Note: Descriptions are shown in the official language in which they were submitted.
PCTIUS95/00626
WO 95/20032
DETERGENT COMPOSITIONS INHIBITING
DYE TRANSFER
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, the present invention relates to dye
transfer inhibiting compositions comprising a mixture of
polyamine N-oxide polymers having a low oxidation degree and
polyamine N-oxide polymers having a high oxidation degree.
Background of the=_ Invention
One of the most persistent and troublesome problems arising
during modern fabric laundering operations is the tendency of
some colored fabrics to release dye into the laundering
solutions. The dye is then transferred onto other fabrics
being washed therewith.
z 1796
WO 95/20032 PCT/US95100626
2
One way of overcoming this problem would be to complex or
adsorb the fugitive dyes washed out of dyed fabrics before
they have the opportunity to become attached to other articles
in the wash.
Polymers have been used within detergent compositions to
inhibit dye transfer. EP-A-O 102 923 describes the use of
carboxyl containing polymers within aqueous compositions. DE-
A-2 814 329 discloses the use of N-vinyl-oxazolidone polymers
and FR-A-2 144 721 discloses the use of 15-35~ of a copolymer
of polyvinylpyrrolidone and acrylic acid nitrile or malefic
anhydride within a washing powder.
EP-265 257 describes detergent compositions comprising an
alkali-metal carboxy-metal carboxymethylcellulose, a
vinylpyrrolidone polymer and a polycarboxylate polymer.
It has now been surprisingly found that a particular
combination of polyamine N-oxide polymers having a low
oxidation degree and polyamine N-oxide polymers having a high
oxidation degree are very efficient in eliminating transfer of
a broad range of solubilized or suspended dyes. This finding
allows to formulate compositions which exhibit excellent dye
transfer inhibiting properties over a broad selection of dyes.
According to another embodiment of this invention a process
is also provided for laundering operations involving colored
fabrics.
Summarv of the Invention
The present invention relates to inhibiting dye transfer
compositions comprising a mixture of polyamine N-oxide
polymers having a low oxidation degree and polyamine N-oxide
polymers having a high oxidation degree.
WO 95/20032 PCTIUS95100626
Detailed description of the invention
The compositions of the present invention comprise a mixture
of polyamine N-oxide polymers having a low oxidation degree
("LOPAO") and polyamine N-oxide polymers having a high
oxidation degree ("HOPAO").
By "polyamine N-oxide polymers having a low oxidation degree"
as used herein, is meant polyamine N-oxide polymers wherein
the ratio of amine to amine N-o~:ide is from 1000:1 to 1:1,
more preferably from 100:1 to 1:1., most preferably from 10:1
to 1:1.
By "polyamine N-oxide polymers having a high oxidation degree"
as used herein, is meant polyamine N-oxide polymers wherein
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 amount of amine oxide groups present in said polyamine
oxide polymer can be varied by appropriate copolymerization or
by appropriate degree of N-oxidation.
The polyamine N-oxide polymers contain units having the
following structure formula .
P
I
(I) Ax
I
R
wherein P is a polymerisable unit, whereto the N-0 group can
be attached to or wherein the N-O group forms part of
the polymerisable unit or a combination of both.
0 0 0
n a n I
A is NC, C0, C, -O-,-S-, -N- : x is 0 or 1:
WO 95/20032 ~ PCT/US95/00626
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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-0 group can be represented by the following general
structures .
O 0
I I
(R1 ) x -N- (R2 ) y =N- (R1 ) x
I
(R3) z
wherein R1, 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-0 group can be attached or wherein
the nitrogen of the N-0 group forms part of these
groups.
The N-0 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-0 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
wherein R is a heterocyclic group such as pyridine, pyrole,
imidazole, pyrolidine, 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-0 group is
attached to the R-group.
WO 95/20032 PCT/US95100626
Other suitable polyamine N-oxides are the polyamine oxides
whereto the N-0 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, pyrole, imidazole and
derivatives thereof.
Another preferred class of pclyamine 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 polymers of the present invention actually encompass
random or block copolymers where one monomer type is an amine
N-oxide and the other monomer types 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 oxides can be obtained in almost any degree of
polymerisation. The degree of po:Lymerisation is not critical
provided the material has the desired water-solubility and
dye-suspending power.
Typically, the average molecular weight is within the range of
500 to 1000,000; preferably from 1,000 to 50,000, more
preferably from 2,000 to 30,000, most preferably from 3,000 to
20, 000.
WO 95!20032 ~ ~ l 9 2 6 5 pCT/US95/00626
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The polyamine N-oxides of the present invention are
typically present from 0.001 to 100 , more preferably from
0.01 to 2%, most preferred from 0.05 to to 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 polyamine N-oxides .
The production of the polyamine-N-oxides 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 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 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 aceton 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.
WO 95/20032 PCT/US95/00626
7
DETERGENT ADJUNCTS
A wide range of surfactants can be used in the detergent
compositions. A typical listing of anionic, nonionic,
ampholytic and zwitterionic classes, and species of these
surfactants, is given in US 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 to 13 carbon atoms in the alkyl radical,
and alpha-sulphonated methyl fatty acid esters in which the
fatty acid is derived from a C12-C:18 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
~_nvention are condensates of ethylene oxide with a
hydrophobic moiety to provide a surfactant having an average
hydrophilic-lipophilic balance (HL:B) in the range from 8 to
17, preferably from 9.5 to 13.5, snore 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.
WO 95/20032 ~ ~ ~ ~ L ~ ~ PCT/US95/00626
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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
and less than 50o 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,
I
0 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.
21 7926 5
9
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 pentamethylenephosphon:ic acid. Though less preferred
' 1
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-6T"' (Hoechst). SKS-6 is a crystalline
layered silicate consisting of sodium silicate (Na2Si205).
Suitable polycarboxylates containing one carboxy group
include lactic acid, glycolic: acid and ether derivatives
thereof as disclosed in Beigia;n Patent Nos. 831,368, 821,369
and 821,370. Polycarboxylates containing two carboxy groups
include the water-soluble salts of succinic acid, malonic
acid, (ethylenedioxy) diacetic acid, malefic acid, diglycollic
acid, tartaric acid, tartronic acid and fumaric acid, as well
as the ether carboxylates described in German
Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent
No. 3,935,257 and the sulfinyl carboxylates described in
Belgian Patent No. 840,623. Polycarboxylates containing
three carboxy groups include, in particular, water-soluble
citrates, aconitrates and citraconates as well as succinate
derivatives such as the carboxymethyloxysuccinates described
in British Patent No. 1.379,241, lactoxysuccinates described
in 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.
217926 5
,o
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.
Polycarboxyla-tes containing su:lfo substituents include the
sulfosuccinate derivatives disclosed in British Patent Nos.
1, 398, 421 and 1, 398, 422 and in LJ. S . Patent No . 3, 936, 448, and
the sulfonated pyrolysed citrates described in British Patent
No. 1,082,179, while polycarboxylates containing phosphone
substituents are disclosed in British Patent No. 1,439,000.
Alicyclic and heterocycli<: polycarboxylates include
cyclopentane-cis,cis,cis-tetraca,rboxylates, cyclopentadienide
pentacarboxylates, 2,3,9,5-tetrahydrofuran - cis, cis, cis-
tetracarboxylates, 2,5-tetrahydrofuran -cis - dicarboxylates,
2,2,5,5-tetrahydrofuran - tet:racarboxylates, 1,2,3,4,5,6-
hexane -hexacarboxylates and and carboxymethyl derivatives of
polyhydric alcohols such as so:rbitol, mannitol and xylitol.
Aromatic polycarboxylates include mellitic acid, pyromellitic
acid and the phthalic 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'-disucciriic 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
~.~~4
WO 95/20032 PCT/US95100626
11
EDDS include Na2EDDS and Na4EDDS. Examples of such preferred
magnesium salts of ED17S include MgEDDS and Mg2EDDS. The
magnesium salts are the most prE:ferred 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 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 the purposes of the
invention include inorganic materials such as alkali metal
carbonates, bicarbonates, silicates, and organic materials
such as the organic phosphonates, amiono polyalkylene
phosphonates and amino polycarboxylates.
Other suitable water-soluble organic salts are the homo- or
co-polymeric acids or their salts, in which the
polycarboxylic acid comprises at least two carboxyl radicals
separated from each other by not more than two carbon atoms.
Polymers of this type' are disclosed in GB-A-1, 596, 756.
Examples of such salts are polyacrylates of MW 2000-5000 and
their copolymers with 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.
Detergent ingredients that can be included in the detergent
compositions of the present invention include bleaching
agents.
,.
-- 21 7926 5
These bleaching agent componenr_s can include one or more
oxygen bleaching agents and, depending upon the bleaching
agent chosen, one cr more bleach activators. When present
bleaching compounds will typically be present at levels of
from about l~s to aboLt 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 compone>nt 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 fabrica, 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
magnesium monoperoxyphthalate hexahydrate, the magnesium salt
of meta-chloro perberzoic acid. 4-nonylamino-4-
oxoperoxybutyric acid and dip~eroxydodecanedioic acid. Such
bleaching agents are disclosed in~U.S. Patent 4,483,781, U.S.
Patent No. 4,634,551, European Patent Application 0,133,354
and U. S . Patent 4, 412, 934 . High.ly 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
2179265
13
sulphonamides. Such materials are normally added at 0.5-lOX
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 bleaches include hydrogen
peroxide releasing agents ~~uch 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 with bleach activators such as
tetraacetylethylenediamine(TAED), nonanoyloxybenzenesulfonate
(NOBS, described in US 4,412,934) , 3,5,-
trimethylhexanoloxybenzenesulfo;nate (ISONOBS, described in EP
120,591) or pentaacetylglucose (PAG). which are perhydrolyze_d
to form a peracid as the active: bleaching species, leading to
improved bleaching effect. Fvlso ,suitable activators are
acylated citrate esters (ATC) such as disclosed in Canadian
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)
which is capable of generating hydrogen peroxide at the
beginning or during the washing and/or rinsing process. Such
enzymatic systems are disclosed in EP Patent Application
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 o:E particular interest includes
photoactivated bleaching agents such as the sulfonated zinc
and/or aluminum phthalocyanines. These materials can be
Bt
-. 217926 5
deposited upca the substrate duri~g 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$, b y weight, of sulfonated zinc
phthalocyanine.
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
B.licheniforms. Proteolytic enzymes suitable for removing
protein-based stains that are commercially available include
those sold under the trademarks Alcalase , Savinase and
Esperase by Novo Industries A./S (Denmark) and Maxatase by
International Hio-Synthetics, Lnc. (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 described in European Patent Application No. 251,446
published January 7, 1988. Amylases include, for example,
-amylases
Bt
2179265
1J
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~'"', Maxamylz'"' (International Bio-Synthetics, Inc. ) and
TermamylT'", (Novo Industries) .
The cellulases usable in the present invention include both
bacterial or fungal cellulase. 1?referably, 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 GH-A-2.075.028 ;
GB-A-2.095.275 and DE-OS-2.247.8:32.
Examples of such cellulases are cellulases produced by a
strain of Humicola insolens (Humicola grisea var.
thermoidea), particularly the Humicola strain DSM 1800, and
cellulases produced by a fungus of Bacillus N or a cellulase
212-producing fungus belonging to the genus Aeromonas, and
cellulase .extracted from the hepatopancreas of a marine
mollusc (Dolabella Auricula Sola:nder).
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.
Suitable lipase enzymes for detergent usage include those
produced by microorganisms of t:he Pseudomonas group, such as
Pseudomonas stutzeri ATCC 19.1.54, as disclosed in British
Patent 1,372,034. Suitable lipases include those which show a
positive immunoligical cross-reaction with the antibody of
the lipase, produced by the microorganism Pseudomonas
fluorescent IAM 1057. This lipase is available from Amano
Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade mark
Lipase P "Amano." hereinafter referred to as "Amano-P".
~B1
217926 5
1 0
Especially suitable Lipase are lipase such as M1 LipaseTh'
(Ibis) and LipolaseT''' (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 of dyes. of pigments removed from
substrates during wash operations to other substrates in the
wash solution. Peroxidase enzymes are known in the art, and
include, for example, horseradish peroxidase, ligninase, and
haloperoxidase such as chl.oro- 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.
In liquid formulations, an enzyme stabilization system is
preferably utilized. Enzyme stabilization techniques for
aqueous detergent compositions are well known in the art. For
example, one technique for enzyme stabilization in aqueous
solutions involves the use of free calcium ions from sources
such as calcium acetate, calcium formate and calcium
propionate. Calcium ions can be used in combination with
short chain carboxylic acid salts, preferably formates. See,
for example, U.S. patent 4,318,~g18. It has also been proposed
to use polyols like glycerol and sorbitol. Alkoxy-alcohols,
dialkylglycoethers, mixtures of polyvalent alcohols with
polyfunctional aliphatic .amines (e.g., such as
diethanolamine, triethanolamine, di-isopropanolamime, etc.),
and boric acid or alkali metal. borate. Enzyme stabilization
techniques are additionally disclosed and exemplified in U.S.
patent 4, 261, 868, U.S. Patent 3, 600, 319, and European Patent
Application Publication No. 0 199 405. Non-boric acid and
borate stabilizers are preferred. Enzyme stabilization
systems are also described, for example, in U.S. Patents
4,261,868, 3,600,319 and 3,519,570.
Other suitable detergent ingredients that can be added are
enzyme oxidation scavengers which are described in Copending
European Patent Application No. 553,607 published August 4,
1993. Examples of such enzyme oxidation scavengers are
ethoxylated tetraethylene polyamines.
B!
-- 21 7926 5
Especially preferred detergent ingredients are combinations
with technologies which also provide a type of color care
benefit. Examples of these technologies are cellulase and/or
peroxidases and/or metallo catalysts for color maintance
rejuvenation.
Another optional ingredient: is a suds suppressor,
exemplified by silicones, and silica-silicone mixtures.
Silicones can be generally represented by alkylated
polysiloxane materials while ailica is normally used in
finely divided forms exemplified by silica aerogels and
xerogels and hydrophobic silic;as 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 cons=rolling agent is disclosed in
Bartollota et al. U.S. Patent 3 933 672. Other particularly
useful suds suppres~ors are t:he self-emulsifying silicone
suds suppressors, described in ~~erman Patent Application DTOS
2 646 126 published April 28, 1977. An example of such a
compound is DC-544, commercially available from Dow Corning,
which is a siloxane-glycol copolymer. Especially preferred
suds controlling agent are the suds suppressor system
comprising a mixture of silicone oils and 2-alkyl-alcanols.
Suitable 2-alkyl-alcanols are: 2-butyl-octanol which are
commercially available under the trade mark Isofol 12 R.
Such suds suppressor system are described in
Canadian Patent Application No. 2,146,636.
Especially preferred silicone suds controlling agents are
described in European Patent Application No. 573,699
published June 6, 1992.
B1
WO 95120032 PCT/US95100626
2~~92s5 18
Said compositions can comprise a silicone/silica mixture in
combination with fumed nonporous silica such as AerosilR.
The suds suppressors described above are normally employed
at levels of from 0 . 001 o to 2 o by weight of the composition,
preferably from O.Olo 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 non-encapsulated and
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-6-ylamino)stilbene-2:21 disulphonate,
disodium 4, - 41-bis-(2-morpholino-4-anilino-s-triazin-6-
ylaminostilbene-2:21 - disulphonate, disodium 4,41 - bis-
(2,9-dianilino-s-triazin-6-ylamino)stilbene-2:21 -
disulphonate, monosodium 41,411 -bis-(2,4-dianilino-s-
triazin-6 ylamino)stilbene-2-sulphonate, disodium 4,41 -bis-
(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-
ylamino)stilbene-2,21 - disulphonate, disodium 4,41 -bis-(4-
phenyl-2,1,3-triazol-2-yl)-stilbene-2,21 disulphonate,
disodium 4,41bis(2-anilino-4-(1-methyl-2-hydroxyethylamino)-
~v s-triazin-6- ylamino)stilbene-2,21disulphonate and sodium
~ ~ ~~~a
_.. WO 95120032 PCTIUS95/00626
19
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 a.nd 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(~r-PEG)0.4~T(PO-
H)0.25((PEG)43CH3)p.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, "primarily", in the present context
most of said copolymers, herein will be end-capped by
sulphobenzoate groups. However, sc>me copolymers will be less
than fully capped, and therefore their end groups may consist
WO 95/20032 PCT/US95/00626
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 10$ filler salt. The liquid compositions according to
the present invention can also be in "concentrated form", in
such case, the liquid detergent compositions according to the
present invention will contain a lower amount of
water, compared to conventional liquid detergents. Typically,
the water content of the concentrated liquid detergent is
less than 30$, more preferably less than 20$, most preferably
less than 10$ by weight of the detergent compositions.
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
,_ WO 95/20032 PCT/US95100626
21
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 treatmE~nt solution is preferably
from 7 to 11, especially from 7.5 to 10.5.
The process and compositions of the invention can also be
used as detergent additive products..
Such additive products are intendE:d to supplement or boost
the performance of conventional detE:rgent compositions.
The detergent compositions according to the present invention
include compositions which are t:o be used for cleaning
substrates, such as fabrics, fibers, hard surfaces, skin
etc., for example hard surface cleaning compositions (with or
without abrasives), laundry detergent compositions, automatic
and non automatic dishwashing compositions.
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 liquid detergent composition according to the present
invention is prepared, having the following compositions .
$ by weight of the total detergent composition
Linear alkylbenzene sulfonate 10
Alkyl sulphate 4
Fatty alcohol (C12-C15) ethoxylate 12
Fatty acid 10
Oleic acid 4
Citric acid 1
NaOH 3.4
Propanediol 1.5
Ethanol 10
Table I
W O 95/20032
PCT/US95/00626
22
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 Dc value which represents the
change in the Hunter a, b values which are determined by
reflecting spectofotometry. The Dc value is defined by the
following equation:
Dc = ~(af -ai)2 + (bf-bi)2}1/2
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.
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 bleeding dye consists of one part direct
blue 90, one part direct blue 112 and one part direct violet
47. The multifiber swatch consists of cotton.
Experimental conditions:
pH =7.8
A: A detergent composition according to Table I which does not
contain any dye transfer inhibition system.
B: 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 10,000 and an amine to amine
N-oxide ratio of 1:10 (HOPAO).
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 l:l (LOPAO).
2~ ~'~~~~'_
._ WO 95120032 PCTIUS95/00626
23
D: A detergent composition according to Table I containing
5ppm of PVNO (poly(4-vinylpyridine-N-oxide)) which has an
average molecular weight of about 3(),000 and an amine to amine
N-oxide ratio of 1:10, and 5ppm of 1?VNO (poly(4-vinylpyridine-
N-oxide)) which has an average molecular weight of about
30,000 and an amine to amine N-oxide ratio of 1:1 (HOPAO +
LOPAO).
Results: Dc values for the cotton pick-up tracer.
Bleeding fabric A B C D
color
Direct Blue 90/ 10.3 4.2 4.5 3
Direct Blue 112 and
Direct Violet 47
EXAMPLE II (A/B/C/D)
Liquid detergent composi~ions according to the present
invention are prepared, having the following compositions .
P. B C D
Linear alkylbenzene sulfonate 1.8 - 6 -
C12-C15 alkyl sulfate -~ 16.0 - -
C12-C15 alkyl ethoxylated
sulfate -~ 11.0 4.0 25.0
C12-C14 N-methyl glucamide -~ 7.0 9.0 9.0
C12-C14 fatty alcohol ethoxylate 1.2.0 5.0 6.0 6.0
C12-C16 fatty acid 9.0 6.8 14.0 14.0
Fatty acid 1.0 10 10 10
Oleic acid 4 4 4 4
Citric acid 1 1 1 1
Diethylenetriaminepentamethylene 1.5 1.5 1.5 1.5
phosphoric acid
,.
Y ~ ~. ~ . . .
.',b
f ,..,
,. , ' f
: '
t
,
,
,
21 7926 5
24
Propanedioi 1.5 1.5 1.5 1.5
Ethanol 10 10 10 10
Ethoxylated tetraethylene
pentamine
0.7 0.7 0.7 0.7
Poly(4-vinylpyridine)-N-oxide
(HOPAO) 0.3 0.3 0.3 0.3
Poly(4-vinylpyridine)-N-oxide
(LOPAO) 0.3 0.3 0.3 0.3
ThermamylT"' 0.13 0.13 0.13 0.13
CarezymeT"' 0.014 0.014 0.014 0.014
EN-Base 1.8 1.8 1.8. 1.8
Lipolase 0.14 0.14 0.14 0.1
Endoglucanase A 0.53 0.53 0.53 0.53
Suds supressor (ISOFOL) 2.5 2.5 2.5 2.5
Water and Minors
up to 100
NaOH and/or MEA to adjust pH '7.8
to
EXAMPLE III (A/H/C/D) --
Compact granular detergent compositions according to the
present invention are prepared, having the following
formulation:
% by weight of the total detergent compoaitioa
A, B C D
Polyhydroxy fatty 'acid amide 10
Alkyl alkoxylated sulfate - 9 9 9
Alkyl sulphate 9.80 4.80 4.80 4.60
C14-15-alcohol 7 times 9.00 4.00 4.00 4.00
ethoxylate
Tallow alcohol 11 times 1.8 1.80 1.8 1.8
ethoxylated
Dispersant 0.07 0.07 0.07 0.07
Silicone fluid 0.80 0.80 0.80 0.80
Trisodium citrate ~ 14.00 14.00 14.00 14.00
Citric acid 3.00 3.00 3.00 3.00
Bi
WO 95/20032
PCT/US95/00626
25
Zeolite 25.00 20.00 20.00 32.50
Diethylenetriamine penta- 0.6 0.6 0.6 0.6
methylene phosphonic acid
Malefic acid acrylic acid 5.00 5.00 5.00 5.00
copolymer
Carezyme T-granulate 0.2 0.5 0.15 0.3
Alcalase T-granulate 0.60 0.60 0.20 0.50
Lipolase T-granulate 0.20 0.10 0.25 0.40
Termamyl T-granulate 0.3 0.3 0.3 0.3
Sodium silicate 2.00 2.00 2.00 2.00
Sodium sulphate 3.50 3.50 3.50 3.50
Percarbonate - - 20 -
Perborate 15 15 - -
TAED - 5 5 -
Encapsulated perfume 0.2 - - -
Perfume 0.3 0.2 0.3 0.2
Poly(4-vinylpyrridine)
N-oxide (HOPAO) 0.3 0.3 0.3 0.3
Poly(4-vinylpyrridine)
N-oxide (LOPAO) 0.3 0.3 0.3 0.3
Minors
up to 100
