Note: Descriptions are shown in the official language in which they were submitted.
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
1
BLEACH PRECURSOR COMPOSITIONS
Technical field of the Invention
The present invention relates to a bleach precursor composition and
incorporation thereof in a detergent composition, whereby the precursor
exhibits effective solubilisation properties.
Background of the invention
The satisfactory removal of soils/stains from soiledlstained substrates is
a particular challenge to the formulator of a detergent composition for
use in a washing method such as a laundry or machine dishwashing
method.
Traditionally, the removal of such soils/stains has been enabled by the
use of bleach components such as oxygen bleaches, including hydrogen
peroxide and organic peroxyacids. The organic peroxyacids are often
obtained by the in situ perhydrolysis reaction between hydrogen peroxide
and an organic peroxyacid bleach precursor, so called "bleach
precursor".
A problem encountered with the use of bleach precursors is that upon
cold temperature washing solutions (5°C to 30°C) or under high
water
hardness conditions, the solubilisation rate of the precursors is
decreased. As the perhydrolysis rate is reduced, so does the cleaning
performance. Such a problem of low solubilisation or dissolution is
further exarcerbated where the precursor exhibits surfactancy properties.
Typical examples of such precursors are the amide substituted bleach
precursor compounds such as (6-octanamido-caproyl) oxy benzene
sulfonate, (6-nonanamidocaproyl) oxy benzene sulfonate and (6-
decanamido-caproyl) oxy benzene sulfonate as described in EP-A-
0170386. Accordingly, the formulator of a bleach precursor
composition is faced with the challenge of formulating a bleach precursor
CA 02258670 2001-10-15
2
composition which provides effective solubilisation or dissolution of the
precursor.
To solve this problem of low dissolution, the coating and/or agglomeration of
the bleach precursor with a water-soluble material has been proposed as
described in co-pending application PCT/US95/15494.
However, notwithstanding the advances in the art, there is still a need for an
alternative composition which provides effective dissolution of the bleach
precursor.
The applicant has now found that this problem can be overcome by the
provision of a peroxyacid bleach precursor in combination with a surfactant
system comprising a non-ethoxylated anionic surfactant and a nonionic
surfactant.
Summary of the Invention
The present invention encompasses a solid bleach precursor composition
comprising: a bleach precursor selected from the group consisting of
nonanoyl oxy benzene sulfonate, (6-octanamido-
caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxy benzene sulfonate,
(6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof; a
surfactant system comprising a non-ethoxylated anionic surfactant component
and a nonionic surfactant component; and from 0.1 % to 20% by weight of the
composition of a hydrotrope selected from the group consisting of salts of
cumene sulfonate, xylene sulfonate, toluene sulfonate and mixtures thereof;
wherein the physical form of said composition is selected from the group
consisting of forms wherein: a bleach precursor particulate is coated with one
or more layers wherein at least one layer contains one of said surfactant
system components and the other of said surfactant system component is in
intimate admixture with said bleach precursor; a bleach precursor particulate
comprises one of the surfactant system components, and is coated with one
or more layers wherein at least one layer contains said bleach precursor in
intimate admixture with the other surfactant system component; a bleach
CA 02258670 2001-10-15
2a
precursor particulate is coated with either one or more layers, wherein at
least
one layer contains both components of said surfactant system, or with at least
two layers wherein at least one layer contains one of said surfactant system
components and at least another layer contains the other said surfactant
system components; and both surfactant system components are coated with
one or more layers wherein at least one layer contains said bleach precursor;
said solid bleach precursor composition being further dusted with zeolite.
It has to be understood by close physical proximity that the precursor and the
surfactant system are not two separate discrete particles in the detergent
composition.
For the purpose of the present invention, the term "close physical proximity"
means one of the following:
i) an agglomerate, granule or extrudate in which said precursor and said
surfactant system are in intimate admixture;
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
3
ii) a bleach precursor particulate coated with one or more layers wherein
at least one layer contains one of the surfactant system component and
the other is in intimate admixture with the bleach precursor component;
iii) a bleach precursor particulate comprising one of the surfactant
system components, coated with one or more layers wherein at least
one layer contains the bleach precursor in intimate admixture with the
other surfactant system component.
iv) a bleach precursor particulate coated either with one or more layers
wherein at least one layer contains both components of the surfactant
system, or with at least two layers wherein at least one layer contains
one of the surfactant system component and at least another layer
contains the other surfactant system component;
v) a bleach precursor particulate comprising both components of the
surfactant system coated with one or more layers wherein at least one
layer contains the bleach activator.
In another embodiment of the invention, the present invention
encompasses a detergent composition incorporating a solid bleach
precursor composition as defined herein.
Detailed description of the invention
Bleach precursor
An essential component of the invention is a bleach precursor. Bleach
precursors for inclusion in the composition in accordance with the
invention typically contain one or more N- or 0- acyl groups, which
precursors can be selected from a wide range of classes. Suitable
classes include anhydrides, esters, imides, nitrites and acylated
derivatives of imidazoles and oximes, and examples of useful materials
within these classes are disclosed in GB-A-1586789.
Suitable esters are disclosed in GB-A-836988, 864798, 1 147871,
2143231 and EP-A-0170386. The acylation products of sorbitol,
CA 02258670 2001-10-15
4
glucose and all saccharides with benzoylating agents and acetylating
agents are also suitable.
Specific 0-acyiated precursor compounds include nonanoyl oxy benzene
sulphonate, 3,5,5-tri-methyl hexanoyl oxybenzene sulfonates, benzoyl
oxybenzene sulfonates, cationic derivatives of the benzoyl oxybenzene
sulfonates, nonanoyl-6-amino caproyl oxybenzene sulfonates,
monobenzoyltetraacetyl glucose and pentaacetyl glucose. Phtalic
anhydride is a suitable anhydride type precursor. Useful N-acyl
compounds are disclosed in GB-A-855735, 907356 and GB-A-1246338.
Preferred precursor compounds of the imide type include N-benzoyl
succinimide, tetrabenzoyl ethylene diamine, N-benzoyl substituted ureas
and the N,N-N'N' tetra acetylated alkylene diamines wherein the alkylene
group contains from 1 to 6 carbon atoms, particularly those compounds
in which the alkylene group contains 1 , 2 and 6 carbon atoms. A most
preferred precursor compound is N,N-N',N' tetra acetyl ethylene diamine
(TAED).
N-acylated precursor compounds of the lactam class are disclosed
generally in GB-A-955735. Whilst the broadest aspect of the invention
contemplates the use of any lactam useful as a peroxyacid precursor,
preferred materials comprise the caprolactams and valerolactams.
Suitable caprolactam bleach precursors are of the formula:
0
C CH2 CH2
CH
2
R1 - C - N
CH2 -- CH2
wherein R1 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing
from 1 to 12 carbon atoms, preferably from 6 to 12 carbon atoms.
Suitable vaiero lactams have the formula:
CA 02258670 2001-10-15
5
O
o C '- CH2 CH2
R1 C N
CH2 CH2
wherein R 1 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing
from 1 to 12 carbon atoms, preferably from 6 to 12 carbon atoms. In
highly preferred embodiments, R 1 is selected from phenyl, heptyl, octyl,
nonyl, 2,4,4-trimethylpentyl, decenyl and mixtures thereof.
The most preferred materials are those which are normally solid at
< 30°C, particularly the phenyl derivatives, ie. benzoyl valerolactam,
benzoyl caprolactam and their substituted benzoyl analogues such as
chioro, amino, vitro, alkyl, alkyl, aryl and alkyoxy derivatives.
Caprolactam and valerolactam precursor materials wherein the R 1 moiety
contains at least 6, preferably from 6 to about 12, carbon atoms provide
peroxyacids on perhydrolysis of a hydrophobic character which afford
nucleophilic and body soil clean-up. Precursor compounds wherein R1
comprises from 1 to 6 carbon atoms provide hydrophilic bleaching
species which are particularly efficient for bleaching beverage stains.
Mixtures of 'hydrophobic' and 'hydrophilic' caprolactams and valero
lactams, typically at weight ratios of 1:5 to 5:1, preferably 1:1, can be
used herein for mixed stain removal benefits.
Another preferred class of bleach precursor materials include the cationic
bleach activators, derived from the valerolactam and acyl caprolactam
compounds, of formula:
CA 02258670 2001-10-15
6
R'
R"
R
X_ \ N/ O
CH? ~ C -(CH~)x-CHI
C
CH2
\CH2 -CH~~
wherein x is 0 or 1, substituents R, R' and R" are each C 1-C 10 alkyl or
C2-C4 hydroxy alkyl groups, or ((CyH2y)O)n-R"' wherein y = 2-4, n =1-
20 and R"' is a C 1-C4 alkyl group or hydrogen and X is an anion.
Suitable imidazoles include N-benzoyl imidazole and N-benzoyl
benzimidazole and other useful N-acyl group-containing peroxyacid
precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl
pyroglutamic acid.
Another preferred class of bleach precursor compounds are the amide
substituted compounds of the following general formulae:
R1 N(R5)C(O)R2C(0)Lor R1 C(0)NIRS)R2C(OIL
wherein R1 is an alkyl, alkylene, aryl or alkaryl group with from about 1
to about 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene
group containing from about 1 to 14 carbon atoms, and R5 is H or an
alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can
be essentially any leaving group. R1 preferably contains from about 6 to
12 carbon atoms. R2 preferably contains from about 4 to 8 carbon
atoms. R1 may be straight chain or branched alkyl, substituted aryl or
alkylaryl containing branching, substitution, or both and may be sourced
from either synthetic sources or natural sources including for example.
tallow fat. Analogous structural variations are permissible for R2. The
substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other
typical substituent groups or organic compounds. R5 is preferably H or
methyl. R 1 and Rb should preferably not contain more than 18 carbon
atoms total. Preferred examples of bleach precursors of the above
formulae include amide substituted peroxyacid precursor compounds
CA 02258670 1998-12-17
WO 98/00504 PCTIUS97/11068
7
selected from (6-octanamido-caproyl)oxybenzenesulfonate, (6-
nonanamidocaproyl)oxy benzene suifonate, (6-decanamido-
caproyi)oxybenzenesulfonate, and mixtures thereof as described in EP-A-
0170386.
Also suitable are precursor compounds of the benzoxazin-type, as
disclosed for example in EP-A-332,294 and EP-A-482,807, particularly
those having the formula:
O
I I
C~O
I
,C-R~
N
including the substituted benzoxazins of the type
R2 O
C
Rs ~O
R ~ ''C _R~
~N
R5
wherein R1 is H, alkyl, alkaryl, aryl, arylalkyl, secondary or tertiary
amines and wherein R2, R3, R4, and R5 may be the same or different
substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl,
alkoxyl, amino, alkyl amino, COOR6 (wherein R6 is H or an alkyl group)
and carbonyl functions.
An especially preferred precursor of the benzoxazin-type is:
O
II
CEO
C
''
N
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
8
The bleach precursor components preferably have a particle size of from
250 micrometers to 2000 micrometers.
These bleach precursors can be partially replaced by preformed peracids
such as N,N phthaloyiaminoperoxy acid (PAP), nonyl amide of
peroxyadipic acid (NAPAA), 1 ,2 diperoxydodecanedioic acid (DPDA) and
trimethyl ammonium propenyl imidoperoxy mellitic acid (TAPIMA).
More preferred among the above described bleach precursors are
nonanoyl oxy benzene sulphonate and/or the amide substituted bleach
precursor compounds. Most preferably, the bleach precursors are the
amide substituted bleach precursor compounds selected from (6-
octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxy
benzene sulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and
mixtures thereof.
The bleach precursors are normally incorporated at a level of from 20%
to 95% preferably 50% to 90% by weight of the bleach precursor
component and most preferably at least 60% by weight thereof.
Surfactant system
An essential feature of the invention is a surfactant system comprising a
non-ethoxylated anionic surfactant and a nonionic surfactant. The
surfactant system will typically be present in an amount of 0.'1 °io to
50%
by weight, more preferably in an amount of 1 % to 20% by weight of the
bleach precursor composition.
Non-ethoxvlated anionic surfactant
Non-ethoxylated anionic surfactants, for use herein, include salts
(including, for example, sodium, potassium, ammonium, and substituted
ammonium salts such as mono-, di- and triethanoiamine salts) of the
anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants.
Other anionic surfactants include the isethionates such as the acyl
isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
9
succinates and sulfosuccinates, monoesters of sulfosuccinate (especially
saturated and unsaturated C ~ 2-C 18 monoesters) diesters of
sulfosuccinate (especially saturated and unsaturated C6-C14 diesters),
N-acyi sarcosinates. Resin acids and hydrogenated resin acids are also
suitable, such as rosin, hydrogenated rosin, and resin acids and
hydrogenated resin acids present in or derived from tallow oil.
Anionic sulfate surfactants suitable for use herein include the linear and
branched primary alkyl sulfates, tatty oleyl glycerol sulfates, the C5-C 1 ~
acyl-N-(C ~ -C4 alkyl) and -N-(C ~ -C2 hydroxyalkyl) glucamine sulfates,
and sulfates of alkylpoiysaccharides such as the sulfates of
alkylpolyglucoside (the nonionic nonsulfated compounds being described
herein).
Alkyl sulfate surfactants are preferably selected from the group
consisting of branched-chain and random C10-C20 alkyl sulphates
("AS"), the C 10-C 18 secondary (2,3) alkyl sulphates of the formula
CH3(CH2)x(CHOS03- M + ) CH3 and CH3(CH2)y(CHOS03- M + )
CHZCH3 where x and (y+ 1 ) are integers of at least 7, preferably at least
about 9, and M is a water-solubifising cation, especially sodium,
unsaturated sulphates such as oleyl sulphate.
Anionic sulfonate surfactants suitable for use herein include the salts of
C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, Cg-C22
primary or secondary alkane sulfonates, Cg-C24 olefin sulfonates,
sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl
glycerol sulfonates, fatty oieyl glycerol sulfonates, and any mixtures
thereof.
Anionic carboxylate surfactants suitable for use herein include the soaps
('alkyl carboxyls'), especially certain secondary soaps as described
herein.
Preferred soap surfactants are secondary soap surfactants which contain
a carboxyl unit connected to a secondary carbon. The secondary carbon
can be in a ring structure, e.g. as in p-octyl benzoic acid, or as in alkyl-
substituted cyclohexyl carboxylates. The secondary soap surfactants
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
should preferably contain no ether linkages, no ester linkages and no
hydroxyl groups. There should preferably be no nitrogen atoms in the
head-group famphiphilic portion). The secondary soap surfactants usually
contain 1 1-15 total carbon atoms, although slightly more (e.g., up to 16)
can be tolerated, e.g. p-octyl benzoic acid.
The following genera! structures further illustrate some of the preferred
secondary soap surfactants:
A. A highly preferred class of secondary soaps comprises the
secondary carboxyl materials of the formula R3 CH(R4)COOM, wherein
R3 is CHg(CHZ)x and R4 is CHgICH2)y, wherein y can be 0 or an
integer from 1 to 4, x is an integer from 4 to 10 and the sum of (x + y)
is 6-10, preferably 7-9, most preferably 8.
B. Another preferred class of secondary soaps comprises those
carboxyl compounds wherein the carboxyl substituent is on a ring
hydrocarbyl unit, i.e., secondary soaps of the formula R5-R6-COOM,
wherein R5 is C~-C10, preferably C8-C9, alkyl or alkenyl and R6 is a ring
structure, such as benzene, cyclopentane and cyclohexane. (Note: R5
can be in the ortho, meta or para position relative to the carboxyl on the
ring.)
C. Still another preferred class of secondary soaps comprises
secondary carboxyl compounds of the formula
CH3(CHR)k-(CH2)m-(CHR)n-CH(COOM1(CHR)o-(CH2)p-(CHR)q-
CH3,
wherein each R is C1-C4 alkyl, wherein k, n, o, q are integers in the
range of 0-8, provided that the total number of carbon atoms (including
the carboxylate) is in the range of 10 to 18.
In each of the above formulas A, B and C, the species M can be any
suitable, especially water-solubifizing, counterion.
Especially preferred secondary soap surfactants for use herein are water-
soluble members selected from the group consisting of the water-soluble
CA 02258670 1998-12-17
WO 98/00504 PCTlUS97/11068
11
salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-
nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.
Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R-CON (R1 ) CH2 COOM, wherein R is a C5-C1 ~ linear or
branched alkyl or alkenyl group, R 1 is a C 1-C4 alkyl group and M is an
alkali metal ion. Preferred examples are the myristyl and oleyl methyl
sarcosinates in the form of their sodium salts.
Among the above described non-ethoxylated anionic surfactants, the
anionic sulfate surfactants, anionic sulfonate surfactants, or mixtures
thereof are preferred. More preferably, the anionic surfactant is selected
from C12-C1 g linear alkyl sulphates, C5-C20 linear alkylbenzene
sulfonates and mixtures thereof, and most preferably is the salt of C5-
C2p linear alkylbenzene sulfonate.
Preferably the anionic surfactant is present in an amount of from 0.1
to 49.9% by weight, more preferably from 1 % to 19% by weight of the
bleach precursor composition.
Nonionic surfactant
Nonionic surfactants, for use herein, include the polyhydroxy fatty acid
amide surfactants, condensates of alkyl phenols, ethoxylated alcohol
surfactants, ethoxylated/propoxylated fatty alcohol surfactant, ethylene
oxide/propylene oxide condensates with propylene glycol, ethylene oxide
condensation products with propylene oxide/ethylene diamine adducts,
alkylpolysaccharide surfactants, fatty acid amide surfactants and
mixtures thereof. Exemplary, non-limiting classes of useful nonionic
surfactants are listed below. -
Polyhydroxy fatty acid amides suitable for use herein are those having
the structural formula R2CONR 1 Z wherein : R 1 is H, C 1-C4 hydrocarbyl,
2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferable C 1-
C4 alkyl, mare preferably C1 or C2 alkyl, most preferably C1 alkyl (i.e.,
methyl); and R2 is a C5-Cg 1 hydrocarbyl, preferably straight-chain C5-
C 1 g alkyl or alkenyl, more preferably straight-chain Cg-C 1 ~ alkyl or
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
12
alkenyl, most preferably straight-chain C 1 1-C 1 ~ alkyl or aikenyl, or
mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear
hydrocarbyl chain with at least 3 hydroxyls directly connected to the
chain, or an alkoxylated derivative (preferably ethoxylated or
propoxylated) thereof. Z preferably will be derived from a reducing sugar
in a reductive amination reaction; more preferably Z is a glycityl.
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 18 carbon atoms in either a straight chain or
branched chain configuration with the alkyiene 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 2 to about 10 moles of ethylene oxide per mole of
alcohol.
As ethoxyiated/propoxyiated fatty alcohol surfactants, the ethoxylated
Cg-C 1 g fatty alcohols and Cg-C 1 g mixed ethoxylated/propoxylated fatty
alcohols are suitable surfactants for use herein, particularly where water
soluble. Preferably, the ethoxylated fatty alcohols are the C10-C18
ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50,
most preferably these are the C12-C1 g ethoxylated fatty alcohols with a
degree of ethoxylation from 3 to 40. Preferably the mixed
ethoxylated/propoxylated fatty alcohols have an alkyl chain length of
from 10 to 18 carbon atoms, a degree of ethoxylation of from 3 to 30
and a degree of propoxylation of from 1 to 10.
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. The hydrophobic portion of these compounds
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
13
preferably has a molecular weight of from about 1500 to about 1800
and exhibits water insolubility. Examples of compounds of this type
include certain of the commercially-available PluronicTM surfactants,
marketed by BASF.
The condensation products of ethylene oxide with the product resulting
from the reaction of propylene oxide and ethylenediamine are suitable for
use herein. The hydrophobic moiety of these products consists of the
reaction product of ethylenediamine and excess propylene oxide, and
generally has a molecular weight of from about 2500 to about 3000.
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 alkylpolyglycosides have the formula
R20(CnH2n0)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl
groups contain from 10 to 18, preferably from 12 to 14, carbon atoms;
n is 2 or 3; t is from 0 to 10, preferably 0, and X is from 1.3 to 8,
CA 02258670 1998-12-17
WO 98!00504 PCT/US97/11068
14
preferably from 1.3 to 3, most preferably from 1.3 to 2.7. The glycosyl
is preferably derived from glucose.
Fatty acid amide surfactants suitable for use herein are those having the
formula: R6CON(R7)2 wherein R6 is an alkyl group containing from 7 to
21, preferably from 9 to 17 carbon atoms and each R7 is selected from
the group consisting of hydrogen, C 1-C4 alkyl, C 1-C4 hydroxyalkyl, and
-(C2H401xH, where x is in the range of from 1 to 3.
Preferred among the above described nonionic surfactants are the
ethoxylated surfactants, preferably selected from ethoxylated alcohol
surfactants, ethoxylated/propoxylated fatty alcohol surfactant, ethylene
oxide/propylene oxide condensates with propylene glycol, ethylene oxide
condensation products with propylene oxide/ethyiene diamine adducts
and mixtures thereof, more preferably the ethoxylated alcohol
surfactants.
Most preferred ethoxylated alcohol surfactants are the condensation
products of alcohols having an alkyl group containing from 8 to 20
carbon atoms with from 2 to 10 moles of ethylene oxide per mole of
alcohol, in particular the linear primary alcohol (C12/C14) condensed
with an average of 3 moles of ethylene oxide.
Preferably the nonionic surfactant is present in an amount of 0.01 % to
20% by weight, more preferably from 0.1 % to 5% by weight of the
bleach precursor composition.
Optionals
Optional components may be present within the bleach precursor
composition. Suitable optionals for use herein include hydrotropes
components, acids, binding agents, additional surface active agents such
as cationic surfactants, and mixtures thereof.
Hydrotropes are particularly useful as optional components of the bleach
precursor composition in that they surprisingly aid the solubilisation of
the bleach precursor composition. When used, hydrotropes will typically
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
be present in an amount of 0.1 % to 20%, preferably from 0.5% to 10%
by weight of the bleach precursor composition.
Optional hydrotropes suitable for use herein are selected from the group
of lower alkyl aryl sulphonate salts, Cg-C12 alkanols, C1-Cg carboxylic
sulphate or sulphonate salts, urea, C 1-C4 hydrocarboxylates, C 1-C4
carboxylates and C2-C4 diacids and mixtures thereof.
Suitable lower alkyl aryl sulphonates are preferably C7-Cg alkyl aryl
suiphonates and include sodium, potassium, calcium and ammonium
xylene sulphonates, sodium, potassium, calcium and ammonium toluene
sulphonates, sodium, potassium, calcium and ammonium cumene
sulphonate, and sodium, potassium, calcium and ammonium napthalene
sulphonates and mixtures thereof.
Suitable C1-Cg carboxylic sulphate or sulphonate salts are any water
soluble salts or organic compounds comprising 1 to 8 carbon atoms
(exclusive of substituent groups), which are substituted with sulphate or
sulphonate and have at least one carboxylic group. The substituted
organic compound may be cyclic, acylic or aromatic, i.e. benzene
derivatives. Preferred alkyl compounds have from 1 to 4 carbon atoms
substiuted with sulphate or sulphonate and have from 1 to 2 carboxylic
groups. examples of suitable hydrotropes include sulphosuccinate salts,
sulphophthalic salts, sulphoacetic salts, m-sulphobenzoic acid salts and
diesters suiphosuccinates, preferably the sodium or potassium salts as
disclosed in US 3 915 903.
Suitable C 1-C4 hydrocarboxylates, C 1-C4 carboxylates for use herein
include acetates and propionates and citrates. Suitable C2-C4 diacids for
use herein include succinic, glutaric and adipic acids.
Other compounds which deliver hydrotropic effects suitable for use
herein as a hydrotrope include C6-C12 alkanols and urea.
CA 02258670 1998-12-17
WO 98/00504 PCT/US97111068
16
Preferred hydrotropes for use herein are selected from the salts of
cumene sulphonate, xylene sulphonate, toluene sulphonate and mixtures
thereof. The salts suitable for use herein are sodium, potassium, calcium
and ammonium. Most preferred are sodium toluene sulphonate.
Acids may also be useful in the composition of the present invention in
particular as stabilising agents. Typical levels of such acids are from 0.1
to 40% by weight, preferably from 1 % to 20% by weight of the bleach
precursor composition. Suitable acids are preferably water-soluble such
as fatty acids, glycolic acid, glutaric acid, citric acid and polymeric
carboxylic acids.
Optionally, binding agents may be used in the composition of the present
invention. Typical levels of such binding agents are from 0.01 % to 20%
by weight, preferably from 0.5 % to 10% by weight of the bleach
precursor composition. Suitable binding agents include starch, cellulose
and cellulose derivatives (e.g. sodium carboxymethyl cellulose), sugar
and film-forming polymers such as polymeric carboxylic acid, including
copolymers, polyvinyl pyrrolidone, polyvinyl acetate. Cellulose and
cellulose derivatives (e.g. sodium carboxymethyl cellulose) are
particularly preferred.
Form of the bleach precursor composition
The surfactant system and the bleach precursor of the solid bleach
precursor composition are in close physical proximity.
It has to be understood by close physical proximity that the precursor
and the surfactant system are not two separate discrete particles in the
detergent composition.
For the purpose of the present invention, the term "close physical
proximity" means one of the following:
i1 an agglomerate, granule or extrudate in which said precursor and said
surfactant system are in intimate admixture;
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
17
ii) a bleach precursor particulate coated with one or more layers wherein
at least one layer contains one of the surfactant system component and
the other is in intimate admixture with the bleach precursor component;
iii) a bleach precursor particulate comprising one of the surfactant
system component, coated with one or more layers wherein at least one
layer contains the bleach precursor in intimate admixture with the other
surfactant system component.
iv) a bleach precursor particulate coated either with one or more layers
wherein at least one layer contains both components of the surfactant
system, or with at least two layers wherein at least one layer contains
one of the surfactant system components and at least another layer
contains the other surfactant system component;
v) a bleach precursor particulate comprising both components of the
surfactant system coated with one or more layers wherein at least one
layer contains the bleach activator.
Preferably, the bleach precursor composition may be in any known
suitable particulate form for incorporation in a detergent composition,
such as an agglomerate, granule, extrudate or spheronised extrudate.
Preferably, the bleach precursor composition is in a form of a
spheronised extrudate.
A preferred process for the manufacture of the bleach precursor
spheronised extrudate comprises the steps of:
(i) preparing a mix of solids, and optionally liquids, comprising the bleach
activator;
(ii) extruding the mix through a die under pressure to form an extrudate;
(iii) breaking the extrudate to form a spheronised extrudate; and
(iv) optionally coating the particles to improve friability and flow
characteristics.
CA 02258670 2001-10-15
The mixing step (ii is carried out using any conventional powder/liquid
mixer, e.g. a Loedige KM mixer. The extruding step Iii) can be achieved
using any conventional extruder which can be axial, radial or more
preferably dome-type, e.g. Fuji Paudal Model DGL-1 ~ most preferably
having a die with < 0.1 mm orifices and extruded at pressures of about
20 bar. Step (iiii is preferably carried out using a rotating disc
spheroniser such as a Fuji Paudal QJ-1000 where the extrudates are
broken down into short lengths and formed into substantially spherical
particles.
Additionally, the extrudates may then be dried in a vibrating fluid bed
drier, e.g. Niro, to result in crisp, free-flowing particles with a particle
size range of from 0.25mm to 20mm and a Heubach dust measurement
of less than 100mg/g.
The optional coating step (iv) could involve materials such as film
forming polymers or preferably a liquid fixative, e.g. nonionic surfactant
and an inert powder such as Zeoiite A.
By effective soiubilisation rate is meant that the use of a composition
comprising the bleach precursor and the surfactant system as described
above provides a better solubilisation of the bleach precursor properties
than the use of the same composition without the surfactant system.
The peroxyacid bleach precursor particulates may suitably be
incorporated in detergent compositions. Detergent compositions
incorporating the peroxy acid bleach precursor particulates will normally
contain from 1 °r6 to 20% of the precursor particulates, mare
frequently
from 1 % to 1096 and most preferably from 1 % to 7°r6, on a composition
weight basis.
Such detergent compositions will, of course, contain a source of alkaline
hydrogen peroxide necessary to form a peroxyacid bleaching species in
the wash solution and preferably will also contain other components
conventional in detergent compositions.
CA 02258670 1998-12-17
WO 98/00504 PC'T/US97/11068
19
Detergent compositions incorporating the particulate peroxyacid
precursors of the present invention will include a hydrogen peroxide or a
source thereof. Preferred sources of hydrogen peroxide include an
inorganic perhydrate bleach, normally in the form of the sodium salt, as
the source of alkaline hydrogen peroxide in the wash liquor. This
perhydrate is normally incorporated at a level of from 3% to 40% by
weight, more preferably from 5% to 35% by weight and most preferably
from 8% to 30% by weight of the composition.
The perhydrate may be any of the alkali metal inorganic salts such as
perborate monohydrate or tetrahydrate, percarbonate, perphosphate and
persilicate salts but is conventionally an alkali metal perborate or
percarbonate.
Sodium percarbonate, which is the preferred perhydrate, is an addition
compound having a formula corresponding to 2Na2C03.3H202, and is
available commercially as a crystalline solid. Most commercially available
material includes a low level of a heavy metal sequestrant such as EDTA,
1-hydroxyethylidene 1, 1-diphosphonic acid (HEDP) or an amino-
phosphonate, that is incorporated during the manufacturing process. For
the purposes of the detergent composition aspect of the present
invention, the percarbonate can be incorporated into detergent
compositions without additional protection, but preferred executions of
such compositions utilise a coated form of the material. A variety of
coatings can be used including borate, boric acid and citrate or sodium
silicate of Si02:Na20 ratio from 1.6:1 to 3.4:1, preferably 2.8:1, applied
as an aqueous solution to give a level of from 2% to 10%, (normally
from 3% to 5%~ of silicate solids by weight of the percarbonate.
However, the most preferred coating is a mixture of sodium carbonate
and sulphate or sodium chloride.
The particle size range of the crystalline percarbonate is from 350
micrometers to 1500 micrometers with a mean of approximately 500-
1000 micrometers.
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
The detergent composition, in addition to the bleach precursor particulate
and the hydrogen peroxide or source thereof, may also contain additional
components. The precise nature of these additional components and
levels of incorporation thereof will depend on the physical form of the
composition, and the nature of the cleaning operation for which it is to
be used. The compositions of the invention may, for example, be
formulated as hand and machine laundry detergent compositions,
including laundry additive compositions and compositions suitable for
use in the pretreatment of stained fabrics and machine dishwashing
compositions. When incorporated in compositions suitable for use in a
machine washing method, e.g.: machine laundry and machine
dishwashing methods, the compositions of the invention preferably
contain one or more additional detersive components.
Thus preferred detergent compositions will incorporate one of more of
surfactants, builders, chelating agnets, enzymes, soil suspending and
anti-redeposition agents, suds suppressors, fluorescent whitening agents
photo activated bleaches, perfumes and colours.
Surfactants
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 USP 3,929,678 issued to
Laughlin and Heuring on December, 30, 1975. A list of suitable cationic
surfactants is given in USP 4,259,217 issued to Murphy on March 31,
1981.
Nonlimiting examples of surfactants useful herein at levels from 1 % to
55%, by weight, typically include the conventional C11-C1g alkyl
benzene sulfonates ("LAS") and primary, branched-chain and random
C 10-020 alkyl sulfates ("AS"1, the C 10-C 1 g secondary (2,3) alkyl
sulfates of the formula CH3(CH2)x(CHOS03 M+) CH3 and CH3
(CH2)y(CHOS03 M + ) CH2CH3 where x and (y + 1 ) are integers of at
least 7, preferably at least 9, and M is a water-solubilizing cation,
especially sodium, unsaturated sulfates such as oleyl sulfate, the
C 10-C 1 g alkyl alkoxy sulfates ("AEXS"; especially EO 1-7 ethoxy
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
21
sulfates), C 10-C 1 g alkyl aikoxy carboxylates (especially the EO 1-5
ethoxycarboxylates), the C10-1 g glycerol ethers, the C10-C1 g alkyl
polyglycosides and their corresponding sulfated polyglycosides, and
C 1 2-C 1 g alpha-sulfonated fatty acid esters. If desired, the conventional
nonionic and amphoteric surfactants such as the C12-C1 g alkyl
ethoxylates ("AE") including the so-called narrow peaked alkyl
ethoxylates and C6-C 12 alkyl phenol aikoxylates (especially ethoxylates
and mixed ethoxy/propoxy), C 12-C 1 g betaines and sulfobetaines
("suitaines"), C10-C1 g amine oxides, and the like, can also be included
in the overall compositions. The C 1 p-C 1 g N-alkyl polyhydroxy fatty acid
amides can also be used. Typical examples include the C 12-C 18 N-
methylglucamides. See WO 9,206,154. Other sugar-derived
surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as
C10-C18 N (3-methoxypropyl) glucamide. The N-propyi through N-hexyl
C12-C1 g glucamides can be used for low sudsing. C10-C2p
conventional soaps may also be used. If high sudsing is desired, the
branched-chain C10-C16 soaps may be used. Other suitable surfactants
suitable for the purpose of the invention are the anionic alkali metal
sarcosinates of formula:
R-CON(R1)CH2COOM
wherein R is a Cg-C 17 linear or branched alkyl or alkenyl group, R 1 is a
C 1-C4 alkyl group and N is an alkali metal ion. Preferred examples are
the lauroyl, cocoyl (C12-C14), myristyl and oleyl methyl sarcosinates in
the form of their sodium salts. Cationic surfactants can also be used in
the compositions herein. Suitable cationic surfactants include the
quaternary ammonium surfactants selected from mono C6-C 16~
preferably C6-C10 N-alkyl or alkenyl ammonium surfactants wherein the
remaining N positions are substituted by methyl, hydroxyethyl or
hydroxypropyl groups. Mixtures of anionic and nonionic surfactants are
especially useful. Other conventional useful surfactants are listed in
standard texts.
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
22
Builders
Detergent builders can optionally be included in the compositions herein
to assist in controlling mineral hardness. Inorganic as well as organic
builders can be used. Builders are typically used in fabric laundering
compositions to assist in the removal of particulate soils. 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. 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 or phosphate-containing detergent builders include, but are not
limited to, the alkali metal, ammonium and alkanolammonium salts of
polyphosphates (exemplified by the tripolyphosphates, pyrophosphates,
and glassy polymeric meta-phosphates).
Non-phosphate builders may also be used. These can include, but are not
restricted to phytic acid, silicates, alkali metal carbonates (including
bicarbonates and sesquicarbonatesl, sulphates, aluminosilicates,
monomeric polycarboxylates, homo or copolymeric polycarboxylic acids
or their salts in which the polycarboxylic acid comprises at least two
carboxylic radicals separated from each other by not more than two
carbon atoms, organic phosphonates and aminoalkylene poly ialkylene
phosphonates?. The compositions herein also function well in the
presence of 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 so called 'amorphous' alkali metal
silicates, particularly those having a Si02:Na20 ratio in the range 1.6:1
to 3.2:1 and crystalline layered silicates, such as the layered sodium
silicates described in U.S. Patent 4,664,839. NaSKS-6 is the trademark
for a crystalline layered silicate marketed by Hoechst (commonly
abbreviated herein as "SKS-6"1. Unlike zeolite builders, the Na SKS-6
silicate builder does not contain aluminum. NaSKS-6 has the delta-
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
23
Na2Si205 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 NaMSix02x + 1 'yH20 wherein M is sodium or hydrogen, x 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-1 1, 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 stabilising 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 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:
Nazf (A1021z(Si02)yJ~xH20
wherein z and y are integers of at least 6, the molar ratio of z to y is in
the range from 1.0 to 0.5, and x is an integer from 15 to 264.
Useful aluminosilicate ion exchange materials are commercially available.
These aluminosiiicates 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. 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:
CA 02258670 1998-12-17
WO 98/00504 PCTIUS97/1I068
24
Na12[(A102) 12(Si02) 12J~xH20
wherein x is from 20 to 30, especially 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 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
neutralised 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 poiycarboxylates, including oxydisuccinate, as
disclosed in U.S. Patent 3,128,287 and U.S. Patent 3,635,830. See
also "TMS/TDS" builders of U.S. Patent 4,663,071. Suitable ether
polycarboxylates 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 hydroxypolycarboxylates, copoly-
mers of malefic anhydride with ethylene or vinyl methyl ether, or acrylic
acid, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and
carboxymethyloxysuccinic acid, the various alkali metal, ammonium and
substituted ammonium salts of polyacetic acids such as ethylenediamine
tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such
as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid,
benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and
soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly
sodium salt), are polycarboxylate builders of particular importance for
heavy duty liquid detergent formulations due to their availability from
renewable resources and their biodegradability. Citrates can also be
CA 02258670 1998-12-17
WO 98/00504 PCT/US97I11068
used in granular compositions, especially in combination with zeolite
and/or. layered silicate builders. Oxydisuccinates are also especially
useful in such compositions and combinations.
Also suitable in the compositions containing the present invention are
the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds
disclosed in U.S. Patent 4,566,984. Useful succinic acid builders
include the C5-C20 alkyl and aikenyl 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 EP 0,200,263.
Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226
and in U.S. Patent 3,308,067. See also U.S. Pat. 3,723,322.
Fatty acids, e.g., C 12-C 1 g monocarboxylic 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 tatty acids will generally
result in a diminution of sudsing, which should be taken into account by
the formulator.
In situations where phosphorus-based builders can be used, and
especially in the formulation of bars used for hand-laundering operations,
the various alkali metal phosphates such as the well-known sodium
tripolyphosphates, sodium pyrophosphate and sodium orthophosphate
can be used. Phosphonate builders such as ethane-1-hydroxy-1,1-
diphosphonate and other known phosphonates (see, for example, U.S.
Patents 3,159, 581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137)
can also be used.
Chelatina Agients
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 carboxylates, amino
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
26
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 carboxylates useful as optional chelating agents include
ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,
nitrilo-triacetates, ethylenediamine tetraproprionates,
triethylenetetraamine-hexacetates, diethylenetriaminepentaacetates, and
ethanoldiglycines, alkali metal, ammonium, and substituted ammonium
salts therein and mixtures 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 and
hydroxy-ethane 1,1 diphosphonic acid (HEDP). Preferred, these amino
phosphonates do not contain alkyl or alkenyi 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 dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
Preferred biodegradable chelating agents for use herein are
ethylenediamine disuccinate f"EDDS"), especially the [S,S1 isomer and/or
hydroxy-ethane 1,1 diphosphonic acid (HEDP).
The compositions herein may also contain water-soluble methyl glycine
diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder useful
with, for example, insoluble builders such as zeolites, layered silicates
and the like.
If utilized, these chelating agents will generally comprise from about
0.1 % to about 1 5% by weight of the detergent compositions herein.
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
27
More preferably, if utilized, the cheiating agents will comprise from about
0.1 % to about 3.0% by weight of such compositions.
Enzymes
Enzymes can be included in the present detergent compositions for a
variety of purposes, including removal of protein-based, carbohydrate-
based, or triglyceride-based stains from substrates, for the prevention of
refugee dye transfer in fabric laundering, and for fabric restoration.
Suitable enzymes include proteases, amylases, lipases, celluiases,
peroxidases, and mixtures thereof of any suitable origin, such as
vegetable, animal, bacterial, fungal and yeast origin. Preferred selections
are influenced by factors such as pH-activity and/or stability optima,
thermostability, and stability to active detergents, builders and the like.
In this respect bacterial or fungal enzymes are preferred, such as
bacterial amylases and proteases, and fungal cellulases.
"Detersive enzyme", as used herein, means any enzyme having a
cleaning, stain removing or otherwise beneficial effect in a laundry, hard
surface cleaning or personal care detergent composition. Preferred
detersive enzymes are hydrolases such as proteases, amylases and
lipases. Preferred enzymes for laundry purposes include, but are not
limited to, proteases, cellulases, lipases and peroxidases. Highly
preferred for automatic dishwashing are amylases and/or proteases,
including both current commercially available types and improved types
which, though more and more bleach compatible through successive
improvements, have a remaining degree of bleach deactivation
susceptibility.
Enzymes are normally incorporated into detergent compositions at levels
sufficient to provide a "cleaning-effective amount". The term "cleaning
effective amount" refers to any amount capable of producing a cleaning,
stain removal, soil removal, whitening, deodorizing, or freshness
improving effect on substrates such as fabrics, dishware and the like. In
practical terms for current commercial preparations, typical amounts are
up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active
enzyme per gram of the detergent composition. Stated otherwise, the
compositions herein will typically comprise from 0.001 % to 5%,
CA 02258670 2001-10-15
28
preferably 0.01 %-1 % by weight of a commercial enzyme preparation.
Protease enzymes are usually present in such commercial preparations at
levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of
activity per gram of composition.
Suitable examples of proteases are the subtilisins which are obtained
from particular strains of B. subtilis and B. licheniformis. One suitable
protease is obtained from a strain of Bacillus, having maximum activity
throughout the pH range of 8-12, developed and sold as ESPERASE° by
Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of
this enzyme and analogous enzymes is described in GB 1,243,784 to
Novo. Other suitable proteases include ALCALASE° and
SAVINASE°
from Novo and MAXATASE'~ from International Bio-Synthetics, Inc., The
Netherlands; as well as Protease A as disclosed in EP 130,756 and
Protease B as disclosed in EP 303,761 and EP 130,756. See also a high
pH protease from Bacillus sp. NCIMB 40338 described in WO 9318140
A to Novo. Enzymatic detergents comprising protease, one or more other
enzymes, and a reversible protease inhibitor are described in WO
9203529 A to Novo. Other preferred proteases include those of WO
9510591 A to Procter & Gamble. When desired, a protease having
decreased adsorption and increased hydrolysis is available as described
in WO 9507791 to Procter & Gamble. A recombinant trypsin-like
protease for detergents suitable herein is described in WO 9425583 to
Novo. In more detail, an especially preferred protease, referred to as
"Protease D" is described in the patent applications of A. Baeck, et al,
entitled "Protease-Containing Cleaning Compositions" having US Patent
No. 5,679,630, and C. Ghosh, et al, "Bleaching Compositions Comprising
Protease Enzymes" having. US Patent No. 5,677, 272, issued October 21,
1997 and October 14, 1997, respectively.
Amylases suitable herein, include, for example, a-amylases described in
GB 1.296,839 to Novo; RAPIDASE°, International Bio-Synthetics,
Inc.
and TERMAMYL°, Novo. FUNGAMYL° from Novo is especially useful.
Engineering of enzymes for improved stability, e.g., oxidative stability, is
known. See, for example J. Biological Chem., Vol. 260, No. 1 1, June
i 985, pp. 657 8-6521. Certain preferred embodiments of the present
compositions can make use of amylases having improved stability in
CA 02258670 1998-12-17
WO 98/00504 PCT/ITS97/11068
29
detergents such as automatic dishwashing types, especially improved
oxidative stability as measured against a reference-point of TERMAMYL~
in commercial use in 1993. These preferred amylases herein share the
characteristic of being "stability-enhanced" amylases, characterized, at a
minimum, by a measurable improvement in one or more of: oxidative
stability, e.g., to hydrogen peroxide / tetraacetylethylenediamine in
buffered solution at pH 9-10; thermal stability, e.g:, at common wash
temperatures such as about 60oC; or alkaline stability, e.g., at a pH from
about 8 to about 1 1, measured versus the above-identified reference-
point amylase. Stability can be measured using any of the art-disclosed
technical tests. See, for example, references disclosed in WO 9402597.
Stability-enhanced amylases can be obtained from Novo or from
Genencor International. One class of highly preferred amylases herein
have the commonality of being derived using site-directed mutagenesis
from one or more of the Bacillus amylases, especially the Bacillus a-
amylases, regardless of whether one, two or multiple amylase strains are
the immediate precursors. Oxidative stability-enhanced amylases vs. the
above-identified reference amylase are preferred for use, especially in
bleaching, more preferably oxygen bleaching, as distinct from chlorine
bleaching, detergent compositions herein. Such preferred amylases
include (a) an amylase according to the hereinbefore incorporated WO
9402597, Novo, Feb. 3, 1994, as further illustrated by a mutant in
which substitution is made, using alanine or threonine, preferably
threonine. of the methionine residue located in position 197 of the B.
licheniformis alpha-amylase, known as TERMAMYL~, or the homologous
position variation of a similar parent amylase, such as B.
amyloliquefaciens, B. subtilis, or B. stearothermophilus; (b1 stability-
enhanced amylases as described by Genencor International in a paper
entitled "Oxidatively Resistant alpha-Amylases" presented at the 207th
American Chemical Society National Meeting, March 13-17 1994, by C.
Mitchinson. Therein it was noted that bleaches in automatic dishwashing
detergents inactivate alpha-amylases but that improved oxidative
stability amylases have been made by Genencor from B licheniformis
NCIB8061. Methionine (Met) was identified as the most likely residue to
be modified. Met was substituted, one at a time, in positions 8, 15,
197, 256, 304, 366 and 438 leading to specific mutants, particularly
important being M 197L and M 197T with the M 197T variant being the
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
most stable expressed variant. Stability was measured in CASCADE~
and SUNLIGHT~; (c) particularly preferred amylases herein include
amylase variants having additional modification in the immediate parent
as described in WO 9510603 A and are available from the assignee,
Novo, as DURAMYL~. Other particularly preferred oxidative stability
enhanced amylase include those described in WO 9418314 to Genencor
International and WO 9402597 to Novo. Any other oxidative stability-
enhanced amylase can be used, for example as derived by site-directed
mutagenesis from known chimeric, hybrid or simple mutant parent forms
of available amylases. Other preferred enzyme modifications are
accessible. See WO 9509909 A to Novo.
Other amylase enzymes include those described in WO 95/26397 and in
co-pending application by Novo Nordisk PCT/DK96/00056. Specific
amylase enzymes for use in the detergent compositions of the present
invention include a-amylases characterized by having a specific activity
at least 25% higher than the specific activity of Termamyl~ at a
temperature range of 25°C to 55°C and at a pH value in the range
of 8
to 10, measured by the Phadebas~ a-amylase activity assay. (Such
Phadebas~ a-amylase activity assay is described at pages 9-10, WO
95/26397.) Also included herein are a-amylases which are at least 80%
homologous with the amino acid sequences shown in the SEQ !D listings
in the references. These enzymes are preferably incorporated into
laundry detergent compositions at a level from 0.00018% to 0.060%
pure enzyme by weight of the total composition, more preferably from
0.00024% to 0.048% pure enzyme by weight of the total composition.
Cellulases usable herein include both bacterial and fungal types,
preferably having a pH optimum between 5 and 9.5. U.S. 4,435,307,
Barbesgoard et al, March 6, 1984, discloses suitable fungal cellulases
from Humicola insolens or Humicoia strain DSM1800 or a cellulase 212-
producing fungus belonging to the genus Aeromonas, and cellulase
extracted from the hepatopancreas of a marine mollusk, Dolabella
Auricula Solander. Suitable cellulases are also disclosed in GB-A-
2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME~ and
CELLUZYME° (Novo) are especially useful. See also WO 9117243 to
Novo.
CA 02258670 2001-10-15
31
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 GB 1,372,034. See also lipases
in Japanese Patent Application 53.20487, laid open Feb. 24, 1978.
This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya,
Japan, under the trade mark Lipase P "Amano," or "Amano-P." Other
suitable commercial lipases include Amano-CES, lipases ex
Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum
NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacier
viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co.,
The Netherlands, and lipases ex Pseudomonas gladioli. LIPOLASE~
enzyme derived from Humicola lanuginosa and commercially available
from Novo, see also EP 341,947, is a preferred lipase for use herein.
Lipase and amylase variants stabilized against peroxidase enzymes are
described in WO 9414951 A to Novo. See also WO 9205249 and RD
94359044. In spite of the large number of publications on lipase
enzymes, only the lipase derived from Humicola lanuginosa and produced
in Aspergillus oryzae as host has so far found widespread application as
additive for fabric washing products. It is available from Novo Nordisk
under the trademark Lipolase'", as noted above. In order to optimize the
stain removal performance of Lipolase, Novo Nordisk have made a
number of variants. As described in WO 92/05249, the D96L variant of
the native Humicola lanuginosa lipase improves the lard stain removal
efficiency by a factor 4.4 over the wild-type lipase (enzymes compared
in an amount ranging from 0.075 to 2.5 mg protein per liter). Research
Disclosure No. 35944 published on March 10, 1994, by Novo Nordisk
discloses that the lipase variant (D96L) may be added in an amount
corresponding to 0.001-100- mg (5-500,000 LUlliter) lipase variant per
liter of wash liquor. Cutinase enzymes suitable for use herein are
described in WO 8809367 A to Genencor.
Peroxidase enzymes may be used in combination with oxygen sources,
e.g., percarbonate, perborate. hydrogen peroxide, etc., for "solution
bleaching" or prevention of transfer of dyes or pigments removed from
substrates during the wash to other substrates present in the wash
solution. Known peroxidases include horseradish peroxidase, ligninase,
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
32
and hafoperoxidases such as chloro- or bromo-peroxidase. Peroxidase-
containing detergent compositions are disclosed in WO 89099813 A,
October 19, 1989 to Novo and WO 8909813 A to Novo.
A range of enzyme materials and means for their incorporation into
synthetic detergent compositions is also disclosed in WO 9307263 A
and WO 9307260 A to Genencor International, WO 8908694 A to
Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes
are further disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and
in U.S. 4,507,27 9, Hughes, March 26, 1985. Enzyme materials useful
for liquid detergent formulations, and their incorporation into such
formulations, are disclosed in U.S. 4,261,868, Hora et al, April 14,
1981. Enzymes for use in detergents can be stabilised by various
techniques. Enzyme stabilisation techniques are disclosed and
exemplified in U.S. 3,600,319, August 17, 1971, Gedge et al, EP
199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme
stabilisation systems are also described, for example, in U.S.
3,519,570. A useful Bacillus, sp. AC13 giving proteases, xylanases and
cellulases, is described in WO 9401532 A to Novo.
Polymeric Dispersing Agents
Polymeric dispersing agents can be utilized at levels from 0.5% to 8%,
by weight, in the compositions herein, especially in the presence of
zeolite and/or layered silicate builders. Suitable polymeric dispersing
agents include polymeric polycarboxylates and polyethylene glycols,
although others known in the art can also be used.
Polymeric polycarboxyiate 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 polycarboxylates are selected from 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 carboxyiate radicals such as vinylmethyl ether,
styrene, ethylene, etc. is suitable provided that such segments do not
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
33
constitute more than 40% by weight. Polymeric polycarboxylate
materials can also optionally include further monomeric units such as
nonionic spacing units. For example, suitable nonionic spacing units may
include vinyl alcohol or vinyl acetate.
Particularly preferred polymeric polycarboxylates are co-polymers derived
from monomers of acrylic acid and malefic acid. The average molecular
weight of such polymers in the acid form preferably ranges from 2,000
to 10,000, more preferably from 4,000 to 7,000 and most preferably
from 4,000 to 5,000. Water-soluble salts of such acrylic/maleic acid
polymers can include, for example, the alkali metal, ammonium and
substituted ammonium salts. Soluble polymers 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. The ratio of acrylate to maleate segments in such
copolymers will generally range from 30:1 to 1:1, more preferably from
10:1 to 2:1. Soluble acrylate/maleate copolymers of this type are known
materials which are described in EP 66915 as well as in EP 193,360,
which also describes such polymers comprising hydroxypropylacrylate.
Of these acrylic/maleic-based copolymers, the water-soluble salts of
copolymers of acrylic acid and malefic acid are preferred.
Another class of polymeric poiycarboxylic acid compounds suitable for
use herein are the homo-polymeric polycarboxylic acid compounds
derived from acrylic acid. The average molecular weight of such homo-
polymers in the acid form preferably ranges from 2,000 to 100,000,
more preferably from 3,000 to 75,000, most preferably from 4,000 to
65,000.
A further example of polymeric polycarboxylic compounds which may be
used herein include the maieic/acrylic/vinyl alcohol terpoiymers. Such
materials are also disclosed in EP 193,360, including, for example, the
45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
Another example of polymeric polycarboxylic compounds which may be
used herein include the biodegradable polyaspartic acid and polyglutamic
acid compounds.
CA 02258670 1998-12-17
WO 98/00504 PCT/US97111068
34
Suds Suaaressors
A wide variety of materials may be used as suds suppressors, and suds
suppressors are well known to those skilled in the art. See, for example,
Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume
7, pages 430-447 fJohn Wiley & Sons, Inc., 1979). One category of
suds suppressor of particular interest encompasses monocarboxylic fatty
acid and soluble salts therein. See U.S. 2,954,347. The monocarboxylic
fatty acids and salts thereof used as suds suppressor typically have
hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18
carbon atoms. Suitable salts include the alkali metal salts such as
sodium, potassium, and lithium salts, and ammonium and
aikanolammonium salts.
The detergent compositions herein may also contain non-surfactant suds
suppressors. These include, for example: high molecular weight
hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid
triglycerides), fatty acid esters of monovalent alcohols, aliphatic C 1 g-
C40 ketones (e.g., stearone), etc. Other suds inhibitors include N-
alkylated amino triazines such as tri- to hexa-alkylmelamines or dl- to
tetra-alkyldiamine chlortriazines formed as products of cyanuric chloride
with two or three moles of a primary or secondary amine containing 1 to
24 carbon atoms, propylene oxide, and monostearyl phosphates such as
monostearyl alcohol phosphate ester and monostearyl di-alkali metal
(e.g., K, Na, and Li) phosphates and phosphate esters. The hydrocarbons
such as paraffin and haloparaffin can be utilized in liquid form. It is also
known to utilize waxy hydrocarbons, preferably having a melting point
below 100°C. The hydrocarbons constitute a preferred category of suds
suppressor for detergent compositions. Hydrocarbon suds suppressors
are described, for example, in U.S. 4,2fi5,779. The hydrocarbons, thus,
include aliphatic, alicyclic, aromatic, and heterocyclic saturated or
unsaturated hydrocarbons having from 12 to 70 carbon atoms. The term
"paraffin," as used in this suds suppressor discussion, is intended to
include mixtures of true paraffins and cyclic hydrocarbons.
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
Another preferred category of non-surfactant suds suppressors
comprises silicone suds suppressors. This category includes the use of
polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or
emulsions of polyorganosiloxane oils or resins, and combinations of
polyorganosiloxane with silica particles wherein the polyorganosiloxane is
chemisorbed or fused onto the silica. Silicone suds suppressors are well
known in the art and are, for example, disclosed in U.S. 4,265,779 and
EP 354016.
Other silicone suds suppressors are disclosed in U.S. 3,455,839 which
relates to compositions and processes for defoaming aqueous solutions
by incorporating therein small amounts of polydimethylsiloxane fluids.
Mixtures of silicone and siianated silica are described, for instance, in
German Patent Application DOS 2,124,526. Silicone defoamers and
suds controlling agents in granular detergent compositions are disclosed
in U.S. 3,933,672 and in U.S. 4,652,392.
An exemplary silicone based suds suppressor for use herein is a suds
suppressing amount of a suds controlling agent consisting essentially of:
(i) polydimethylsiloxane fluid having a viscosity of from 20 cs.
to 1, 500 cs. at 25 ° C;
(ii) from 5 to 50 parts per 100 parts by weight of (i) of siloxane
resin composed of (CH3)3Si01/2 units of Si02 units in a
ratio of from (CH3)3 Si01/2 units and to Si02 units of from
U.6:1 to 1.2:1; and
(iii) from 1 to 20 parts per 100 parts by weight of (i) of a solid
silica gel.
In the preferred silicone suds suppressor used herein, the solvent for a
continuous phase is made up of certain polyethylene glycols or
polyethylene-polypropylene glycol copolymers or mixtures thereof
(preferred), or polypropylene glycol. The primary silicone suds suppressor
is branched/crosslinked and preferably not linear.
The silicone suds suppressor herein preferably comprises polyethylene
glycol and a copolymer of polyethylene glycol/polypropylene glycol, all
having an average molecular weight of less than 1,000, preferably
CA 02258670 1998-12-17
WO 98100504 PCTIUS97/11068
36
between 100 and 800. The polyethylene glycol and
polyethylene/polypropylene copolymers herein have a solubility in water
at room temperature of more than 2 weight %, preferably more than 5
weight %.
The preferred solvent herein is polyethylene glycol having an average
molecular weight of less than 1,000, more preferably between 100 and
800, most preferably between 200 and 400, and a copolymer of
polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300.
Preferred is a weight ratio of between 1:7 and 1:10, most preferably
between 1 :3 and 1:6, of polyethylene giycol:copolymer of polyethylene-
polypropylene glycol.
The preferred silicone suds suppressors used herein do not contain
polypropylene glycol, particularly of 4,000 molecular weight. They also
preferably do not contain block copolymers of ethylene oxide and
propylene oxide, like PLURONIC L101.
Other suds suppressors useful herein comprise the secondary alcohols
(e.g., 2-alkyl aikanolsl and mixtures of such alcohols with silicone oils,
such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP
150,872. The secondary aicohols include the C6-C16 alkyl alcohols
having a C 1-C 16 chain. A preferred alcohol is 2-butyl octanol, which is
available from Condea under the trademark ISOFOL 12. Mixtures of
secondary alcohols are available under the trademark ISALCHEM 123
from Enichem. Mixed suds suppressors typically comprise mixtures of
alcohol + silicone at a weight ratio of 1:5 to 5:1.
For any detergent compositions to be used in automatic laundry washing
machines, suds should not form to the extent that they overflow the
washing machine. Suds suppressors, when utilized, are preferably
present in a "suds suppressing amount. By "suds suppressing amount" is
meant that the formulator of the composition can select an amount of
this suds controlling agent that will sufficiently control the suds to result
in a low-sudsing laundry detergent for use in automatic laundry washing
machines.
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
37
The compositions herein will generally comprise from 0% to 5% of suds
suppressor. When utilized as suds suppressors, monocarboxylic fatty
acids, and salts therein, will be present typically in amounts up to 5 %,
by weight, of the detergent composition. Preferably, from 0.5% to 3%
of fatty monocarboxylate suds suppressor is utilized. Silicone suds
suppressors are typically utilized in amounts up to 2.0%, by weight, of
the detergent composition, although higher amounts may be used. This
upper limit is practical in nature, due primarily to concern with keeping
costs minimized and effectiveness of lower amounts for effectively
controlling sudsing. Preferably from 0.01 % to 1 % of silicone suds
suppressor is used, more preferably from 0.25 % to 0.5 %. As used
herein, these weight percentage values include any silica that may be
utilized in combination with polyorganosiioxane, as well as any adjunct
materials that may be utilized. Monostearyl phosphate suds suppressors
are generally utilized in amounts ranging from 0.1 % to 2%, by weight,
of the composition. Hydrocarbon suds suppressors are typically utilized
in amounts ranging from 0.01 % to 5.0%, although higher levels can be
used. The alcohol suds suppressors are typically used at 0.2%-3% by
weight of the finished compositions.
Polymeric Soil Release Aqent
Polymeric soil release agents are characterised 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 (i1 polyoxyethylene segments with
a degree of polymerization of at least 2, or (ii) oxypropylene or
polyoxypropylene segments with a degree of polymerization of from 2 to
10, wherein said hydrophile segment does not encompass any
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
38
oxypropylene unit unless it is bonded to adjacent moieties at each end by
ether linkages, or (iii) a mixture of oxyalkylene units comprising
oxyethylene and from 1 to 30 oxypropylene 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 hydrophiie
segments preferably comprising at least 25% oxyethylene units and
more preferably, especially for such components having 20 to 30
oxypropylene units, at least 50% oxyethylene units; or (b) one or more
hydrophobe components comprising (i) C3 oxyalkylene terephthaiate
segments, wherein, if said hydrophobe components also comprise
oxyethylene terephthalate, the ratio of oxyethylene terephthalate:C3
oxyalkylene terephthalate units is 2:7 or lower, (ii) C4-Cg alkylene or oxy
Cq.-Cg alkylene segments, or mixtures therein, (iii) poly (vinyl ester)
segments, preferably polyvinyl acetate), having a degree of
polymerization of at least 2, or (iv) C 1-C4 alkyl ether or C4 hydroxyalkyl
ether substituents, or mixtures therein, wherein said substituents are
present in the form of C 1-C4 alkyl ether or C4 hydroxyalkyl ether
cellulose derivatives, or mixtures therein, and such cellulose derivatives
are amphiphilic, whereby they have a sufficient level of C 1-C4 alkyl ether
and/or C4 hydroxyalkyl ether units to deposit upon conventional
polyester synthetic fiber surfaces and retain a sufficient level of
hydroxyls, once adhered to such conventional synthetic fiber surface, to
increase fiber surface hydrophilicity, or a combination of (a) and (b).
Typically, the polyoxyethylene segments of (a)(i) will have a degree of
polymerization of from 200, although higher levels can be used,
preferably from 3 to 150, more preferably from 6 to 100. Suitable oxy
C4-Cg alkyiene 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. 4,721,580.
Polymeric soil release agents useful in the present invention also include
cellulosic derivatives such as hydroxyether cellulosic polymers,
copolymeric blocks of ethylene terephthalate or propylene terephthalate
with polyethylene oxide or polypropylene oxide terephthalate, and the
CA 02258670 2001-10-15
39
like. Such agents are commercially available and include hydroxyethers
rM
of cellulose such as METHOCEL (Dow) and carboxy alkyl of cellulose
such as Metolose (Shin Etsu). Cellulosic soil release agents for use herein
also include those selected from C ~ -C4 alkyl and C4 hydroxyalkyl
cellulose; see U.S. 4,000,093.
Soil release agents characterised by poiy(vinyl ester) hydrophobe
segments include graft copolymers of polyvinyl ester), e.g., C1-C6 vinyl
esters, preferably poiylvinyl acetate) grafted onto polyalkylene oxide
backbones, such as polyethylene oxide backbones (see EP 0 219 048).
CommercraMlly available soil release agents of this kind include the
SOKALAN type of material, e.g., SOKALAN HP-22, available tram 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 25,000 to 55,000. See U.S. 3,959,230 and U.S.
3,893,929.
Another preferred polymeric soil release agent is a polyester with repeat
units of ethylene terephthalate units which contains 10-15% by weight
of ethylene terephthalate units together with 90-80% by weight of
polyoxyethyiene terephthalate units, derived from a polyoxyethylene
glycol of average molecular weight 300-5,000. Exa M pies of this polymer
include the c~ mercially available material ZELCON 5126 (from Dupont)
and MILEASE T (from ICI). See also U.S. 4,702,857.
Another preferred polymeric soil release agent is a sulfonated product of
a substantially linear ester oligomer comprising an oligomeric ester
backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal
moieties covalently attached to the backbone. These soil release agents
are described in U.S. 4,968,451. Other suitable polymeric soil release
agents include the terephthalate polyesters of U.S. 4,71 1,730, the
anionic end-capped oligomeric esters of U.S. 4,721,580 and the block
polyester oligomeric compounds of U.S. 4,702,857.
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
Still another preferred soil release agent is an oligomer with repeat units
of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and
oxy-1,2-propylene units. The 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
one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and
oxy-1,2-propyleneoxy units in a ratio of from 1.7 to 1.8, and two end-
cap units of sodium 2-(2-hydroxyethoxyl-ethanesulfonate. Said soil
release agent also comprises from 0.5 % to 20%, by weight of the
oligomer, of a crystalline-reducing stabilizer, preferably selected from
xylene sulfonate, cumene sulfonate, toluene sulfonate and mixtures
thereof.
Preferred polymeric soil release agents also include the soil release
agents of U.S. 4,877,896, which discloses anionic, especially sulfoaroyl,
end-capped terephthalate esters.
If utilized, soil release agents will generally comprise from 0.01 % to
10.0%, by weight, of the compositions herein, typically from 0.1 % to
5%, preferably from 0.2% to 3.0%.
Clav Soil Removal/Anti-redeposition Agents
Granular detergent compositions which contain these compounds
typically contain from 0.01 % to 10.0% by weight of the water-soluble
ethoxylates amines; liquid detergent compositions typically contain
0.01 % to 5%.
The most preferred soil release and anti-redeposition agent is ethoxyiated
tetraethylenepentamine. Exemplary ethoxylated amines are further
described in U.S. 4,597,898. Another group of preferred clay soil
removal-antiredeposition agents are the cationic compounds disclosed in
EP 1 1 1,965. Other clay soil removal/antiredeposition agents which can
be used include the ethoxyiated amine polymers disclosed in EP
111,984; the zwitterionic polymers disclosed in EP 112,592; and the
amine oxides disclosed in U.S. 4,548,744 and the carboxy methyl
cellulose (CMC) mat~;rials. These materials are well known in the art.
CA 02258670 1998-12-17
WO 98/00S04 PCT/US97/11068
41
Dve Transfer Inhibiting Agents
Generally, such dye transfer inhibiting agents include polyvinyl
pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-
vinylpyrrolidone and N-vinylimidazole, manganese phthaiocyanine,
peroxidases, 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 mere preferably from 0.05% to 2%.
Briahteners
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 1.2% by
weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present invention are
those having the structural formula:
Rt Rz
--r( H _ H N O
IV 00 Ij O C ._C O ~ j 00 N
R,~~
S03M S03M R
t
wherein R1 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, chlorv 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-
CA 02258670 2001-10-15
42
bis-hydroxyethyll-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.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and M is a canon such as sodium, the brightener is 4,4'-
bis[[4-aniiino-6-[N-2-hydroxyethyl-N-methylamino)-s-triazine-2-
yl)amino)2,2'-stilbenedisulfonic acid disodium salt. This particular
brightener species is commercially marketed under the trademark Tinopal
5BM-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-yllamino)2,2'-stiibenedisulfonic acid, sodium salt. This
particular brightener species is commercially marketed under the
trademark Tinopal AMS-GX by Ciba Geigy Corporation.
Conventional optical brighteners or other brightening or whitening agents
known in the art can be incorporated at levels typically from 0.005% to
5%, preferably from 0.01 % to 1.2% and most preferably from 0.05% to
1.2%, by weight, into the detergent compositions herein. Commercial
optical brighteners which may be useful can be classified into subgroups,
which include, but are not necessarily limited to, derivatives of stilbene,
pyrazoline, coumarin, carboxylic acid, methinecyanines,
dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ring
heterocycles, and other miscellaneous agents. Examples of such
brighteners are disclosed in "The Production and Application of
Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley
& Sons, New York ( 19821. Further optical brightener which may also be
used include naphthalimide, benzoxazole, benzofuran, benzimidazole and
any mixtures thereof.
Fabric Softeners
Various through-the-wash fabric softeners, especially the impalpable
smectite clays of U.S. 4,062,647, as well as other softener clays known
in the art, can optionally be used typically at levels of from 0.5% to
CA 02258670 1998-12-17
WO 98!00504 PCT/US97/11068
43
10%, preferably from 0.5% to 2% by weight in the present
compositions to provide fabric softener benefits concurrently with fabric
cleaning. Clay softeners can be used in combination with amine and
cationic softeners as disclosed, for example, in U.S. 4,375,41 fi and U.S.
4,291,071.
Other Inc,~redients
A wide variety of other functional ingredients useful in detergent
compositions can be included in the compositions herein, including other
active ingredients, carriers, hydrotropes, processing aids, dyes or
pigments, solvents for liquid formulations, solid fillers for bar
compositions. The detergent compositions herein will preferably be
formulated such that, during use in aqueous cleaning operations, the
wash water will have a pH of between 6.5 and 1 1, preferably between
7.5 and 10.5. Techniques for controlling pH at recommended usage
levels include the use of buffers, alkalis, acids, etc., and are well known
to those skilled in the art.
Other optional ingredients
Other optional ingredients suitable for inclusion in the compositions of
the invention include colours and filler salts, with sodium sulfate being a
preferred filler salt.
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
44
Form of the compositions
The detergent compositions of the invention can be formulated in any
desirable form such as powders, granulates, pastes, liquids, and gels.
Preferably, the detergent composition of the invention is in granular
form.
Gel compositions
The detergent compositions of the present invention may also be in the
form of gels. Such compositions are typically formulated with polyakenyl
polyether having a molecular weight of from 750,000 to 4,000,000.
Solid comaositions
The detergent compositions of the invention may also be in the form of
solids, such as powders and granules.
Preferably, the mean particle size of the components of granular
compositions should be such that no more than 5% of particles are
greater than l.4mm in diameter and not more than 5% of particles are
less than 0.15mm in diameter.
The term "mean particle size" as defined herein is determined by sieving
a sample of the composition into a number of fractions (typically 5
fractions) on a series of Tyler sieves. The weight fractions thereby
obtained are plotted against the aperture size of the sieves. The mean
particle size is taken to be the aperture size through which 50% by
weight of the sample would pass.
The bulk density of granular detergent compositions in accordance with
the present invention is particularly useful in concentrated granular
detergent compositions that are characterised by a relatively high density
in comparison with conventional laundry detergent compositions. Such
high density compositions typically have a bulk density of at least 400
g/litre, more preferably from 650 g/litre to 1200 g/litre, most preferably
. from 800g/litre to 1000g/litre.
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
Making processes - granular compositions
In general, granular detergent compositions in accordance with the
present invention can be made via a variety of methods including dry
mixing, spray drying, agglomeration and granulation.
The invention is illustrated in the following non-limiting examples, in
which all percentages are on a weight basis unless otherwise stated.
In the detergent compositions of the invention, the abbreviated
component identifications have the following meanings:
RYAS . Sodium C 1 X - C 1 Y alkyl sulfate
XYEZ . A C1 x-1 y Predominantly linear primary
alcohol
condensed with an average of Z moles of
ethylene oxide
XYEZS . C1 X - C1 Y sodium alkyl sulphate condensed
with
an average of Z moles of ethylene oxide per
mole
TFAA . C1 g-C1 g alkyl N-methyl glucamide
CEQ : R1COOCH2CH2.N+(CH3~3 with R1 = C11-C13
QAS : R2.N+fCH3)2(C2H40H) with R2 = C12 - C14
LAS . Sodium linear C12 alkyl benzene sulphonate
TAS : Sodium tallow alcohol sulphate
Soap . Sodium linear alkyl carboxylate derived
from an
80/20 mixture of tallow and a coconut oils.
STPP . Anhydrous sodium tripolyphosphate
Zeolite A : Hydrated Sodium Aluminosilicate of formula
Nal2(A102Si02)12. 27H20
having a primary particle size in the range
from
0.1 to 10 micrometers
NaSKS-6 . Crystalline layered silicate of formula
S -Na2Si205
Carbonate . Anhydrous sodium carbonate with a particle
size between 200pm and 900pm
CA 02258670 1998-12-17
WO 98/00504 PCT/LJS97111068
46
Silicate : Amorphous Sodium Silicate (Si02:Na20; 2.0
ratio)
Sulphate . Anhydrous sodium sulphate
Citrate : Tri-sodium citrate dihydrate of activity 86.4%
with a particle size distribution between 425p
m and 850~m
MA/AA : Copolymer of 1:4 maleic/acrylic acid, average
molecular weight about 70,000.
CMC : Sodium carboxymethyl cellulose
Savinase . Proteolytic enzyme of activity 4KNPU/g
Carezyme . Cellulytic enzyme of activity 1000 CEVU/g
Termamyl . Amylolytic enzyme of activity 60KNU/g
Lipolase . Lipolytic enzyme of activity 100kLU/g
all sold by NOVO industries A/S and of activity
mentioned above unless otherwise specified
PB4 . Sodium perborate tetrahydrate of nominal
formula NaB02.3H20.H202
PB1 : Anhydrous sodium perborate bleach of
nominal formula NaB02.H202
Percarbonate Sodium Percarbonate of nominal formula
:
2Na2C03.3H202
TAED : Tetraacetyl ethylene diamine
NACA-OBS . (6-nonanamidocaproyl)oxy benzene sulfonate
NOBS . Nonanoyloxybenzene sulfonate in the
form of
the sodium salt
DTPMP : Diethylene triamine penta (methylene
phosphonate), marketed by Monsanto under
the Trade name bequest 2060
Photoactivated Sulphonated Zinc Phthalocyanin encapsulated
.
in bleach dextrin soluble polymer
Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl
.
Brightener 2 Disodium 4,4'-bis(4-anilino-6-morpholino-
.
1.3.5-triazin-2-yl)amino) stilbene-2:2'-
disulphonate.
CA 02258670 2001-10-15
47
HEDP . 1,1-hydroxyethane diphosphonic acid
STS . Sodium toluene sulfonate
SRP . Sulfobenzoyl end capped esters with
oxyethylene oxy and terephtaloyl backbone
Silicone antifoam : Polydimethyldiloxane foam controller with
Siloxane-oxyalkylene copolymer as dispersing
agent with a ratio of said foam controller
to said dispersing agent of 10:1 to 100:1.
Example 1
The following bleach precursor particulates were made:
Example 1 2 3 4 5 6 7 8
NACA-OBS 65 65 - 65 38 74.5 65
NOES - 65 - - -
TAED 65 - 27 - -
LAS 9.8 9.8 9.8 9.8 10 10
28AS 9.8 9.8 - - - -
24E3 0.3 0.3 0.3 0.3 0.3 0.5 0.5 0.5
STS 0.96 0.96 0.96 0.96 0.9 1.0 1.0
citric acid11.3 1 11.3 1 - 11.3 10 10
1.3 1.3
CMC 6.2 6.2 6.2 6.2 6.2 2.0 10
Water to
balance
to100r6
In each of examples 1-6, the bleach precursor (i.e. NACA-OBS and/or
TAED or NOBS) was premixed with CMC and then water was added,
with (example 2 to 7) or without (example 1 ) nonionic surfactant. The
TM
remaining ingredients were added and mixed in a Loedige FM mixer. The
premix was then fed into a dome extruder (Fuji Paudal Model DGL-1
having a die with 0.8 mm orifices and extruded at a pressure of about
20 bar. The resulting extrudate was then fed into a rotating disc
CA 02258670 1998-12-17
WO 98100504 PCT/US97/11068
48
spheroniser (Fuji Paudal QJ-400) where they were broken down into
short lengths and formed into substantially spherical particles. The
particles were then dried in a Niro vibrating fluid-bed dryer resulting in
crisp, free-flowing dust free particles with a particle size range of from
0.25 mm to 2.00 mm and a Heubach dust measurement of less than
1 OOmg/g.
The particulate of Examples 1 was taken and coated in a drum mixer
with 24E3 surfactant and then further dusted with 1 part of Zeoiite in a
second drum mixer. The resultant particles remained crisp and free-
flowing and showed improved resistance to dust-generation as
demonstrated by a reduction in Heubach dust value from 35mg/g (un-
coated) to 12 mg/g.
The particulate of Examples 7 was taken and coated in a drum mixer
with 0.4 parts of 24E3 surfactant and then further dusted with 1 part of
Zeolite in a second drum mixer. The resultant particles remained crisp
and free-flowing and showed improved resistance to dust-generation as
demonstrated by a reduction in Heubach dust value from 35mg/g (un-
coated) to 12 mg/g.
The bleach particulate of Example 8 was made by premixing the bleach
precursor with CMC and 20 parts of water were added. The mixture was
mixed for 5 minutes in a Loedige FM mixer. The remaining ingredients
were added and the mixing continued for a further 5 minutes. The
resultant wet agglomerate was then passed to a fluid bed drier to
remove water to give crisp free flowing particles.
Example 2
The following detergent formulations, according to the present invention
were prepared, where formulation A is a phosphorus-containing
detergent composition, formulation B is a zeolite-containing detergent
composition and formulation C is a compact detergent composition:
B C
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/I1068
49
Blown Powder
STPP 24.0 - 24.0
Zeolite A - 24.0
Sulphate 9.0 6.0 13.0
MA/AA 2.0 4.0 2.0
LAS 6.0 8.0 1 1.0
TAS 2.0 - -
Silicate 7.0 3.0 3.0
CMC 1.0 1.0 p,5
Brightener 2 0.2 0.2 0.2
Soap 1.0 1.0 1.0
DTPMP 0.4 0.4 0,2
Spray On
C45E7 2.5 2.5 2.0
C25E3 2.5 2.5 2.0
Silicone antifoam 0.3 0.3 0.3
Perfume 0.3 0.3 0.3
Dry additives
Carbonate 6.0 13.0 15.0
PB4 18.0 18.0 10
PB 1 4.0 4.0 -
Bleach precursor 3.0 3.0 1.0
particulate) ~" )
Photoactivated bleach 0.02% 0.02% 0.02%
~
Savinase 1.0 1.0 1.0
Lipolase 0.4 0.4 0.4
Termamyl 0.25 0.30 0.15
Sulphate 3.0 3.0 5.0
Balance (Moisture and
Miscellaneous) to 100
Density (g/litre) 630 670 670
('") Bleach precursor particulate as made in any one of examples 1-8
Example 3
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
The following detergent formulations D to E, according to the present
invention were prepared:
D E
LAS 20.0 14.0
QAS 0.7 1.0
TFAA - 1.0
C25E5/C45E7 - 2.0
C45E3S - 2.5
STPP 30.0 18.0
Silicate 9.0 5.0
Carbonate 13.0 7.5
Bicarbonate - 7.5
DTPMP 0.7 1.0
SRP 1 0.3 0.2
MA/AA 2.0 1.5
CMC 0.8 0.4
Savinase 0.8 1.0
Termamyl 0.8 0.4
Lipolase 0.2 0.1
Carezyme (5T) 0.15 0.05
Photoactivated bleach (ppm) 70ppm 45ppm
Brightener 1 0.2 0.2
PB1 6.0 2.0
Bleach precursor particulatel'") 2.0 1.0
Balance (Moisture and Miscellaneous)
to
100
( ~") Bleach precursor particulate as made in any one of examples 1-8
Example 4
The following detergent formulations F to H, according to the present
invention were prepared:
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
51
G H
Blown Powder .
Zeolite A 30.0 22.0 6.0
Sulphate 19.0 10.0 7.0
MA/AA 3.0 3.0 6.0
LAS 14.0 12.0 22.0
C45AS 8.0 7.0 7,0
Silicate - 1.0 5.0
Soap - _
2.0
Brightener 1 0.2 0.2 0.2
Carbonate 8.0 16.0 20.0
DTPM P - 0.4 0.4
Spray On
C45E7 1.0 1.0 1.0
Dry additives
PVPVI/PVNO 0.5 0.5 0.5
Savinase 1.0 1.0 1.0
Lipolase 0.4 0.4 0.4
Termamyl 0.1 0.1 0.1
Carezyme 0.1 0.1 0.1
Bleach precursor - 6.1 4.5
particulate( ~")
PB 1 1.0 5.0 6.0
Sulphate - 6.0 -
Balance (Moisture and
Miscellaneous) to 100
('") Bleach precursor particulate as made in any one of examples 1-8
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
52
Example 5
The following high density and bleach-containing detergent formulations
I to K, according to the present invention were prepared:
i J K
Blown Powder
Zeolite A 15.0 15.0 15.0
Sulphate - 5.0 -
LAS 3.0 3.0 3.0
QAS - 1.5 1.5
DTPMP 0.4 0.4 0.4
CMC 0.4 0.4 0.4
MA/AA 4.0 2.0 2.0
Agglomerates
LAS 5.0 5.0 5.0
TAS 2.0 2.0 2.0
Silicate 3.0 3.0 4.0
Zeolite A 8.0 8.0 8.0
Carbonate 8.0 8.0 4.0
Spray On
Perfume 0.3 0.3 0.3
C45E7 2.0 2.0 2.0
C25E3 2.0 -
Dry additives
Citrate 5.0 - 2.0
Bicarbonate - 3.0
Carbonate 8.0 15.0 10.0
Bleach precursor particulate()6.0 2.0 5.0
pg 1 14.0 7.0 10.0
Polyethylene oxide of MW - - 0.2
5,000,000
Bentonite - - 10.0
Savinase 1.0 1.0 1.0
Lipolase 0.4 0.4 0.4
Termamyl 0.6 0.6 0.6
Carezyme 0.6 0.6 0.6
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
53
Silicone antifoam granule 5.0 5.0 5.0
Dry additives
Sulphate - 3.0 -
Balance (Moisture and Miscellaneous)
to 100
Density (g/litrel 850 850 850
(") Bleach precursor particulate as made in any one of examples 1-8
Example 6
The following high density detergent formulations L and M, according to
the present invention were prepared:
L M
Agglomerate
C45AS 1 1.0 14.0
Zeolite A 15.0 6.0
Carbonate 4.0 8.0
MA/AA 4.0 2.0
CMC 0.5 0.5
DTPMP 0.4 0.4
Spray On
C25E5 5.0 5.0
Perfume 0.5 0.5
Dry Additives
HEDP 0.5 0.3
SKS 6 13.0 10.0
Citrate 3.0 1.0
Bleach precursor particulate()5.0 7.0
PC 20.0 20.0
SRP 1 0.3 0.3
Savinase 1.4 1.4
Lipolase 0.4 0.4
Carezyme 0.6 0.6
Termamyl 0.6 0.6
Silicone antifoam particle 5.0 5.0
CA 02258670 1998-12-17
WO 98/00504 PCT/US97/11068
54
Brightener 1 0.2 0.2
Brightener 2 0.2
Balance (Moisture and Miscellaneous)
to 100
Density (g/litre) 850 850
(~') Bleach precursor particulate as made in any one of examples 1-8
Example 7
The following laundry detergent compositions N to O were prepared in
accord with the invention:
N O
LAS 8.0 8.0
C25E3 3.4 3.4
CEQ 0.8 -
QAS - 0.8
Zeolite A 18.1 18.1
Carbonate 13.0 13.0
Silicate 1.4 1.4
Sulfate 26.1 26.1
PB4 9.0 9.0
Bleach precursor particuiate(~) 1.5. 1.5
DTPMP 0.25 0.25
HEDP 0.3 0.3
Protease 0.26 0.26
Amylase 0.1 0.1
MA/AA 0.3 0.3
CMC 0.2 0.2
Photoactivated bleach (ppm) 15 ppm 15 ppm
Brightener 1 0.09 0.09
Perfume 0.3 0.3
Silicone antifoam 0.5 0.5
Misc/minors to 100%
Density in A/litre I 850 I 850
( ~" ) Bleach precursor particulate as made in any one of examples 1-8
