Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
W096/00771 -- PCT/U595/07795
I
DETERGENT CONfPOSTTIONS
The present invention relates to detergent compositions
comprising a builder system, nonionic polysaccharide ethers and a
specific surfactant system for improved greasy soil and clay soil
removal.
During the fabric laundering operation it is highly desirable to
provide the fabrics, particularly man-made fabrics produced from
synthetic fibres, with soil release properties and anti-redeposition
properties.
A common problem encountered during the laundering process
of fabrics is mineral salt deposition. Insoluble salts of calcium may be
formed in the wash liquor and be deposited onto the fabric which
results in the fabric gaining an undesirable grey and dull appearance.
Detergency builders are thus incorporated into detergent compositions
in order to reduce this effect by aiding the suspension of such insoluble
salts in the wash liquor.
Builders typically employed in detergent compositions include
phosphates. However, in some locales a low phosphate formulation is
required. In such circumstances the soil suspension of the formulation
is reduced and the greying of fabrics is increased.
Another problem commonly encountered during the laundering
process is the effective removal of greasy soils. Due to the
hydrophobic nature of fabrics composed partially or completely of
synthetic fibres, the removal of greasy soils and stains therefrom is
particularly difficult. In order to address this problem, soil release
polymers may be incorporated into the detergent composition. During
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laundering, the soil release agents are adsorbed onto the surface of the
fabric, thereby reducing the hydrophobicity of the fabric surface. Once
the fabric is treated with a soil release agent, the ease of removal of ,
soils and stains from the surface of the fabric is considerably
improved. -
The main types of soil release agents incorporated into detergent
compositions, which provide benefits to primarily hydrophobic
synthetic fabrics include synthetic soil release agents, preferably
terephthalate based and polysaccharide ethers.
It has also been observed that the presence of a surfactant system
may affect the performance of the polysaccharide ether. Indeed it is
known in the art that the performance of the nonionic polysaccharide
ethers may be optimised in the presence of nonionic surfactants as the
major surfactant species. Indeed, polysaccharide ethers such as
cellulose ethers have been described for example in GB 1 534 641,
which discloses nonionic surfactant detergent compositions comprising
cellulose ether soil release agents such as alkyl and hydrozyalkyl
cellulose ethers.
Numerous other examples of such systems have been disclosed in
the art. For example, EPO 320296 relates to fabric softening additives
for detergent compositions which soften natural fibres without causing
redeposition problems on synthetics. An intimate mixture of cellulose
ethers and fabric softener at a ratio of 1:1 to 0.06:1 is disclosed.
Anionic, nonionic and mixtures of surfactants and phosphate builders
are disclosed.
EPO 213730 relates to detergent compositions for treating fabrics
which soften natural fibres without causing redeposition problems. The
compositions comprise nonionic cellulose ethers, a non-soap anionic
detergent (2-50%) and a fabric softening agent. Nonionic surfactants
are also disclosed, as are phosphate builders.
EPO 213729 discloses detergent compositions comprising 5-50%
soap, 2-25% nonionic surfactants and 0.05-5% cellulose ether which
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3
exhibit improved low temperature solubility and low level soil
redeposition. The ratio of soap to nonionic surfactant is 1:1 to 10:1.
EPO 256696 discloses a detergent composition for improved soil
suspension comprising anionic surfactants (5-90%), vinyl pyrrolidone
polymer and nonionic cellulose ether. Optional ingredients include
nonionic surfactants and phosphate builders.
EPO 054 325 discloses detergent compositions with reduced soil
redeposition effect comprising a ternary mixture of CMC, carbozylate
and cellulose ether with 5-50% detergent active. The actives include
anionic and nonionic surfactants and miz.tures thereof, but no ratios are
specified.
FR 2237960 discloses a detergent composition comprising a
cellulose ether and a malefic anhydride copolymer. Detergent actives
including anionic and nonionic surfactants, soaps and builders
including phosphates are disclosed.
However, the incorporation of nonionic polysaccharide ethers in
a detergent formulation, where the surfactant system comprises
substantially high levels of nonionic surfactants has been observed to
detrimentally affect the soil release performance of the
polysaccharides. This problem is further exacerbated in the presence
of builder systems comprising reduced phosphate levels. It is believed
that the presence of free cations resulting from the use of underbuilt
detergent compositions encourage the absorption of the polysaccharide
onto soil clay particles present in the aqueous wash liquor. Thus, the
amount of polysaccharide available for soil release is reduced.
Furthermore, the clay particles containing adsorbed polysaccharide
ether readily deposit onto the fabric which results in poorer
particulate/clay soil removal performance.
Thus, it is an objective of the present invention to provide a
detergent composition comprising a nonionic polysaccharide ether and
a surfactant system having improved soil removal performance and
reduced clay soil removal negatives.
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2?94157
It has now been found that these objectives may be addressed by
the use of a surfactant system comprising a non 'soap anionic surfactant
and a nonionic surfactant at specific ratios. It is believed that the
interference of the clay particles with the nonionic polysaccharide
ethers may be reduced and the clay soil removal performance of the
composition thus improved, by incorporating a specific amount of non
soap anionic surfactant with respect to the nonionic surfactant.
Summary of the Invention
The present invention is a detergent composition comprising from
0.01 % to 10% of a nonionic polysaccharide ether, a builder system
comprising less than 20% of a phosphate builder and at least 1 % of a
surfactant system, wherein said system comprises a non soap anionic
surfactant and a nonionic surfactant at a ratio of from 0.6:1 to 10:1.
All amount, weights, percentages and ratios are given as a %
weight of the detergent composition unless otherwise stated.
Detailed Descri~jon of the Invention _..
According to the present invention the detergent composition
comprises as essential components a nonionic polysaccharide ether,
and a surfactant system comprising non-soap anionic surfactants and
nonionic surfactants.
CA 02194157 2000-O1-27
Nonionic Polvsaccharide ether
According to the present invention as essential component of the
detergent composition is a nonionic polysaccharide ether. Chemically,
the polysaccharides are composed of pentoses or hexoses. Suitable
polysaccharide ethers for use herein are selected from cellulose ethers,
starch ethers, dextran ethers and mixtures thereof. Preferably said
nonionic polysaccharide ether is a cellulose ether. Cellulose ethers are
generally obtained from vegetable tissues and fibres, including cotton
and wood pulp.
The hydroxy group of the anhydro glucose unit of cellulose can
be reacted with various reagents thereby replacing the hydrogen of the
hydroxyl group with other chemical groups. Various allcylating and
hydroxyalkylating agents can be reacted with cellulose ethers to
produce either alkyl-, hydroxyalkyl- or alkylhydroxyalkyl-cellulose
ethers or mixtures thereof. The most preferred for use in the present
invention are C 1-C4 alkyl cellulose ether or a C 1-C4 hydroxyalkyl
cellulose ether or a C1-C4 allcylhydroxy alkyl cellulose ether or
mixtures thereof. Preferably the polysaccharides of the present
invention have a degree of substitution of from 0.5 to 2.8, preferably
from 1 to 2.5, most preferably from 1.5 to 2 inclusive.
Suitable nonionic cellulose ethers include methyl- and ethyl-
cellulose ether, hydroxypropyl-, hydroxybutyl- and hydroxyethyl-
methylceUulose ether, hydroxypropyl and hydroxyethyl- cellulose
ether, hydroxybutyl methylcellulose ether, ethylhydroxy ethylcellulose
ether, hydroxy ethylcellulose ether, methylhydroxy ethyl carboxy
methyl cellulose and carboxymethyl hydroxyethyl cellulose.
Most preferably said polysaccharide are methylcellulose ether
commercially available such as MetoloseM (Shin Etsu), ethyl
hydroxyethyl cellulose, commercially available as sermocouTM
(Akzo/Nobel), mMt6y1 hydroxyethyl cellulose ether commercially
available as Tylose MH300 (Hoechst) and mixtures thereof.
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According to the present invention said polysaccharide ether
preferably has a molecular weight from 10000 to 200000, most
preferably from 30000 to 150000. The weight average molecular .
weight is obtained by standard analytical methods as described in
Polymer handbooks. A preferred method is light scattering from .
polymer solutions as originally defined by Debye.
The compositions of the present invention comprise from 0.01 %
to 10%, preferably from 0.01% to 3%, most preferably from 0.1% to
2% of said nonionic polysaccharide ethers.
Detersive Surfactants _ __. _
According to the present invention the detergent composition
comprises at least 1 % of a surfactant system, preferably from 2% to
40% of a surfactant system. According to the present invention the
surfactant system comprises as essential ingredients a non soap anionic
surfactant and a nonionic surfactant.
Non soap anionic surfactants useful herein include the
conventional primary, branched-chain and random C10-C2p alkyl
sulphates ("AS"), the Clp-Clg secondary (2,3) alkyl sulphates of the
formula CH3(CH~)R(CHOSOg-M+) CH3 and
CH3(CH~y(CHOSOg M ) CH2CH3 where x and (y + 1) are
integers of at Ieast about 7, preferably at least about 9, and M is a
water-solubilizing cation, especially sodium, unsaturated sulphates
such as oleoyl sulphate, the C10-Clg alkyl alkoxy sulphates ("AEzS";
especially EO 1-7 ethozy sulphates), Clp-Clg alkyl alkozy
carbozylates (especially the EO 1-5 ethozycarbozylates), sulphated
Clp-Clg alkyl polyglycosides, and C12-Clg alpha-sulphonated fatty
acid esters.
According to the present invention suitable alkyl or hydroxyalkyl
alkozylated sulphates for use herein are of the formula RO(A)mS03M,
wherein R is an unsubstituted C11-C24 alkyl or hydroxyalkyl
component, preferably a C 12-C20 , alkyl or hydroxyalkyl, more
preferably a C12-Clg alkyl or hydrogyalkyl component, A is an
WO 96/00771 PCTIUS95107795
~ ,
ethozy or propozy group, m is from 1 to 15, more preferably from 1
to ,10, and M is H or a cation which may be selected from metal
cations such as sodium, potassium, lithium, calcium, magnesium, ,
ammonium or substituted ammonium. Specific examples of substituted
ammonium cations include methyl-, dimethyl-, trimethyl-ammonium
and quaternary ammonium cations such as tetramethyl-ammonium,
dimethyl piperidium and cations derived from alkanolamines, e.g.
monoethanolamine, diethanolamine and triethanolamine and mixtures
thereof. Exemplary surfactants are C12-Clg alkyl polyethozylate
(2.25) sulphate, C12-Clg alkyl polyethozylate (3) sulphate and C12-
Clg alkyl polyethozylate (4) sulphate wherein M is selected from
sodium or potassium. C12-C14 alkyl sulphate which has been
ethozylated with an average of from 0.5 to 4. moles of ethylene oxide
per molecule is especially preferred.
Other suitable anionic surfactants for use herein include salts (e.g.
alkali metal and ammonium salts) of C11-C24, Preferably C12-C20
linear alkylaryl sulphonates, particularly linear alkyl benzene
sulphonates, primary or secondary alkane sulphonates, alkene
sulphonates such as a-olefin sulphonates, ether sulphonates,
sulphonated polycarbozylic acids, ozyalkane sulphonates (fatty acid
isethionates), acylamino alkane sulphonates (taurides), alkyl and
alkenyl sarcosinates, alkyl glycerol sulphonates, fatty acyl glycerol
sulphonates, fatty oleyl glycerol sulphonates, and any mixtures thereof.
According to the present invention the compositions comprise
from 1% to 80%, preferably from 2% to 50%, most preferably from
3 ~ to 25 % of a non soap anionic surfactant.
According to the present invention another essential component
of the surfactant system is a nonionic surfactant.
CA 02194157 2000-O1-27
8
The polyethylene, polypropylene, and polybutylene oxide
condensates of alkyl phenols are suitable for use herein. In general,
the polyethylene oxide condensates are preferred. These compounds
include the condensation products of alkyl phenols having an alkyl
group containing from about 6 to about 12 carbon atoms in either a
straight chain or branched chain configuration with the alkylene oxide.
The alkyl ethoxylate condensation products of aliphatic alcohols
with from about 1 to about 25 moles of ethylene oxide are suitable for
use herein. The alkyl chain of the aliphatic alcohol can either be
straight or branched, primary or secondary, and generally contains
from 6 to 22 carbon atoms. Particularly preferred are the
condensation products of alcohols having an alkyl group containing
from 8 to 20 carbon atoms with from . about Z to about 10 moles of
ethylene oxide per mole of alcohol. Most preferred are the
condensation products of alcohols having an alkyl group containing
from 8 to 15 carbon atoms with from about 3 to about 9 moles of
ethylene oxide per mole of alcohol. Examples of commercially
available nonionic surfactants of this type include TergitoITM 15-S-9
(the condensation product of C 11-C 15 linear alcohol with 9 moles
ethylene oxide), TergitolTM 24-L-6 NMW (the condensation product
of C 12-C 14 Pri~'y alcohol with 6 moles ethylene oxide with a
narrow molecular weight distribution), both marketed by Union
Carbide Corporation; NeodolTM 45-9 (the condensation product of
C 14-C 15 ~~ ~cohol with 9 moles of ethylene oxide), NeodolTM
23-b.5 (the condensation product of C 12-C 13 1~~' alcohol with 6.54
moles of ethylene oxide), NeodolTM 45-7 (the condensation product of
C 14-C 15 linear alcohol with 7 moles of ethylene oxide), NeodolTM
45-4 (the condensation product of C 14-C 15 linear alcohol with 4 moles
of ethylene oxide), Neodo1TM23-3 (the condensation product of C 12-
C 13 linear alcohol with 3 moles of ethyene o~tide) marketed by Shell
Chemical Company, KyroTM EOBN (the condensation product of
C 13-C 15 alcohol with 9 moles ethylMne oxide), marketed by The
Procter & Gamble Company, Dobano M91 and Dobanol 25 marketed by
the Shell Chemical Company and Lial 111 marketed by Enichem.
WO 96100771 PGTIUS95/07795
2?9~.i57
Nonionic EO/PO condezicatec with ~rorylene glycol
The condensation products of ethylene oxide with a hydrophobic
base formed by the condensation of propylene oxide with propylene
glycol are suitable for use herein. Examples of compounds of this type
include certain of the commercially-available PluronicTM surfactants,
marketed by BASF.
Nonionic EO condensation ~roductc with propylene
ozide/ethylene diamine dduc s
The condensation products of ethylene oxide with the product
resulting from the reaction of propylene oxide and ethylenediamine are
suitable for use herein. Examples of this type of nonionic surfactant
include certain of the commercially available TetronicTM compounds,
marketed by BASF.
Suitable alkylpolysaccharides for use herein are 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. The
preferred alkyIpolyglycosides have the formula
R20(CnH2n0)t(glycosyl)x
WO 96!00771 PCTlUS95107795
2194157 ro
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydrozyalkyl, hydrozyalkylphenyl, and mixtures thereof in which the
alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon
atoms; n is 2 or 3, z is from 0 to 10 preferably from about 1.3 to about
3, most preferably from about 1.3 to about 2.7 and t is from 0 to 10.
The glycosyl is preferably derived from glucose.
Suitable nonionic surfactants for use herein also the C10-Clg N-
alkyl polyhydrozy fatty acid amides. Typical examples include the
C12-Clg N-methylglucamides. See VJO 9,206,134. Other sugar-
derived surfactants include the N-alkozy polyhydrozy fatty acid
amides, such as C10-Clg N-(3-methozypropyl) glucamide. The N-
propyl through N-hezyl C 12-C 1 g glucamides can be used for low
sudsing.
The compositions of the present invention comprise from I % to
50%, preferably from 2% to 35%, more preferably from 2% to 30%
of said nonionic surfactants.
Preferred surfactants for use herein are linear alkyl benzene
sulphonate, alkyl sulphates, alkyl alkozylated sulphates and alkyl
alkozylated nonionics and polyhydrozyfatty acid amides. According to
the present invention the anionic and nonionic surfactant are present in
the detergent composition at a ratio of from 0.6:1 to 10:1, preferably
from 0.6:1 to 8:1, more preferably from 0.8:1 to 6:1.
The surfactant system of the present invention may optionally
comprise zwitterionic, amphoteric surfactants such as C 12-C 18
betaines, sulphobetaines ("sultaines") and C 10-C 1 g amine oxides and
cationic surfactants.
Cationic detersive surfactants suitable for use herein are those
having one long chain hydrocarbyl group. Examples of such cationic
surfactants include the ammonium surfactants such as
R'09G/00771 _ .PCTlIJS95107795
2194152 is
alkyldimethylammonium halogenides and surfactants having the
formula:
[R2(OR3)ylCR4(OR3)y12R5N+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(CHg)-, -CH2CH(CH20H)-, -
CH2CH2CH2-, and miztures thereof; each R4 is selcted from the
group consisting of Cl-Cq, alkyl, Cl-Cq. hydrozyalkyl, benzyl ring
structures formed by joining the two R4 groups, -CH2CHOH-
CHOHCOR6CHOHCH20H wherein R6 is any hezose or hezose
polymer having a molecular weight less than about 1000 and hydrogen
when y is not 0; RS is the same as R4 or is an alkyl chain wherein the
total number of carbon atoms of R2 plus RS is not more than about 18;
each y is from about 0 to about 10 and the sum of the y values is from
0 to about 15; and X is any compatible anion.
Preferred cationic surfactants are the water soluble quaternary
amonium compounds useful in the present composition have the
formula:
Rl RZR3R4N +X-
wherein Rl is a Cg-C16 alkyl, each of R2~ Rg and R4 is independently
C1-Cq. alkyl, C1-Cq. hydrozy alkyl, benzyl and (C2Hq.0)zH where z
has a value of from 1 to 5 and X is an anion. Not more than one of the
R2, R3 or Rq, should be benzyl.
The preferred alkyl chain length for Rl is from C12-C15
particularly where the alkyl group is a mizture of chain lengths derived
from coconut or palm kernel fat or is derived from synthetically by
olefin build up or OXO alcohols synthesis. Preferred groups for the
_ R2R3 and Rq. are methyl and hydrozyethyl groups and the anion X
may be selected from halide, methosulphate, acetate and phosphate
Ions.
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n
Examples of suitable quaternary ammonium compounds for use
herein are:
coconut trimethyl ammonium chloride or bromide; coconut methyl
dihydrozyethyl ammonium chloride or bromide; decyl trimethyl
ammonium chloride; decyl dimethyl hydrozyethyl ammonium chloride
or bromide; C12-C15 dimethyl hydrozyethyl ammonium chloride or
bromide; coconut dimethyl hydrozyethyl ammonium chloride or
bromide; myristyl trimethyl ammonium methyl sulphate; lauryl
dimethyl benzyl ammonium chloride or bromide; lauryl dimethyl
(ethozy)4 ammonium chloride or bromide and choline esters.
Euilder s, s
According to the present invention the detegent composition
comprises as an essential ingredient a builder system. Said builder
system comprises less than 20%, preferably less than 10%, more
preferably less than 1 % phosphate builder. Most preferably the
compositions of the present invention are substantially free of
phosphate builder. Such phosphate builders include the alkali metal,
ammonium and alkanolammonium salts of polyphosphates (exemplified
by the tripolyphosphates, pyrophosphates, orthophosphates and glassy
polymeric meta-phosphates) and phosphonates.
According to the present invention the builder system may
comprise non phosphate builders to assist in controlling mineral
hardness and the removal of particulate soils. Inorganic as well as
organic builders can be used. The level of builder can vary widely
depending upon the end use of the composition and its desired physical
form. When present, the compositions will typically comprise at least
1% builder. Liquid~formulations typically comprise from 5% to 50%,
more typically about 5% to 30%, by weight, of detergent builder.
Granular formulations typically comprise from 10% to 80% , more
typically from 15% to 50% by weight, of the detergent builder. Lower
or higher levels of builder, however, are not meant to be excluded.
Inorganic detergent builders include, but are not limited to, phytic
acid, silicates, carbonates (including bicarbonates and
WO 96/00771 2 ~ g 4~ ~ 5 7 PCTIUS95107795
13
sesquicarbonates), sulphates, and aluminosilicates (see, for example,
U.S. Patents 3,159,5$1; 3,213,030; 3,422,021; 3,400,148 and
3,422,137) and the so-called "weak" builders (as compared with
phosphates) such as citrate, or in the so-called "underbuilt" situation
that may occur with zeolite or layered silicate builders.
Examples of silicate builders are the alkali metal silicates,
particularly those having a Si02:Na20 ratio in the range 1.6:1 to 3.2:1
and layered silicates, such as the layered sodium silicates described in
U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6
is the trademark for a crystalline layered silicate marketed by Hoechst
(commonly abbreviated herein as "SKS-6"). Unlike zeolite builders,
the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has
the delta-Na2Si20g morphology form of layered silicate. It can be
prepared by methods such as those described in German DE-A-
3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred layered
silicate for use herein, but other such layered silicates, such as those
having the general formula NaMSiz02z+1'YH20 wherein M is
sodium or hydrogen, z is a number from 1.9 to 4, preferably 2, and y
is a number from 0 to 20, preferably 0 can be used herein. Various
other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and
NaSKS-11, as the alpha, beta and gamma forms. As noted above, the
delta-Na2Si205 (NaSKS-6 form) is most preferred for use herein.
Other silicates may also be useful such as for example magnesium
silicate, which can serve as a crispening agent in granular
formulations, as a stabilizing agent for oxygen bleaches, and as a
component of suds control systems.
Examples of carbonate builders are the alkaline earth and alkali
metal carbonates as disclosed in German Patent Application No.
2,321,001 published on November 15, 1973.
Aluminosilicate builders are useful in the present invention.
Aluminosilicate builders are of great importance in most currently
marketed heavy duty granular detergent compositions, and can also be
a significant builder ingredient in liquid detergent formulations.
Aluminosilicate builders include those having the empirical formula:
wo 9600"' 219 415 7 PCT~S95107795
14
Mz[(Si02)w(zA102)y] ~ xH20
wherein w, z and y are integers of at least 6, the molar ratio of z to y
is in the range from 1.0 to about 0.5, and x is an integer from about 15 ,
to about 264.
Useful aluminosilicate ion exchange materials are commercially
available. These aluminosilicates can be crystalline or amorphous in
structure and can be naturally-occurring aluminosilicates or
synthetically derived. A method for producing aluminosilicate ion
exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et
al, issued October 12, 1976. Preferred synthetic crystalline
aluminosilicate ion exchange materials useful herein are available
under the designations Zeolite A, Zeolite P (B), Zeolite MAP and
Zeolite X. In an especially preferred embodiment, the crystalline
aluminosilicate ion exchange material has the formula:
Nal2[(AlO2)12(Si02)12]~xH20
wherein x is from about 20 to about 30, especially about 27. This
material is known as Zeolite A. Dehydrated zeolites (x =-0 - 10) may
also be used herein. Preferably, the aluminosilicate has a particle size
of about 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the
present invention include, but are not restricted to, a wide variety of
polycarboxylate compounds. As used herein, "polycarboxylate" refers
to compounds having a plurality of carboxylate groups, preferably at
least 3 carboxylates. Polycarboxylate builder can generally be added
to the composition in acid form, but can also be added in the form of a
neutralized salt. When utilized in salt form, alkali metals, such as
sodium, potassium, and lithium, or alkanolammonium salts are
preferred.
Included among the polycarboxylate builders are a variety of
categories of useful materials. One important category of
polycarboxylate builders encompasses the ether polycarboxylates,
including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287,
W0 96100771 PC1YUS95107795
2194 i S7 ___
issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830,
issued January 18, 1972. See also "TMS/T'DS" builders of U.S. Patent
4,663,071, issued to Bush et al, on May 5, 1987. Suitable ether
polycarbozylates also include cyclic compounds, particularly alicyclic
compounds, such as those described in U.S. Patents 3,923,679;
3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether
hydrozypolycarbozylates, copolymers of malefic anhydride with
ethylene or vinyl methyl ether, 1, 3, 5-trihydrozy benzene-2, 4, 6-
trisulphonic acid, and carboxymetliylozysuccinic acid, the various
alkali metal, ammonium and substituted ammonium salts of polyacetic
acids such as ethylenediamine tetraacetnc acid and nitrilotriacetic acid,
as well as polycarbozylates such as mellitic acid, succinic acid,
ozydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarbozylic acid,
carbozymethylozysuccinic acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof
(particularly sodium salt), are polycarbozylate builders of particular
importance for heavy duty liquid detergent formulations due to their
availability from renewable resources and their biodegradability.
Citrates can also be used in granular compositions, especially in
combination with zeolite and; or layered silicate builders.
Ozydisuccinates are also especially useful in such compositions and
combinations.
Also suitable in the detergent compositions of the present
invention are the 3,3-dicarboxy-4-oza-1,6-hezanedioates and the
related compounds disclosed in U.S. Patent 4,566,984, Bush, issued
January 28, 1986. Useful succinic acid builders include the CS-C20
alkyl and alkenyl succinic acids and salts thereof. A particularly
preferred compound of this type is dodecenylsuccinic acid. Specific
examples of succinate builders include: laurylsuccinate,
myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred),
2-pentadecenylsuccinate, and the like. Laurylsuccinates are the
preferred builders of this group, and are described in European Patent
Application 86200690.SJ0,200,263, published November 5, 1986.
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2194157 16 ~ '
Other suitable polycarbozylates are disclosed in U.S. Patent
4,144,226, Crutchfield et al, issued March 13, 1979 and in U.S. Patent
3,308,067, Diehl, issued March 7, 1967. See also Diehl U.S. Patent
3,723,322.
Fatty acids, e.g., C12-Clg monocarbozylic acids, can also be
incorporated into the compositions alone, or in combination with the
aforesaid builders, especially citrate and/or the succinate builders, to
provide additional builder activity. Such use of fatty acids will
generally result in a diminution of sudsing, which should be taken into
account by the formulator.
Optional ingredients
According to the present invention the detergent compositions
may comprise a number of optional conventional detergent adjuncts
such as builders, chelants, polymers, antiredeposition agents and the
like.
The detergent compositions herein may also optionally contain
one or more iron and/or manganese chelating agents. Such chelating
agents can be selected from the group consisting of amino
carbozylates, amino phosphonates, polyfunctionally-substituted
aromatic chelating agents and mixtures therein, all as hereinafter
defined. Without intending to be bound by theory, it is believed that
the benefit of these materials is due in part to their exceptional ability
to remove iron and manganese ions from washing solutions by
formation of soluble chelates.
Amino carbozylates useful as optional chelating agents include
ethylenediaminetetracetates, N-hydrozyethylethylenediaminetriacetates,
nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetra-
aminehezacetates, diethylenetriaminepentaacetates, and ethanoldi-
PCTIUS95/07795
WO 96100771 2 ~ 9 415 7
17
glycines, alkali metal, ammonium, and substituted ammonium salts
therein and miztures therein.
Amino phosphonates are also suitable for use as chelating agents
in the compositions of the invention when at least low levels of total
phosphorus are permitted in detergent compositions, and include
ethylenediaminetetrakis (methylenephosphonates) as DEQUEST.
Preferred, these amino phosphonates to not contain alkyl or alkenyl
groups with more than about 6 carbon atoms.
Polyfunctionally-substituted aromatic chelating agents are also
useful in the compositions herein. See U.S. Patent 3,812,044, issued
May 21, 1974, to Connor et al. Preferred compounds of this type in
acid form are dihydrozydisulfobenzenes such as 1,2-dihydrozy-3,5-
disulfobenzene.
A preferred biodegradable chelator for use herein is
ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as
described in U.S. Patent 4,704,233, November 3, 1987, to Hartman
and Perkins.
If utilized, these chelating agents will generally comprise from
0.1 % to 10% more preferably, from 0.1 % to 3.0% by weight of such
compositions.
w0 96100771 PCTIIJS95/07795
219415 .
Is
Polymeric Soil Release Agent
Any polymeric soil release agent known to those skilled in the art
can optionally be employed in the compositions and processes of this
invention. Polymeric soil release agents are characterized by having
both hydrophilic segments, to hydrophilize the surface of hydrophobic
fibers, such as polyester and nylon, and hydrophobic segments, to
deposit upon hydrophobic fibers and remain adhered thereto through
completion of washing and rinsing cycles and, thus, serve as an anchor
for the hydrophilic segments. This can enable stains occurring
subsequent to treatment with the soil release agent to be more easily
cleaned in later washing procedures.
The polymeric soil release agents useful herein especially include
those soil release agents having: (a) one or more nonionic hydrophile
components consisting essentially of (i) polyozyethylene segments with
a degree of polymerization of at least 2, or (ii) ozypropylene or
polyoaypropytene segments with a degree of polymerization of from 2
to 10, wherein said hydrophile segment does not encompass any
ozypropylene unit unless it is bonded to adjacent moieties at each end
by ether linkages, or (iii) a mixture of ozyalkylene units comprising
ozyethylene and from 1 to about 30 ozypropylene units wherein said
mixture contains a sufficient amount of oxyethylene units such that the
hydrophile component has hydrophilicity great enough to increase the
hydrophilicity of conventional polyester synthetic fiber surfaces upon
deposit of the soil release agent on such surface, said hydrophile
segments preferably comprising at least about 25% ozyethylene units
and more preferably, especially for such components having about 20
to 30 oxypropylene units, at least about 50% oayethylene units; or (b)
one or more hydrophobe components comprising (i) Cg oayalkylene
terephthalate segments, wherein, if said hydrophobe components also
comprise oxyethylene terephthalate, the ratio of ozyethylene
terephthalate:C3 oxyalkylene terephthalate units is about 2:1 or lower,
(ii) Cø-C6 alkylene or oay Cø-C6 alkylene segments, or mixtures
therein, or (iii) poly (vinyl ester) segments, preferably polyvinyl
acetate), having a degree of polymerization of at least 2.
CA 02194157 2000-O1-27
19
Typically, the polyoxyethylene segments of (a)(i) will have a
degree of polymerization of from about 200, although higher levels can
be used, preferably from 3 to about 150, more preferably from 6~ to
about 100. Suitable oxy C4-C6 alkylene hydrophobe segments
include, but are not limited to, end-caps of polymeric soil release
agents such as M03S(CH2)nOCH2CH20-, where M is sodium and n
is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued
January 26, 1988 to Gosselink.
Polymeric soil release agents useful in the present invention also
include copolymeric blocks of ethylene terephthalate or propylene
terephthalate with polyethylene oxide . or polypropylene oxide
terephthalate, and the like.
Soil release agents characterized by polyvinyl ester) hydrophobe
segments include graft copolymers of polyvinyl ester), e.g., Cl-C6
vinyl esters, preferably polyvinyl acetate) grafted onto polyallrylene
oxide backbones, such as polyethylene oxide backbones. See European
Patent Application 0 219 048, published April 22, 1987 by Kud, et al.
CommerciaMly available soil release agents of this kind include the
SOKALAN type of material, e.g., SOKALAN HP-22, available from
BASF (West Germany).
One type of preferred soil release agent is a copolymer. having
random blocks of ethylene terephthalate and polyethylene oxide (PEO)
terephthalate. The molecular weight of this polymeric soil release
agent is in the range of from about 25,000 to about 55,000. See U.S.
Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent
3,893,929 to Basadur issued July 8, 1975.
Another preferred polymeric soil release agent is a polyester with
repeat units of ethylene terephthalate units contains IO-1596 by weight
of ethylene terephthalate units together with 90-8096 by weight of
polyoxyethylene terephthalate units, derived from ~ a polyoxyethylene
glycol of average molecular weight 300-5,000. Examples oM this
polymer include the commercially available material ZELCON 5126
CA 02194157 2000-O1-27
TM
(from Dupont) and MILEASE T (from ICI). See also U.S. Patent
4,702,857, issued October 27, 1987 to Gosselink.
Another preferred polymeric soil release agent is a sulfonated
product of a substantially linear ester oligomer comprised of an
oligomeric ester backbone of terephthaloyl and oxyalkyleneozy repeat
units and terminal moieties covalently attached to the backbone. These
soil release agents are described fully in U.S. Patent 4,968,451, issued
November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Other suitable
polymeric soil release agents include the terephthalate polyesters of
U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al,
the anionic end-capped oligomeric esters of U.S. Patent 4,721,580,
issued January 26, 1988 to Gosselink, and the block polyester
oligomeric compounds of U.S. Patent 4,702,857, issued October 27,
1987 to Gosselink.
Preferred polymeric soil release agents also include the soil
release agents of U.S. Patent 4,877,896, issued October 31, 1989 to
Maldonado et al, which discloses anionic, especially sulfoarolyl, end-
capped terephthalate esters.
If utilized, soil release agents will generally comprise from about
0.01 % to about 10.0 WO , by weight, of the detergent compositions
herein, typically from about 0.1 ~Ro to about 59b, preferably from about
0.296 to about 3.0%.
Still another preferred soil release agent is an oligomer with
repeat units of terephthaloyl units, sulfoisoterephthaloyl units,
oxyethyleneoxy and oxy-1,2-propylene units. T6e repeat units form the
backbone of the oligomer and are preferably terminated with modified
isethionate end-caps. A particularly preferred soil release agent of this
type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units,
oxyethyleneoxy and oay-1,2-propyleneoxy units in a ratio of from
about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-
hydroxyethoxy~ethanesulfoaate. Said soil release agent also comprises
from about 0.59~r to about 209, by weight of the oligomer, of a
crystalline-reducing stabilizer, preferably selected from the group
wo 9sroo~n
2 ~ ~ 415 7 - PCTIUS95/07795
21
consisting of zylene sulfonate, cumene sulfonate, toluene sulfonate,
and miztures thereof.
CA 02194157 2000-O1-27
22
t .v
.The detergent compositions herein may optionally contain
bleaching agents or bleaching compositions containing a bleaching
agent and one or more bleach activators. When present, bleaching
agents will typically be at levels of from 1 % to 40%, more typically
from 5 % to 30 % , of the detergent composition, especially for fabric
laundering. If present, the amount of bleach activators will typically be
from 0.1 % to 60 % , more typically from 0.5 % to 40 % of the bleaching
composition comprising the bleaching agent-plus-bleach activator.
The bleaching agents used herein can be any of the bleaching
agents useful for detergent compositions in textile cleaning, hard
surface cleaning, or other cleaning purposes that are now known or
become known. These include oxygen bleaches as well as other
bleaching agents.
Peroxygen bleaching agents can also be used. Suitable
peroxygen bleaching compounds include sodium carbonate
peroxyhydrate and equivalent "percarbonate" bleaches, sodium
pyrophosphate peroxyhydrate, urea peroxyhydraMe, and sodium
peroxide. Persulfate bleach (e.g., OXONE, manufactured
commercially by DuPont) can also be used.
A preferred percarbonate bleach comprises dry particles having
an average particle size in the range from about 500 micrometers to
about 1,000 micrometers, not more than about 1096 by weight of said
particles being smaller than about 200 micrometers and not more than
about 1096 by weight of said particles being larger than about 1,250
micrometers. Optionally, the percarbonate can be coated with silicate,
borate or water-soluble surfactants. Preferred coatings are based on
carbonate/sulphate mixtures. Percarbonate is available from various
commercial sources such as FMC, Solvay and Tokai Denka.
Another category of bleaching agent that can be used without
restriction encompasses percarboxylic acid bleaching agents and salts
thereof. Suitable examples of this class of agents include magnesium
PCTIIT595107795
WO 96100771 2 1 9 4 1 5 l
23 '
monoperozyphthalate hezahydrate, the magnesium salt of metachlorc
perbenzoic acid, 4-nonylamino-4-ozoperozybutyric acid and
diperozydodecanedioic acid. Such bleaching agents are disclosed in
U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S.
Patent Application 740,446, Burns et al, filed June 3, 1985, European
Patent Application 0,133,354, Banks et al, published February 20,
1985, and U.S. Patent 4,412,934, Chung et al, issued November 1,
1983. Highly preferred bleaching agents also include 6-nonylamino-6-
oxoperozycaproic acid as described in U.S. Patent 4,634,551, issued
January 6, 1987 to Burns et al.
Mixtures of bleaching agents can also be used. Perozygen
bleaching agents, the perborates, e.g., sodium perborate (e.g., mono-
or tetra-hydrate) , the percarbonates, etc., are preferably combined
with bleach activators, which lead to the in situ production in aqueous
solution (i.e., during the washirsg process) of the perozy acid
corresponding to the bleach activator. Various nonlimiting examples
of activators are disclosed in U.S. Patent 4,915,854, issued April 10,
1990 to Mao et al, and U.S. Patent 4,412,934. The
nonanoylozybenzene sulfonate (HOBS) and tetraacetyl ethylene
diamine (TAED) activators are typical, and mixtures thereof can also
be used. See also U.S. 4,634,551 for other typical bleaches and
activators useful herein. It has also been observed that the
incorporation of nonanoylozybenzene sulphonate in a nonionic
polysaccharide ether containing composition (as illustrated in Example
4, II-II)] provides an additional colour care performance benefit. It
appears that the colour fidelity of certain coloured fabrics when
subjected to repetitive washing with a composition comprising NOBS
in combination with polysaccharide ethers improves the colour fidelity
of the fabrics versus a composition without nonionic polysaccharide
ether.
Highly preferred amido-derived bleach activators are those of
the formulae:
R1N(RS)C(O)R2C(O)L or R1C(O)N(RS)R2C(O)L
wherein R1 is an alkyl group containing from about 6 to about 12
carbon atoms, R2 is an alkylene containing from 1 to about 6 carbon
CA 02194157 2000-O1-27
24
atoms, RS is H or alkyl, aryl, or alkaryl containing from about I to
about 10 carbon atoms, and L is any suitable leaving group. A leaving
group_ is any group that is displaced from the bleach activator as .a
consequence of the nucleophilic attack on the bleach activator by the
perhydroxyl anion. A preferred leaving group is phenol sulfonate.
Preferred examples of bleach activators of the above formulae
include (6-octanamido-caproyl)oxybenzenesulfonate,
nonanamidocaproyl)- oxybenzenesulfonate, (6-decanamido-
caproyl)oxybenzenesulfonate, and mixtures thereof as described in
U.S. Patent 4,634,551.
Another class of bleach activators comprises the benzoxazin-type
activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued
October 30, 1990 . A highly preferred activator of the benzoxazin-
type is: _ ' - _
O
II
CEO
C
N, O
Still another class of preferred bleach activators includes the acyl
lactam activators, especially acyl caprolactams, acyl pyrolidone and
acyl valerolactams of the formulae:
O
' O C-C HZ-C HZ
Rg-C-~C -C H ~C H2
H2 2
O
II
R6-C C-CH2-~ H2
~C H2-C H2
CA 02194157 2000-O1-27
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group
containing from 1 to about 12 carbon atoms. Highly preferred lactam
activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-
trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl
caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl
valerolactam, decanoyl valerolactam, undecenoyl valerolactam,
nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and
mixtures thereof. See also U.S. Patent 4,545,784, issued to
Sanderson, October 8, 1985, which discloses acyl caprolactams,
adsorbed into sodium perborate. Other preferred activators are
cationic bleach activators.
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.
See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If
used, detergent compositions will typically contain from 0.025 % to
1.2590, by weight, of such bleaches, especially sulfonate zinc
phthalocyanine.
If desired, the bleaching compounds can be catalyzed by means
of a manganese compound. Such compounds are well known in the art
and include, for example, the manganese-based catalysts disclosed in
U.S. Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S.
Pat. 5, I 14,606; and European Pat. App. Pub. Nos. 549,271 A 1,
549,272A1, 544,444A2, and 54.4.,490A1; Preferred examples of these
catalysts include MnN2(u-03(1,4,7-trimethyl-1,4,?-
' triazacyclononane~(PF~, Mn~2(u-O)I(u-OAc~(1,4,7-trimethyl-
1,4,7-triazacyclononane~-(C104~, MnN4(u-O)6(1,4,7-
triazacyclononane)4(C104)4, Mn~Mn~4(u-O)1(u-0Ac~_(1,4,7- ,
trimethyl-1,4,7-triazacyclononane~(C104)3, Mn~(1,4,7-trimethyl-
1,4,7-triazacyclononane~- (OCH3~(PF~, and mixtures thereof. Other
metal-based bleach catalysts include those disclosed in U.S. Pat.
4,430,243 and U.S. Pat. 5,114,611. The use of manganese with
various complex ligands to enhance bleaching is also reported in the
w0 96100771 PCTIU595107795
219417 26 .
following United States Patents: 4,728,455; 5,284,944; 5,246,612;
5,256,779; 5,280,117; 5,274,147; 5,153,161; 5,227,084;
polymeric Dispersing Agents
Polymeric dispersing agents can advantageously be utilized at
levels from 0.1 % to 7%, by weight, in the compositions herein,
especially in the presence of zeolite and/or layered silicate builders.
Suitable polymeric dispersing agents include polymeric
polycarbosylates and polyethylene glycols, although others known in
the art can also be used. It is believed, though it is not intended to be
limited by theory, that polymeric dispersing agents enhance overall
detergent builder performance, when used in combination with other
builders (including lower molecular weight polycarbozylates) by
crystal growth inhibition, particulate soil release peptization, and anti-
redeposition.
Polymeric polycarboaylate materials can be prepared by
polymerizing or copolymerizing suitable unsaturated monomers,
preferably in their acid form. Unsaturated monomeric acids that can be
polymerized to form suitable polymeric polycarbozylates include
acrylic acid, malefic acid (or malefic anhydride), fumaric acid, itaconic
acid, aconitic acid, mesaconic acid, citraconic acid and
methylenemalonic acid. The presence in the polymeric
polycarboxylates herein of monomeric segments, containing no
carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc.
is suitable provided that such segments do not constitute more than
about 40% by weight.
Particularly suitable polymeric polycarbozylates can be derived
from acrylic acid. Such acrylic acid-based polymers which are useful
herein are the water-soluble salts of polymerized acrylic acid. The
average molecular weight of such polymers in the acid form preferably
ranges from about 2,000 to 10,000, more preferably from about 4,000
to 7,000 and most preferably from about 4,000 to 5,000. Water-soluble
salts of such acrylic acid polymers can include, for example, the alkali
metal, ammonium and substituted ammonium salts. Soluble polymers
WO 96/00771 219 4115 7 PCT~S95I07795
27
of this type are known materials. Use of polyacrylates of this type in
detergent compositions has been disclosed, for example, in Diehl, U.S.
Patent 3,308,067, issued march 7, 1967.
Acrylic/maleic-based copolymers may also be used as a
preferred component of the dispersinglanti-redeposition agent. Such
materials include the water-soluble salts of copolymers of acrylic acid
and malefic acid. The average molecular weight of such copolymers in
the acid form preferably ranges from about 2,000 to 100,000, more
preferably from about 5,000 to 90,000, most preferably from about
7,000 to 80,0(10. The ratio of acrylate to maleate segments in such
copolymers will generally range from about 30:1 to about 1:1, more
preferably from about 70:30 to 30:70. Water-soluble salts of such
acrylic acid/maleic acid copolymers can include, for example, the
alkali metal, ammonium and substituted ammonium salts. Soluble
acrylate/maleate copolymers of this type are known materials which
are described in European Patent Application No. 6691, published
December 15, 1982, as well as in EP 193,360, published September 3,
1986, which also describes such polymers comprising
hydrozypropylacrylate. Still other useful dispersing agents include the
maleic/acrylic/vinyl alcohol or acetate terpolymers. Such materials are
also disclosed in EP 193,360, including, for example, the 45/45/10
terpolymer of acrylic/maleic/vinyl alcohol.
Another polymeric material which can be included is
polyethylene glycol (PEG). PEG can exhibit dispersing agent
performance as well as act as a clay soil removal-antiredeposition
agent. Typical molecular weight ranges for these purposes range from
about 500 to about 100,000, preferably from about 1,000 to about
50,000, more preferably from about 1,500 to about 10,000.
Polyamino acid dispersing agents such as polyaspartate and
poIyglutamate may also be used, especially in conjunction with zeolite
builders. Dispersing agents such as polyaspartate preferably have a
molecular weight (avg.) of about 10,000.
Clay Soil Removal/Anti-rede o i ion A~ n c
W 0 96100771 PCTIUS95J07795
2194157 2g
The compositions of the present invention can also optionally
contain water-soluble ethozylated amines having clay soil removal and
antiredeposition properties. Granular detergent compositions which
contain these compounds typically contain from about 0.01 % to about
10.0% by weight of the water-soluble ethozylates amines; liquid
detergent compositions typically contain about 0.01 % to about 5%.
The most preferred soil release and anti-redeposition agent is
ethozylated tetraethylenepentamine. Exemplary ethozylated amines
are further described in U.S. latent 4,597,898, VanderMeer, issued
July 1, 1986. Another group of preferred clay soil removal-
antiredeposition agents are the cationic compounds disclosed in
European Patent Application 111,965, Oh and Gosselink, published
June 27, 1984. Other clay soil removal/antiredeposition agents which
can be used include the ethozylated amine polymers disclosed in
European Patent Application 111,984, Gosselink, published June 27,
1984; the zwitterionic polymers disclosed in European Patent Appli-
cation 112,592, Gosselink, published July 4, 1984; and the amine
oxides disclosed in U.S. Patent 4,548,744., Connor, issued October 22,
1985. Other clay soil removal andlor anti redeposition agents known in
the art can also be utilized in the compositions herein. Another type of
preferred antiredeposition agent includes the carbozy methyl cellulose
(CMC) materials. These materials are well known in the art.
~,~gTrancfer Inhibiting Aeents _
The compositions of the present invention may also include one
or more materials effective for inhibiting the transfer of dyes from one
fabric to another during the cleaning process. Generally, such dye
transfer inhibiting agents include polyvinyl pyrrolidone polymers,
polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and
N-vinylimidazole, manganese phthalocyanine, perozidases, and
mixtures thereof. If used, these agents typically comprise from 0.01
to 10 % by weight of the composition, preferably from 0.01 % to 5 % ,
and more preferably from 0.05 % to 2 % .
wo 96/0077a 2 ~ g 4 ~ 5 7 --- PGTJUS95I07795
29
More specifically, the poIyamine N-oxide polymers preferred for
use 'herein contain units having the following structural formula: R-Ax-
P; wherein P is a polymerizable unit to which an N-O group can be
attached or the N-O group can form part of the polymerizable unit or
the N-O group can be attached to both units; A is one of the following
structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; z is 0 or 1; and R is
aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclic~
groups or any combination thereof to which the nitrogen of the N-O
group can be attached or the N-O group is part of these groups.
Preferred polyamine N-oxides are those wherein R is a heterocyclic
group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and
derivatives thereof.
The N-O group can be represented by the following general
structures:
O 0
I I
~thc- ~ ~a~: =N-(Rihc
0~)z
wherein Rl, R2; Rg are aliphatic, aromatic, heterocyclic or alicyclic
groups or combinations thereof; z, y and z are 0 or 1; and the nitrogen
of the N-O group can be attached or form part of any of the
aforementioned groups. The amine oxide unit of the polyamine N-
oxides has a pKa < 10, preferably pKa < 7, more preferred pKa < 6.
Any polymer backbone can be used as long as the amine oxide
polymer formed is water-soluble and has dye transfer inhibiting
properties. Examples of suitable polymeric backbones are polyvinyls,
polyalkylenes, polyesters, polyethers, polyamide, polyimides,
polyacrylates and mixtures thereof. These polymers include random or
block copolymers where one monomer type is an amine N-oxide and
the other monomer type is an N-oxide. The amine N-oxide polymers
typically have a ratio of amine to the amine N-oxide of 10:1 to
1:1,000,000. However, the number of amine oxide groups present in
the polyamine oxide polymer can be varied by appropriate
CA 02194157 2000-O1-27
copolymerization or by an appropriate degree of N-oxidation. The polyamine
oxides can be obtained in almost any degree of polymerization. Typically, the
average molecular weight is within the range of 500 to 1,000,000; more
preferred 1,000 to 500,000; most preferred 5,000 to 100,000. This preferred
class of materials can be referred to as "PVNO".
The most preferred polyamine N-oxide useful in the detergent
compositions herein is poly(4-vinylpyridine-N-oxide) which has an average
molecular weight of about 50,000 and an amine to amine N-oxide ratio of about
1:4.
Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers
(referred to as a class as "PVPVI") are also preferred for use herein.
Preferably the PVPVI has an average molecular weight range from 5,000 to
1,000,000, more preferably from 5,000 to 200,000, and most preferably from
10,000 to 20,000. (The average molecular weight range is determined by light
scattering as described in Barth, et al., Chemical Analysis, Vol 113. "Modern
Methods of Polymer Characterization".) The PVPVI copolymers typically
have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to
0.2:1,
more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1.
These
copolymers can be either linear or branched. It has also been observed that
additional dye transfer inhibition benefits are provided by compositions
comprising nonionic polysaccharide ethers and dye transfer inhibitors such as
PVNO and PVPVI such as illustrated in Example 1, reference B and
formulation B. It is believed that a synergic effect due to the combination of
polysaccharides and dye transfer inhibitors provides the unexpected whiteness
maintenance performance benefits to white fabrics which have been subjected
to repetitive washing.
The present invention compositions also may employ 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,
and more preferably from about 5,000 to about 50,000.
CA 02194157 2000-O1-27
31
PVP's are known to persons skilled in the detergent field; see, for
- example, EP-A-262,897 and EP-A-256;696, incorporated herein by
reference. Compositions containing PVP can also contain polyethylene
glycol (" PEG") having an average molecular weight from about 500 to
about 100,000, preferably from about 1,000 to about 10,000.
Preferably, the ratio of PEG to PVP on a ppm basis delivered m wash
solutions is from about 2:1 .to about 50:1, and more preferably from
about 3:1 to about 10:1.
The detergent compositions herein may also optionally contain
from 0:005 % to 5 % by weight of certain types of hydrophilic optical
brighteners which also provide a dye transfer inhibition action. If
used, the compositions herein will preferably comprise from 0.01 % to
1 % by weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present
invention are those having the structural formula:
R~ RZ
N H H N
N O~N O C=C O N ~O N
,.._N H H N
RZ~ S03M SO~ Ri
wherein Rl is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-
hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is
a salt-forming cation such as sodium or potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-
hydroxyethyl and M is a cation such as sodium, the brightener is 4,4' ,-
bis[(4-anilino-6-(N-2-bis-hydroxyethyl}-s-triazine-2-yl)amino]-2,2'-
stilbenedisulfonic acid and disodium salt. This particular brightener
species is commercially marketed under the trademark Tinopal-UNPA-
GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred
hydrophilic optical brightener useful in the detergent compositions
herein.
CA 02194157 2000-O1-27
32
When in the above formula, R1 is anilino, R2 is N-2-
hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the
brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-
s-triazine-2-y1)amino]2,2'-stilbenedisulfonic acid disodium salt. This
particular brightener species is commercially marketed under the
trademark Tinopal SBM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and
M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-
morphilino-s-triazine-2-yl)aminoJ2,2'-stilbenedisulfonic acid, sodium
salt. This particular brightener species is commercially marketed vender
the trademark Tinopal AMS-GX by Ciba Geigy Corporation.
The specific optical brightener species selected for use in the
present invention provide especially effective dye transfer inhibition
performance benefits whea used in combination with the selected
polymeric dye transfer inhibiting agents hereinbefore described. The
combination of such selected polymeric materials (e.g., PVNO and/or
PVPVn with such selected optical brighteners (e.g., Tinopal UNPA-
GX, Tinopal SBM-GX and/or Tinopal AMS-GX) provides significantly
better dye transfer inhibition in aqueous wash solutions than does either
of these two detergent composition components when used alone.
Without being bound by theory, it is believed that such brighteners
work this way because they have high affinity for fabrics in the wash
solution and therefore deposit relatively quick on these fabrics. The
extent to which brighteners deposit on fabrics in the wash solution can
be defined by a parameter called the "exhaustion coefficient" . The
exhaustion coefficient is in general as the ratio of a) the brightener
material deposited on fabric to b) the initial brightener concentration in
the wash liquor. Brighteners with relatively high exhaustion
coefficients are the most suitable for inhibiting dye transfer in the
context of the present invention.
Of course, it will be appreciated that other, conventional optical
brightener types of compounds can optionally be used in the present
compositions to provide conventional fabric "brightness" benefits,
WO 96/00771 PCT/US95107795
2194157 3~ - ,
rather than a true dye transfer inhibiting effect. Such usage is
conventional and well-known to detergent formulations.
According to the present invention the detergent composition
may comprise any other ingredients commonly employed in
conventional detergent compositions -such as suds suppressors,
softeners, brighteners, additional enzymes and enzyme stabilisers.
The compositions of the present invention may be used in
laundry detergent compositions, fabric treatment compositions and
fabric softening compositions in addition to hard surface cleaners. The
compositions may be formulated as conventional granules, bars,
pastes, powders or liquids. The detergent compositions are
manufactured in conventional manner, for ezample in the case of
powdered detergent compositions, spray drying, agglomeration or
spray mining processes may be utilised.
Preferably granular detergent compositions according to the
present invention have a density of from 400g11 to 1200g1I, more
preferably from SOOg/1 to 1000g/1, most preferably from 600g/1 to
1000g/l.
The mean particle size of the components in accordance with the
invention should preferably be such that no more than 5% of the
particles are greater than 1.7mm in diameter and not more than 5 % are
less than O.lSmm in diameter.
The combination of the min of the polysaccharide ether and
anionic and nonionic surfactant are present at at least l0ppm in the
aqueous wash solution having a pH of from 7 to 11, preferably from 9
to 10.5.
The present invention also relates to a method of laundering
fabrics which comprises contacting said fabric with an aqueous laundry
liquor containing conventional detersive ingredients described herein in
addition to the nonionic polysaccharide ether and nonionic and anionic
W 0 96100771 PGTIUS95/07795
2194157
34
surfactants of the present invention. In a preferred method polyester
and polyester-cotton blends fabrics are used.
z is
Abbreviations used in Examples
In the detergent compositions, the abbreviated component
identifications have the following meanings:
XYAS . Sodium C1X - Cly alkyl sulphate
25EY : A C 12-15 Predominantly linear primary
alcohol condensed with an average of Y moles
of ethylene oxide
XYEZ : A Clz - Cly predominantly linear primary
alcohol condensed with an average of Z moles
of ethylene oxide
XYEZS ~ C1X - C lY sodium alkyl sulphate condensed
with an average of Z moles of ethylene oxide
per mole
TFAA ~ C16-C18 alkyl N-methyl glucamide.
Silicate . Amorphous Sodium Silicate (Si02:Na20 ratio
= 2.0)
NaSKS-6 . Crystalline layered silicate of formula 8
Na2Si20g
Carbonate . Anhydrous sodium carbonate
MAJAA . Copolymer of 30:70 maleicJacrylic acid,
average molecular weight about 70,000.
CA 02194157 2000-O1-27
Zeolite A : Hydrated Sodium Aluminosilicate of formula
Nal2(A102Si02)12~ 2~H20 having a primary
particle size in the range from 1 to 10
micrometers
Citrate : Tri-sodium citrate dihydrate
Percarbonate . Anhydrous sodium percarbonate bleach coated
with a coating of sodium silicate (Si20:Na20
ratio = 2:1 ) at a weight ratio of percarbonate
to sodium silicate of 39:1
CMC . Sodium carbozymethyl cellulose
DETPMP . Diethylene triamine penta (Methylene
phosphonic acid), marketed by Monsanto under
the Trademark bequest 2060
PVNO . Poly (4-vinylpyridine~N-ozide copolymer of
vinylimidazole and vinylpyrrolidone having an
average molecular weight of 10,000.
Smectite Clay . Calcium montmorillonite ez. Colin Stewart
Minchem Ltd.
Granular Suds . 12% Siliconelsilica, 1896 stearyl alcoho1,70~
Suppressor starch in granular form
LAS . Sodium linear C 12 alkyl benzene sulphonate
TAS . Sodium tallow alkyl sulphate
SAS . C 12-C 14 secondary (2,3) alkyl sulfate in the
form of the sodium salt.
R'O 96!00771 PCfIU595107795
2194157
36
SS . Secondary soap surfactant of formula 2-butyl
octanoic acid
Phosphate . Sodium tripolyphosphate
TAED . Tetraacetyl ethylene diamine
pVp . Polyvinyl pyrrolidone polymer
HMVJPEO . High molecular weight polyethylene oxide
MC : Methyl cellulose ether with molecular weight
from 110000 to 130000, available from Shin
Etsu Chemicals under the tradename Metolose
HMEC . Tylose MH300, available from Hoechst
EHEC . Bermocoll E230, available from Berol/Akzo
EDDS . [s,s] ethylene diamine disuccinate
HEDP . 1,1 hydrozyethane diphosphonic acid
Sulphate . Sodium sulphate
PEO . Polyethylene oxide ml. wt. SMM
DHAC . Dimethyl hydrozyethyl ammonium chloride
TAE 25 . TalIow alcohol ethozylate (25)
wo 9sroorn 2 ~ ~ 4 ~ 5 l rcrrus9sro~~9s
37
The following laundry detergent compositions reference A,
formulation A, reference B, formulation B were prepared.
Formulation B is according to the present invention.
Reference Formutatio Reference Formulatio
A nA B nB
C45AS/AE3S 6 6 8.6 8.6
C25E3 6 6 - -
C45E7 6 6 - -
C24E5 - - 4.8 4.8
SKS6 - - 12 12
Zeolite A 38 38 10 10
PVNO - - 0.03 0.03
HEDP - - 0.8 0.8
Carbonate 7 7 8 g
Percarbonate 14 14 22 22
Savinase TM 2 2 2 2
(4 kNPU)
Lipolase TM 0.2 0.2 0.4 0.4
(100 kL
Suds 2 2 1.5 1.5
su ressor
Silicate 3 3 - -
TAED 6 6 5 5
EHEC - 0.5 - 0.5
Miscellaneous100 100 100 100
Balance
Soil removal testing was conducted in a Hotpoint washing
machine, short cycle, at 40°C, Newcastle city water with hardness of
l2dH, using 75g of the detergent composition. The cotton and
polycotton fabrics were first pretreated with each one of the
compositions described above and using the condition outlined above.
The staining mixtures were evenly spread over the fabric with a brush
and left to dry on a bench overnight. The fabrics were then washed
using the same formulation.
R'O 96100771 PCT/US95107795
2194157
38
Differences in greasy soil removal performance are recorded in
panel score units (psu), positive having a better performance than the
reference product. The following grading scale (psu grading) was
used:
0 = equal
1 = I this one is better
2 = I know this one is a little better
3 = This one is ~ better
4 = This one is a whole lot better
Grading was done under controlled light conditions by expert graders.
The number of replicates used in this test was six. 's' denotes that the
observed difference is statistically significant at a 95 % confidence
level. The significance of the differences between the formulations was
obtained using a two way ANOVA calculation. Thus, the differences
between the formulations and the differences between replicates were
separately calculated using their corresponding variances and the
difference was analysed using the F test.
Cotton substrate
PSU Reference Formulatio Reference Formulatio
A n A B nB
Anionic: 0.5 0.5 1.8 1.8
nonionic
ratio
Average 0 0.2 0 ' + 1.1
reas stain
Ra u* 0 -0.25 0 +0.4s
Pizza** 0 -0.5 0 +0.4
Tuna*** 0 -0.1 0 + 1.3s
Curr **** 0 +1.7 0 +2.2s
Clay soil 0 -3.1s 0 ~ -I.0
WO 96100771 PCTYUS95107795
2194157 - .
39
Polycotton substrate
PSU Reference FormuIatio Reference Formulatio
A n B n
A g
Anionic: 0.5 0.5 1.8 1.8
nonionic
ratio
Average 0 -0.6 0 +0.4
greasy food
stain
Ra u* 0 -0.8 0 +0.6s
Pizza** 0 -1.4 0 -0.1
Tuna*** 0 +0.9 0 +0.8
Cur **** 0 -1.1 0 +0.4
Cla soil 0 -2.2s 0 -0.2
Ragu* : Pasta Sauce.
Pizza**: Pizza topping sauce
Tuna*** : Tuna mayonnaise.
Curry****: Curry sauce.
WO 96/00771 1 ' ~ ~ t, ; , FGTIU595107795
2 ? 9 ~ 15 7 40 'w
E~ple 2: Granular detergent compositions of the present invention
I II III
Blown Powder
Phos hate 19 - 19
Zeolite A - 24
Sul hate 9 6 13
MAIAA 2 4 2
LAS 6 8 I I
TAS 2 - -
Silicate 7 3 3
CMC 1 1 0.5
Bri htener 0.2 0.2 0.2
DETPMP 0.4 0.4 0.2
S ra On
AE7 2.5 2.5 2.0
AE3 2.5 2.5 2.0
Silicone antifoam 0.3 0.3 0.3
Perfume 0.3 0.3 0.3
Dr additives
Carbonate 6.0 13.0 15.0
PB4 18.0 18.0 10
PB 1 4.0 4.0 0
TAED 3.0 3.0 1.0
Zinc Phtalocyanine 0.02% 0.02% 0.02%
enca sulate
Savinase protease(TM) 1.0 I.0 1.0
4.0 KNPU / )
Lipolase lipase (TM) 0.4 0.4 0.4
(100.000 LUII)
Termamyl amylase )TM) 0.25 0.30 0.15
60KNU/
MC 0.5 - 0.5
HMEC_ - 0.5 _
Dr mined Sul hate 3.0 3.0 5.0
R'O 96100771 ~ ty ~ ~ S, 2 ~ 9 415 l PCflUS95/07795
41
E3alance (Moisture 100.0 100.0 100.0
&
Miscellaneous)
V1'O 96100771 ' ~ ~ PGTl1TS95107795
2194157
42
Example 3: Granular detergent compositions
I II III ,
Blown Powder
Zeolite A 15.0 15.0 -
Sul hate 0.0 5.0 -
LAS 3.0 3.0 -
DETPMP 0.4 0.5 -
CMC 0.4 0.4 -
MA/AA 4.0 4.0 -
A lomerates
45AS I 1.0
LAS 6.0 5.0
TAS 3.0 2.0
Silicate 4.0 4.0
Zeolite A 10.0 15.0 13.0
CMC 0.5
MAIAA 2.0
Carbonate 9.0 7.0 7.0
S ra On
Perfume 0.3 0.3 0.5
AE7 4.0 4.0 4.0
AE3 2.0 2.0 2.0
Dr additives
MAIAA 3.0
SKS6 12.0
Citrate 10.0 0.0 8.0
Na Bicarbonate 7.0 3.0 5
Na Carbonate 8.0 5 7
PVP 0.5 0.5 0.5
Alcalase protease TM (3.0 0.5 0.3 0.9
AU l
Lipolase lipase TM(100.000 0.4 0.4 0.4
LU/I)
Termamyl amylase TM 0.6 0.6 0.6 '
60KNUI
Carezyme cellulase TM 0.6 0.6 0.6
(1000CEVUl )
-2 ~_g9 X57
WO 96/00771 PCT1ITS95I07795
43
MC - 0.6 0.6
HMEC 0.6 - -
Silicone antifoam ranule 5.0 5.0 5.0
Dr mixed Sul hate 0.0 9.0 0.0
Balance (Moisture and 100.0 100.0 7f00.~
Miscellaneous I
)
Example 4:
Com osition I II III
Blown Powder
Zeolite A 30.0 22.0 6.0
Sul hate 19.0 10.0 7.0
MA/AA 3.0 3.0 6.0
LAS 11.0 10.0 22.0
45AS 5.0 5.0 7.0
Silicate 1.0 5.0
Bri htener 0.2 0.2 0.2
Carbonate 8.0 16.0 20.0
DETPMP 0.4 0.4
S ra On
AE7 3.0 3.0 3.0
AE3
D additives
PVP 0.5 0.5 0.5
Savinase protease 1.0 1.0 1.0
TM 4.0 KNPU / )
Lipolase lipase 0.4 0.4 0.4
TM
100.000 LU/I
Termamyl amylase 0.1 0.1 0.1
TM 60KNU/
Carezyme cellulase 0.1 0.1 0.1
TM(1000CEVU/ )
NOBS 6.1 4.5
PB 1 1.0 5.0 6.0
MC 0.4 - 0.4
HMEC - 0.4 -
w0 96100771 PCTIU595I07795
..- 44 219~15~-
Dr mined Sul hate 6.0
Balance / 100 100 100
Miscellaneous
Example 5:
I II III
Blown Powder
Zeolite A 15.0 15.0 15.0
Sul hate 0.0 5.0 0.0
LAS 3.0 3.0 3.0
DHAC 1.5 1.5
DETPMP 0.4 0.4 0.4
CMC 0.4 0.4 0.4
MA/AA 4.0 2.0 2.0
A lomerates
LAS 5.0 5.0 5.0
TAS 2.0 2.0 2.0
Silicate 3.0 3.0 4.0
Zeolite A 8.G 8.0 8
Carbonate 8.0 8.0 4.0
S ra On
Perfume 0.3 0.3 0.3
AE7 2.0 2.0 2.0
AE3 2.0
D additives
Citrate 5.0 0.0 2.0
Na Bicarbonate 3.0 0.0
Carbonate 8.0 15.0 10.0
TAED 6.0 2.0 5.0
PB1 14 7.0 10.0
PEO 0.2
Bentonite 10.0 '
Savinase proteaseTM 1.0 1.0 1.0
(4.0 KNPU / ) '
Lipolase lipaseTM 0.4 0.4 0.4
(100.000 LUI ) _ .
W O 96100771 ~ ~ ~ 9 415 7 ', a! 2 =~ '' ~ y PCT/US95/07795
Termamyl amylaseTM 0.6 0.6 0.6
60KNU/
Carezyme cellulaseTM 0.6 0.6 0.6
(1000CEVU/ )
MC 0.6 -
HMEC - 0.6 0.6
Silicone antifoam 5.0 5.0 5.0
ranule
Dr mixed Sul hate 0.0 3.0 0.0
Balance (Moisture 100.0 100.0 100.0
and
Miscellaneous)
I II
A lomerate
45AS 11.0 14.0
Zeolite A 15.0 6.0
Carbonate 4.0 8.0
MA/AA 4.0 2.0
CMC 0.5 0.5
DETPMP 0.4 0.4
S ra On
AES 5.0 5.0
Perfume 0.5 0.5
D Adds
HEDP 0.5 0.3
SKS 6 13.0 10.0
Citrate 3.0 1.0
TAED 5.0 7.0
Percarbonate (14.0% 20.0 20.0
AvOz)
Terephtalate based soil0.3 0.3
release of mer
Savinase protease TM 1.4 1.4
4 KNPU/
Lipolase lipaseTM 0.4 0.4
100,000LU/
R'O 96!00771 219 415 7 ~' ~ ~ ~ ~~ ' pCT~S95I0779S
46
Carezyme cellulase TM 0.6 0.6
(1000CEVU/ )
Termamyl amylase TM 0.6 0.6
(60KNUI )
Silicone antifoam article5.0 5.0
Bri htener 0.4 0.2
MC 0.6 -
HMEC - 0.6
Balance/ miscellaneous 100 100
I
total
s
