Field of Invention
[0001] The present invention relates to detergent compositions containing a silicate softening
system. More in particular, the present invention relates to softening through the
wash detergent compositions comprising layered silicates and flocculating polymers.
Background of the Invention
[0002] Detergent compositions providing fabric softening throughout the wash cycle have
been described in art. In particular, clays are well known as fabric softening agents
through the wash. The relative ability of the softening clays to meet various performance
criteria is very much depending on the presence and concentration of adjunct detergent
ingredients.
An example of such adjunct detergent ingredient is the presence of nonionic surfactants.
Said nonionic surfactants, when used at substantial concentrations inhibit the deposition
of the clay onto the fabric. So far it was therefore necessary to limit the level
of nonionic surfactants in clay containing softening through the wash compositions.
[0003] It has now been found that the combination of layered silicate and a flocculating
polymer provide an efficient softening system which is fully compatible with nonionic
surfactants. This finding allows to formulate detergent compositions which have both
excellent softening and cleaning performance.
[0004] Another type of adjunct detergent ingredient that can be added to detergent compositions
are dye transfer inhibiting polymers. Said polymers are added to detergent compositions
in order to inhibit the transfer of dyes from colored fabrics onto other fabrics washed
therewith. These polymers have the ability to complex or adsorb the fugitive dyes
washed out of dyed fabrics before the dyes have the opportunity to become attached
to other articles in the wash.
[0005] Polymers have been used within detergent compositions to inhibit dye transfer. Examples
of such polymers are vinylpyrrolidone polymers such as described EP-A-265 257 and
EP 508 034. Unfortunately, said vinylpyrrolidone polymers tend to interact with the
clays formulated therewith. Accordingly, the dye transfer inhibiting performance of
the polymers and the softening performance of the clays are negatively affected.
[0006] It has now been found that polyvinylpyrrolidone polymers are very compatible with
the silicate softening system in that the dye transfer inhibiting performance of the
polymers is not negatively affected in the presence of the silicate softening system.
In addition, it has been found that the softening performance of layered silicates
formulated with dye transfer inhibiting polymers has been maintained.
[0007] This finding allows us to formulate detergent compositions which have both excellent
dye transfer inhibiting properties and softening performance.
[0008] According to the present invention, an alternative softening system is obtained which
provides softening through the wash performance without adversely affecting the overall
detergency performance of the detergent formulated therewith.
[0009] Layered silicates have been described in WO 92/03525 as builders in detergent compositions.
Accordingly, the present invention allows to use the silicates in a dual function,
e.g. builder and softener thereby facilitating the formulation of compact detergents.
Summary of the Invention
[0010] The present invention relates to detergent compositions comprising layered silicate
and flocculating polymers.
Detailed description of the invention
[0011] The compositions of the present invention comprise as an essential element a crystalline
layered sodium silicate having the general formula
NaMSi
xO
2x+1 yH₂O
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number
from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-0
164 514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043.
For the purposes of the present invention x, in the general formula above has a value
of 2,3 or 4 and is preferably 2. More preferably M is sodium and y is 0 and preferred
examples of this formula comprise the α, β, γ and δ-forms of Na₂Si₂0₅. These materials
are available from Hoechst AG FRG as respectively NaSKS-5, NaSKS7, NaSKS-11 and NaSKS-6.
The most preferred material is -Na₂Si₂0₅, NaSKS-6.
Flocculating agents
[0012] The softening system herein comprises a flocculating agent.
The compositions herein comprise, from 0.05% to 20% by weight of the silicate, of
flocculating agent, if its molecular weight is 150.000-800.000 and from 0.005% to
2%, by weight of the silicate, if its molecular weight is from 800.000 to 5 million.
Most of these materials are fairly long chain polymers and copolymers derived from
such monomers as ethylene oxide, acrylamide, acrylic acid, dimethylamino ethyl methacrylate,
vinyl alcohol, vinyl pyrrolidone, ethylene imine. Gums, like guar gum, are suitable
as well.
[0013] Preferred are polymers of ethylene oxide, acryl amide, or acrylic acid. For proper
interaction with the silicate, the polymers should be fairly long chain, i.e., have
a weight average molecular weight of at least 100,000. For sufficient water-solubility
the weight average molecular weight of the polymers should not exceed 10 million.
Most preferred are polymers having a weight average molecular weight of from 150.000
to 1 million.
It should be understood that clay is present in the detergent compositions according
to the present invention by less than 5% by weight of the detergent composition. More
preferably, the clay is present in the detergent composition by less than than 1%,
most preferably the detergent composition is substantially free of clay.
DETERGENT ADJUNCTS
[0014] A wide range of surfactants can be used in the detergent compositions. A typical
listing of nonionici, anionic, ampholytic and zwitterionic classes, and species of
these surfactants, is given in US Patent 3,664,961.
NONIONICS :
[0015] Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols
are suitable for use as the nonionic surfactant of the surfactant systems of the present
invention, with the polyethylene oxide condensates being preferred. These compounds
include the condensation products of alkyl phenols having an alkyl group containing
from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon
atoms, in either a straight-chain or branched-chain configuration with the alkylene
oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal
to from about 5 to about 25 moles, more preferably from about 3 to about 15 moles,
of ethylene oxide per mole of alkyl phenol. Commercially available nonionic surfactants
of this type include Igepal™ CO- 630, marketed by the GAF Corporation; and Triton™
X-45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants
are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
[0016] The condensation products of primary and secondary aliphatic alcohols with from about
1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant
of the nonionic surfactant systems of the present invention. The alkyl chain of the
aliphatic alcohol can either be straight or branched, primary or secondary, and generally
contains from about 8 to about 22 carbon atoms. Preferred are the condensation products
of alcohols having an alkyl group containing from about 8 to about 20 carbon atoms,
more preferably from about 10 to about 18 carbon atoms, with from about 2 to about
10 moles of ethylene oxide per mole of alcohol. Examples of commercially available
nonionic surfactants of this type include Tergitol™ 15-S-9 (the condensation product
of C₁₁-C₁₅ linear alcohol with 9 moles ethylene oxide), Tergitol™ 24-L-6 NMW (the
condensation product of C₁₂-C₁₄ primary alcohol with 6 moles ethylene oxide with a
narrow molecular weight distribution), both marketed by Union Carbide Corporation;
Neodol™ 45-9 (the condensation product of C₁₄-C₁₅ linear alcohol with 9 moles of ethylene
oxide), Neodol™ 23-6.5 (the condensation product of C₁₂-C₁₃ linear alcohol with 6.5
moles of ethylene oxide), Neodol™ 45-7 (the condensation product of C₁₄-C₁₅ linear
alcohol with 7 moles of ethylene oxide), Neodol™ 45-4 (the condensation product of
C₁₄-C₁₅ linear alcohol with 4 moles of ethylene oxide) marketed by Shell Chemical
Company, and Kyro™ EOB (the condensation product of C₁₃-C₁₅ alcohol with 9 moles ethylene
oxide), marketed by The Procter & Gamble Company.
[0017] Also useful as the nonionic surfactant of the surfactant systems of the present invention
are the alkylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued January
21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms,
preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g. a polyglycoside,
hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3
to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing
saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and
galactosyl moieties can be substituted for the glucosyl moieties (optionally the hydrophobic
group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose
as opposed to a glucoside or galactoside). The intersaccharide bonds can be, e.g.,
between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or
6- positions on the preceding saccharide units.
[0018] Optionally, and less desirably, there can be a polyalkyleneoxide chain joining the
hydrophobic moiety and the polysaccharide moiety. The preferred alkyleneoxide is ethylene
oxide. Typical hydrophobic groups include alkyl groups, either saturated or unsaturated,
branched or unbranched containing from about 8 to about 18, preferably from about
10 to about 16, carbon atoms. Preferably, the alkyl group is a straight chain saturated
alkyl group. The alkyl group can contain up to about 3 hydroxy groups and/or the polyalkyleneoxide
chain can contain up to about 10, preferably less than 5, alkyleneoxide moieties.
Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl,
pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides,
galactosides, lactosides, glucoses, fructosides, fructoses and/or galactoses. Suitable
mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow
alkyl tetra-, penta-, and hexaglucosides.
[0019] The preferred alkylpolyglycosides have the formula
R²O(C
nH
2nO)
t(glycosyl)
x
wherein R² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl,
hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about
10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably
2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably
from about 1.3 to about 3, most preferably from about 1.3 to about 2.7.
The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol
or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source
of glucose, to form the glucoside (attachment at the 1-position).
The additional glycosyl units can then be attached between their 1-position and the
preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately the
2-position.
[0020] Although not preferred, the condensation products of ethylene oxide with a hydrophobic
base formed by the condensation of propylene oxide with propylene glycol are also
suitable for use as the additional nonionic surfactant of the nonionic surfactant
systems of the present invention. The hydrophobic portion of these compounds will
preferably have a molecular weight of from about 1500 to about 1800 and will exhibit
water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion
tends to increase the water solubility of the molecule as a whole, and the liquid
character of the product is retained up to the point where the polyoxyethylene content
is about 50% of the total weight of the condensation product, which corresponds to
condensation with up to about 40 moles of ethylene oxide. Examples of compounds of
this type include certain of the commercially-available Pluronic™ surfactants, marketed
by BASF.
[0021] Also suitable for use as the nonionic surfactant of the nonionic surfactant system
of the present invention, are the condensation products of ethylene oxide with the
product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic
moiety of these products consists of the reaction product of ethylenediamine and excess
propylene oxide, and generally has a molecular weight of from about 2500 to about
3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that
the condensation product contains from about 40% to about 80% by weight of polyoxyethylene
and has a molecular weight of from about 5,000 to about 11,000. Examples of this type
of nonionic surfactant include certain of the commercially available Tetronic™ compounds,
marketed by BASF.
[0022] Preferred for use as the nonionic surfactant of the surfactant systems of the present
invention are polyethylene oxide condensates of alkyl phenols, condensation products
of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of
ethylene oxide, alkylpolysaccharides, and mixtures thereof. Most preferred are C₈-C₁₄
alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and C₈-C₁₈ alcohol ethoxylates
(preferably C₁₀ avg.) having from 2 to 10 ethoxy groups, and mixtures thereof.
[0023] Highly preferred nonionic surfactants are polyhydoxy fatty acid amide surfactants.
[0024] Also suitable as nonionic surfactants are poly hydroxy fatty acid amide surfactants
of the formula

wherein R¹ is H, or R¹ is C₁₋₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a
mixture thereof, R² is C₅₋₃₁ hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having
a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain,
or an alkoxylated derivative thereof. Preferably, R¹ is methyl, R² is a straight C₁₁₋₁₅
alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived
from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive
amination reaction.
[0025] When included in such laundry detergent compositions, the nonionic surfactant systems
of the present invention act to improve the greasy/oily stain removal properties of
such laundry detergent compositions across a broad range of laundry conditions.
ANIONIC SURFACTANTS
[0026] Suitable anionic surfactants include alkyl alkoxylated sulfate surfactants hereof
are water soluble salts or acids of the formula RO(A)
mSO3M wherein R is an unsubstituted C₁₀-C₂₄ alkyl or hydroxyalkyl group having a C₁₀-C₂₄
alkyl component, preferably a C₁₂-C₂₀ alkyl or hydroxyalkyl, more preferably C₁₂-C₁₈
alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically
between about 0.5 and about 6, more preferably between about 0.5 and about 3, and
M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium,
lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation. Alkyl
ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
Specific examples of substituted ammonium cations include methyl-, dimethyl, trimethyl-ammonium
cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl
piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine,
triethylamine, mixtures thereof, and the like. Exemplary surfactants are C₁₂-C₁₈ alkyl
polyethoxylate (1.0) sulfate (C₁₂-C₁₈E(1.0)M), C₁₂-C₁₈ alkyl polyethoxylate (2.25)
sulfate (C₁₂-C₁₈E(2.25)M), C₁₂-C₁₈ alkyl polyethoxylate (3.0) sulfate (C₁₂-C₁₈E(3.0)M),
and C₁₂-C₁₈ alkyl polyethoxylate (4.0) sulfate (C₁₂-C₁₈E(4.0)M), wherein M is conveniently
selected from sodium and potassium.
[0027] Suitable anionic surfactants to be used are alkyl ester sulfonate surfactants including
linear esters of C₈-C₂₀ carboxylic acids (i.e., fatty acids) which are sulfonated
with gaseous SO₃ according to "The Journal of the American Oil Chemists Society",
52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances
as derived from tallow, palm oil, etc.
[0028] The preferred alkyl ester sulfonate surfactant, especially for laundry applications,
comprise alkyl ester sulfonate surfactants of the structural formula :

wherein R³ is a C₈-C₂₀ hydrocarbyl, preferably an alkyl, or combination thereof, R⁴
is a C₁-C₆ hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation
which forms a water soluble salt with the alkyl ester sulfonate. Suitable salt-forming
cations include metals such as sodium, potassium, and lithium, and substituted or
unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine.
Preferably, R³ is C₁₀-C₁₆ alkyl, and R⁴ is methyl, ethyl or isopropyl. Especially
preferred are the methyl ester sulfonates wherein R³ is C₁₀-C₁₆ alkyl.
[0029] Other suitable anionic surfactants include the alkyl sulfate surfactants hereof are
water soluble salts or acids of the formula ROSO₃M wherein R preferably is a C₁₀-C₂₄
hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C₁₀-C₂₀ alkyl component,
more preferably a C₁₂-C₁₈ alkyl or hydroxyalkyl, and M is H or a cation, e.g., an
alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted
ammonium (e.g. methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium
cations such as tetramethylammonium and dimethyl piperdinium cations and quaternary
ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine,
and mixtures thereof, and the like). Typically, alkyl chains of C₁₂-C₁₆ are preferred
for lower wash temperatures (e.g. below about 50°C) and C₁₆₋₁₈ alkyl chains are preferred
for higher wash temperatures (e.g. above about 50°C).
[0030] Other anionic surfactants useful for detersive purposes can also be included in the
laundry detergent compositions of the present invention. These can include salts (including,
for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-,
di- and triethanolamine salts) of soap, C₉-C₂₀ linear alkylbenzenesulfonates, C₈-C₂₂
primary of secondary alkanesulfonates, C₈-C₂₄ olefinsulfonates, sulfonated polycarboxylic
acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates,
e.g., as described in British patent specification No. 1,082,179, C₈-C₂₄ alkylpolyglycolethersulfates
(containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl
glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether
sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates,
N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates
(especially saturated and unsaturated C₁₂-C₁₈ monoesters) and diesters of sulfosuccinates
(especially saturated and unsaturated C₆-C₁₂ diesters), acyl sarcosinates, sulfates
of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated
compounds being described below), branched primary alkyl sulfates, and alkyl polyethoxy
carboxylates such as those of the formula RO(CH₂CH₂O)
k-CH₂COO-M+ wherein R is a C₈-C₂₂ alkyl, k is an integer from 0 to 10, and M is a soluble
salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such
as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present
in or derived from tall oil. Further examples are described in "Surface Active Agents
and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants
are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to
Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated
by reference).
[0031] When included therein, the laundry detergent compositions of the present invention
typically comprise from about 1% to about 40%, preferably from about 3% to about 20%
by weight of such anionic surfactants.
[0032] The laundry detergent compositions of the present invention may also contain cationic,
ampholytic, zwitterionic, and semi-polar surfactants, as well as nonionic surfactants
other than those already described herein. Preferred cationic surfactant systems include
nonionic and ampholytic surfactants. Cationic detersive surfactants suitable for use
in the laundry detergent compositions of the present invention are those having one
long-chain hydrocarbyl group. Examples of such cationic surfactants include the ammonium
surfactants such as alkyldimethylammonium halogenides, and those surfactants having
the formula :
[R²(OR³)
y][R⁴(OR³)
y]₂R⁵N+X-
wherein R² is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon
atoms in the alkyl chain, each R³ is selected from the group consisting of -CH₂CH₂-,
-CH₂CH(CH₃)-, -CH₂CH(CH₂OH)-, -CH₂CH₂CH₂-, and mixtures thereof; each R⁴ is selected
from the group consisting of C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, benzyl ring structures
formed by joining the two R⁴ groups, -CH₂CHOH-CHOHCOR⁶CHOHCH₂OH wherein R⁶ is any
hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen
when y is not 0; R⁵ is the same as R⁴ or is an alkyl chain wherein the total number
of carbon atoms of R² plus R⁵ is not more than about 18; each y is from 0 to about
10 and the sum of the y values is from 0 to about 15; and X is any compatible anion.
[0033] Preferred cationic surfactants are the water-soluble quaternary ammonium compounds
useful in the present composition having the formula :
R₁R₂R₃R₄N⁺X⁻ (i)
wherein R₁ is C₈-C₁₆ alkyl, each of R₂, R₃ and R₄ is independently C₁-C₄ alkyl, C₁-C₄
hydroxy alkyl, benzyl, and - (C₂H₄₀)
xH where x has a value from 2 to 5, and X is an anion. Not more than one of R₂, R₃
or R₄ should be benzyl.
The preferred alkyl chain length for R₁ is C₁₂-C₁₅ particularly where the alkyl group
is a mixture of chain lengths derived from coconut or palm kernel fat or is derived
synthetically by olefin build up or OXO alcohols synthesis.
Preferred groups for R₂R₃ and R₄ are methyl and hydroxyethyl groups and the anion
X may be selected from halide, methosulphate, acetate and phosphate ions.
[0034] Examples of suitable quaternary ammonium compounds of formulae (i) for use herein
are :
coconut trimethyl ammonium chloride or bromide;
coconut methyl dihydroxyethyl ammonium chloride or bromide;
decyl triethyl ammonium chloride;
decyl dimethyl hydroxyethyl ammonium chloride or bromide;
C₁₂₋₁₅ dimethyl hydroxyethyl ammonium chloride or bromide;
coconut dimethyl hydroxyethyl ammonium chloride or bromide;
myristyl trimethyl ammonium methyl sulphate;
lauryl dimethyl benzyl ammonium chloride or bromide;
lauryl dimethyl (ethenoxy)₄ ammonium chloride or bromide;
choline esters (compounds of formula (i) wherein R₁ is

alkyl and R₂R₃R₄ are methyl).
di-alkyl imidazolines [compounds of formula (i)].
[0035] Other cationic surfactants useful herein are also described in U.S. Patent 4,228,044,
Cambre, issued October 14, 1980.
[0036] When included therein, the laundry detergent compositions of the present invention
typically comprise from 0% to about 25%, preferably from about 3% to about 15% by
weight of such cationic surfactants.
[0037] Ampholytic surfactants are also suitable for use in the laundry detergent compositions
of the present invention. These surfactants can be broadly described as aliphatic
derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic
secondary and tertiary amines in which the aliphatic radical can be straight- or branched-chain.
One of the aliphatic substituents contains at least about 8 carbon atoms, typically
from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing
group, e.g. carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin
et al., issued December 30, 1975 at column 19, lines 18-35, for examples of ampholytic
surfactants.
[0038] When included therein, the laundry detergent compositions of the present invention
typically comprise from 0% to about 15%, preferably from about 1% to about 10% by
weight of such ampholytic surfactants.
[0039] Zwitterionic surfactants are also suitable for use in laundry detergent compositions.
These surfactants can be broadly described as derivatives of secondary and tertiary
amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives
of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See
U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19,
line 38 through column 22, line 48, for examples of zwitterionic surfactants.
[0040] When included therein, the laundry detergent compositions of the present invention
typically comprise from 0% to about 15%, preferably from about 1% to about 10% by
weight of such zwitterionic surfactants.
[0041] Semi-polar nonionic surfactants are a special category of nonionic surfactants which
include water-soluble amine oxides containing one alkyl moiety of from about 10 to
about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups
and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble
phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms
and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl
groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides
containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety
selected from the group consisting of alkyl and hydroxyalkyl moieties of from about
1 to about 3 carbon atoms.
[0042] Semi-polar nonionic detergent surfactants include the amine oxide surfactants having
the formula

wherein R³ is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures therof containing
from about 8 to about 22 carbon atoms; R⁴ is an alkylene or hydroxyalkylene group
containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to
about 3; and each R⁵ is an alkyl or hydroxyalkyl group containing from about 1 to
about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about
3 ethylene oxide groups. The R⁵ groups can be attached to each other, e.g., through
an oxygen or nitrogen atom, to form a ring structure.
[0043] These amine oxide surfactants in particular include C₁₀-C₁₈ alkyl dimethyl amine
oxides and C₈-C₁₂ alkoxy ethyl dihydroxy ethyl amine oxides.
[0044] When included therein, the laundry detergent compositions of the present invention
typically comprise from 0% to about 15%, preferably from about 1% to about 10% by
weight of such semi-polar nonionic surfactants.
[0045] The present invention further provides laundry detergent compositions comprising
at least 1% by weight, preferably from about 3% to about 65%, more preferably from
about 10% to about 25% by weight of total surfactants.
[0046] The compositions according to the present invention may further comprise a builder
system. Any conventional builder system is suitable for use herein including aluminosilicate
materials, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate,
metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine
tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid.
Though less preferred for obvious environmental reasons, phosphate builders can also
be used herein.
Suitable builders can be an inorganic ion exchange material, commonly an inorganic
hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite
such as hydrated zeolite A, X, B or HS.
[0047] Suitable polycarboxylates containing one carboxy group include lactic acid, glycolic
acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831,368, 821,369
and 821,370. Polycarboxylates containing two carboxy groups include the water-soluble
salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid,
diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether
carboxylates described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S.
Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No.
840,623. Polycarboxylates containing three carboxy groups include, in particular,
water-soluble citrates, aconitrates and citraconates as well as succinate derivatives
such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241,
lactoxysuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate
materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent
No. 1,387,447.
[0048] Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed
in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane
tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing
sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent
Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated
pyrolysed citrates described in British Patent No. 1,082,179, while polycarboxylates
containing phosphone substituents are disclosed in British Patent No. 1,439,000.
[0049] Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-tetracarboxylates,
cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran - cis, cis, cis-tetracarboxylates,
2,5-tetrahydrofuran -cis - dicarboxylates, 2,2,5,5-tetrahydrofuran - tetracarboxylates,
1,2,3,4,5,6-hexane -hexacarboxylates and and carboxymethyl derivatives of polyhydric
alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include
mellitic acid, pyromellitic acid and the phtalic acid derivatives disclosed in British
Patent No. 1,425,343.
[0050] Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up
to three carboxy groups per molecule, more particularly citrates. Preferred builder
systems for use in the present compositions include a mixture of a water-insoluble
aluminosilicate builder such as zeolite A or of a layered silicate (sks/6), and a
water-soluble carboxylate chelating agent such as citric acid.
[0051] A suitable chelant for inclusion in the detergent compositions in accordance with
the invention is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal,
alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures
thereof. Preferred EDDS compounds are the free acid form and the sodium or magnesium
salt thereof. Examples of such preferred sodium salts of EDDS include Na₂EDDS and
Na₄EDDS. Examples of such preferred magnesium salts of EDDS include MgEDDS and Mg₂EDDS.
The magnesium salts are the most preferred for inclusion in compositions in accordance
with the invention.
[0052] Preferred builder systems include a mixture of a water-insoluble aluminosilicate
builder such as zeolite A, and a watersoluble carboxylate chelating agent such as
citric acid. Other builder materials that can form part of the builder system for
use in granular compositions the purposes of the invention include inorganic materials
such as alkali metal carbonates, bicarbonates, silicates, and organic materials such
as the organic phosphonates, amiono polyalkylene phosphonates and amino polycarboxylates.
Other suitable water-soluble organic salts are the homo- or co-polymeric acids or
their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals
separated from each other by not more than two carbon atoms.
Polymers of this type are disclosed in GB-A-1,596,756. Examples of such salts are
polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers
having a molecular weight of from 20,000 to 70,000, especially about 40,000.
[0053] Detergency builder salts are normally included in amounts of from 10% to 80% by weight
of the composition preferably from 20% to 70% and most usually from 30% to 60% by
weight.
[0054] Detergent ingredients that can be included in the detergent compositions of the present
invention include bleaching agents.
These bleaching agent components can include one or more oxygen bleaching agents and,
depending upon the bleaching agent chosen, one or more bleach activators. When present
bleaching compounds will typically be present at levels of from about 1% to about
10%, of the detergent composition. In general, bleaching compounds are optional components
in non-liquid formulations, e.g. granular detergents. If present, the amount of bleach
activators will typically be from about 0.1% to about 60%, more typically from about
0.5% to about 40% of the bleaching composition.
[0055] The bleaching agent component for use herein can be any of the bleaching agents useful
for detergent compositions including oxygen bleaches as well as others known in the
art.
[0056] In a method aspect, this invention further provides a method for cleaning fabrics,
fibers, textiles, at temperatures below about 50°C, especially below about 40°C, with
a detergent composition containing polyamine N-oxide containing polymers, optional
auxiliary detersive surfactants, optional detersive adjunct ingredients, and a bleaching
agent.
The bleaching agent suitable for the present invention can be an activated or non-activated
bleaching agent.
[0057] One category of oxygen bleaching agent that can be used encompasses percarboxylic
acid bleaching agents and salts thereof. Suitable examples of this class of agents
include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro
perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
Such bleaching agents are disclosed in U.S. Patent 4,483,781, U.S. Patent Application
740,446, European Patent Application 0,133,354 and U.S. Patent 4,412,934. Highly preferred
bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in
U.S. Patent 4,634,551.
[0058] Another category of bleaching agents that can be used encompasses the halogen bleaching
agents. Examples of hypohalite bleaching agents, for example, include trichloro isocyanuric
acid and the sodium and potassium dichloroisocyanurates and N-chloro and N-bromo alkane
sulphonamides. Such materials are normally added at 0.5-10% by weight of the finished
product, preferably 1-5% by weight.
[0059] Preferably, the bleaches suitable for the present invention include peroxygen bleaches.
Examples of suitable water-soluble solid peroxygen bleaches include hydrogen peroxide
releasing agents such as hydrogen peroxide, perborates, e.g. perborate monohydrate,
perborate tetrahydrate, persulfates, percarbonates, peroxydisulfates, perphosphates
and peroxyhydrates. Preferred bleaches are percarbonates and perborates.
[0060] The hydrogen peroxide releasing agents can be used in combination with bleach activators
such as tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described
in US 4,412,934), 3,5,-trimethylhexanoloxybenzenesulfonate (ISONOBS, described in
EP 120,591) or pentaacetylglucose (PAG), which are perhydrolyzed to form a peracid
as the active bleaching species, leading to improved bleaching effect. Also suitable
activators are acylated citrate esters (ATC) such as disclosed in Copending European
Patent Application No. 91870207.7.
[0061] The hydrogen peroxide may also be present by adding an enzymatic system (i.e. an
enzyme and a substrate therefore) which is capable of generating hydrogen peroxide
at the beginning or during the washing and/or rinsing process. Such enzymatic systems
are disclosed in EP Patent Application 91202655.6 filed October 9, 1991.
[0062] Other peroxygen bleaches suitable for the present invention include organic peroxyacids
such as percarboxylic acids.
[0063] Bleaching agents other than oxygen bleaching agents are also known in the art and
can be utilized herein. One type of non-oxygen bleaching agent of particular interest
includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum
phthalocyanines. These materials can be deposited upon the substrate during the washing
process. Upon irradiation with light, in the presence of oxygen, such as by hanging
clothes out to dry in the daylight, the sulfonated zinc phthalocyanine is activated
and, consequently, the substrate is bleached. Preferred zinc phthalocyanine and a
photoactivated bleaching process are described in U.S. Patent 4,033,718. Typically,
detergent compositions will contain about 0.025% to about 1.25%, by weight, of sulfonated
zinc phthalocyanine.
[0064] Other detergent ingredients that can be included are detersive enzymes which can
be included in the detergent formulations for a wide variety of purposes including
removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example,
and prevention of refugee dye transfer.
The enzymes to be incorporated include proteases, amylases, lipases, cellulases, and
peroxidases, as well as mixtures thereof. Other types of enzymes may also be included.
They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and
yeast origin.
[0065] Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg
by weight, more typically about 0.05 mg to about 3 mg, of active enzyme per gram of
the composition.
[0066] Suitable examples of proteases are the subtilisins which are obtained from particular
strains of B.subtilis and B.licheniforms. Proteolytic enzymes suitable for removing
protein-based stains that are commercially available include those sold under the
tradenames Alcalase, Savinase and Esperase by Novo Industries A/S (Denmark) and Maxatase
by International Bio-Synthetics, Inc. (The Netherlands) and FN-base by Genencor, Optimase
and opticlean by MKC.
[0067] Of interest in the category of proteolytic enzymes, especially for liquid detergent
compositions, are enzymes referred to herein as Protease A and Protease B. Protease
A is described in European Patent Application 130,756. Protease B is described in
European Patent Application Serial No. 87303761.8. Amylases include, for example,
-amylases obtained from a special strain of B.licheniformis, described in more detail
in British Patent Specification No. 1,296,839 (Novo). Amylolytic proteins include,
for example, Rapidase, Maxamyl (International Bio-Synthetics, Inc.) and Termamyl,
(Novo Industries).
[0068] The cellulases usable in the present invention include both bacterial or fungal cellulase.
Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases
are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, which discloses fungal
cellulase produced from Humicola insolens. Suitable cellulases are also disclosed
in GB-A-2.075.028 ; GB-A-2.095.275 and DE-OS-2.247.832.
[0069] Examples of such cellulases are cellulases produced by a strain of Humicola insolens
(Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800, and
cellulases produced by a fungus of Bacillus N or a cellulase 212-producing fungus
belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas
of a marine mollusc (Dolabella Auricula Solander).
Other suitable cellulases are cellulases originated from Humicola Insulens having
a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415
amino acids. Such cellulase are described in Copending European patent application
No. 93200811.3, filed March 19, 1993.
[0070] Especially suitable cellulase are the cellulase having color care benefits. Examples
of such cellulases are cellulase described in European patent application No. 91202879.2,
filed November 6, 1991 Carezyme (Novo).
[0071] Suitable lipase enzymes for detergent usage include those produced by microorganisms
of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in
British Patent 1,372,034. Suitable lipases include those which show a positive immunoligical
cross-reaction with the antibody of the lipase, produced by the microorganism
Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan,
under the trade name Lipase P "Amano," hereinafter referred to as "Amano-P".
Especially suitable Lipase are lipase such as M1 Lipase (Ibis) and Lipolase (Novo).
[0072] Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate,
perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching",
i.e. to prevent transfer of dyes of pigments removed from substrates during wash operations
to other substrates in the wash solution. Peroxidase enzymes are known in the art,
and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such
as chloro- and bromo-peroxidase.
Peroxidase-containing detergent compositions are disclosed, for example, in PCT Internation
Application WO 89/099813 and in European Patent application EP No. 91202882.6, filed
on November 6, 1991.
In liquid formulations, an enzyme stabilization system is preferably utilized. Enzyme
stabilization techniques for aqueous detergent compositions are well known in the
art. For example, one technique for enzyme stabilization in aqueous solutions involves
the use of free calcium ions from sources such as calcium acetate, calcium formate
and calcium propionate. Calcium ions can be used in combination with short chain carboxylic
acid salts, preferably formates. See, for example, U.S. patent 4,318,818. It has also
been proposed to use polyols like glycerol and sorbitol. Alkoxy-alcohols, dialkylglycoethers,
mixtures of polyvalent alcohols with polyfunctional aliphatic amines (e.g., such as
diethanolamine, triethanolamine, di-isopropanolamime, etc.), and boric acid or alkali
metal borate. Enzyme stabilization techniques are additionally disclosed and exemplified
in U.S. patent 4,261,868, U.S. Patent 3,600,319, and European Patent Application Publication
No. 0 199 405, Application No. 86200586.5. Non-boric acid and borate stabilizers are
preferred. Enzyme stabilization systems are also described, for example, in U.S. Patents
4,261,868, 3,600,319 and 3,519,570.
Other suitable detergent ingredients that can be added are enzyme oxidation scavengers
which are described in Copending European Patent aplication N 92870018.6 filed on
January 31, 1992. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene
polyamines.
[0073] Especially preferred detergent ingredients are combinations with technologies which
also provide a type of color care benefit. Examples to these technologies are polyvinylpyrrolidone
polymers such as described in EP 0 508 034. The detergent compositions herein contain
a polyvinylpyrrolidone ("PVP" having an average molecular weight of from about 5,000
to about 400,000, preferably from about 5,000 to about 200,000, more preferably from
about 5,000 to about 50,000, and most preferably from about 5,000 to about 20,000.
Suitable polyvinylpyrrolidones are commercially available from GAF Corporation, New
York, NY and Montreal, Canada under the product names PVP K-15 (average molecular
weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average
molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000).
PVP K-15 is also available from ISP Corporation. Other suitable polyvinylpyrrolidones
which are commercially available from BASF Cooperation include Sokalan HP 165 and
Sokalan HP 12.
Polyvinylpyrrolidones known to persons skilled in the detergent field; see for example
EP-A-262,897 and EP-A-256,696. Th amount of polyvinylpyrrolidone used in the present
detergent compositions should be from about 0.01% to about 5% by weight of the detergent,
preferably from about 0.05% to about 3% by weight, and more preferably from about
0.1% to about 2% by weight. The amount of polyvinylpyrrolidone delivered in the wash
solution is from about 0.5 ppm to about 300 ppm, preferably from about 1 ppm to about
60 ppm, more preferably from about 1 ppm to about 30 ppm, and most preferably from
about 1 ppm to about 20 ppm.
[0074] Preferred polymers for inhibiting dye transfer are polyamine-N-oxide containing polymers
such as described in Copending European patent application No. 92202168.8 and No.
93201198.4.
[0075] The amine N-oxide polymers of the present invention typically have a ratio of amine
to the amine N-oxide of 10:1 to 1:1000000. However, the amount of amine oxide groups
present in the polyamine oxide containing polymer can be varied by appropriate copolymerization
or by appropriate degree of N-oxidation. Preferably, the ratio of amine to amine N-oxide
is from 2:3 to 1:1000000. More preferably from 1:4 to 1:1000000, most preferably from
1:7 to 1:1000000.
Typically, the average molecular weight is within the range of 500 to 1000,000; preferably
from 1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000
to 20,000.
[0076] The polyamine N-oxide containing polymers of the present invention are typically
present from 0.001 to 10%, more preferably from 0.0-1 to 2%, most preferred from 0.05
to 1% by weight of the detergent composition.
[0077] Other preferred polymers are N-vinylimidazole N-vinylpyrrolidone copolymers such
as described in Copending European patent application No. 93870155.4.
The N-vinylimidazole N-vinylpyrrolidone polymers have an average molecular weight
range from 5000-1,000,000, preferably from 20 000-200,000.
Highly preferred polymers for use in detergent compositions according to the present
invention comprise a polymer selected from N-vinylimidazole N-vinylpyrrolidone copolymers
wherein said polymer has an average molecular weight range from 5,000 to 50,000 more
preferably from 8,000 to 30,000, most preferably from 10,000 to 20,000.
[0078] Other examples of detergent ingredients that provide a type of color care benefit
are cellulase, peroxidase and metallo catalysts. Such metallo catalysts are described
in copending European Patent application No. 92870181.2.
[0079] Another optional ingredient is a suds suppressor, exemplified by silicones, and silica-silicone
mixtures.
Silicones can be generally represented by alkylated polysiloxane materials while silica
is normally used in finely divided forms exemplified by silica aerogels and xerogels
and hydrophobic silicas of various types. These materials can be incorporated as particulates
in which the suds suppressor is advantageously releasably incorporated in a water-soluble
or water-dispersible, substantially non-surface-active detergent impermeable carrier.
Alternatively the suds suppressor can be dissolved or dispersed in a liquid carrier
and applied by spraying on to one or more of the other components.
[0080] A preferred silicone suds controlling agent is disclosed in Bartollota et al. U.S.
Patent 3 933 672. Other particularly useful suds suppressors are the self-emulsifying
silicone suds suppressors, described in German Patent Application DTOS 2 646 126 published
April 28, 1977. An example of such a compound is DC-544, commercially available from
Dow Corning, which is a siloxane-glycol copolymer. Especially preferred suds controlling
agent are the suds suppressor system comprising a mixture of silicone oils and 2-alkyl-alcanols.
Suitable 2-alkyl-alcanols are 2-butyl-octanol which are commercially available under
the trade name Isofol 12 R.
Such suds suppressor system are described in Copending European Patent application
N 92870174.7 filed 10 November, 1992.
[0081] Especially preferred silicone suds controlling agents are described in Copending
European Patent application N°92201649.8. Said compositions can comprise a silicone/silica
mixture in combination with fumed nonporous silica such as Aerosil
R.
[0082] Other preferred suds controlling agents are described in EP 495 345. These suds controlling
agents comprise a silicone antifoam compound, a carrier material and an organic coating
material further containing glycerol at a weight ratio with the silicone antifoam
compound of 1:2 to 3:1.
[0083] The suds suppressors described above are normally employed at levels of from 0.001%
to 2% by weight of the composition, preferably from 0.01% to 1% by weight.
[0084] Other components used in detergent compositions may be employed, such as soil-suspending
agents soil-release agents, optical brighteners, abrasives, bactericides, tarnish
inhibitors, coloring agents, and non-encapsulated and encapsulated perfumes.
[0085] Especially suitable encapsulating materials are water soluble capsules which consist
of a matrix of polysaccharide and polyhydroxy compounds such as described in GB 1,464,616.
[0086] Other suitable water soluble encapsulating materials comprise dextrins derived from
ungelatinized starch acid-esters of substituted dicarboxylic acids such as described
in US 3,455,838. These acid-ester dextrins are,preferably, prepared from such starches
as waxy maize, waxy sorghum, sago, tapioca and potato. Suitable examples of said encapsulating
materials include N-Lok manufactured by National Starch. The N-Lok encapsulating material
consisits of a modified maize starch and glucose. The starch is modified by adding
monofunctional substituted groups such as octenyl succinic acid anhydride.
[0087] Antiredeposition and soil suspension agents suitable herein include cellulose derivatives
such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo-
or co-polymeric polycarboxylic acids or their salts. Polymers of this type include
the polyacrylates and maleic anhydrideacrylic acid copolymers previously mentioned
as builders, as well as copolymers of maleic anhydride with ethylene, methylvinyl
ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent
of the copolymer. These materials are normally used at levels of from 0.5% to 10%
by weight, more preferably from 0.75% to 8%, most preferably from 1% to 6% by weight
of the composition.
[0088] Preferred optical brighteners are anionic in character, examples of which are disodium
4,4¹-bis-(2-diethanolamino-4-anilino -s- triazin-6-ylamino)stilbene-2:2¹ disulphonate,
disodium 4, - 4¹-bis-(2-morpholino-4-anilino-s-triazin-6-ylaminostilbene-2:2¹ - disulphonate,
disodium 4,4¹ - bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2¹ - disulphonate,
monosodium 4¹,4¹¹ -bis-(2,4-dianilino-s-triazin-6 ylamino)stilbene-2-sulphonate, disodium
4,4¹ -bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2¹
- disulphonate, disodium 4,4¹ -bis-(4-phenyl-2,1,3-triazol-2-yl)-stilbene-2,2¹ disulphonate,
disodium 4,4¹bis(2-anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazin-6- ylamino)stilbene-2,2¹disulphonate
and sodium 2(stilbyl-4¹¹-(naphtho-1¹,2¹:4,5)-1,2,3 - triazole-2¹¹-sulphonate.
[0089] Other useful polymeric materials are the polyethylene glycols, particularly those
of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably
about 4000.
These are used at levels of from 0.20% to 5% more preferably from 0.25% to 2.5% by
weight. These polymers and the previously mentioned homo- or co-polymeric polycarboxylate
salts are valuable for improving whiteness maintenance, fabric ash deposition, and
cleaning performance on clay, proteinaceous and oxidizable soils in the presence of
transition metal impurities.
[0090] Soil release agents useful in compositions of the present invention are conventionally
copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene
glycol units in various arrangements. Examples of such polymers are disclosed in the
commonly assigned US Patent Nos. 4116885 and 4711730 and European Published Patent
Application No. 0 272 033. A particular preferred polymer in accordance with EP-A-0
272 033 has the formula
(CH₃(PEG)₄₃)
0.75(POH)
0.25[T-PO)
2.8(T-PEG)
0.4]T(PO- H)
0.25((PEG)₄₃CH₃)
0.75
where PEG is -(OC₂H₄)O-,PO is (OC₃H₆O) and T is (pcOC₆H₄CO).
[0091] Also very useful are modified polyesters as random copolymers of dimethyl terephtalate,
dimethyl sulfoisophtalate, ethylene glycol and 1-2 propane diol, the end groups consisting
primarily of sulphobenzoate and secondarily of mono esters of ethylene glycol and/or
propane-diol. The target is to obtain a polymer capped at both end by sulphobenzoate
groups, "primarily", in the present context most of said copolymers herein will be
end-capped by sulphobenzoate groups. However, some copolymers will be less than fully
capped, and therefore their end groups may consist of monoester of ethylene glycol
and/or propane 1-2 diol, thereof consist "secondarily" of such species.
[0092] The selected polyesters herein contain about 46% by weight of dimethyl terephtalic
acid, about 16% by weight of propane - 1.2 diol, about 10% by weight ethylene glycol
about 13% by weight of dimethyl sulfobenzoid acid and about 15% by weight of sulfoisophtalic
acid, and have a molecular weight of about 3.000. The polyesters and their method
of preparation are described in detail in EPA 311 342.
[0093] The detergent compositions according to the invention can be in liquid, paste, gels,
bars or granular forms. Granular compositions according to the present invention can
also be in "compact form", i.e. they may have a relatively higher density than conventional
granular detergents, i.e. from 550 to 950 g/l; in such case, the granular detergent
compositions according to the present invention will contain a lower amount of "inorganic
filler salt", compared to conventional granular detergents; typical filler salts are
alkaline earth metal salts of sulphates and chlorides, typically sodium sulphate;
"compact" detergents typically comprise not more than 10% filler salt. The liquid
compositions according to the present invention can also be in "concentrated form",
in such case, the liquid detergent compositions according to the present invention
will contain a lower amount of water, compared to conventional liquid detergents.
Typically, the water content of the concentrated liquid detergent is less than 30%,
more preferably less than 20%, most preferably less than 10% by weight of the detergent
compositions.
[0094] The present invention also relates to a process for inhibiting dye transfer from
one fabric to another of solubilized and suspended dyes encountered during fabric
laundering operations involving colored fabrics.
[0095] The process comprises contacting fabrics with a laundering solution as hereinbefore
described.
[0096] The process of the invention is conveniently carried out in the course of the washing
process. The washing process is preferably carried out at 5 °C to 75 °C, especially
20 to 60, but the polymers are effective at up to 95°C and higher temperatures. The
pH of the treatment solution is preferably from 7 to 11, especially from 7.5 to 10.5.
[0097] The process and compositions of the invention can also be used as detergent additive
products.
Such additive products are intended to supplement or boost the performance of conventional
detergent compositions.
The detergent compositions according to the present invention include compositions
which are to be used for cleaning substrates, such as fabrics, fibers, hard surfaces,
skin etc., for example hard surface cleaning compositions (with or without abrasives),
laundry detergent compositions, automatic and non automatic dishwashing compositions.
[0098] The following examples are meant to exemplify compositions of the present invention,
but are not necessarily meant to limit or otherwise define the scope of the invention,
said scope being determined according to claims which follow.
EXAMPLE I (A/B/C/D)
[0099] The efficiency of the layered silicate/flocculating polymer combination as a softening
system was assessed by measuring the softening performance.
[0100] The softening performance was measured by a launderometer test. The test procedure
was as follows : 3.5 kg of clean fabric laundry loads were washed in an automatic
drum washing machine Miel 423 at 60°C. The hardness of the water was 2mM Calcium and
the composition concentration was 0.7% in the wash liquor.
[0101] A bundle of soiled fabrics containing fabrics which were stained with particulate
soil was washed with a detergent composition with/without the silicate softening system.
Comparative softening assessment was done by expert judges using a scale of 0 to 4
panel-score-units (PSU). In this scale 0 is given for no difference and 4 is given
for maximum difference.
[0102] A granular detergent composition according to the present invention is prepared,
having the following compositions :
Table I
% by weight of the total detergent composition |
Linear alkyl benzene sulphonate |
13.70 |
Tallow alkyl sulphate |
5.9 |
C₄₅ alcohol 7 times ethoxylated |
4.00 |
Trisodium citrate |
5.00 |
Zeolite |
26.00 |
Maleic acid actylic acid copolymer |
4.9 |
Diethylenetriaminepentamethylene |
0.6 |
Phosphonic acid |
|
Protease |
1.5 |
carboxymethylcellulose |
1.5 |
suds supressor (silicone) |
0.3 |
[0103] Example I demonstrates the softening performance of the layered silicate in combination
with the flocculating polymer versus compositions containing layered silicate without
flocculating polymers. The flocculating polymer that was used is polyethylene oxide
having an average molecular weight of 300,000. The layered silicate that was used
is layered silicate (SKS-6).
Experimental conditions :
[0104] pH = 10.5
Wash Temperature : 40°C
- A :
- A detergent composition according to Table I which contains no layered silicate and
no flocculating polymer.
- B :
- A detergent composition according to Table I which contains 9% of layered silicate
and no flocculating polymer.
- C :
- A detergent composition according to Table I containing 0.3% of flocculating polymer
and no layered silicate.
- D :
- A detergent composition according to Table I containing 0.3% flocculating polymer
and 9% layered silicate.
Results :
[0105] PSU values for the softening performance (reference IA).
Bleeding fabric composition: 100% cotton) and PSU values
The above results demonstrate that the combination of the flocculating polymers and
silicate provides statistically significant softening performance.
EXAMPLE II (A/B) :
[0106] The efficiency of the silicate softening system was assessed by measuring the softening
and cleaning performance.
[0107] The softening and cleaning performance was measured by a launderometer test. The
test procedure was as follows : 3.5 kg of clean fabric laundry loads were washed in
an automatic drum washing machine Miel 423 at 60°C. The hardness of the water was
2mM Calcium and the composition concentration was 0.7% in the wash liquor.
[0108] A bundle of soiled fabrics containing fabrics which were stained with particulate
soil was washed with a detergent composition with/without the silicate softening system.
Comparative softening and cleaning assessment was done by expert judges using a scale
of 0 to 4 panel-score-units (PSU).
In this scale 0 is given for no difference and 4 is given for maximum difference.
- A :
- A detergent composition according to Table I which contains no layered silicate and
no flocculating polymer.
- B :
- A detergent composition according to Table I which contains 9% of layered silicate
and 0.3% of a flocculating polymer.
Experimental conditions :
[0109] pH = 10.5
Wash Temperature : 40°C
RESULTS
[0110]
|
A |
B |
SOFTENING (psu) |
0 |
+1.5 |
CLEANING (psu) |
0 |
+0 |
[0111] As can be seen from the above, the cleaning performance is not negatively affected
by the presence of the silicate softening system.
EXAMPLE I (A/B/C/D/E)
[0112] A compact granular detergent composition according to the present invention is prepared,
having the following formulation:
% by weight of the total detergent composition |
|
A |
B |
C |
D |
E |
Linear alkyl benzene sulphonate |
11.40 |
- |
- |
- |
5 |
Polyhydroxy fatty acid amide |
- |
10 |
- |
5 |
5 |
Alkyl alkoxylated sulfate |
- |
- |
9 |
9 |
9 |
Tallow alkyl sulphate |
1.80 |
1.80 |
1.80 |
4 |
4 |
C₄₅ alkyl sulphate |
3.00 |
3.00 |
3.00 |
- |
- |
C₄₅ alcohol 7 times ethoxylated |
4.00 |
4.00 |
4.00 |
- |
- |
Tallow alcohol 11 times ethoxylated |
1.80 |
1.80 |
1.80 |
5 |
5 |
Dispersant |
0.07 |
0.07 |
0.07 |
0.07 |
0.07 |
Silicone fluid |
0.80 |
0.80 |
0.80 |
0.80 |
0.80 |
Trisodium citrate |
14.00 |
14.00 |
14.00 |
14.00 |
14.00 |
Citric acid |
3.00 |
3.00 |
3.00 |
3.00 |
3.00 |
Zeolite |
32.50 |
32.50 |
32.50 |
32.50 |
32.50 |
Maleic acid acrylic acid co-polymer |
5.00 |
5.00 |
5.00 |
5.00 |
5.00 |
Carezyme |
0.1 |
0.1 |
0.1 |
0.1 |
0.1 |
Alkalase/BAN |
0.60 |
0.60 |
0.60 |
0.60 |
0.60 |
Lipolase |
0.36 |
0.36 |
0.36 |
0.36 |
0.36 |
Savinase |
0.6 |
0.6 |
0.6 |
0.6 |
0.6 |
Sodium silicate |
2.00 |
2.00 |
2.00 |
2.00 |
2.00 |
Sodium sulphate |
3.50 |
3.50 |
3.50 |
3.50 |
3.50 |
Polyvinyl pyrrolidone |
0-1 |
0-1 |
0-1 |
0-1 |
0-1 |
Perborate |
- |
- |
- |
15 |
- |
TAED |
|
- |
|
5 |
5 |
Percarbonate |
- |
- |
- |
|
20 |
Layered Silicate |
9 |
9 |
9 |
9 |
9 |
polyethylene oxide |
0.3 |
0.3 |
0.3 |
0.3 |
0.3 |
foam control agent(*) |
0.1 |
0.1 |
0.1 |
0.1 |
0.1 |
Perfume |
0.4 |
0.4 |
0.4 |
0.4 |
0.4 |
Perfume encapsulated |
0.4 |
0.4 |
0.4 |
0.4 |
0.4 |
Minors |
up to 100 |
(*) Suds suppressor : agglomerate comprising 11% by weight of the component of polydimethylsiloxane,
14% Tallow alcohol ethoxylated, 5% of C12-C22 hydrogenated fatty acids and 70% starch. |
[0113] The above compositions (Example I (A/B/C/D/E)) were very good at displaying excellent
softening, cleaning and detergency performance with outstanding color-care performance
on colored fabrics and mixed loads of colored and white fabrics.
EXAMPLE II (A/B/C/D)
[0114] A liquid detergent composition according to the present invention is prepared, having
the following compositions :
% by weight of the total detergent composition |
|
A |
B |
C |
D |
Linear alkylbenzene sulfonate |
10 |
- |
- |
- |
Polyhydroxy fatty acid amide |
- |
5 |
- |
3 |
Alkyl alkoxylated sulfate |
- |
- |
9 |
4 |
Alkyl sulphate |
4 |
8 |
4 |
15 |
Fatty alcohol (C₁₂-C₁₅) ethoxylate |
12 |
12 |
12 |
5 |
Fatty acid |
10 |
10 |
10 |
10 |
Oleic acid |
4 |
4 |
4 |
- |
Citric acid |
1 |
1 |
1 |
1 |
Diethylenetriaminepentamethylene |
1.5 |
1.5 |
1.5 |
1.5 |
Phosphonic acid |
|
|
|
|
NaOH |
3.4 |
3.4 |
3.4 |
3.4 |
Propanediol |
1.5 |
1.5 |
1.5 |
1.5 |
Ethanol |
10 |
10 |
10 |
10 |
Ethoxylated tetraethylene pentamine |
0.7 |
0.7 |
0.7 |
0.7 |
Thermamyl R 300 KNU/g |
0.1 |
0.1 |
0.1 |
0.1 |
Carezyme R 5000 CEVU/g |
0.02 |
0.02 |
0.02 |
0.02 |
Protease 40 mg/g |
1.8 |
1.8 |
1.8 |
1.8 |
Lipolase R 100 KLU/g |
0.1 |
0.1 |
0.1 |
0.1 |
Endoglucanase A 5000 CEVU/g |
0.5 |
0.5 |
0.5 |
0.5 |
Suds supressor (ISOFOLr) |
2.5 |
2.5 |
2.5 |
2.5 |
H₂O₂ |
7.5 |
7.5 |
- |
- |
Polyvinyl pyrrolidone |
0.1-1 |
0.1-1 |
0.1-1 |
0.1-1 |
layered silicate |
9 |
9 |
9 |
9 |
polyethylene oxide |
0.3 |
0.3 |
0.3 |
0.3 |
Minors |
up to 100 |
EXAMPLE III (A/B/C/D/E)
[0115] A compact granular detergent composition according to the present invention is prepared,
having the following formulation:
% by weight of the total detergent composition |
|
A |
B |
C |
D |
E |
Linear alkyl benzene sulphonat |
11.40 |
- |
- |
- |
- |
Polyhydroxy fatty acid amide |
- |
10 |
- |
- |
- |
Alkyl alkoxylated sulfate |
- |
- |
9 |
9 |
9 |
Tallow alkyl sulphate |
1.80 |
1.80 |
1.80 |
1.80 |
1.80 |
C₄₅ alkyl sulphate |
3.00 |
3.00 |
3.00 |
3.00 |
3.00 |
C₄₅ alcohol 7 times ethoxylate |
4.00 |
4.00 |
4.00 |
4.00 |
4.00 |
Tailors alcohol 11 times |
1.80 |
1.80 |
1.80 |
1.80 |
1.80 |
ethoxylated |
|
|
|
|
|
Dispersant |
0.07 |
0.07 |
0.07 |
0.07 |
0.07 |
Silicone fluid |
0.80 |
0.80 |
0.80 |
0.80 |
0.80 |
Trisodium citrate |
14.00 |
14.00 |
14.00 |
14.00 |
14.00 |
Citric acid |
3.00 |
3.00 |
3.00 |
3.00 |
3.00 |
Zeolite |
32.50 |
32.50 |
32.50 |
32.50 |
32.50 |
Diethylenetriamine pentanethylene phosphonic acid |
0.6 |
0.6 |
0.6 |
0.6 |
0.6 |
Maleic acid acrylic acid copolymer |
5.00 |
5.00 |
5.00 |
5.00 |
5.00 |
Carezyme |
0.1 |
0.1 |
0.1 |
0.1 |
0.1 |
Savinase |
0.60 |
0.60 |
0.60 |
0.60 |
0.60 |
Lipolase |
0.36 |
0.36 |
0.36 |
0.36 |
0.36 |
Sodium silicate |
2.00 |
2.00 |
2.00 |
2.00 |
2.00 |
Sodium sulphate |
3.50 |
3.50 |
3.50 |
3.50 |
3.50 |
Percarbonate |
- |
- |
- |
20 |
- |
Perborate |
15 |
15 |
15 |
- |
- |
TAED |
5 |
- |
5 |
5 |
- |
N-vinylimidazole N-vinylpyrrolidone copolymer |
0.1-1 |
0.1-1 |
0.1-1 |
0.1-1 |
0.1-1 |
Metallo catalyst |
0.1-1 |
0.1-1 |
0.1-1 |
0.1-1 |
0.1-1 |
Poly(4-vinylpyridine)-N-oxide |
0.1-1 |
0.1-1 |
0.1-1 |
0.1-1 |
0.1-1 |
layered silicate |
9 |
9 |
9 |
9 |
9 |
polyethylene oxide |
0.3 |
0.3 |
0.3 |
0.3 |
0.3 |
peroxidase |
- |
0.1 |
0.1 |
- |
- |
Minors |
up to 100 |
EXAMPLE IV (A/B/C/D)
[0116] A liquid detergent composition according to the present invention is prepared, having
the following compositions :
% by weight off the total detergent composition |
|
A |
B |
C |
D |
Linear alkylbenzene sulfonate |
10 |
- |
- |
- |
Polyhydroxy fatty acid amide |
- |
5 |
- |
3 |
Alkyl alkoxylated sulfate |
- |
- |
9 |
4 |
Alkyl sulphate |
4 |
8 |
4 |
15 |
Fatty alcohol (C₁₂-C₁₅) ethoxylate |
12 |
12 |
12 |
5 |
Fatty acid |
10 |
10 |
10 |
10 |
Oleic acid |
4 |
4 |
4 |
- |
Citric acid |
1 |
1 |
1 |
1 |
Diethylenetriaminepentamethylene Phosphonic acid |
1.5 |
1.5 |
1.5 |
1.5 |
NaOH |
3.4 |
3.4 |
3.4 |
3.4 |
Propanediol |
1.5 |
1.5 |
1.5 |
1.5 |
Ethanol |
10 |
10 |
10 |
10 |
Ethoxylated tetraethylene pentamine |
0.7 |
0.7 |
0.7 |
0.7 |
Thermamyl R 300 KNU/g |
0.1 |
0.1 |
0.1 |
0.1 |
Carezyme R 5000 CEVU/g |
0.02 |
0.02 |
0.02 |
0.02 |
Protease 40 mg/g |
1.8 |
1.8 |
1.8 |
1.8 |
Lipolase R 100 KLU/g |
0.1 |
0.1 |
0.1 |
0.1 |
Endoglucanase A 5000 CEVU/g |
0.5 |
0.5 |
0.5 |
0.5 |
Suds supressor (ISOFOLr) |
2.5 |
2.5 |
2.5 |
2.5 |
H₂O₂ |
7.5 |
7.5 |
- |
- |
N-vinylimidazole N-vinylpyrrolidone copolymer |
0.1-1 |
0.1-1 |
0.1-1 |
0.1-1 |
Metallo catalyst |
0.1-1 |
0.1-1 |
0.1-1 |
0.1-1 |
Poly(4-vinylpyridine)-N-oxide |
0.1-1 |
0.1-1 |
0.1-1 |
0.1-1 |
layered silicate |
9 |
9 |
9 |
9 |
polyethylene oxide |
0.3 |
0.3 |
0.3 |
0.3 |
peroxidase |
0.1 |
0.1 |
- |
- |
Minors |
up to 100 |
[0117] The above compositions (Example II (A/B/C/D), III (A/B/C/D/E) and IV (A/B/C/D) were
very good at displaying excellent cleaning and detergency performance with outstanding
color-care performance on colored fabrics and mixed loads of colored and white fabrics.