Note: Descriptions are shown in the official language in which they were submitted.
214028'
PCT/US93/06224
~O 94/02581
DYE TRAN8F8R INHIBITING COI~IP08ITIONB
COI~tPRIBING HLBaCHING 71GENTB
Field of the Invention
The present invention relates to a composition and a process
for inhibiting dye transfer between fabrics during washing.
More in particular, this invention relates to dye transfer
inhibiting compositions comprising polyamine N-oxide containing
polymers and bleaching agents.
Backaround of the Invention
Bleaching agents have been commonly used in detergent
compositions to assist in stain removal, as well as for
whitening of fabrics.
In general, bleaches remove soil and colored stains from
fabrics by oxidation to make the soil or stain more soluble,
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WO 94/02581 ~ PCT/US93/06224 _
w
and thus more easily to remove it. Bleaches have also been used
to whiten light colored fabrics that have suffered from
yellowing over time and use.
The relative ability of the bleaching agent to meet various
performance criteria is among others depending on the presence
of adjunct detergent ingredients. As a consequence, the
detergent formulator is faced with a difficult task of
providing detergent compositions which have an excellent
overall performance.
One of the types of adjunct detergent ingredients that is
added to detergent compositions are dye transfer inhibiting
polymers.
Said polymers are added to detergent compositions in order to
inhibit the transfer of dyes from colored fabrics onto other
fabrics washed therewith. These polymers have the ability to
complex or adsorb the fugitive dyes washed out of dyed fabrics
before the dyes have the opportunity to become attached to
other articles in the wash.
Polymers have been used within detergent compositions to
inhibit dye transfer. Copending European Patent Application N°
92202168.8 describes polyamine N-oxide containing polymers
which are very efficient in eliminating transfer of solubilized
or suspended dyes.
It has now been found that polyamine N-oxide containing
polymers are very compatible with bleaching agents. In
addition, it has been found that the dye transfer inhibiting
performance of the polyamine N-oxide containing polymers has
been increased in the presence of bleaching agents.
This finding allows us to formulate detergent compositions
which have both excellent dye transfer inhibiting properties
and overall detergency performance.
According to another embodiment of this invention a process
is also provided for laundering operations involving colored
fabrics.
Summary of the Invention
The present invention relates to a dye transfer inhibiting
composition for use in aqueous wash solutions comprising a) a dye
transfer inhibiting amount of poly(4-vinylpyridine-N-oxide)
having a ratio of amine to amine N-oxide of from about 2:3 to
about 1:1,000,000; and b) a cleaning effective amount of a
bleaching agent selected from the group consisting of
percarboxylic acids, halogen bleaching agents, perborates,
persulfates, percarbonates, peroxydisulfates, perphosphates,
peroxyhydrates, bleach activators, hydrogen peroxide-generating
enzymes, non-oxygen-type bleaching agents, or mixtures thereof.
Detailed Description of the Invention
The compositions of the present invention comprise as an
essential element polyamine N-oxide containing polymers which
contain units having the following structural formula:
P
(I) A,
R
214 0 2 8 7 PCT/US93/06224 ,_.
WO 94/02581
wherein P is a polymerisable unit, whereto the R-N-O group can
be attached to or wherein the R-N-O group forms part of
the polymerisable unit or a combination of both.
O O O
n a i~
A is NC, CO, C, -O-,-S-, -N- : x is O or 1:
R are aliphatic, ethoxylated aliphatics, aromatic,
heterocyclic or alicyclic groups or any combination
thereof whereto the nitrogen of the N-O group can be
attached or wherein the nitrogen of the N-O group is
part of these groups.
The N-O group can be represented by the following general
structures .
O O
(Rl)x -N- (R2)y =N- (Rl)x
(R3 ) z
wherein Rl, R2, R3 are aliphatic groups, aromatic,
heterocyclic or alicyclic groups or combinations
thereof , x or/and y or/and z is 0 or 1 and wherein the
nitrogen of the N-O group can be attached or wherein
the nitrogen of the N-O group forms part of these
groups.
The N-O group can be part of the polymerisable unit (P) or
can be attached to the polymeric backbone or a combination of
both.
Suitable polyamine N-oxides wherein the N-O group forms part
of the polymerisable unit comprise polyamine N-oxides wherein
R is selected from aliphatic, aromatic, alicyclic or
heterocyclic groups.
One class of said polyamine N-oxides comprises the group of
polyamine N-oxides wherein the nitrogen of the N-O group forms
part of the R-group. Preferred polyamine N-oxides are those
~1402~
~~VO 94/02581 PCT/US93/06224
wherein R is a heterocyclic group such as pyridine, pyrrole,
imidazole, pyrrolidine, piperidine, quinoline, acridine and
derivatives thereof.
Another class of said polyamine N-oxides comprises the group
of polyamine N-oxides wherein the nitrogen of the N-O group is
attached to the R-group.
Other suitable polyamine N-oxides are the polyamine oxides
whereto the N-O group is attached to the polymerisable unit.
Preferred class of these polyamine N-oxides are the polyamine
N-oxides having the general formula (I) wherein R is an
aromatic, heterocyclic or alicyclic groups wherein the nitrogen
of the N-0 functional group is part of said R group.
Examples of these classes are polyamine oxides wherein R is a
heterocyclic compound such as pyridine, pyrrole, imidazole and
derivatives thereof.
Another preferred class of polyamine N-oxides are the polyamine
oxides having the general formula (I) wherein R are aromatic,
heterocyclic or alicyclic groups wherein the nitrogen of the N-
0 functional group is attached to said R groups.
Examples of these classes are polyamine oxides wherein R groups
can be aromatic such as phenyl.
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.
The amine N-oxide polymers of the present invention typically
have a ratio of amine to the amine N-oxide of 10:1 to
1:1000000. However the amount of amine oxide groups present in
the polyamine N-oxide containing polymer can be varied by
appropriate copolymerization or by appropriate degree of N-
oxidation. Preferably, the ratio of amine to amine N-oxide is
from 2:3 to 1:1000000. More preferably from 1:4 to 1:1000000,
most preferably from 1:7 to 1:1000000. The polymers of the
present invention actually encompass random or block copolymers
WO 94/02581 214 0 2 8 7 PCT/US93/06224
where one monomer type is an amine N-oxide and the other
monomer type is either an amine N-oxide or not. The amine oxide
unit of the polyamine N-oxides has a PKa < 10, preferably PKa <
7, more preferred PKa < 6.
The polyamine N-oxide containing polymer can be obtained in
almost any degree of polymerisation. The degree of
polymerisation is not critical provided the material has the
desired water-solubility and dye-suspending power.
Typically, the average molecular weight of the polyamine N-
oxide containing polymer is within the range of 500 to
1000,000; preferably from 1,000 to 50,000, more preferably from
2,000 to 30,000, most preferably from 3,000 to 20,000.
The polyamine N-oxide containing polymers of the present
invention are typically present from 0.001% to 10%, more
preferably from 0.01% to 2%, most preferred from 0.05% to 1% by
weight of the dye transfer inhibiting composition.
The present compositions are conveniently used as additives to
conventional detergent compositions for use in laundry
operations. The present invention also encompasses dye transfer
inhibiting compositions which will contain detergent
ingredients and thus serve as detergent compositions.
Methods for making ool5ramine N-oxides .
The production of the polyamine-N-oxide containing polymers
may be accomplished by polymerizing the amine monomer and
oxidizing the resultant polymer with a suitable oxidizing
agent, or the amine oxide monomer may itself be polymerized to
obtain the polyamine N-oxide.
The synthesis of polyamine N-oxide containing polymers can be
exemplified by the synthesis of polyvinyl-pyridine N-oxide.
Poly-4-vinylpyridine ex Polysciences (mw. 50 000, 5.0 g.,
0.0475 mole) was predisolved in 50 ml acetic acid and treated
with a peracetic acid solution (25 g of glacial acetic acid,
6.4 g of a 30% vol. solution of H202, and a few drops of H2S04
give 0.0523 mols of peracetic acid) via a pipette. The mixture
was stirred over 30 minutes at ambient temperature (32 C). The
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.~r0 94/02581 ~ PCT/US93/06224
mixture was then heated to 80-85 C using an oil bath for 3
hours before allowing to stand overnight. The polymer solution
then obtained is mixed with 11 of acetone under agitation. The
resulting yellow brown viscous syrup formed on the bottom is
washed again with 11 of acetone to yield a pale crystalline
solid.
The solid was filtered off by gravity, washed with acetone and
then dried over P205.
The amine . amine N-oxide ratio of this polymer is 1:4
(determined by NI~t) .
Bleaching agent
The detergent compositions hereof contain oxygen bleaching
agent components. These bleaching agent components can include
one or more oxygen bleaching agents and, depending upon the
bleaching agent chosen, one or more bleach activators. When
present bleaching compounds will typically be present at levels
of from about 1% to about 10%, of the detergent composition. In
general, bleaching compounds are optional components in non-
liquid formulations, e.g. granular detergents. If present, the
amount of bleach activators will typically be from about 0.1%
to about 60%, more typically from about 0.5% to about 40% of
the bleaching composition.
The bleaching agent component for use herein can be any of
the bleaching agents useful for detergent compositions
including oxygen bleaches as well as others known in the art.
In a method aspect, this invention further provides a
method for cleaning fabrics, fibers, textiles, at temperatures
below about 50'C, especially below about 40'C, with a detergent
composition containing polyamine N-oxide containing polymers,
optional auxiliary detersive surfactants, optional detersive
adjunct ingredients, and a bleaching agent.
The bleaching agent suitable for the present invention can be
an activated or non-activated bleaching agent.
One category of oxygen bleaching agent that can be used
encompasses percarboxylic acid bleaching agents and salts
thereof. Suitable examples of this class of agents include
CA 02140287 1999-06-17
8
magnesium monoperoxyphthalate hexahydrate, the magnesium salt of
meta-chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid
and diperoxydodecanedioic acid. Such bleaching agents are
disclosed in U.S. Patent 4,483,781, U.S. Patent 4,634,551,
European Patent Application 0,133,354 and U.S. Patent 4,412,934.
Highly preferred bleaching agents also include 6-nonylamino-6-
oxoperoxycaproic acid as described in U.S. Patent 4,634,551.
Another category of bleaching agents that can be used
encompasses the halogen bleaching agents. Examples of hypohalite
bleaching agents, for example, include trichloro isocyanuric acid
and the sodium and potassium dichloroisocyanurates and N-chloro
and N-bromo alkane sulphonamides. Such materials are normally
added at 0.5-10% by weight of the finished product, preferably
1-5% by weight.
Preferably, the bleaches suitable for the present invention
include peroxygen bleaches. Examples of suitable water-soluble
solid peroxygen b7.eaches include hydrogen peroxide releasing
agents such as hydrogen peroxide, perborates, e.g. perborate
monohydrate, perborate tetrahydrate, persulfates, percarbonates,
peroxydisulfates, perphosphates and peroxyhydrates. Preferred
bleaches are percarbonates and perborates.
The hydrogen peroxide releasing agents can be used in
combination w_Lth bleach activators such as
tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate
(NOBS, described in US 4,412,934), 3,5,-
trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP
120,591) or pentaacetylglucose (PAG), which are perhydrolyzed to
form a peracid as the active bleaching species, leading to
improved bleaching effect. Also suitable activators are acylated
citrate esters (ATC) such as disclosed in Copending Canadian
Patent Application No. 2,124,787.
The hydrogen peroxide may also be present by adding an
enzymatic system (i.e. an enzyme and a substrate therefore)
' CA 02140287 1999-06-17
9
which is capable of generating hydrogen peroxide at the beginning
or during the washing and/or rinsing process. Such enzymatic
systems are disclo:~ed in EP 537,381 published April 4, 1993.
Other peroxygen bleaches suitable for the present invention
include organic peroxyacids such as percarboxylic acids.
Bleaching agents other than oxygen bleaching agents are also
known in the art and can be utilized herein. One type of non-
oxygen bleaching agent of particular interest includes
photoactivated bleaching agents such as the sulfonated zinc
and/or aluminum phthalocyanines. These materials can be
deposited upon the substrate during the washing process. Upon
irradiation with light, in the presence of oxygen, such as by
hanging clothes out: to dry in the daylight, the sulfonated zinc
phthalocyanine is activated and, consequently, the substrate is
bleached. Preferred zinc phthalocyanine and a photoactivated
bleaching process are described in U.S. Patent 4,033,718.
Typically, detergent compositions will contain about 0.025% to
about 1.25%, by weight, of sulfonated zinc phthalocyanine.
DETERGENT ADJUNCTS
A wide range of surfactants can be used in the detergent
compositions. A typical listing of anionic, nonionic, ampholytic
and zwitterionic c:Lasses, and species of these surfactants, is
given in U.S. Patent 3,664,961 issued to Norris on May 23, 1972.
Mixtures of anionic surfactants are particularly suitable
herein, especially mixtures of sulphonate and sulphate
surfactants in a weight ratio of from 5:1 to 1:2, preferably from
3:1 to 2:3, more preferably from 3:1 to 1:1. Preferred
sulphonates include alkyl benzene sulphonates having from 9 to
15, especially 11 too 13 carbon atoms in the alkyl radical, and
alpha-sulphonated methyl fatty acid esters in which the fatty
214 0 2 8 7 pCT/US93/06224 .~
J~O 94/02581
lfl
acid is derived from a C12-Clg fatty source preferably from a
C16-Clg fatty source. In each instance the cation is an alkali
metal, preferably sodium. Preferred sulphate surfactants are
alkyl sulphates having from 12 to 18 carbon atoms in the alkyl
radical, optionally in admixture with ethoxy sulphates having
from 10 to 20, preferably 10 to 16 carbon atoms in the alkyl
radical and an average degree of ethoxylation of 1 to 6.
Examples of preferred alkyl sulphates herein are tallow alkyl
sulphate, coconut alkyl sulphate, and C14-15 alkyl sulphates.
The cation in each instance is again an alkali metal cation,
preferably sodium.
One class of nonionic surfactants useful in the present
invention are condensates of ethylene oxide with a hydrophobic
moiety to provide a surfactant having an average hydrophilic-
lipophilic balance (HLB) in the range from 8 to 17, preferably
from 9.5 to 13.5, more preferably from 10 to 12.5. The
hydrophobic (lipophilic) moiety may be aliphatic or aromatic in
nature and the length of the polyoxyethylene group which is
condensed with any particular hydrophobic group can be readily
adjusted to yield a water-soluble compound having the desired
degree of balance between hydrophilic and hydrophobic elements.
Especially preferred nonionic surfactants of this type are
the Cg-C15 primary alcohol ethoxylates containing 3-8 moles of
ethylene oxide per mole of alcohol, particularly the C14-C15
primary alcohols containing 6-8 moles of ethylene oxide per
mole of alcohol and the C12-C14 primary alcohols containing 3-5
moles of ethylene oxide per mole of alcohol.
Another class of nonionic surfactants comprises alkyl
polyglucoside compounds of general formula
RO (CnH2n0)tZx
wherein Z is a moiety derived from glucose; R is a saturated
hydrophobic alkyl group that contains from 12 to 18 carbon
atoms; t is from 0 to 10 and n is 2 or 3 ; x is from 1. 3 to 4 ,
the compounds including less than 10% unreacted fatty alcohol
21428'7
~.y0 94/02581 PCT/US93/06224
~1
and less than 50% short chain alkyl polyglucosides. Compounds
of this type and their use in detergent are disclosed in EP-B 0
070 077, 0 075 996 and 0 094 118.
Also suitable as nonionic surfactants are poly hydroxy fatty
acid amide surfactants of the formula
R2 - C - N - Z,
O R1
wherein R1 is H, or R1 is C1-4 hydrocarbyl, 2-hydroxy ethyl, 2-
hydroxy propyl or a mixture thereof, R2 is C5_31 hydrocarbyl,
and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl
chain with at least 3 hydroxyls directly connected to the
chain, or an alkoxylated derivative thereof. Preferably, R1 is
methyl, R2 is a straight C11-15 alkyl or alkenyl chain such as
coconut alkyl or mixtures thereof, and Z is derived from a
reducing sugar such as glucose, fructose, maltose, lactose, in
a reductive amination reaction.
The compositions according to the present invention may further
comprise a builder system. Any conventional builder system is
suitable for use herein including aluminosilicate materials,
silicates, polycarboxylates and fatty acids, materials such as
ethylenediamine tetraacetate, metal ion sequestrants such as
aminopolyphosphonates, particularly ethylenediamine
tetramethylene phosphonic acid and diethylene triamine
pentamethylenephosphonic acid. Though less preferred for
obvious environmental reasons, phosphate builders can also be
used herein.
Suitable builders can be an inorganic ion exchange
material, commonly an inorganic hydrated aluminosilicate
material, more particularly a hydrated synthetic zeolite such
as hydrated zeolite A, X, B or HS.
Another suitable inorganic builder material is layered
silicate, e.g. SKS-6 (Hoechst). SKS-6 is a crystalline layered
silicate consisting of sodium silicate (Na2Si205).
CA 02140287 1999-06-17
12
Suitable polycarboxylates containing one carboxy group
include lactic acid, glycolic acid and ether derivatives thereof
as disclosed in Belgian Patent Nos . 831, 368, 821, 369 and 821, 370 .
Polycarboxylates containing two carboxy groups include the water-
soluble salts of :~uccinic acid, malonic acid, (ethylenedioxy)
diacetic acid, ma:Leic acid, diglycolic acid, tartaric acid,
tartronic acid a:nd fumaric acid, as well as the ether
carboxylates described in German Offenlegenschrift 2,446,686, and
2, 446, 687 and U. S. :Patent 3, 935, 257 and the sulfinyl carboxylates
described in Belgian Patent No. 840,623. Polycarboxylates
containing three c;arboxy groups include, in particular, water-
soluble citrates, aconitrates and citraconates as well as
succinate derivatives such as the carboxymethyloxysuccinates
described in Britp_sh Patent No. 1,379,241, lactoxysuccinates
described in Canadian Patent No. 973,771, and the
oxypolycarboxylate materials such as 2-oxa-1,1,3-propane
tricarboxylates described in British Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups include
oxydisuccinates disclosed in British Patent No. 1,261,829,
1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane
tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
Polycarboxylates containing sulfo substituents include the
sulfosuccinate derivatives disclosed in British Patent Nos.
1,398,421 and 1,398,422 and in U.S. Patent 3,936,448, and the
sulfonated pyrolysed citrates described in British Patent No.
1,082,179, while polycarboxylates containing phosphone
substituents are d~.sclosed in British Patent No. 1,439,000.
Alicyclic anal heterocyclic polycarboxylates include
cyclopentane-cis, c:is, cis-tetracarboxylates, cyclopentadienide
pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-
tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates,
2,2,5,5-tetrahydrofuran-tetracarboxylates, 1,2,3,4,5,6-hexane-
hexacarboxylates and carboxymethyl derivatives of polyhydric
alcohols such as sorbitol, mannitol and xylitol. Aromatic
polycarboxylates include mellitic acid, pyromellitic
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..BYO 94/02581 PCT/US93/06224
13
acid and the phtalic acid derivatives disclosed in British
Patent No. 1,425,343.
Of the above, the preferred polycarboxylates are
hydroxycarboxylates containing up to three carboxy groups per
molecule, more particularly citrates.
Preferred builder systems for use in the present compositions
include a mixture of a water-insoluble aluminosilicate builder
such as zeolite A or of a layered silicate (sks/6), and a
water-soluble carboxylate chelating agent such as citric acid.
A suitable chelant for inclusion in the detergent
compositions in accordance with the invention is
ethylenediamine-N, N'-disuccinic acid (EDDS) or the alkali
metal, alkaline earth metal, ammonium, or substituted ammonium
salts thereof, or mixtures thereof. Preferred EDDS compounds
are the free acid form and the sodium or magnesium salt
thereof. Examples of such preferred sodium salts of EDDS
include Na2EDDS and Na4EDDS. Examples of such preferred
magnesium salts of EDDS include MgEDDS and Mg2EDDS. The
magnesium salts are the most preferred for inclusion in
compositions in accordance with the invention.
Especially for the liquid execution herein, suitable fatty acid
builders for use herein are saturated or unsaturated C10-18
fatty acids, as well as the corresponding soaps. Preferred
saturated species have from 12 to 16 carbon atoms in the alkyl
chain. The preferred unsaturated fatty acid is oleic acid.
Preferred builder systems for use in granular compositions
include a mixture of a water-insoluble aluminosilicate builder
such as zeolite A, and a watersoluble carboxylate chelating
agent such as citric acid.
Other builder materials that can form part of the builder
system for use in granular compositions include inorganic
materials such as alkali metal carbonates, bicarbonates,
silicates, and organic materials such as the organic
phosphonates, amiono polyalkylene phosphonates and amino
polycarboxylates.
PCT/US93/06224 _
WO 94/02581
Other suitable water-soluble organic salts are the homo- or co-
polymeric acids or their salts, in which the polycarboxylic
acid comprises at least two carboxyl radicals separated from
each other by not more than two carbon atoms.
Polymers of this type are disclosed in GB-A-1,596,756.
Examples of such salts are polyacrylates of MW 2000-5000 and
their copolymers with malefic anhydride, such copolymers having
a molecular weight of from 20,000 to 70,000, especially about
40,000.
Detergency builder salts are normally included in amounts of
from 10% to 80% by weight of the composition preferably from
20% to 70% and most usually from 30% to 60% by weight.
Other detergent ingredients that can be included are
detersive enzymes which can be included in the detergent
formulations for a wide variety of purposes including removal
of protein-based, carbohydrate-based, or triglyceride-based
stains, for example, and prevention of refugee dye transfer.
The enzymes to be incorporated include proteases, amylases,
lipases, cellulases, and peroxidases, as well as mixtures
thereof. Other types of enzymes may also be included. They may
be of any suitable origin, such as vegetable, animal,
bacterial, fungal and yeast origin.
Enzymes are normally incorporated at levels sufficient to
provide up to about 5 mg by weight, more typically about 0.05
mg to about 3 mg, of active enzyme per gram of the composition.
Suitable examples of proteases are the subtilisins which are
obtained from particular strains of B.subtilis and
H.licheniforms. Proteolytic enzymes suitable for removing
protein-based stains that are commercially available include
those sold under the tradenames Alcalase , Savinase and
Esperase by Novo Industries A/S (Denmark) and Maxatase by
International Bio-Synthetics, Inc. (The Netherlands) and FN-
base by Genencor, Optimase and opticlean by MKC.
Of interest in the category of proteolytic enzymes,
especially for liquid detergent compositions, are enzymes
referred to herein as Protease A and Protease B. Protease A is
described in European Patent Application 130,756. Protease B is
' CA 02140287 1999-06-17
described in EP 25:1,446 published January 7, 1988.
Amylases include, for example, -amylases obtained from a
special strain of B.licheniforms, described in more detail in
British Patent Specification No. 1,296,839 (Novo). Amylolytic
proteins include, for example, Rapidase, Maxamyl (International
Bio-Synthetics, Inc.) and Termamyl, (Novo Industries).
The cellulase,a usable in the present invention include both
bacterial or fungal cellulase. Preferably, they will have a pH
optimum of between 5 and 9.5. Suitable cellulases are disclosed
in U.S. Patent 4,435,307, Barbesgoard et al, which discloses
fungal cellulase produced from Humicola insolens. Suitable
cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275
and DE-OS-2.247.832.
Examples of such cellulases are cellulases produced by a
strain of Humicola insolens (Humicola grisea var. thermoidea),
particularly the Humicola strain DSM 1800, and cellulases
produced by a fungus of Bacillus N or a cellulase 212-producing
fungus belonging to the genus Aeromonas, and cellulase extracted
from the hepatopan<:reas of a marine mollusc (Dolabella Auricula
Solander) .
Other suitable cellulases are cellulases originated from
Humicola Insulens having a molecular weight of about 50KDa, an
isoelectric point of 5.5 and containing 415 amino acids.
Especially suitable cellulase are the cellulase having color
care benefits. Examples of such cellulases are cellulase
described in United States Patent No. 5,520,838 issued May 28,
1996 Carezyme (Nova).
Suitable lipase enzymes for detergent usage include those
produced by microorganisms of the Pseudomonas group, such as
Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent
1,372,034. Suitable lipases include those which show a positive
immunological cross-reaction with the antibody of the lipase,
produced by the microorganism Pseudomonas fluorescent IAM 1057.
This lipase is available from Amano Pharmaceutical
' CA 02140287 1999-06-17
16
Co. Ltd., Nagoya, .Japan, under the trade name Lipase P "Amano,"
hereinafter referred to as "Amano-P".
Especially suitable Lipase are lipase such as M1 Lipase
(Ibis) and Lipolase (Novo).
Peroxidase enzymes are used in combination with oxygen
sources, e.g. percarbonate, perborate, persulfate, hydrogen
peroxide, etc. They are used for "solution bleaching", i.e. to
prevent transfer c>f dyes of pigments removed from substrates
during wash operations to other substrates in the wash solution.
Peroxidase enzymes are known in the art, and include, for
example, horseradish peroxidase, ligninase, and haloperoxidase
such as chloro- and bromo-peroxidase. Peroxidase-containing
detergent compositions are disclosed, for example, in PCT
International Application WO 89/099813 and in Canadian Patent
Application No. 2,122,987, filed on October 28, 1992.
In liquid formulations, an enzyme stabilization system is
preferably utilized. Enzyme stabilization techniques for aqueous
detergent composit_Lons are well known in the art. For example,
one technique for enzyme stabilization in aqueous solutions
involves the use of free calcium ions from sources such as
calcium acetate, calcium formate and calcium propionate. Calcium
ions can be used in combination with short chain carboxylic acid
salts, preferably formates. See, for example, U.S. Patent
4,318,818. It ha.s also been proposed to use polyols like
glycerol and sorb_itol. Alkoxy-alcohols, dialkylglycoethers,
mixtures of polyvalent alcohols with polyfunctional aliphatic
amines (e.g., such as diethanolamine, triethanolamine, di-
isopropanolamine, eac.), and boric acid or alkali metal borate.
Enzyme stabilization techniques are additionally disclosed and
exemplified in U.S. Patent 4,261,868, U.S. Patent 3,600,319, and
European Patent Application Publication No. 0 199 405. Non-boric
acid and borate stabilizers are preferred. Enzyme stabilization
systems are also described, for example, in U.S. Patents
4,261,868, 3,600,37_9 and 3,519,570.
CA 02140287 1999-06-17
17
Other suitable detergent ingredients that can be added are enzyme
oxidation scavengers which are described in EP 553,607 published
August 4, 1993. Examples of such enzyme oxidation scavengers are
ethoxylated tetraethylene polyamines.
Especially preferred detergent ingredients are combinations
with technologies which also provide a type of color care
benefit. Examples of these technologies are polyvinylpyrrolidone
polymers and other polymers which have dye transfer inhibiting
properties. Other. examples are cellulase and/or peroxidases
and/or metallo catalysts for color maintenance rejuvenation.
Such metallo catalysts are described in EP 596,184 published
November 6, 1992.
In addition, it has been found that the polyamine-N-oxide
containing polymers eliminate or reduce the deposition of the
metallo catalyst onto the fabrics resulting in improved whiteness
benef it .
Another optional ingredient is a suds suppressor,
exemplified by ;silicones, and silica-silicone mixtures.
Silicones can be generally represented by alkylated polysiloxane
materials while silica is normally used in finely divided forms
exemplified by silica aerogels and xerogels and hydrophobic
silicas of various types. These materials can be incorporated
as particulates in which the suds suppressor is advantageously
releasably incorporated in a water-soluble or water-dispersible,
substantially non-:surface-active detergent impermeable carrier.
Alternatively the suds suppressor can be dissolved or dispersed
in a liquid carrier and applied by spraying on to one or more of
the other components .
A preferred silicone suds controlling agent is disclosed in
Bartollota et al. U.S. Patent 3,933,672. Other particularly
useful suds suppressors are the self-emulsifying silicone suds
suppressors, descr_Lbed in German Patent Application DTOS 2 646
126 published April_ 28, 1977. An example of such a compound is
DC-544, commercially available from Dow Corning, which is a
siloxane-glycol copolymer. Especially preferred suds controlling
agent are the suds suppressor system comprising a
CA 02140287 1999-06-17
18
mixture of silicone oils and 2-alkyl-alcanols. Suitable 2-alkyl-
alcanols are 2-butyl-octanol which are commercially available
under the trade name Isofol 12 R.
Such suds suppressor system are described in Canadian Patent
Application No. 2,:L46,636 filed October 15, 1993.
Especially preferred silicone suds controlling agents are
described in EP 573,699 published June 6, 1992. Said
compositions can comprise a silicone/silica mixture in
combination with fumed nonporous silica such as AerosilR.
The suds supp~°essors described above are normally employed
at levels of from 0.001% to 2% by weight of the composition,
preferably from 0.01% to 1% by weight.
Other components used in detergent compositions may be
employed, such as soil-suspending agents soil-release agents,
optical brighteners, abrasives, bactericides, tarnish inhibitors,
coloring agents, and/or encapsulated or more encapsulated
perfumes .
Antiredeposition and soil suspension agents suitable herein
include cellulose derivatives such as methylcellulose,
carboxymethylcellulose and hydroxyethylcellulose, and homo- or
co-polymeric polycarboxylic acids or their salts. Polymers of
this type include the polyacrylates and malefic anhydride-acrylic
acid copolymers previously mentioned as builders, as well as
copolymers of malefic anhydride with ethylene, methylvinyl ether
or methacrylic acid, the malefic anhydride constituting at least
20 mole percent of the copolymer. These materials are normally
used at levels of from 0.5% to 10% by weight, more preferably
from 0.75% to 8%, most preferably from 1% to 6% by weight of the
composition.
Preferred optical brighteners are anionic in character,
examples of which are disodium 4,41-bis-(2-diethanolamino-4-
anilino-s-triazin-E>-ylamino)stilbene-2:21disulphonate, disodium
4,-41-bis-(2-morpholino-4-anilino-s-triazin-6-ylaminostilbene-
2:21-disulphonate,disodium 4,41-bis-(2,4-dianilino-s-triazin-6-
ylamino)stilbene-2:21-disulphonate,
~~~4~2~
..BYO 94/02581 ~ 9 PCT/US93/06224
monosodium 41,411 -bis-(2,4-dianilino-s-triazin-6
ylamino)stilbene-2-sulphonate, disodium 4,41 -bis-(2-anilino-4-
(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-
2,21 - disulphonate, disodium 4,41 -bis-(4-phenyl-2,1,3-
triazol-2-yl)-stilbene-2,21 disulphonate, disodium 4,41bis(2-
anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazin-6-
ylamino)stilbene-2,21disulphonate and sodium 2(stilbyl-411-
(naphtho-11,21:4,5)-1,2,3 - triazole-211-sulphonate.
Other useful polymeric materials are the polyethylene
glycols, particularly those of molecular weight 1000-10000,
more particularly 2000 to 8000 and most preferably about 4000.
These are used at levels of from 0.20% to 5% more preferably
from 0.25% to 2.5% by weight. These polymers and the previously
mentioned homo- or co-polymeric polycarboxylate salts are
valuable for improving whiteness maintenance, fabric ash
deposition, and cleaning performance on clay, proteinaceous and
oxidizable soils in the presence of transition metal
impurities.
Soil release agents useful in compositions of the present
invention are conventionally copolymers or terpolymers of
terephthalic acid with ethylene glycol and/or propylene glycol
units in various arrangements. Examples of such polymers are
disclosed in the commonly assigned US Patent Nos. 4116885 and
4711730 and European Published Patent Application No. 0 272
033. A particular preferred polymer in accordance with EP-A-0
272 033 has the formula
(CH3(PEG)43)0.75(POH)0.25~T-PO)2.8(T-PEG)0.4~T(PO
H)0.25((PEG)43CH3)0.75
where PEG is -(OC2H4)O-,PO is (OC3H60) and T is (pcOC6H4C0).
Also very useful are modified polyesters as random copolymers
of dimethyl terephtalate, dimethyl sulfoisophtalate, ethylene
glycol and 1-2 propane diol, the end groups consisting
primarily of sulphobenzoate and secondarily of mono esters of
ethylene glycol and/or propane-diol. The target is to obtain a
polymer capped at both end by sulphobenzoate groups,
pCT/US93/06224
WO 94/02581
"primarily", in the present context most of said copolymers
herein will be end-capped by sulphobenzoate groups. However,
some copolymers will be less than fully capped, and therefore
their end groups may consist of monoester of ethylene glycol
and/or propane 1-2 diol, thereof consist "secondarily" of such
species.
The selected polyesters herein contain about 46% by weight of
dimethyl terephtalic acid, about 16% by weight of propane -1.2
diol, about 10% by weight ethylene glycol about 13% by weight
of dimethyl sulfobenzoid acid and about 15% by weight of
sulfoisophtalic acid, and have a molecular weight of about
3.000. The polyesters and their method of preparation are
described in detail in EPA 311 342.
The detergent compositions according to the invention can be
in liquid, paste, gels or granular forms. Granular compositions
according to the present invention can also be in "compact
form", i.e. they may have a relatively higher density than
conventional granular detergents, i.e. from 550 to 950 g/1; in
such case, the granular detergent compositions according to the
present invention will contain a lower amount of "inorganic
filler salt", compared to conventional granular detergents;
typical filler salts are alkaline earth metal salts of
sulphates and chlorides, typically sodium sulphate; "compact"
detergents typically comprise not more than l0% filler salt.
The liquid compositions according to the present invention can
also be in "concentrated form", in such case, the liquid
detergent compositions according to the present invention will
contain a lower amount of water, compared to conventional liquid
detergents. Typically, the water content of the concentrated
liquid detergent is less than 30%, more preferably less than
20%, most preferably less than 10% by weight of the detergent
compositions. Other examples of liquid compositions are
anhydrous compositions containing substantially no water.
Both aqueous and non-aqueous liquid compositions can be
structured or non-structured.
CA 02140287 1999-06-17
21
The present invention also relates to a process for
inhibiting dye transfer from one fabric to another of solubilized
and suspended dyes encountered during fabric laundering
operations involving colored fabrics.
The process comprises contacting fabrics with a laundering
solution as hereinbefore described.
The process of: the invention is conveniently carried out in
the course of the washing process. The washing process is
preferably carried out at 5°C to 75°C, especially 20 to 60, but
the polymers are effective at up to 95°C and higher temperatures.
The pH of the treatment solution is preferably from 7 to 11,
especially from 7.5 to 10.5.
The process a:nd compositions of the invention can also be
used as detergent additive products.
Such additive products are intended to supplement or boost
the performance of conventional detergent compositions.
The detergent compositions according to the present
invention include compositions which are to be used for cleaning
substrates, such a;s fabrics, fibers, hard surfaces, skin etc.,
for example hard surface cleaning compositions (with or without
abrasives), laundry detergent compositions, automatic and non
automatic dishwash_Lng compositions.
The following examples are meant to exemplify compositions
of the present invention, but are not necessarily meant to limit
or otherwise define the scope of the invention, said scope being
determined according to claims which follow.
A granular detergent composition according to the present
invention is prepared, having the following compositions:
% by weight of the total detergent composition
Linear alkyl benzene sulphonate 11.40
Tallow alkyl sulphate 1.80
C45 alkyl sulphate 3.00
C45 alcohol 7 times ethoxylated 4.00
CA 02140287 1999-06-17
22
Tallow alcohol 11 'times ethoxylated 1.80
Dispersant 0.07
Silicone fluid 0.80
Trisodium citrate 14.00
Citric acid 3.00
Zeolite 32.50
Malefic acid acrylic acid copolymer 5.00
Cellulase (active protein) 0.03
Lipase 0.36
Sodium silicate 2.00
Sodium sulphate 3.50
Table I
EXAMPLE I:
The extent of dye transfer from different colored fabrics
was studied using a launder-o-meter test that simulates a 30 min
wash cycle. The launder-o-meter beaker contains 200 ml of a
detergent solution,, a lOcmxlOcm piece of the colored fabric and
a multifiber swatch which is used as a pick-up tracer for the
bleeding dye. The multifiber swatch consists of 6 pieces
(l.5cmx5cm each) of different material (polyacetate, cotton,
polyamide, polyestEsr, wool and orlon) which are sewn together.
The extent of dye transfer is assessed by a Hunter Colour
measurement. The :Hunter Colour system evaluates the colour of
a fabric sample in. terms of the OE value which represents the
change in the Hunger L, a, b, values which are determined by
reflecting spectrophotometer. The DE value is defined by the
following equation:
~E = { (af-ai) 2 f (bp-by) 2 + (Lf-Li) 2}#
where the subscripts i and f refer to the Hunter value before and
after washing in the presence of the bleeding fabric,
respectively. The' least significant difference is 1 at 95%
confidence level.
' CA 02140287 1999-06-17
23
Example I demonstrates the increased dye transfer inhibiting
performance of the polyamine N-oxide containing polymers in
combination with bleaching agents. The bleaching agent that is
used is an activated bleaching agent (Perborate (PB)/TAED).
The performance of said combination was determined by
measuring the whiteness of textile items washed with compositions
containing the PB/TAED and/or poly(4-vinylpyridine-N-oxide)
( PVNO ) .
$xperimental conditions:
pH = 10
Wash Temperature . 40°C
A : A detergent composition according to Table I which contains
no PB/TAED and no PVNO (poly(4-vinylpyridine-N-oxide)).
B . A detergent composition according to Table I which contains
16% PB and 5% TAED and no PVNO (poly(4-vinylpyridine-N-oxide)).
C . A detergent composition according to Table I containing 10
ppm of PVNO (poly(4-vinylpyridine-N-oxide)) which has an average
molecular weight of about 30,000 and an amine to amine N-oxide
ratio of 1:10 (measured by NMR) .
D . A detergent composition according to Table I containing 10
ppm of PVNO (poly(4-vinylpyridine-N-oxide)) which has an average
molecular weight o:E about 30,000 and an amine to amine N-oxide
ratio of 1:10 (mea;3ured by NMR) and 16% PB, 5% TAED.
Results: DE values for the cotton pick-up tracer.
Bleeding fabric Bleeding fabric A B C D
composition color
100% cotton Direct Blue 90 23.1 21.6 6.9 4.5
' CA 02140287 1999-06-17
24
EXAMPLE II (A/B/C)
A liquid detergent composition according to the present
invention is prepared, having the following compositions:
~ by weight of the total detergent composition
A B C
Linear alkylbenzene sulfonate 10 - -
Polyhydroxy fatty acid amide - 9 -
Alkyl alkoxylated sulfate - - 9
Alkyl sulphate 4 4 4
Fatty alcohol (C12-Cls) ethoxylate 12 12 12
Fatty acid 10 10 10
Oleic acid 4 4 4
Citric acid 1 1 1
Diethylenetriaminepentamethylene 1.5 1.5 1.5
Phosphonic acid
NaOH 3.4 3.4 3.4
Propanediol 1.5 1.5 1.5
Ethanol 10 10 10
Ethoxylated tetraethylene pentamine 0.7 0.7 0.7
Poly(4-vinylpyridine)-N-oxide 0-1 0-1 0-1
Thermamyl 0.13 0.13 0.13
Carezyme 0.014 0.014 0.014
FN-Base 1.8 1.8 1.8
Lipolase 0.14 0.14 0.14
Endoglucanase A 0.53 0.53 0.53
Suds suppressor ( ISOFOLr) 2 . 5 2 . 2 .
5 5
HZOZ 7.5 7.5 7.5
ATC 5 5 5
Minors up to 100
EXAMPLE III (A/B/C)
A compact granular detergent composition according to the
present invention is prepared, having the following formulation:
' CA 02140287 1999-06-17
by weight of the total detergent composition
A B C
Linear alkyl benzene sulphonate 11.40 - -
Polyhydroxy fatty acid amide - 10 -
Alkyl alkoxylated :sulfate - - 9
Tallow alkyl sulphate 1.80 1.80 1.80
C45 alkyl sulphate 3.00 3.00 3.00
C45 alcohol 7 times ethoxylated 4.00 4.00 4.00
Tallow alcohol 11 times ethoxylated 1.80 1.80 1.80
Dispersant 0.07 0.07 0.07
Silicone fluid 0.80 0.80 0.80
Trisodium citrate 14.00 14.00 14.00
Citric acid 3.00 3.00 3.00
Zeolite 32.50 32.50 32.50
Malefic acid acrylic. acid copolymer 5.00 5.00 5.00
Cellulase (active protein) 0.03 0.03 0.03
Alkalase/BAN 0.60 0.60 0.60
Lipase 0.36 0.36 0.36
Sodium silicate 2.00 2.00 2.00
Sodium sulphate 3.50 3.50 3.50
Poly(4-vinylpyridine)-N-oxide 0-1 0-1 0-1
Perborate 15 15 15
TAED 5 - 5
ATC - 5 -
Minors up to 100
The above compositions (Example II (A/B/C) and III (A/B/C))
were very good at displaying excellent cleaning and detergency
performance with outstanding color-care performance on colored
fabrics and mixed loads of colored and white fabrics.
