboxylates, nitrilotriacetates,
phytates, phosphonates, alkanehydroxyphosphonates,
oxydisuccinates, alkyl and alkenyl disuccinates,
oxydiacetates, carboxymethyloxy succinates, ethylenediamine
tetraacetates, tartrate monosuccinates, tartrate
disuccinates, tartrate monoacetates, tartrate diacetates,
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C 6362 (V)
16
oxidized starches, oxidized heteropolymeric
polysaccharides, and polyhydroxysulfonates.
Polycarboxylates include polyacrylates, polymaleates,
polyacetates, polyhydroxyacrylates,
polyacrylate/polymaleate and polyacrylate/ polymethacrylate
copolymers, acrylate/maleate/vinyl alcohol terpolymers,
aminopolycarboxylates and polyacetal carboxylates, and
polyaspartates and mixtures thereof. Such carboxylates are
described in US-A-4,144,226, US-A-4,146,495 and US-A-
4,686,062, herein incorporated by reference.
Alkali metal citrates, nitrilotriacetates, oxydisuccinates,
polyphosphonates and acrylate/maleate copolymers and
acrylate/maleate/vinyl alcohol terpolymers are especially
preferred organic builders.
When the builder is comprised primarily of either monomeric
or polymeric carboxylates or mixtures thereof the builder
should be present in an amount of 10 to 60 wt. ~, most
preferably 15 to 50 wt. ~.
The foregoing detergent builders are meant to illustrate
but not limit the types of builders that can be employed in
the present invention.
EnzYmes
Additional enzymes capable of facilitating the removal of
soils from a substrate may also be present in an amount of
up to about 10% by wt., preferably 1 to about 5 wt. ~.
Such enzymes include proteases (e.g., Alcalase~, Savinase~
and Esperase~ from Novo Industries A/S and Purafect OxP~,
ex. Genencor) and amylases (e.g., Termamyl~ and Duramyl~
from Novo Industries and Purafect OxAm~, ex. Genencor).
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C 6362 (V)
ODtional Inqredients
Minor amounts of various other components may optionally be
present in the cleaning composition. These include filler,
non-carboxylic thickening agents, defoamer, bleach
5 scavengers including but not limited to sodium bisulfite,
reducing sugars, and short chain alcohols; solvents and
hydrotropes such as ethanol, isopropanol and xylene
sulfonates; enzyme stabilizing agents; soil suspending
agents; antiredeposition agents; anti-corrosion agents,
such as benzotriazole and isocyanuric acid described in US-
A-5,374,369; ingredients to enhance decor care such as
certain aluminum salts described in U.S. Serial No.
08/444,502 and 08/444,503, herein incorporated by
reference; colorants; perfumes; opacifiers such as titanium
15 dioxide; and other functional additives.
Sequestrants
The detergent compositions herein may also optionally
contain one or more transition metal tsuch as Fe, Mn, or
20 Cu) chelating agents. Such chelating agents can be
selected from the group consisting of amino carboxylates,
amino phosphonates, polyfunctionally-substituted aromatic
chelating agents and mixtures therein. Without intending
to be bound by theory, it is believed that the benefit of
25 these materials is due in part to their exceptional ability
to remove transition metal ions such as Fe, Mn, and Cu
from washing ~olutions by formation of soluble chelates.
Amino carboxylates useful as optional chelating agents
30 include ethylenediaminetetraacetates; N-
hydroxyethylethylenediaminetriacetates; nitrilotriacetates;
ethylenediamine tetraproprionates; triethylenetetraamine-
hexaacetates; diethylenetriaminepentaacetates;
ethylenediamine disuccinate; ethanoldiglycines; alkali
35 metal, ammonium, and substituted ammonium salts therein and
mixtures therein.
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.
18
Phosphonates and amino phosphonates are also suitable for
use as chelating agents in the compositions of the
invention when at least low levels of total phosphorus are
permitted in detergent compositions, and include
ethylenediaminetetrakis (methylenephosphonates),
nitrilotris (methylenephosphonates) and
diethylenetriaminepentakis (methylenephosphonates).
Preferably, these phosphonates and aminophosphonates do not
contain alkyl or alkenyl groups with more than about 6
carbon atoms.
Polyfunctionally-substituted aromatic chelating agents are
also useful in the compositions herein. See US-A-
3,812,044, Preferred compounds of this type in acid formare dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-
disulfobenzene.
If utilized, these chelating agents will generally comprise
from about 0.1~ to about 10~ by weight of the detergent
compositions herein. More preferably, if utilized, the
chelating agents will comprise from about 0.1~ to about
3.0~ by weight of such composition.
Anti-Scalants
Scale formation on dishes and machine parts is an important
problem that needs to be resolved or at least mitigated in
formulating a machine warewashing product, especially in
the case of low-pho~phate (e. g. less than the equivalent of
20% by weight, particularly 10~ by weight of sodium
triphosphate) and phosphate-free machine warewashing
compositions, particularly zero-P machine warewashing
compositions.
In order to reduce this problem, co-builders, such as
polyacrylic acids or polyacrylates (PAA), acrylate/maleate
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C 6362 (V)
19
copolymers, polyaspartates, ethylenediamine disuccinate and
the various organic polyphosphonates, e.g. Dequest series,
may be incorporated in one or more system components. For
improved biodegradability, (as such co-builders), the block
co-polymers of formula (I) as defined in published PCT
patent specification WO 94/17170 may also be used. In any
component, the amount of anti-scalant may be in the range
of from 0.5 to 10, preferably from 0.5 to 5, and more
preferably from 1 to 5% by weight.
Surfactants
Useful surfactants include anionic, nonionic, cationic,
amphoteric, amphoteric types and mixtures of these surface
active agents. It is understood that surfactants should be
selected and used at such levels as conventionally known in
the art so as not to deactivate enzymes in the formula.
Such surfactants are well known in the detergent art and
are described at length in "Surface Active Agents and
Detergents", Vol. II, by Schwartz, Perry & Birch,
Interscience Publishers, Inc. 1959, herein incorporated by
reference.
Surfactants, if present in the composition, may be selected
from the following:
Anionic surfactants
Anionic synthetic detergents can be broadly described as
surface active compounds with one or more negatively
charged functional groups. An important class of anionic
compounds are the water-soluble salts, particularly the
alkali metal salts, of organic sulfur reaction products
having in their molecular structure an alkyl radical
containing from about 6 to 24 carbon atoms and a radical
selected from the group consisting of sulfonic and sulfuric
acid ester radicals.
CA 022l46l~ l997-09-03
C 6362 (V)
Primary Alkyl Sulfates
Rl 70503M
where Rl7 is a primary alkyl group of 8 to 18 carbon atoms
and M is a solubilizing cation. The alkyl group Rl7 may
have a mixture of chain lengths. It is preferred that at
least two thirds of the Rl7 alkyl groups have a chain
length of 8 to 14 carbon atoms. This will be the case if
R17 is coconut alkyl, for example. The solubilizing cation
may be a range of cations which are in general monovalent
and confer water solubility. Alkali metal, notably sodium,
is especially envisaged. Other possibilities are
ammonium and substituted ammonium ions, such as
trialkanolammonium or trialkylammonium.
Alkyl Ether Sulfates
Rl70 (CH2CH20) nSO3M
where Rl7 is a primary alkyl group of 8 to 18 carbon atoms,
n has an average value in the range from 1 to 6 and M is a
solubilizing cation. The alkyl group Rl7 may have a
20 mixture of chain lengths. It is preferred that at least
two thirds of the Rl7 alkyl groups
have a chain length of 8 to 14 carbon atoms. This will be
the case if Rl7 is coconut alkyl, for example. Preferably
n has an average value of 2 to 5.
Fatty Acid Ester Sulfonates
Rl~CH (SO~M) COzRl9
where Rl8 is an alkyl group of 6 to 16 atoms, R19 is an
alkyl group of 1 to 4 carbon atoms and M is a solubilizing
cation. The group Rla may have a mixture of chain lengths.
Preferably at least two thirds of these groups have 6 to 12
carbon atoms.
This will be the case when the moiety Rl~CH(-)CO2(-) is
derived from a coconut source, for instance. It is
CA 0221461~ 1997-09-03
C 636~
~ .~
21
preferred that Rl9 is a straight chain alkyl, notably
methyl or ethyl.
Alkyl Benzene Sulfonates
R20ArSO~M
where RZ~ is an alkyl group of 8 to 18 carbon atoms, Ar is
-a benzene ring (C6H4) and M is a solubilizing cation. The
group R20 may be a mixture of chain lengths. Straight
chains of 11 to 14 carbon atoms are preferred.
Organic phosphate based anionic surfactants include organic
phosphate esters such as complex mono- or diester
phosphates of hydroxyl- terminated alkoxide condensates, or
salts thereof. Included in the organic phosphate esters
are phosphate ester derivatives of polyoxyalkylated
alkylaryl phosphate esters, of ethoxylated linear alcohols
and ethoxylates of phenol.
Also included are nonionic alkoxylates having a sodium
alkylenecarboxylate moiety linked to a terminal hydroxyl
group of the nonionic through an ether bond. Counterions
to the salts of all the foregoing may be those of alkali
metal, alkaline earth metal, ammonium, alkanolammonium and
alkylammonium types.
Particularly preferred anionic surfactants are the fatty
acid ester sulfonates with formula:
R CH (503M) CO2R
where the moiety Rl8CH(-) CO2 (-) is derived from a coconut
source and Rl9 is either methyl or ethyl.
Nonionic surfactants
Nonionic surfactants can be broadly defined as surface
active compounds with one or more uncharged hydrophilic
substituents. A major class of nonionic surfactants are
those compounds produced by the condensation of alkylene
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C 63 62 ' (V)
oxide groups with an organic hydrophobic material which may
be aliphatic or alkyl aromatic in nature. The length of
the hydrophilic or polyoxyalkylene radical which is
condensed with any particular hydrophobic group can be
readily adjusted to yield a water-soluble compound having
the desired degree of balance between hydrophilic and
hydrophobic elements. Illustrative, but not limiting
examples, of various suitable nonionic surfactant types
are:
polyoxyethylene or polyoxypropylene condensates of
aliphatic carboxylic acids, whether linear- or
branched-chain and unsaturated or saturated, containing
from about 8 to about 18 carbon atoms in the aliphatic
chain and incorporating from about 2 to about 50 ethylene
oxide and/or propylene oxide units. Suitable carboxylic
acids include "coconut" fatty acids (derived from coconut
oil) which contain an average of about 12 carbon atoms,
"tallow" fatty acids (derived from tallow-class fats) which
contain an average of about 18 carbon atoms, palmitic acid,
myristic acid, stearic acid and lauric acid,
polyoxyethylene or polyoxypropylene condensates of
aliphatic alcohols, whether linear- or branched-chain and
unsaturated or saturated, containing from about 6 to about
24 carbon atoms and incorporating from about 2 to about 50
ethylene oxide and/or propylene oxide units. Suitable
alcohols include "coconut" fatty alcohol, "tallow" fatty
alcohol, lauryl alcohol, myristyl alcohol and oleyl
alcohol.
Ethoxylated fatty alcohols may be used alone or in
admixture with anionic surfactants, especially the
preferred surfactants above. The average chain lengths of
the alkyl group R21 in the general formula: R2lO(CH2CH20)nH
CA 0221461~ 1997-09-03
C 63 62 (V)
is from 6 to 24 carbon atoms. Preferably the group R21 may
have chain lengths in a range from 9 to 18 carbon atoms.
The average value of n should be at least 2. The numbers
of ethylene oxide residues may be a statistical
distribution around the average value. However, as is
known, the distribution can be affected by the
manufacturing process or altered by fractionation after
ethoxylation. Particularly preferred ethoxylated fatty
alcohols have a group R2l which has 9 to 18 carbon atoms
while n is from 2 to 8.
Also included within this category are nonionic surfactants
having a formula:
R22 (CH~CHO~(CH2CH2O~(CH2CIHO~H
R23 R24
wherein R22 is a linear alkyl hydrocarbon radical having an
average of 6 to 18 carbon atoms, R23 and R24 are each linear
alkyl hydrocarbons of about 1 to about 4 carbon atoms, x is
an integer of from 1 to 6, y is an integer of from 4 to 20
and z is an integer from 4 to 25.
One preferred nonionic surfactant of the above formula is
Poly-Tergent SLF-18~ a registered trademark of the Olin
Corporation, New Haven, Conn. having a composition of the
above formula where R22 is a C6-C10 linear alkyl mixture, R23
and R24 are methyl,
x averages 3, y averages 12 and z averages 16. Another
preferred nonionic surfactant is
CA 022l46l~ l997-09-03
C 6362 (V~
' ~
24
R25O(CH2lHO)j(CH2CH20~(CH2CH(O~R26)z
CH3
5 wherein R2s is a linear, aliphatic hydrocarbon radical
having from about 4 to about 18 carbon atoms including
- mixtures thereof; and R26 is a linear, aliphatic
hydrocarbon radical having from about 2 to about 26 carbon
atoms including mixtures thereof; j is an integer having a
value of from 1 to about 3; k is an integer having a value
from 5 to about 30; and z is an integer having a value of
from 1 to about 3. Most preferred are compositions in
which j is 1, k is from about 10 to about 20 and z is 1.
These surfactants are described in WO 94/22800. Other
15 preferred nonionic surfactants are linear fatty alcohol
alkoxylates with a capped terminal group, as described in
U. S . 4,340,766 to BASF.
Another nonionic surfactant included within this category
20 are compounds of formula:
R27~(CH2CH20)qH
wherein R27 is a C6-C24 linear or branched alkyl hydrocarbon
radical and q is a number from 2 to 50; more preferably R27
25 iS a C8-C18 linear alkyl mixture and q is a number from 2 to
15.
polyoxyethylene or polyoxypropylene condensate~ of alkyl
phenols, whether linear- or branched-chain and unsaturated
30 or saturated,containing from about 6 to 12 carbon atoms and
incorporating from about 2 to about 25 moles of ethylene
oxide and/or propylene oxide.
polyoxyethylene derivatives of sorbitan mono-, di-, and
tri-fatty acid esters wherein the fatty acid component has
between 12 and 24 carbon atoms. The preferred
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C 6362 (~1)
' .
sorbitan trilaurate, sorbitan monopalmitate, sorbitan
tripalmitate, sorbitan monostearate, sorbitan
monoisostearate, sorbitan tripalmitate, sorbitol
tristearate, sorbitan monooleate, and sorbitan trioleate.
The polyoxyethylene chains may contain between about 4 and
30 ethylene oxide units, preferably about 10 to 20. The
sorbitan ester derivatives contain 1, 2 or 3
polyoxyethylene chains dependent upon whether they are
mono-, di- or tri-acid esters.
polyoxyethylene-polyoxypropylene block copolymers having
formula:
HO (CH2cH20) a (CH (CH3) CH20) b (CH2CH20) CH
or
HO (CH (CH3) CH2O) d (CH2CH20) e (CH (CH3) CH20) fH
wherein a, b, c, d, e and f are integers from 1 to 350
reflecting the respective polyethylene oxide and
polypropylene oxide blocks of said polymer. The
polyoxyethylene component of the block polymer constitutes
at least about 10% of the block polymer. The material
preferably has a molecular weight of between about 1,000
and 15,000, more preferably from about 1,500 to about
6,000. These materials are well-known in the art. They
are available under the trademark "Pluronic" and "Pluronic
R", a product of BASF Corporation.
Amine oxides having formula:
R28R29R30N=o
wherein R29, R29 and R30 are saturated aliphatic radicals or
substituted saturated aliphatic radicals. Preferable amine
oxides are those wherein R29 is an alkyl chain of about 10
CA 0221461~ 1997-09-03
C 6362 (V)
26
to about 20 carbon atoms and R29 and R30 are methyl or ethyl
groups or both R28 and R29 are alkyl chains of about 6 to
about 14 carbon atoms and R30 is a methyl or ethyl group.
Amphoteric synthetic detergents may also be broadly
described as derivatives of aliphatic and tertiary amines,
in which the aliphatic radical may be straight chain or
branched and wherein one of the aliphatic substituents
contain from about 8 to about 18 carbons and one contains
an anionic water-solubilizing group, i.e., carboxy, sulpho,
sulphato, phosphato or phosphono. Examples of compounds
falling within this definition are sodium 3-dodecylamino
propionate and sodium 2-dodecylamino propane sulfonate.
Amphoteric synthetic detergents can be broadly described as
derivatives of aliphatic quaternary ammonium, phosphonium
and sulphonium compounds in which the aliphatic radical may
be straight chained or branched, and wherein one of the
aliphatic substituents contains from about 8 to about 18
carbon atoms and one contains an anionic water-solubilizing
group, e.g., carboxy, sulpho, sulphato, phosphato or
phosphono. These compounds are frequently referred to as
betaines. Besides alkyl betaines, alkyl amino and alkyl
amido betaines are encompassed within this invention.
Alkyl Glycosides
R31o (R320) (Zl)
wherein R31 is a monovalent organic radical (e.g., a
monovalent saturated aliphatic, unsaturated aliphatic or
aromatic radlcal such as alkyl, hydroxyalkyl, alkenyl,
hydroxyalkenyl, aryl, alkylaryl, hydroxyalkylaryl,
arylalkyl, alkenylaryl, arylalkenyl, etc.) containing from
about 6 to about 30 (preferably from about 8 to 18 and
more preferably from about 9 to about 13) carbon atoms; R32
is a divalent hydrocarbon radical containing from 2 to
about 4 carbon atoms such as ethylene, propylene or
CA 0221461~ 1997-09-03
C 6362 (V)
. ~
27
butylene (most preferably the unit (R320) n represents
repeating units of ethylene oxide, propylene oxide and/or
random or block combinations thereof); n is a number having
an average value of from 0 to about 12; Zl represents a
moiety derived from a reducing saccharide containing 5 or 6
carbon atoms (most preferably a glucose unit); and p is a
number having an average value of from 0.5 to about 10
preferably from about 0.5 to about 5 .
Examples of commercially available materials from Henkel
Kommanditgesellschaft Aktien of Dusseldorf, Germany include
APG~ 300, 325 and 350 with R3l being C9-Cll, n is 0 and p is
1.3, 1. 6 and 1.8-2.2 respectively; APG~ 500 and 550 with R3
is Cl2-Cl3, n is 0 and p is 1.3 and 1.8-2.2, respectively;
and APG~ 600 with R3l being Cl2-Cl4, n is 0 and p is 1.3.
While esters of glucose are contemplated especially, it is
envisaged that corresponding materials based on other
reducing sugars, such as galactose and mannose are also
suitable.
- The amount of surfactant present in the final formula
should be from about 0.5 to about 30~ by weight of the
composition. The preferred range of surfactant is from 0.5
to 20~ by weight, more preferably from 0.5 to 10~ by
weight.
Filler
An inert filler material which is water-soluble may also be
present in cleaning compositions. This material should not
precipitate calcium or magnesium ions at the filler use
level. Suitable for this purpose are organic or inorganic
compounds. Organic fillers include sucrose esters and
urea. Representative inorganic fillers include sodium
sulfate, sodium chloride and potassium chloride. A
preferred filler is sodium sulfate. Its concentration may
CA 0221461~ 1997-09-03
C 6362 (~)
28
range from 0~ to 20~, preferably from about 2~ to about 10
by weight of the cleaning composition.
Thickeners & Stabilizers
Thickeners are often desirable for liquid cleaning
compositions. Thixotropic thickeners such as smectite
clays including montmorillonite (bentonite), hectorite,
saponite, and the like may be used to impart viscosity to
liquid cleaning compositions. Silica, silica gel, and
aluminosilicate may also be used as thickeners. Salts of
polyacrylic acid (of molecular weight of from about 300,000
up to 6 million and higher), including polymers which are
cross-linked may also be used alone or in combination with
other thickeners. Use of clay thickeners for machine
dishwashing compositions is disclosed for example in US-A-
4,431,559; US-A-4,511,487; US-A-4,740,327; US-A-4,752,409.
Commercially available synthetic smectite clays include
Laponite supplied by Laporte Industries. Commercially
available bentonite clays include Korthix H and VWH ex
Combustion Engineering, Inc.; Polargel T ex American
Colloid Co.; and Gelwhite clays (particularly Gelwhite GP
and H) ex English China Clay Co. Polargel T is preferred as
imparting a more intense white appearance to the
composition than other clays. The amount of clay thickener
employed in the compositions is from 0.1 to about 10~,
preferably 0.5 to 5~. Use of salts of polymeric carboxylic
acids is disclosed for example in GB-A-2,164,350, US-A-
4,859,358 and US-A-4,836,948.
For liquid formulations with a "gel" appearance and
rheology, particularly if a clear gel is desired, a
chlorine-resistant polymeric thickener is particularly
useful. US-A-4,260,528 discloses natural gums and resins
for use in clear machine dishwashing detergents, which are
not chlorine stable. Acrylic acid polymers that are
cross-linked manufactured by, for example, B.F. Goodrich
CA 0221461~ 1997-09-03
C 6362 (~)
and sold under the trade name "Carbopol" have been found to
be effective for production of clear gels, and Carbopol
940, 617 and 627, having a molecular weight of about
4,000,000 are particularly preferred for maintaining high
5 viscosity with excellent chlorine stability over extended
periods. Further suitable chlorine-resistant polymeric
thickeners are described in US-A-4,867,896 incorporated by
reference herein.
The amount of thickener employed in the compositions is
from 0 to 5~, preferably 0. 5-3~ .
Stabilizers and/or co-structurants such as long-chain
calcium and sodium soaps and C12 to C1~ sulfates are
15 detailed in US-A- 3,956,158 and US-A-4,271,030 and the use
of other metal salts of long-chain soaps is detailed in US-
A-4,752,409. Other co-structurants include Laponite and
metal oxides and their salts as described in US-A-
4,933,101, herein incorporated by reference. The amount of
20 stabilizer which may be used in the liquid cleaning
compositions is from about 0.01 to about 5~ by weight of
the composition, preferably 0. 01-2~. Such stabilizers are
optional in gel formulations. Co-structurants which are
found especially suitable for gels include trivalent metal
25 ions at 0. 01-4~ of the compositions, Laponite and/or
water-soluble structuring chelants at 0. 01-5~ . These
co-structurants are more fully described in the US-A-
5,141,664, hereby incorporated by reference.
30 De f oamer
The formulations of the cleaning composition comprising
surfactant may further include a defoamer. Suitable
defoamers include mono-and distearyl acid phosphate,
silicone oil and mineral oil. Even if the cleaning
35 composition has only defoaming surfactant, the defoamer
assists to minimize foam which food soils can generate.
CA 0221461~ 1997-09-03
C 63 62 (~1)
The compositions may include 0. 02 to 2~ by weight of
defoamer, or preferably 0.05-1.0~. Preferred antifoam
systems are described in Angevaare et al.; US S/N
08/539,923, herein incorporated by reference.
The following examples will serve to distinguish this
invention from the prior art and illustrate its embodiments
more fully. Unless otherwise indicated, all parts,
percentages and proportions referred to are by weights.
Example 1
The lime soap dispersant properties of amphoteric polymers
within the scope of the invention was compared to that of
lime soap dispersants known in the prior art as described
15 below.
The polymers were evaluated for their lime soap dispersing
power value (LSDP), which is a conventional measurement of
the effectiveness of a material for dispersing lime soap.
20 The lime soap dispersing power value (LSDP) is defined as
the (weight ratio of dispersant to sodium oleate X 100)
based on the amount of dispersant required to disperse lime
soap curd formed by 0. 025g sodium oleate and 30mls of water
of 333 ppm. CaC03 equivalent hardness. According to the
25 test, a low LSDP value is an indication of an effective
lime soap dispersant. A detailed description of the test
is found in an article by H.C. Borghetty and C.A. Bergman,
J. Am. Oil Chem. Soc., 27, pages 88-90, (1950). The
materials used in the comparison are described in Table I
below:
CA 0221461~ 1997-09-03
C 6362 (V)
Table 1
MAT~T~TAT.S SOURCE LSDP
Amphoteric Polymer PC2 Supplied by Rohm
& Haas 1.5
5 Amphoteric Polymer E-2072 Supplied By
ALCO 1.5
Amphoteric Polymer E-2075 Supplied By
ALCO 2.5
C13-C15 Alcohol Described in WO
Ethoxylate (12EO) 94/07985 6.0
C12-C18 Alcohol Described in WO
Ethoxy Sulfate (3EO) 94/07985 4.0
Polyacrylic Acid
(200,000 MW) 22.0
Polyacrylic Acid Acusol 445 supplied
(4,500 MW) by Rohm and Haas 15.0
15 Polyacrylic Acid/ Supplied by Aldrich
Acrylamide (200,000 17.5
MW)
As this example illustrates, amphoteric polymers within the
scope of the invention are extremely effective lime soap
dispersants in comparison to similar polymers outside the
scope of the invention and in comparison to the preferred
lime soap dispersants claimed in WO 94/07984 and WO
94/07985
Example 2
The effect on glass and plasticware appearance of polymers
and surfactants having an LSDP of less than 8 were compared
by determining the effectiveness of each material in
preventing the formation of mineral spots and films on
clear glass tumblers and inhibition of lime soap filming on
CA 0221461~ 1997-09-03
C 6362 (V)
polyethylene plates when incorporated into the lipase
containing base formulation.
A base machine dishwashing detergent composition was
prepared as described in Table 2 below.
Table 2
INGREDIENTS % BY WT.
STPP 51 . O
Sodium silicate (PQ Britesil 30.0
H20)
Sodium Percarbonate 9.0
TAED 3.6
(tetraacetylethylenediamine)
Protease (Novo Savinase 6T) 3.0
Amylase (Novo Termamyl 60T) 1.8
Lipase (Novo Lipolase lOOT) 0.2
Nonionic (BASF Plurafac 1.4
LF403)
Lime soap dispersants were incorporated into the
described base at a level of 5~ by wt. in addition to the
above composition.
A ten cycle test procedure was used as follows:
Five glass tumblers and two polyethylene plates were placed
in a Bosch model 6082 dishwasher along with a ballast load
of clean dishware consisting of 9 ceramic dinner plates, 2
ceramic tea cups, 2 stainless steel plates, and 2 melamine
plates. Twenty grams of ASTM standard soil consisting of
CA 0221461~ 1997-09-03
C 6362 ~V)
80~ margarine and 20~ powdered milk was added to the
dishwasher by spreading it onto the inside of the machine
door. The 50~ C. Economy wash setting was used, with water
of 300/320 ppm. permanent/temporary hardness expressed as
CaCO3 equivalent (4:1 Ca/Mg ratio). 18.0 g detergent was
added at the start of the main wash, along with lipase
(Lipolase lOOT ex. Novo) and selected polymer (5~ by wt. in
addition to the detergent composition) as specified. At the
end of each complete cycle, fresh soil and detergent were
added and the process repeated for a total of ten washes.
At the end of this process the tumblers and polyethylene
items were visually graded for spotting and filming.
Grading scales of from 0 to 5 were used to measure film
deposition, where a grade of 0 indicates no visible film
and a grade of 5 indicates coverage with a very heavy,
opaque film. When lipase is present in the detergent
composition, a film buildup can occur on the hydrophobic
polyethylene articles, caused primarily by precipitated Ca
soap. Thus, film scores for the polyethylene articles give
an indication of lime soap dispersant efficacy.
For spotting, the number of spots on each item was counted,
with the average number of spots per article reported. The
number of spots on the glass tumblers gives an indication
of the effectiveness of the lipase. When lipase is present
in the detergent composition, the lowest number of spots
corresponds to the most effective lipase action.
The following spotting and filming grades were obtained (as
30 noted, filming on polyethylene items in the presence of
lipase is primarily caused by lime soap deposition):
CA 0221461~ 1997-09-03
C 6362 (V)
34
Composition Glass TumblersPolYethylene Items
mineral film lime soap
film score # of spots film score # of SPots
(1) Base formulation 1.0 225 3.0 138
(2) Base + lipase,
no dispersant 1.0 1 5.0 0
(3) Base + lipase +
amphoteric 1. 5 0 2.5 0
polymer ( PC2)
15 (4) Base + Lipase +
C13-C15 EO12 0.5 51 2.0 33
alcohol ethoxylate
(5) Base + Lipase +
C12-C15 EO3
alcohol 0. 5 120 0.0 127
ethoxysulfate
As this example demonstrates, addition of lipase to the
25 base formulation results in a significant reduction in the
number of spots on the glass tumblers (Composition 2) . This
is indicative of lipase functioning in the system. However,
filming on polyethylene items is very high, due to lime
soap deposition. Addition of an amphoteric polymer within
30 the scope of the invention (Composition 3) significantly
reduces the film score on polyethylene items, while the
excellent glassware appearance produced by lipase is
retained, as seen by the low spotting scores on the glass
tumblers. In contrast, while the materials described in
35 W094/07984 and WO/07985 (incorporated in Compositions 4 and
5) reduce lime soap deposition, they also greatly reduce
C 6362 (V) CA 0221461~ 1997-09-03
the antispotting benefit originally provided by the lipase
in the detergent composition.
Exam~le 3
The ability of amphoteric polymers to reduce lime soap
deposition without inhibiting the antispotting benefit
provided by lipase was further demonstrated as follows:
The ten wash cycle test procedure described in example 2
was followed. The base dishwashing detergent composition
as described in Table 2 was used for this example, but was
dosed at 26.0 g instead of the 18.0 g used in example 2.
Amphoteric polymers were added to this composition at a
level of 4%, as opposed to the 5% used in the previous
example. All other test parameters were identical to those
for example 1.
The following spotting and filming grades were obtained (as
noted, filming on polyethylene items is primarily caused by
lime soap deposition):
CA 022l46l~ l997-09-03
C 6362 ~V)
36
Composition Glass TumblersPolyethylene Items
mineral film lime soap
5 film score # of spots film score # of spots
(1) Base + lipase,
no dispersant 2.1 0 1.5 225
(2) Base + lipase +
amphoteric polymer
(PC2) 2.2 2 0 23
15 (3) Base + lipase +
amphoteric polymer
(Alco E-2072) 2.3 2 0.3 30
(4) Base + lipase +
amphoteric polymer
(Alco E-2075) 1.9 2 0.3 16
This example further illustrates the effectiveness of
amphoteric polymers within the scope of the invention in
25 improving glass and plasticware appearance by inhibiting
the deposition of lime soap while maintaining the
antispotting benefit provided by lipase.
