Note: Descriptions are shown in the official language in which they were submitted.
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WATER SOLUBLE DYE COMPLEXING POLYMERS
AS DYE TRANSFER INHIBITORS IN LAUNDRY
DETERGENT AND FABRIC SOFTENER COMPOSITIONS
This invention relates to dye complexing polymers, and, more
particularly, to water soluble poly(vinylpyridine betaines)
containing a quaternary nitrogen and a carboxylate salt. The
polymers herein have effective dye transfer inhibitor (DTI)
properties for use, for example, in laundry detergent and fabric
softener compositions.
Dye complexing polymers have been used in laundry detergent and
fabric softener compositions. In such application, during washing a
mixture of colored and white fabrics, some of the dyes may bleed out
of a colored fabric under washing conditions. The degree of bleeding
is influenced by the structure of the dye, the type of cloth and the
pH, temperature and mechanical efficiency of the agitation process.
The bled dye in the wash liquor can be totally innocuous and get
washed off in the wash liquor. However, in reality, this fugitive
dye has a tendency to redeposit either onto the same fabric or onto
another fabric leading to patches and an ugly appearance of the
washed material. This redeposition of the bled dye can be inhibited
in several ways. One method is to introduce a DTI compound which can
complex with the fugitive dye and get washed off thus preventing
redeposition.
Polyvinylpyrrolidone (PVP), by virtue of its dye complexation
ability, has been used to inhibit dye deposition during washing of
colored fabrics under laundry conditions. The performance of PVP as
a DTI, however, is adversely affected by the presence of anionic
surfactants in the washing process.
Other polymers which have been used as DTIs in laundry
detergent compositions include polyvinylpyridine N-oxide (PVPNO);
polyvinylimidazole (PVI) and copolymers of polyvinylpyridine and
polyvinylimidazole (PVP-PVI).
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The prior art in this field is represented by the following
patents and publications:
Patent Subject Matter
(1) JP 53-50732 Formulas Nos. 3, 6 and (1) are water
insoluble compounds and polymers used in
printing ink compositions;
(2) PCT/US94/06849 Dye inhibiting composition polymers
WO 95/03390 of PVP, polyamine N-oxide, vinyl-
imidazole are used in laundry
detergent compositions;
(3) USP 5,460,752 Polyamine N-oxide polymers described for use
in laundry detergent compositions;
(4) EPA 664335 Al Polysulfoxide polymers;
(5) PCT/US93/10542 Laundry compositions include
WO 94/11473 polyamine-N-oxide and brighteners and
surfactants;
(6) PCT/EP93/02851 PVP and PVI are present in laundry
WO 94/10281 compositions;
(7) PCT/US94/11509 Poly(4-vinylpyridine-N-oxide) (PVPNO)
WO 95/13354 and copolymers of VP and VI are
described;
(8) EP 754748 Al Vinylpyridine copolymers and formic
acid;
(9) EP 0664332A1 Polyamine oxide polymers;
(10) USP 5,604,197 PVPNO + clay softening;
(11) USP 5,458,809 PVPNO;
(12) USP 5,466,802 PVPNO and PVP-VI;
(13) USP 5,627,151 Copolymers of VP or VI; vinylpyridine
or dimethylaminoethyl methacrylate or
dimethylaminopropylmethacrylamide,
including up to 20% vinylacetate;
(14) PCT/US95/04019 PVPNO, PVP, PVP-PI and copolymers of
WO 95/27038 VP and VI;
(15) EPA 628624 Al PVPNO with protease;
(16) DE 4224762 Al VP polymers;
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6'4369-639
(17) J. Polymer Water-insoluble poly(4-vinylpyridine)
Sci. 26, compounds and polymers
No. 113, p.
25-254 (1957)
(18) WO 94/11482 Fabric softener compositions
containing PVP as DTI
(19) USP 2,977,341 Betaines in plastics
A feature of the invention is the provision of a water soluble
poly(vinylpyridine betaine) compound containing a quaternary nitrogen
and a carboxylate salt in laundry detergent and fabric softener
compositions which compounds exhibit particularly effective dye
transfer inhibition properties during the washing process even in the
presence of anionic surfactants.
The water soluble poly(vinylpyridine betaine) polymer of the
invention contains a quaternary nitrogen and a carboxylate salt. The
polymer has the formula:
; CH2-CH -}m-
O
N Xe
(iR:R2) n
COOe M
where m is indicative of the degree of polymerization;
X is an anion;
R1 and RZ are independentlv hydrogen, alkyl or aryl;
n is 1-5; and
M is a cation.
Preferred embodiments of the invention are polymers in which X
is a halide; most preferably chloride or bromide; P.1 and R2 are both
hydrogen; n is 1; M is an alkali me-Lal; preferably sodium or
potassium; and the polymer is 25-100% quaternized; most preferably
75-100%.
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A preferred polymer has a weight average molecular weight of
about 5,000 to 1,000,000; preferably 20,000 to 200,000, where m is
about 30-5000, preferably 100-1000. Water soluble copolymers of the
defined polymer above with polymerizable monomers, such as vinyl
pyrrolidone, vinyl imidazole, acrylamide and vinyl caprolactam also
are useful herein.
A preferred use of the polymer and copolymers herein are
laundry detergent and fabric softener compositions including in a dye
transfer inhibiting amount. Generally, this amount is about 2-1000
ppm of the polymer or copolymer; preferably 2-50 ppm.
In a preferred embodiment of the invention, the water soluble
polymers of the invention are made by polymerizing a vinylpyridine
under suitable polymerization conditions to form a
poly(vinylpyridine) intermediate, and then reacting the intermediate
polymer with sodium chloroacetate in an aqueous medium. The reaction
product is a poly(vinylpyridine betaine) polymer containing a
quaternary nitrogen and a carboxylate salt.
In the polymerization step, which may be solution,
precipitation or emulsion polymerization, any suitable solvent may be
used, for example, an alcohol, such as methanol, ethanol or
isopropanol; water; or mixtures of water and alcohol. The reaction
temperature is about 40 to 150 C, nreferably 50 to 90 C, and most
preferably about 60 to 85 C. The polymerization initiator is a free
radical initiator, such as perester, peroxide, percarbonate, or Vazo
type initiators may be used. The polymerization is carried out at a
solids level of about 5 to 80%, preferably 20 to 50%.
A preferred polymer* made herein is poly(4-vinylpyridine)
sodium carboxymethyl betaine chloride having the formula:
-f-CH2-CH-)-m
0
N C1e
I
IHZ
COOe Na
* POLYMER A
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SURFACTANT SYSTEM:
The compositions according to the present invention comprise in
addition to the water soluble poly(vinylpyridine betaine) polymers a
surfactant system wherein the surfactant can be selected from
nonionic and/or anionic and/or cationic and/or ampholytic and/or
zwitterionic and/or semi-polar surfactants.
Anionic surfactants may be used in the compositions of the
invention without being affected by the presence of the DT1 polymer
therein.
ANIONIC SURFACTANTS:
Suitable anionic surfactants include alkyl alkoxylated sulfate
surfactants, water soluble salts or acids of the formula RO(A)mSO3M
wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group
having a Clo-Czg 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 C1Z-C18 alkyl polyethoxylate (1.0) sulfate (C12-C18E(1.0)M), C12-C1e
alkyl polyethoxylate (2.25) sulfate (C12-C1BE(2.25)M), C12-C28 alkyl
polyethoxylate (3.0)sulfate (C12-C18E(3.0)M), and C12-Cle alkyl
polyethoxylate (4.0) sulfate (C12-C18E(4.0)M), wherein M is
conveniently selected from sodium and potassium.
Suitable anionic surfactants to be used are alkyl ester
sulfonate surfactants including linear esters of CB-CZO 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.
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The preferred alkyl ester sulfonate surfactant, especially for
laundry applications, comprise alkyl ester sulfonate surfactants of
the structural formula:
0
il
R3-CH-C-OR4
I
S03M
wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or
combination thereof, R" 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.
Other suitable anionic surfactants include the alkyl sulfate
surfactants, 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 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 derived from alkylamines such as
ethylamine, diethylamine, triethylamine, and mixtures thereof, and
the like). Typically, alkyl chains of C1Z-C16 are preferred for lower
wash temperatures (e.g. below about 50 C) and C16-C18 alkyl chains are
preferred for higher wash temperatures (e.g. above about 50 C).
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 or 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, CB-C24 alkylpolyglycolethersulfates (containing up to 10
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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 C1Z-Cle 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 blow), branched primary alkyl sulfates, and
alkyl polyethoxy carboxylates such as those of the formula
RO (CH2CHZ0) k-CHZC00-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. Pat. No. 3,929,678, issued Dec. 30, 1975 to
Laughlin, et al. at Column 23, line 58 through Column 29, line 23.
When included therein, the laundry detergent compositions of
the present invention typically comprise from about 5% to about 50%,
preferably from about 10% to about 40% by weight of such anionic
surfactants.
The laundry detergent compositions of the present invention may
also contain nonionic, cationic, ampholytic, zwitterionic, and semi-
polar surfactants, as well as nonionic surfactants other than those
already described herein.
NONIONICS:
Polyethylene, polypropylene, and polybutylene oxide condensates
of alkyl phenols are suitable fo= 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 ccnfiguration with the alkyler.e oxide. In a preferred
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embodiment, the ethylene oxide is present in an amount equal to from
about 1 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 Triton7' 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).
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 abut 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), TergitolTM 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), Neodoll" 23-6.5 (the
condensation product of C12-C13 linear alcohol with 6.5 moles of
ethylene oxide), Neodol7' 45-7 (the condensation product of C14-C15
linear alcohol with 7 moles of ethylene oxide), Neodol'l" 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.
Also useful as the nonionic surfactant of the surfactant
systems of the present invention are the alkylpolysaccharides
disclosed in U.S. Pat. No. 4,565,647, Llenado, issued Jan. 21, 1986,
having a hydrophobic group containing from about 6 to about 30 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
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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.
Optionally, and less desirably, there can be a polyalkylene-
oxide chain joining the hydrophobic moiety and the polysaccharide
moiety. The preferred alkyleneoxide is ethylene oxide. Typically
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.
The preferred alkylpolyglycosides have the formula
R20(CnH2n0)t (g1yCOSyl)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
alkylpolyethoxyalcohol is formed first and then reacted with glucose,
or a source of glucose, to form the glucoside (attachment at the
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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.
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'n' surfactants,
marketed by BASF.
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.
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 Ce-C18 alcohol ethoxylates (preferably Clo avg.) having from 2 to
ethoxy groups, and mixtures thereof.
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Highly preferred nonionic surfactants are polyhydroxy fatty
acid amine surfactants.
Also suitable as nonionic surfactants are poly hydroxy fatty
acid amide surfactants of the formula
R2-C-N-Z
O R1
wherein R' is H, or R' is C1_4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy
propyl or a mixture thereof, R 2 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, R' is methyl, R2 is a straight Cl_15
alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and
maltose, lactose, in a reductive amination reaction.
It is preferred that the level of non-ionic surfactant is from
1 wt% to 35 wt%. The ratio of anionic to non-ionic surfactant is
from 7:3 to 90:1, preferably 3:1 to 60:1. The total amount of
surfactant present will also depend on the intended use and may be as
high as 65 wt%. However, for machine washing fabrics, an amount of 5
to 40 wt% is most appropriate.
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) yl [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)-,
-CH2CH2CHZ-, and mixtures thereof; each R' is selected from the group
consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures
formed by joining the two R 4 groups, -CH2CHOHCHOHCOR6CHOHCH2OH-
wherein R6 is any hexose or hexose polymer having a molecular weight
less than about 1000, and hydrogen when y is not 0; RS is the same as
R or is an alkyl chain wherein the total number of carbon atoms of
RZ plus R5 is not more than about 18; each y is from 0 to about 10
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and the sum of the y values is from 0 to about 15; and X is any
compatible anion.
The detergent compositions of the invention will generally.also
contain one or more detergency builders. The total amount of
'detergency builder in the compositions will suitably range from 5 to
80 wt%, preferably from 10 to 60 wt%.
Inorganic builders that may be present include sodium
carbonate, if desired in combination with a crystallization seed for
calcium carbonate, as disclosed in GB 1 437 950 (Unilever);
crystalline and amorphous aluminosilicates, for example, zeolites as
disclosed in GB 1 473 201 (Henkel), amorphous aluminosilicates as
disclosed in GB 1 473 202 (Henkel) and mixed crystalline/amorphous
aluminosilicates as disclosed in GB 1 470 250 (Procter & Gamble); and
layered silicates as disclosed in EP 164 514B (Hoechst). Inorganic
phosphate builders, for example, sodium orthophosphate, pyrophosphate
and tripolyphosphate are also suitable for use with this invention.
The detergent compositions of the invention preferably contain
an alkali metal, preferably sodium, aluminosilicate builder. Sodium
aluminosilictes may generally be incorporated in amounts of from 10
to 70% by weight (anhydrous basis), preferably from 25 to 50 wt%.
The alkali metal aluminosilicate may be either crystalline or
amorphous or mixtures thereof, having the general formula:
0.8-1.5 Na20. A1203. 0.8-6 Si02
These materials contain some bound water and are required to have a
calcium ion exchange capacity of at least 50 mg CaO/g. The preferred
sodium aluminosilicates contain 1.5-3.5 Si02 units (in the formula
above). both the amorphous and the crystalline materials can be
prepared readily by reaction between sodium silicate and sodium
aluminate, as amply described in the literature.
Suitable crystalline sodium aluminosilicate ion-exchange
detergency builders are described, for example, in GB 1 429 143
(Procter & Gamble). The preferred sodium aluminosilicates of this
type are the well-known commercially available zeolites A and X, and
mixtures thereof.
The zeolite may be the commercially available zeolite 4A now
widely used in laundry detergent powders. However, according to a
preferred embodiment of the invention, the zeolite builder
incorporated in the compositions of the invention is maximum aluminum
zeolite P (zeolite MAP) as described and claimed in EP 384 070A
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(Unilever). Zeolite MAP is defined as an alkali metal
aluminosilicate of the zeolite P type having a silicon to aluminum
ratio not exceeding 1.33, preferably within the range of from 0.90 to
1.33, and more preferably within the range of from 0.90 to 1.20.
Especially preferred is zeolite MAP having a silicon to
aluminum ratio not exceeding 1.07, more preferably about 1.00. The
calcium binding capacity of zeolite MAP is generally at least 150 mg
Ca0 per g of anhydrous material.
Organic builders that may be present include polycarboxylate
polymers such as polyacrylates, acrylic/maleic copolymers, and
acrylic phosphinates; monomeric polycarboxylates such as citrates,
gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates,
carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates,
hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and
succinates; and sulphonated fatty acid salts. This list is not
intended to be exhaustive.
Especially preferred organic builders are citrates, suitably
used in amounts of from 5 to 30 wt%, preferably from 10 to 25 wt%;
and acrylic polymers, more especially acrylic/maleic copolymers,
suitably used in amounts of from 0.5 to 15 wt%, preferably from 1 to
wt%.
Builders, both inorganic and organic, are preferably present in
alkali metal salt, especially sodium salt, form.
The detergent compositions according to the present invention
can be in liquid, paste or granular forms. Such compositions can be
prepared by combining the essential and optional components in the
requisite concentrations in any suitable order and by an y
conventional means.
Granular compositions, for example, are generally made by
combining base granule ingredients (e.g. surfactants, builders,
water, etc.) as a slurry, and spray drying the resulting slurry to a
low level of residual moisture (5-12%). The remaining dry
ingredients can be admixed in granular powder form with the spray
dried granules in a rotary mixing drum and the liquid ingredients
(e.g. enzymes, binders and perfumes) can be sprayed onto the
resulting granules to form the finished detergent composition.
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
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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.
Liquid detergent compositions can be prepared by admixing the
essential and optional ingredients thereof in any desired order to
provide compositions containing components in the requisite
concentrations. Liquid compositions according to the present
invention can also be in "compact 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.
The invention will now be illustrated by the following
examples, in which:
EXAMPLE 1
A 1-liter, 4-necked resin kettle was fitted with an anchor
agitator, a nitrogen purge adaptor, a thermometer, two subsurface
feeding tubes connected with two feeding pumps, and a reflux
condenser. The kettle was charged with 150 g of 4-vinylpyridine and
150 g of isopropanol. Nitrogen purging was started and continued
throughout the process as was agitation at 200 rpm. Then the
reactants were heated to BO C in 20 minutes and held at that for 30
minutes. Then 390 microliter of t-butyl peroxypivalate (Lupersol
11) was charged. The solution polymerization reaction was carried
out at 80 C for 2 hours. Then a 195 microliter portion of Lupersol
11 was added and reaction continued at 80 C for another two hours.
The latter step was repeated another 6 times. Then 150 g water and
166.2 g of sodium chloroacetate was charged and the contents were
rinsed with 100 g of water. The resultant mixture was heated to
remove 100 g of distillate then 100 g of water was added to the
mixture; the step was repeated and yet another 50 g of distillate was
removed. Then the mixture was cooled to room temperature. The
product was obtained as a solution whose solids level was adjusted to
about 48%.
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EXAMPLE 2
The process of Example 1 was repeated using 125 g of sodium
chloroacetate. A similar product was obtained.
EXAMPLE 3
The process of Example 1 was repeated using 83 g of sodium
chloroacetate. A similar product was obtained.
EXAMPLE 4
A 1-1, 4-necked resin kettle, fitted with an anchor agitator, a
nitrogen purge adaptor, a thermometer and a reflux condenser, was
charged with 50 g of 4-vinylpyridine, 50 g of vinylpyrrolidone and
150 g of isopropanol. Nitrogen purging was started and continued
throughout the reaction, and the agitator was set at 20 rpm. The
reactants were heated from ambient temperature (20-25 C) to 80 C in
20 minutes and held at 80 C for 30 minutes. Then 0.1% (based on
total weight of monomers) of t-butyl peroxypivalate (Lupersol 11)
was charged into the kettle and the reaction temperature was held at
80 C for 2 hours. Thereafter 0.05% (based on total weight of
monomers) of Lupersol 11 was added every 2 hours and the reaction
temperature was held at 80 C until the residual 4-vinylpyridine level
was reduced to less than 2%.
Then 250 g of water and 55.4 g of sodium chloroacetate were
mixed and charged. The mixture was heated to remove the distillate.
Additional water was added while removing distillate until all the
ethanol was removed at about 105 C. The final solids level was
controlled by addition of water to the final product.
EXAMPLE 5
Example 4 was repeated using 25 g of 4-vinylpyridine, 75 g of
vinylpyrrolidone and 27.7 g of sodium chloroacetate, with similar
results.
EXAMPLE 6
Example 1 was repeated using 186.5 g of sodium 2-chloro-
propionate in place of sodium chloroacetate with similar results.
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EXAMPLE 7
Example 1 was repeated using 186.5 g of sodium 1-chloro-
propionate with similar results.
EXAMPLE 8
A 1-1, 4-necked resin kettle, fitted with anchor agitator, a
nitrogen purge adaptor, a thermometer and a reflux condenser was
charged with 150 g of 4-vinylpyridine and 150 g of isopropanol. The
reactants were heated from ambient temperature (20-25 C) to 80 C in
20 minutes and held at 80 C for 30 minutes. Then 0.1% (based on
total weight of monomers) of t-butyl peroxypivalate (Lupersol 11) was
charged into the kettle and the reaction temperature was held at 80 C
for 2 hours. Then 0.05% (based on total weight of monomers) of
Lupersol 11 was added every 2 hours at 80 C until residual
4-vinylpyridine was reduced to less than 2%.
The reaction mixture was cooled to 40 C and 250 g of water and
57.2 g of sodium hydroxide were mixed and charged. Then 135.1 g of
chloroacetic acid was pumped into the reactor by melting chloroacetic
acid. The mixture was heated to remove the distillate, and water was
added while removing distillate until all the ethanol was removed.
TEST RESULTS
The effectiveness of the polymers of the invention as a DTI
additive in a laundry detergent composition including at least 1% by
weight of a suitable surfactant, was tested against control and other
known DTI polymers in a test simulating actual laundry washing
conditions. The test was carried out on a composition containing 10
ppm of the polymer, 10 ppm of a dye and 1 g/1 of a laundry detergent
which contained a mixture of both an anionic and a nonionic
surfactant. The solution was diluted with water to 1-1.
Three white cotton cloth swatches #400 (bleached and desized)
were immersed in the test solution at 100 F_ and the solutions were
agitated for 10 minutes in a Terg-o-tometer (Instrument Marketing
Services Co.). The cloths were then removed, excess solution
squeezed out, the cloths washed again in clean water for 3 minutes,
squeezed again and dried. Reflectance measurements were taken on
this test material on a colorimeter. The reflectance readings were
recorded as AE, which is a composite of the degree of whiteness,
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redness and blueness indices in the dyed cloth. These readings were
taken as a direct measure of the degree of dye deposition under the
test washing conditions.
The test results are shown in Tables 1 and 2 below.
TABLE 1*
TEST SAMPLES AE
Control
White cloth 0
No polymer 33
Invention Polymers
Example 1 (Polymer A; 100% quat) 6.6
Example 2 (Polymer A; 75% quat) 7.7
Example 3 (Polymer A; 50% quat) 10.4
Example 4 (Copolymer of VPyr + VP; 10.9
100% quat) (50:50)**
Example 5 (Copolymer of VPyr + VP; 14.3
100% quat) (25:75)**
Other Polymers AE
PVP 23.7
PVPNO 11.9
PVI 10.1
PVP + PVI (60:40) 8.2
* Direct Red 80
** Weight percent
TABLE 2*
TEST SAMPLES A$
Control
No polymer 34.2
Invention Polymers
Polymer A 21.7
Other Polymers
PVP 28.1
PVPNO 25.7
P(VI-VP) 31.7
* The dye was Direct Blue No. 1
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TEST RESULTS FOR SOIL ANTI-REDEPOSITION
The effectiveness of the polymers of the invention, to prevent
redeposition of soil in a laundry detergent composition was tested
'against control and other known polymers in a test simulating actual
laundry washing conditions. The test was carried out on a
composition containing 2 gm/L of Dust Sebum and 50 ppm of the polymer
in solution. The solution was diluted with water to 1-1.
Three white polycotton cloth (polyester-cotton 65:35) swatches
were immersed in the test solution maintained at 100 F. and the
solutions were agitated for 10 minutes in a Terg-o-tometer
(Instrument Marketing Services Co.). The cloths were then removed,
excess solution squeezed out, the cloths washed again in clean water
for 3 minutes, squeezed again and dried. Reflectance measurements
were taken on this test material on a colorimeter. The reflectance
readings were recorded at 460 nm, and the difference with respect to
the blank was recorded. The closer the reflectance to a white cloth,
the higher is the polymer's ability in preventing soil redeposition.
These readings were taken as a direct measure of the degree of soil
deposition under the test washing conditions.
The test results are shown in Tables 3 and 4 below.
TABLE 3*
TEST SAMPLES AR4
Control
White cloth 0
No polymer -59
Invention Polymers
Example 1(Polymer A; 100% quat) -20
Other Polymers
PVP -48
CMC -46
* The soil used was dust sebum on nylon cloth
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TABLE 4*
TEST SAMPLES ALkd
Control
No polymer -16
Invention Polymers -
Polymer A -1
Other Polymers
PVP -10
CMC -13
* The soil used was dust sebum on nylon cloth
Preferably, and more specifically, fabric softening
compositions are provided in the form of liquid, preferably aqueous,
compositions comprising:
I. from about 3% to about 50%, preferably from about 4% to
about 30%, of fabric softening agent (fabric softener);
and
II. from about 0.03% to about 25%, preferably from about 0.1%
to about 15%, of water-soluble polymeric dye transfer
inhibiting agent (dye transfer inhibitor or DTI) having
the formula given above.
III. The balance comprising a liquid carrier, preferably
water; wherein the liquid compositions are essentially
free of aerosol propellants.
The present invention also comprises dryer-added fabric
softener compositions comprising:
I. from about 50% to about 99%, preferably from about 70% to
about 99%, of fabric softening agent;
II. from about 0.2% to about 50%, preferably from about 1% to
about 30%, of polymeric dye transfer inhibiting agent
selected from (A), (B), (C), and (D), above; and
III. optionally, a dispensing means which provides for release
of an effective amount of said composition to fabrics.
Solid, particulate fabric softening compositions of the present
invention typically comprise.
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I. from about 20% to about 90%, preferably from about 30% to
about 70%, of fabric softening agent; and
II. from about 0.1% to about 80%, preferably from about 0.3%
to about 50%, more preferably from about 0.5% to about
25%, of dye transfer inhibiting agent also selected from
(A), (B), (c), and (D), above.
Fabric Softening Agents
The amount of fabric softening agent (fabric softener) in
liquid compositions of this invention is typically from about 3% to
about 50%, preferably from about 4% to about 30%, by weight of the
composition. The lower limits are amounts needed to contribute
effective fabric softening performance when added to laundry rinse
baths in the manner which is customary in home laundry practice. The
higher limits are suitable for concentrated products which provide
the consumer with more economical usage due to a reduction of
packaging and distributing costs.
Examples of Liquid Fabric Softening Compositions
The following liquid softener compositions, when added to the
rinse cycle of an automatic laundry operation, show dye transfer
inhibition in the subsequent wash cycle.
Example 9
Components (Wt. %)
DTDMAC/MTTMAC* Blend (83%) 4.5
1-Tallow(amidoethyl)-2-
Tallowimidazoline 3.4
HC1 0.2
Polymer A (75% quat) 0.5
Perfume 0.4
Minor Ingredients** 0.5
Deionized Water Balance
100.00
* Ditallowdimethylammonium chloride/monotallow-
trimethyl-ammonium chloride
** Minor ingredients include: Dow Corning
polydimethylsiloxane emulsion, calcium chloride,
Kathon CG/ICP bacteriocide,
and Liquitint Blue 65 dye.
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EXAMPLE 9
The composition of Example 9 is made by the following
procedures:
Adding Polymer A (75% quat) (average molecular weight of about
10,000, either as a powder or in aqueous solution) with mixing to a
vessel containing deionized water, heated to about 65 C. Molten
DTDMAC/MTTMAC blend (at about 80 C) is added with high shear mixing
to the aqueous solution. After softener incorporation, the mixture
is cooled, and the minor ingredients are added during the cooling
process.
Examples of Fabric Conditioning Substrate Articles
The following fabric conditioning compositions and substrate
articles, when added to the tumble dryer with the wet laundry load,
show dye transfer inhibition in the subsequent wash cycle.
Example 10
Components (Wt. %)
DTDMAC 80.00
Calcium Bentonite Clay 4.00
Polymer A (75% quat) 16.00
Total 100.00
EXAMPLE 10
Preparation of the Coating Mix
An approximately 200 gram batch of the coating mix is prepared
as follows. An amount of about 160 g of ditallowdimethylammonium
chloride (DTDMAC) is melted at 80 C. The calcium bentonite clay
(about 8 g of Bentolite L, available from Southern Clay Co.) is
slowly added to the mixture with high shear mixing. During the
mixing, the mixture is kept molten in a boiling water bath. About 32
g of Polymer A (75% quat) is then slowly added to the mixture with
high shear mixing, and the formula is mixed until the mixture is
smooth and homogenous.
Preparation of Fabric Conditioning Sheets
The coating mixture is applied to preweighed nonwoven substrate
sheets of about 9 inch x 11 inch (approximately 23 cm x 28 cm)
dimensions. The substrate sheets are comprised of 70% 3-denier, 1-
9/16-inch (approximately 4 cm) long rayon fibers with 30% polyvinyl
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acetate binder. The substrate weight is about 16 g per square yard
(about 1.22 g/sheet). A small amount of formula is placed on a
heated metal plate with a spatula and then is spread evenly with a
wire metal rod. A nonwoven substrate sheet is placed on the metal
plate to absorb the coating mixture. The sheet is then removed from
the heated metal plate and allowed to cool to room temperatUre so
that the coating mix can solidify. The sheet is weighed to determine
the amount of coating mixture on the sheet. The target coating is
2.0 g per sheet. If the weight is in excess of the target weight,
the sheet is placed back on the heated metal plate to remelt the
coating mixture and remove some of the excess. If the weight is
under the target weight, the sheet is also placed on the heated metal
plate and more coating mixture is added.
Example 11
Components (Wt. %)
Octadecyldimethylamine 11.89
C12_14 Fatty Acid 8.29
C16_1e Fatty Acid 10.69
DTDMAMS 19.32
Sorbitan Monostearate 19.32
Clay 3.86
Polymer A (75% quat) 26.62
Total 100.00
EXAMPLE 11
Preparation of the Coating Mix and Fabric Conditioning Sheets
A first blend of about 11.89 parts octadecyldimethylamine
(Ethyl Corporation), 8.29 parts C12_14 fatty acid (The Procter &
Gamble Co.), and 10.69 parts C16_1e fatty acid (Emery Industries,
Inc.) are melted together at 80 C, and a second blend of about 19.32
parts sorbitan monostearate (Mazer Chemicals, Inc.) and 19.32 parts
ditallowdimethylammonium methylsulfate, DTDMAMS, (Sherex Chemical
Co.) are melted together to form the softener component of the
composition during which time the mixture is kept molten in a boiling
water bath. The calcium bentonite clay (3.86 parts Bentolite L,
available from Southern Clay Co.) is then slowly added to the mixture
while high shear mixing. An amount of about 26.62 parts of Polymer A
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is then added in small portions, and the formula is mixed until the
mixture is smooth and completely homogenous.
The coating mixture is applied to preweighed nonwoven substrate
sheets as in Example 10. The target coating is 2.33 g per sheet.
Each sheet contains about 1.62 g of softener, about 0.09 g of clay,
and about 0.62 g of Polymer A.
While the invention polymers has been described as an additive
in a laundry detergent and fabric softener composition, it will be
understood that they can be used in other applications which require
anti-deposition properties. Accordingly, the water soluble polymers
of the invention can be used effectively to inhibit dirt or soil
redeposition in institutional, household and industrial cleaners, and
textile applications, for example. Accordingly, the following is a
list of suitable uses for the polymers and copolymers of the
invention:
soil anti-redeposition;
digital printing ink application;
textile dye stripping;
textile dye strike rate control;
flocculating agent;
adhesive;
ion-exchange/membranes;
removal of trace metals from water (Hg, Cd, Cu, Ni)/water
softening agent;
colloidal stabilization;
pumping oil from underground reservoirs;
personal care market, shampoos and hair conditioner;
cleaners and dish washing detergents, rinse aids;
water treatment to prevent hot water salts from
precipitation on sides of the wall; and
pigment dispersion.
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