Note: Descriptions are shown in the official language in which they were submitted.
W0 96!06148 PCT/US95J09SlZ4
1
DETERGENT COMIPOSITIONS
CORIPRISING LIPOLYTIC ENZY1VIES
Field of the Invention
The present invention relates to detergent compositions comprising
enzymes, in particular lipases and a lipase compatible anionic surfactant
system.
background of the Invention
One of the most common surfactants currently incorporated in
detergent compositions is alkyl benzene sulphonate, particularly linear
benzene sulphonate, herein referred to as LAS. The use of alkyl benzene
sulphonate usually in combination with other anionic or nonionic
surfactants has been found to give particularly effective cleaning
~1~~~~~
wo 9srasias Prrnlsssra9sas
2
performance, especially on greasy and oily stains over a wide range of
temperatures and conditions.
It is also highly beneficial to incorporate enzymes into detergent
compositions in order to improve overall performance. In particular
lipases have been found to provide improvement in the removal of oily
stains.
However, it is known from the art ( for example EP 373 850} that
lipases are particularly sensitive to the other ingredients in the
composition in the wash liquor. In particular they are unstable in the
presence of surface active agents. This problem is particularly acute in the
presence of LAS, which has been shown to significantly reduce the
activity of lipase.
Low LAS detergent compositions have been described in the art,
for example in EP-A 544 490 and US 4 260 529. However, such
detergent compositions often have an low overall level of anionic
surfactant which may result in a lower soil suspension capacity and less
effective neutralisation of cationic fabric conditioners which may be
present in the wash or on the fabric surface.
The art also describes the use of anionic surfactant based detergent
compositions, preferably alkyl sulphate, comprising low levels of LAS.
For example GE 1 399966 discloses detergent compositions comprising
primary alcohol sulphate (PAS) and nonionic surfactants. EP-A 342 917
discloses detergent compositions comprising PA5 having a range of chain
lengths to improve the cleaning performance at lower temperatures.
However, it has been observed that such detergent compositions do
exhibit the same cleaning performance as the corresponding LAS
compositions.
Therefore, it is an object of the present invention to replace the
alkyl benzene sulphonate in surfactant systems with a surfactant which
provides excellent cleaning benefits, giving similar overall performance
compared to the alkyl benzene sulphonate surfactant systems and in the
presence of which lipases are stable in the wash. In addition, another aim
CA 02198094 2000-02-04
3
of the detergent manufactures is to develop a surfactant system which is
readily biodegradable.
It has now been found that these objectives can be achieved by the
use of a surfactant system comprising an alkyl alkoxylated sulphate
having an average alkoxylation degree of from 0.1 to 10, having specific
ratios of alkyl monoalkoxylated sulphate, alkyl dialkoxylated sulphate and
alkyl alkoxylates sulphates with 3 or more alkoxy groups per alkyl group.
It has been found that said alkyl alkoxy sulphates provide excellent
cleaning benefits over a wide range of temperatures and show enhanced
lipase stability.
Another advantage of the surfactant system of the present invention
are the excellent wetting properties, which is a highly desirable property
in detergent compositions.
Furthermore, the surfactant systems of the present invention is
particularly efficient in the removal of oily stains.
Detergent compositions comprising alkyl ethoxy sulphates (referred
to herein as AES) and lipases have been described in various contexts in
the art. For example WO 92/06158 discloses detergent compositions
comprising AES with an ethoxylation degree greater than 0, comprising
lipases. CA 2,113,413 discloses detergent compositions comprising AES
with a preferred average ethoxylation of from 0.5 to 2. Lipases are
mentioned. CA 2,131,171 discloses granular detergent compositions
comprising AES with an ethoxylation degree of 1 to 7. Lipases are
disclosed.
JP 4072395 discloses a liquid detergent composition comprising
alkyl/alkenyl sulphates having an average ethoxylation of 1 to 7 and
enzymes. JP 1161096 discloses a detergent composition comprising
alkenyl ether sulphates having from 0.5 to 8 ethoxylation, alkyl sulphates,
LAS and lipases.
However, none of the identified art recognise the performance
benefits associated with anionic surfactant systems comprising alkyl
CA 02198094 2000-02-04
4
alkoxylated sulphates having specific ratios of mono-, di- and trialkoxylated
sulphates in combination with lipases as in the present invention.
Summary of the Invention
The present invention is a detergent composition comprising from 1 % to 90%
of an anionic surfactant system, from about 0.25% to about 10% of a borate
compound, a lipolytic enzyme having from 50 to 100 000 (LU) lipase units per
gram
of detergent composition, and a gemini polyhydroxy fatty amide as defined
below
wherein said anionic surfactant system comprises less than 40% alkyl benzene
sulphonate and
at least 30% of an alkyl alkoxylated sulphate having an average degree of
alkoxylation of from 0.1 to 10 characterised in that
the ratio of the combined weight of alkyl monoalkoxylated sulphates and alkyl
dialkoxylated sulphates to the total weight of anionic surfactant is at least
0.2 to 1 and
the ratio of the combined weight of alkyl monoalkoxylated sulphates and alkyl
dialkoxylated sulphates to the total weight of alkyl alkoxylated sulphates
having 3 or
more alkoxyl groups per alkyl group is 1 or greater.
All weights, ratios and percentages are given as a % weight of the total
composition unless otherwise stated.
Detailed Description of the Invention
The present invention is a detergent composition comprising a lipolytic
enzyme and an anionic surfactant system having improved lipase compatibility.
Thus, an essential component of the present invention is a lipolytic enzyme.
The compositions of the present invention comprise a lipolytic enzyme having
from
50 to 100 000 (LU) lipase units per gram of detergent composition, preferably
from
100 to 10,000 (LU), more preferably from 200 to 1000 (LU) per gram of
detergent
composition.
CA 02198094 2000-02-04
Suitable lipases for use herein include those produced by microorganisms of
the Pseudomonas group, such as Pseudomonas group, such as Pseudomonas stutzeri
ATCC 19.154, as disclosed in British Patent 1,372,034. Suitable lipases
include those
which show a positive immunological cross-reaction with the antibody of the
lipase,
produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase
and
a method for its purification have been described in Japanese Patent
Application 53-
20487, laid open to public inspection on February 24, 1978. This lipase is
available
from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade mark Lipase
P
"Amano," hereinafter referred to as "Amano-P". Such lipases of the present
invention
should show a positive immunological cross-reaction with the Amano-P antibody,
using the standard and well-known immunodiffusion procedure according to
Ouchterlongy (Acta., Med., Scan., 133, pages 76-79 (1950)). These lipases, and
a
method for their immunological cross-reaction with Amano-P, are also described
in
US Patent 4,707,291, Thom et al, issued November 17, 1987. Typical examples
thereof are the Amano-P lipase, the lipase ex Pseudomonas fragi FERM P 1339
(available under the trade mark Amano-B), lipase ex Pseudomonas nitroreducens
var.
lipolyticum FERM P 1338 (available under the trade mark Amano-CES), lipases ex
Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB
3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further
Chromobacter viscosum lipases from US Biochemical Corp., USA and Disoynth Co.,
The Netherlands, and lipases ex Pseudomonas gladioli. Especially suitable
Lipase are
lipase such as Ml Lipase (Ibis) and LipolaseTM (Novo).
Another essential component of the compositions of the present invention is
an anionic surfactant system. Said compositions comprise from 1 % to 90% of an
anionic surfactant system. Said system comprises less than 40% alkyl benzene
sulphonates and more than 30%, preferably more than 50%, most preferably more
than 70% an alkyl alkoxylated sulphate. The alkoxylated sulphate of the
present
invention is represented by the formula:
R~ (CmH2m0)~S03M
PCTJUS95l09584
w0 96/06148
6
wherein Rl is a Clp_2q. , preferably a C12-CI8> most preferably a C1~-
CIS linear or branched hydrocarbyl, m is from 1 to 4, preferably 2 to 4,
most preferably 2, n is 0 to I0, preferably from 1 to 3, and M is an alkali
metal, alkaline earth metal, alkanol amine or ammonium or mixtures
thereof.
According to the present invention the alkyl alkoxylated sulphates
preferably have an average degree of alkoxylation of from 0.1 to 10,
preferably from 0.5 to 3, more preferably from 0.5 to 2, most preferably
from 0.5 to 1. The ratio of the combined weight of alkyl monoalkoxy
sulphates and alkyl dialkoxy sulphates to the kotal weight of anionic
surfactant is at least 0.2 to 1, preferably 0.25 to 1, most preferably 0.~ to
1. The ratio of the combined weight of alkyl monoalkoxy sulphates and
alkyl dialkoxy sulphates to total alkyl alkoxy sulphates having 3 or more
alkoxy groups per alkyl group is 1 or greater, preferably 2 to 8, more
preferably 4 to 6.
The anionic surfactant system of the present invention may optionally
comprise other anionic surfactants known in the art. According to the
present invention the compositions comprise from 1% to 90%, preferably
from 1 % to 70%, most preferably from 5% to 60% of said anionic
surfactant system.
Anionic sulphate surfactants
The anionic sulphate surfactant may be any organic sulphate
surfactant, other than the alkyl alkoxylated sulphates of the present
invention, preferably a C10-C16 alkyl sulphate. The counterion for the
anionic sulphate surfactant component is preferably selected from
calcium, sodium, potassium, magnesium, ammonium, or alkanol-
ammonium, and mixtures thereof.
Anionic sulphate surfactants suitable for use herein include Cg-C 17
acyl-N-(C1-C4 alkyl) glucamine sulphates, fatty oleyl glycerol sulphates,
alkyl phenol ethylene oxide ether sulphates, N-acyl C(_20 sarcosinates
and sulphates of alkylpolysaecharides such as the sulphates of CIp-20
alkylpolyglucoside.
~39~~94
WO 96/06148 PCT/US95109584
7
Anionic sulphonate surfactant
Anionic sulphonate surfactants suitable for use herein include, for
example, the salts (e.g. alkali metal salts) of Cg-C20 linear alkylbenzene
sulphonates, Cg-C22 primary or secondary alkane sulphonates, Cg-C24
olefin sulphonates, sulphonated polycarboxylic acids, alkyl glycerol
sulphonates, fatty acyl glycerol sulphonates, fatty oleyl glycerol
sulphonates, paraffin sulphonates, and any mixtures thereof.
Anionic alkyl ethoxy carboxylate surfactant
Alkyl ethoxy carboxylates suitable for use herein include those with
the formula RO(CH2CH20)x CH2C00-M+ wherein R is a C12 to C16
alkyl group, x ranges from O to 10, and the ethoxylate distribution is such
that, on a weight basis, the amount of material where x is 0 is less than
20%, preferably less than IS%, most preferably less than 10%, and the
amount of material where x is greater than 7, is less than 25%, preferably
less than 15%, most preferably less than 10%, the average x is from 2 to
4 when the average R is C13 ar Iess, and the average x is from 3 to 6
when the average R is greater than Clg, and M is a cation, preferably
chosen from alkali metal, alkaline earth metal, ammonium mono, di-,
and tri-ethanol-ammonium, most preferably from sodium, potassium,
ammonium and mixtures thereof with magnesium ions. The preferred
alkyl ethoxy carboxylates are those where R is a C12 to C14 alkyl group.
Anionic alk~rl aol, ey thoxv nolycarboxvlate surfactant
Alkyl polyethoxy polycarboxylate surfactants suitable for use herein
include those having the formula:
R-0-(CH-CH-0)x-R3
i i
R.~ R2
wherein R is a C6 to Clg alkyl group, x is from I to 25, RI and R2 are
selected from the group consisting of hydrogen, methyl acid radical,
succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof,
2198~9~
WO 96J06148 PCTlLT895109584
wherein at least one RI or R~ is a succinic acid radical or
hydroxysuccinic acid radical, and R3 is selected from the group
consisting of hydrogen, substituted or unsubstituCed hydrocarbon having
between I and $ carbon atoms, and mixtures thereof.
2~9R094
W O 9GlOG 148 PCTlUS95109584
9
Anionic secondary soap surfactant
Secondary soap surfactants (aka "alkyl carboxyl surfactants") useful
herein are those which contain a carboxyl unit connected to a secondary
carbon. It is to be understood herein that 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 should contain
no ether linkages, no ester linkages and no hydroxyl groups. There
should be no nitrogen atoms in the head-group (amphiphilic portion). The
secondary soap surfactants usually contain 11-15 total carbon atoms,
although slightly more (e.g., up to 16) can be tolerated, e.g. p-octyl
benzoic acid.
The following general structures further illustrate some of the
secondary soap surfactants (ar their precursor acids) useful herein.
A. A highly preferred class of secondary soaps useful herein
comprises the secondary carboxyl materials of the formula R3
CH(R4)COOM, wherein R3 is CH3(CH2)x and R4 is CH3(CH2)y,
wherein y can be O or an integer from 1 to 4, x is an integer from 4 to 10
and the sum of (x + y) is 6-14, preferably 7-13, most preferably 12.
B. Another class of secondary soaps useful herein comprises those
carboxyl compounds wherein the carboxyl substituent is on a ring
hydrocarbyl unit, i.e., secondary soaps of the formula RS-R6-COOM,
wherein RS is C7-C10, preferably C8-Cg, alkyl or alkenyl and R6 is a
ring structure, such as benzene, cyclopentane and cyclohexane. (Note:
RS can be in the ortho, meta or para position relative to the carboxyl on
the ring.)
C. Still another class of secondary soaps comprises secondary
carboxyl compounds of the formula CH3(CHR)k-(CH2)m-(CHR)n-
CH(COOM)(CHR)o-(CH2)p-(CHR)q-CH3, wherein each R is C1-Cq.
alkyl, wherein k, n, o, q are integers in the range of 0-8, provided that
the total number of carbon atoms (including the carbaxylate) is in the
range of 10 to 18.
WO 91~I0614A 2 ~ ~ ~ ~ ~~ ~ PCTlU895109584
In each of the above formulas A, B and C, the species M can be
any suitable, especially water-solubilizing, counterion, e.g., H, alkali
metal, alkaline earth metal, ammonium, alkanolammonium, di- and tri-
alkanolammonium, and Cl-CS alkyl substituted ammonium. Sodium is
convenient, as is diethanalammonium.
Preferred secondary soap surfactants far use herein are water-
saluble members selected from the group consisting of the water-soluble
salts of 2-methyl-i-undecanoic acid, 2-ethyl-I-decanoic acid, 2-propyI-I-
nonanoic acid, 2-butyl-1-octanoic acid, 2-pentyl-I-heptanoic acid and
isopentadecanoic acid.
Other anionic surfactants
Other anionic surfactants useful for detersive purposes can also be
included in the compositions hereof. These can include salts (including,
for example, sodium, potassium, ammonium, and substituted ammonium
salts such as mono-, di- and triethanolamine salts) of soap, alkyl
phosphates, isethionates such as the acyl isethionates, N-acyl taurates,
acyl alkyl taurines, fatty acid amides of methyl tauride, alkyl succinates
and sulphosuccinates, monoesters of sulphosuccinate (especially saturated
and unsaturated .CIZ-CIg monoesters) diesters of sulphosuccinate
(especially saturated and unsaturated C6-CI4 diesters). Resin acids and
hydrogenated resin acids are also suitable, such as rosin, hydrogenated
rosin, and resin acids and hydrogenated resin acids present in or derived
from tall oil. Further examples are given in "Surface Active Agents and
Detergents" (Vol. I and II by Schwartz, Perry and Berch}.
According to the present invention the anionic surfactant system
preferably comprises less than 40% linear alkyl benzene sulphonate,
preferably less than 20~, more preferably less than 10% linear alkyl
benzene sulphonate. Most preferably the anionic surfactant system of the
present invention is free of alkyl benzene sulphonates.
According to the present invention the compositions may
additionally comprise as optional ingredients other surfactants such
cationic, nonionic, zwitterionic arid amphateric surfactants.
PCTIUS95t09584
W 0 96106148
11
Nonionic surfactant
Suitable nonionic detergent surfactants for use herein include
nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols,
nonionic alkylpolysaccharides and nonionic fatty acid amides. According
to the present invention the compositions comprise from 1 % to 20%,
preferably from 2% to 15% of said nonionic surfactants.
Nonionic condensates of alk~phenols
The polyethylene, polypropylene, and pofybutylene oxide
condensates of alkyl phenols are suitable for use herein. In general, the
polyethylene oxide condensates are preferred. These compounds include
the condensation products of alkyl phenols having an alkyl group
containing from about 6 to about 12 carbon atoms in either a straight
chain or branched chain configuration with the alkylene oxide.
Nonionic ethoxvlated alcohol surfactant
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.
Most preferred are the condensation products of alcohols having an alkyl
group containing from 8 to 14 carbon atoms with from about 6 to about
moles of ethylene oxide per mole of alcohol. Examples of
commercially available nonionic surfactants of this type include
TergitolT~'! 15-S-9 (the condensation product of C11-C15 linear alcohol
with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the
condensation product of C12-C14 Primary alcohol with 6 moles ethylene
oxide with a narrow molecular weight distribution), both marketed by
Union Carbide Corporation; NeodolTM 45-9 (the condensation product of
C14-C1$ linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-
6.5 {the condensation product of C12-C13 linear alcohol with 6.54 moles
CA 02198094 2000-02-04
12
of ethylene oxide), NeodolTM 45-7 (the condensation product of C14-
C15 linear alcohol with 7 moles of ethylene oxide), NeodolTM 45-4 (the
condensation product of C 14-C 15 linear alcohol with 4 moles of ethylene
oxide), NeodolTM23-3 (the condensation product of C 12-C 13 linear
alcohol with 3 moles of ethyene oxide) marketed by Shell Chemical
Company, KyroTM EOBN (the condensation product of C 13-C 15 alcohol
with 9 moles ethylene oxide), marketed by The Procter & Gamble
Company, DobanolTM 91 marketed by the Shell Chemical Company and Liar
111 marketed by Enichem.
Nonionic EO/PO condensatec with ~pylene glycol
The condensation products ,of ethylene oxide with a hydrophobic
base formed by the condensation of propylene oxide with propylene
glycol are suitable for use herein. Examples of compounds of this type
include certain of the commercially-available PluronicTM surfactants,
marketed by BASF.
Nonionic EO condensation products with oroovlene oxide/eth~lene
diamine adducts
The condensation products of ethylene oxide with the product
resulting from the reaction of propylene oxide and ethylenediamine are
suitable for use herein: Examples of this type of nonionic surfactant
include certain of the commercially available TetronicTM compounds,
marketed by BASF.
Nonionic alkvlnolvsac haride surfactant
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 S or 6 carbon atoms can be used, e.g., glucose, galactose and
WO 96/OG148 ~ ~ ~' ~ ~ ~ ~ PCTlU595109584
13
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
R~O(CnH2n0)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl, hydroxyalkyIphenyl, 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, preferably from about 1.3 to about 3, most preferably
from about 1.3 to about 2.7, t is from 0 to 10 and x is from 0 to 10. The
glycosyl is preferably derived from glucose.
Nonionic fat~v acid amide surfacranr
Fatty acid amide surfactants suitable for use herein are those
having the formula:
0 R~
R2-CI -N-Z
wherein R1 is H or a C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy
propyl and R~ is a CS-C31 hydrocarbyl and Z is a
polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3
liydroxy groups directly connected to the chain or an alkoxylated
derivative thereof. Preferably R is a methyl, R is a straight chain C11-
C15 alkyl or alkenyl such as cocnut alkyl or mixtures thereof and Z is
derived from a reducing sugar such as glucose, fructose, maltose, lactose
in a reductive amination reaction
Other polyhydroxy fatty acid amides suitable for use herein are
gemini polyhydroxy fatty acid amides having the formula:
WO 9fi/06t48 ~ ~ ~ ~ ~~ ~ ~ PCTlUS95I0958.t
14
Z Z
I
I
N-X -N
I
I
0=C C=0
I I
R R'
wherein: X is a bridging group having from about 2 to about 200 atoms; Z
and Z' are the same or different alcohol-containing moieties having two or
more hydroxyl groups (e.g., glycerol, and units derived from reducing
sugars such as glucose, maltose and the like), or either one (but not both) of
Z or Z' is hydrogen; and R and R' are the same or different hydrocarbyl
moieties having from about 1 to about 21 carbon atoms and can be
saturated, branched or unsaturated (e.g., oleoyl) and mixtures thereof.
Preferred X groups are selected from substituted or unsubstituted,
branched or linear alkyl, ether alkyl, amino alkyl, or amido alkyl moieties
having from about 2 to about 15 carbon atoms. Preferred alkyl moieties
are unsubstituted, linear alkyl moieties having the formula -(CH2)n-,
wherein n is an integer from 2 to about 15, preferably from 2 to about 10,
and most preferably from 2 to about 6; and also unsubstituted, branched
alkyl moieties having from 3 to about 15 carbon atoms, preferably from 3
to about 10 carbon atoms, and most preferably from 3 to about 6 carbon
atoms. Most preferred are ethylene and propylene (branched or linear)
alkyl moieties. Also preferred are unsubstituted, branched or linear ether
alkyl moieties having the formula -R2-(O-R2)m-, wherein each R2 is
independently selected from C2-Cg branched or linear alkyl and/or aryl
moieties (preferably ethyl, prapyl or combinations thereof and m is an
integer from 1 to about 5. X may also be unsubstituted, branched or linear
amino and/or amido alkyl moieties having the formula -R2-(N(R3)-R2)m-,
wherein each R2 is independently selected from C2-Cg branched or linear
alkyl and/or aryl moieties (preferably ethyl, propyl or combinations
thereof), m is an integer from 1 to about 5, and R3 is selected from
hydrogen, C1-CS alkyl, and -C(O)R4-, wherein R4 is C1-C21 alkyl,
including -C(O)R. The X moiety may be derived from commercially
available amine compounds such as, for example, JeffaminesR (supplied by
w0961OG148 ~ ~ PCTIUS9S/09584
Texaco) such as JED600, JEDR148, JEDR192, JED230, JED2000, J-D230
and J-D400.
Preferred X moieties therefore include: -(CH2}2-, -(CH2)3-, -
(CH2)4-~ -(CH2)5-~ -(CH2)6-~ -CH2CH(CH3)(CH2)3-~ -(CH2)2-O-(CH2)2-
> -(CH2)3-O-(CH2)3-, -(CH2)2-O-(CH2)3-~ -(CH2)2-O-(CH2)2-O-(CH2)2->
-(CH2)3-O-(CH2)2-O-(CH2)3-~ -(CH2)2-O-(CH2)3-O-(CH2)2-> -(CH2)2-
NH-(CH2)2-~ -(CH2)3-NH-(CH2)3-~ -(CH2)2-NH-(CH2)3-. -(CH2)2-
N(C(O)R)-(CH2)2-~ -(CH2)3-N(C(O)R)-(CH2)3-~ -(CH2)2-N(C(O)R)_
(~H2)3-~ -(CH2)2-NH(C6H4}NH-(CH2)2-, -(CH2)3-NH(C6H4)NH-
(CH2)3-~ -(CH2)2-NHCH2(C6H4)CH2NH-(CH2)2-, -(CH2)3-
NHCH2(C6H4)CH2NH-(CH2)3-, etc.
Preferred Z and Z' groups are independently selected from
polyhydroxyhydrocarbyl moieties having a linear hydrocarbyl chain with at
least 2 hydroxyls (in the case of glycerol} or at least 3 hydroxyls ( in the
case of other sugars) directly connected to the chain, or an alkoxylated
derivative (preferably ethoxylated or propoxylated) thereof. Z and Z'
preferably will be derived from a reducing sugar, more preferably Z and/or
Z' is a glycityl moiety. Suitable reducing sugars include glucose, fructose,
maltose, lactose, galactose, mannose, and xylose, as well as
glyceraldehyde. As raw materials, high dextrose corn syrup, high fructose
corn syrup, and high maltose corn syrup can be utilized as well as the
individual sugars listed above. These corn syrups may yield a mix of sugar
components for Z and Z'. It should be understood that it is by no means
intended to exclude other suitable raw materials. Z and/or Z' preferably
will be selected from the group consisting of -CH2-(CHOH)-p-CH20H, -
CH(CH20H)-(CHOH}p-1-CH20H, -CH2-(CHOH)2(CHORI)(CHOH)-
CH20H, where p is an integer from 1 to S, inclusive, and Rl is H or a
cyclic mono- or polysaccharide, and alkoxylated derivatives thereof. Most
preferred are glycityls wherein p is 4, particularly -CH2-(CHOH}4-
CH20H.
Preferred R and R' groups are independently selected from C3-C21
hydrocarbyl moieties, preferably straight or branched chain C3-C13 alkyl
or alkenyl, more preferably straight chain CS-C11 alkyl or alkenyl, most
preferably straight chain Cg-Cg alkyl or alkenyl, or mixtures thereof. R-
w09GI0G148 ~ ~ ~~ ~ ~ t~ ~ PCTIUS95/0958d
i6
CO-N < and/or R"-CO-N < can be, for example, cocamide, stearamide,
oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide,
etc.
Examples of such compounds therefore include, but are not limited
to: CH3(CH2)6C(O)N[CH2(CHOHj~.CH~OH]-(CH2)2-
[CH2(CHOH)q.CHZOH]NC(O}(CH2)6CH3;
CHI(CHI)gC(O)N[CH2(CHOH)4CH20H]-(CH2)2-
[CHI,(CHOH)4CH20H]NC(O)(CH2)8CH3;
CH3(CHZ) 1pC(O)N[CH2(CHOH)4CHZOH]-(CH2)2-
[CH~ (CHOH)øCH20H] NC(O)(CH2) I OCH3;
CH3(CH2)gC(O)N[CH2(CHOH)~CHZOH]-(CH2)~-O-(CH2)2-O-(CH2)2-
[CH2(CHOH),~CH20H]NC(O){CH2)gCH3;
CH3(CH2)gC(O)N[CH2(CHOH)q.CH20H]-CH2CH(CH3)(CH2)3-
[CH2(CHOH)q.CH20H]NC(O)(CH2)gCHg;
CH3(CH2}gC(O)N[CH2(CHOH)q.CHZOH]-(CHZ)3-O-(CH2)2-O-(CHZ)3-
[CH2(CHOH)q.CH20H]NG(O)(CH2)gCH3;
CH3(CH2)3CH(CH~CH3)C(O)N[CHZ(CHOH)~CHZOH]-(CH2)~-
[CHZ(CHOH)4CH20H]NC(O)CH(CH2CH3)(CH2)3CH3;
CHg(CH2)6C(O)N[CHa(CHOH)q.CHZOH]-(CH2)g-0-(CH~)2-O-(CH~)3-
[CH2(CHOH)4CH~OH]NC(O)(CH2)6CHg;
CH3(CH2)4C(O)N[CH2(CHOH}qCH20H]-(CH2)3-O-(CH2)'-O-{CH2)3-
[CH2(CHOH)~CH20H]NC(O)(CH2)8CH3;
CbH$C(O)N[CH2(CHOH)q.CH2OH]-(CH~)3-O-(CH2)2-O-(CH2)3-
[CH2(CHOH)4CH~OH]NC(O)C6H5;
CH3(CHZ)4C(O)N[CH2{CHOH)q.CH2OH]-(CH2)2-
[CH2(CHOH)4CH~OH]NC(O)(CH2)gCH3.
These compounds can be readily synthesized from the following
disugar diamines: HN[CH2(CHOH}4CH~OH]-(CH2)2-
[CH2(CHOH)4CH20H]NH; HN[CH2{CHOH)4CHZOH]-
CH2CH(CH3)(CHZ)3-[CH2(CHOH}~CH20H]NH;
HN[CH2(CHOH)4CH20H]- (CHZ)2-0-(CHZ)~'O-(CH2)2-
[CH2(CHOH)4CH~OH]NH; HN[CH2(CHOH)q.CH20H]-(CHZ)g-O-
(CH2)2-O-(CH2)3-[CHZ{CHOH)~CH20H]NH; and
HN[CH2(CHOH)4CH20H]-(CH2)3-[CH2(CHOH)q.CH20H]NH.
w0 96106148 PCT/US95/09584
17
Amohoteric surfactant
Suitable amphoteric surfactants for use herein include the alkyl
amphocarboxylic acids of the formula:
O
RC-NHCH2CH2Ri
wherein R is a Cg-Clg alkyl group, and Ri is of the general formula:
(CH2)xC00-M , (CH2)xC00 -M
or
N N (+)-CHZCH20H
~\R~ SRI
wherein RI is a (CH2)xCOOM or CH2CH20H, and x is 1 or 2 and M is
preferably chosen from alkali metal, alkaline earth metal, ammonium,
mono-, di-, and tri-ethanolammonium, most preferably from sodium,
potassium, ammonium and mixtures thereof with magnesium ions. The
preferred R alkyl chain length is a C lp to C 14 alkyl group. A preferred
amphocarboxylic acid is produced from fatty imidazolines wherein the
dicarboxylic acid functionality of the amphodicarboxylic acid is diacetic
acid and/or dipropionic acid. A suitable example of an alkyl
amphodicarboxylic acid for use herein in the amphoteric surfactant
Miranol(TM) C2M Conc. manufactured by Miranol, Inc., Dayton, NJ.
Amine oxide surfactant
According to the present invention in amine oxides useful as
amphoteric surfactants may be used herein. Amine oxides suitable for use
herein have the formula:
O
i
R6R7NRg
rc~r~us9~ogssa
wa ssiosias
~a
wherein R6 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl
and alkyl phenyl group, or mixtures thereof, containing from 6 to 18
carbon atoms, preferably 12 to 14 carbon atoms; and R~ and R8 are
independently C1_3 alkyl or C2_g hydyroxyalkyl groups, or a
polyethylene oxide group containing from 1 to 3, preferable 1, ethylene
oxide groups. These amine oxide surfactants in particular include CIp-
C14 alkyl dimethyl amine oxides and C6-C12 alkoxy ethyl dihydroxyethyl
amine oxides. Examples of such materials include dimethyloctylamine
oxide, diethyldecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide,
dimethyldodecylamine oxide, dipropyltetradecylamine oxide and
dodecylamidopropyl dimethylamine oxide. Preferred are CI2-C14 alkyl
dimethylamine oxides and mixtures thereof.
Zwitterionic surfactant
Zwitterionic surfactants can also be incorporated into the detergent
compositions herein.
Betaine surfactant
According to the present invention the compositions may thus
comprise betaines. The betaines useful as zwitterionic surfactants, in the
present invention are those compounds having the formula
R(R1)2N+R2C00- wherein R is a C6-Clg hydrocarbyl group,
preferably a Clp-CI6 alkyl group or Clp_16 acylamido alkyl group, each
R1 is typically C1-C3 alkyl, preferably methyl, and R2 is a C1-Cg
hydrocarbyl group, preferably a C 1-C3 alkylene group, more preferably a
C1-C2 alkylene group. Examples of suitable betaines include coconut
acylamidapropyldimethyl betaine; hexadecyl dimethyl betaine; C12-14
acylamidopropyIbetaine; Cg-14 acylamidohexyldiethyl betaine; 4[C14_16
acylmethylamidodiethylammonio]-1-carboxybutane; C 16-18
acylamidodimethylbetaine; C12-16 acylamidopentanediethyl-betaine;[C12_
16 acylmethylamidodimethylbetaine. Preferred betaines are C 12-18
dimethyl-ammonio hexanoate and the C10-18 acylamidopropane (or
ethane) dimethy! (or diethyl) betaines.
The complex betaines suitable for use herein have the formula:
w0 96H16148 PCTJUS93109584
19
R - (A)n IN - (CHR1)xly N - Q (1)
B B
wherein R is a hydrocarbon group having from 7 to 22 carbon atoms,
preferably 12 to 14 carbon atoms, A is the group (C(O)), n is 0 or I , R1
is hydrogen or a lower alkyl group, x is 2 or 3, y is an integer of 0 to 4,
Q is the group -R2COOM wherein R2 is an alkylene group having from 1
to 6 carbon atoms and M is hydrogen or an ion from the groups alkali
metals, alkaline earth metals, ammonium and substituted ammonium and
B is hydrogen or a group Q as defined.
According to the present invention the composition may comprise
from 0% to 10%, preferably from 0% to 5% of said betaines.
ultaine
The sultaines useful in the present invention are those compounds
having the formula (R(R1)2N+R2S03- wherein R is a C6-Clg
hydrocarbyl group, preferably a C10-C16 alkyl group, more preferably a
C12-C13 alkyl group, each RI is typically C1-C3 alkyl, preferably
methyl, and R2 is a C1-C6 hydrocarbyl group, preferably a C1-C3
alkylene or, preferably, hydroxyalkylene group. The zwitterionics herein
above may also be present in small quantities so as to deliver suds
enhancing benefits to the compositions.
Cationic surfactant
Cationic detersive surfactants suitable for use herein are those having
one long chain hydrocarbyl group. Examples of such cationic surfactants
include the ammonium surfactants such as alkyldimethylammonium
halagenides and surfactants having the formula:
jR2(OR3)yl IR4(OR3)yl2R5N t X_
WO 96/06148 PCTlITS951U9584
wherein Rv is an alkyl or alkyl benzyl group having from about 8 to about
18 carbon atoms in the alkyl chain, each R3 is selected from the group
consisting of CH2CH2-, -CH2CH(CH3)-, -CH2CH(CH~OH)-,
CH~CH2CH2-, and mixtures thereof; each Rø is selected from the group
consisting of C1-Cø alkyl, C1-Cø hydroxyalkyi, benzyl ring structures
formed by joining the two Rø groups, -CH2CHOH-
CHOHCORbCHOHCH20H wherein R6 is any hexose or hexose polymer
having a molecular weight less than about 1000 and hydrogen when y is
not 0; RS is the same as R4 or is an alkyl chain wherein the total number
of carbon atoms of R2 plus RS is not more than about 18; each y is from
about 0 to abaut 10 and the sum of the y values is from 0 to about 15; and
X is any compatible anion.
Preferred cationic surfactants are the water soluble quaternary
amonium compounds useful in the present composition have the formula:
Rl R2R3R4N +X_
wherein RI is a Cg-C16 alkyl, each of R2~ R3 and Rø is independently
Cl-Cø alkyl, C1-Cø hydroxy alkyl, benzyl and (C~HøO)xH where x has
a value of from I to S and X is an anion. Not more than one of the. R2,
R3 or Rø should be benzyl.
The preferred alkyl chain length for Rl is from C12-C1~,
particularly where the alkyl group is a mixture of chain lengths derived
from coconut or palm kernel fat or is derived from synthetically by olefn
build up or OXO alcohols synthesis. Preferred groups for the R~R3 and
Rø are methyl and hydroxyethyl groups and the anion X may be selected
from halide, methosulphate, acetate and phosphate ions.
Examples of suitable quaternary ammonium compounds for use
herein are:
coconut trimethyl ammonium chloride or bromide; coconut methyl
dihydroxyethyl ammonium chloride or bromide; decyl trimethyl
ammonium chloride; decyl dimethyl hydroxyethyl ammonium chloride or
bromide; C12-C15 dimethyl hydroxyethyl ammonium chloride or
broimde; coconut dimethyl hydroxyethyl ammonium chloride or bromide;
myristyl trimethyl ammonium methyl sulphate; lauryl dimethyl benzyl
2~9~~94
w0 9b106148 PCTlU595/09584
21
ammonium chloride or bromide; lauryl dimethyl (ethoxy)4 ammonium
chloride or bromide and choline esters.
Other cationic surfactants useful herein are also described in U.S.
patent 4 228 044. When included therein the laundry detergent
compositions of the present invention typically comprise from 0.5% to
about 5~! by weight of said cationic surfactants.
According to the present invention the compositions may also
comprise optional ingredients such as builders, enzymes, antiredeposition
agents, polymeric soil release agents, chelating agents, dispersing agents
and suds supressors or enhancers.
Enzymes
In addition to lipase the detergent composition of the present
invention may comprise additional enzymes such as proteases, amylases,
cellulases, and peroxidases, as well as mixtures thereof. Other types of
enzymes may also be included. They may be of any suitable origin, such
as vegetable, animal, bacterial, fungal and yeast origin. However, their
choice is is also governed by several factors such as pH-activity andlor
stability Qptima, thermostability, stability versus active detergents,
builders and so on. In this respect bacterial or fungal enzymes are
preferred, such as bacterial amylases and proteases, and fungal cellulases.
Enzymes are normally incorporated at levels sufficient to provide
up to about 5 mg by weight, more typically about 0.01 mg to about 3 mg,
of active enzyme per gram of the composition. Stated otherwise, the
compositions herein will typically comprise from about 0.001 ~ to about
k , 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. licheniforms.
Another suitable protease is obtained from a strain of Bacillus, having
CA 02198094 2000-02-04
22
maximum activity throughout the pH range of 8-12, developed and sold by Novo
industries A/S under the trade mark ESPERASE. The preparation of this enzyme
and
analogous enzymes is described in British Patent Specification No. 1,243,784
of
Novo. Proteolytic enzymes suitable for removing protein-based stains that are
commercially available include those sold under the trademarks ALCALASE and
SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International
Bio-Synthetics, Inc. (The Netherlands). Other proteases include Protease A
(see
European Patent Application 130,756, published January 9, 1985) and Protease B
(see European Patent Publication 251446 published January 7, 1988, and
European
Patent Application 130,756, Bott et al, published January 9, 1985).
Amylases include, for example, a-amylases described in British Patent
Specification No. 1,296,839 (Novo), RAPIDASETM International Bio-Synthetics,
Inc.
and TERMAMYLTM, Novo Industries.
The cellulase usable in the present invention include both bacterial or fungal
cellulase. Preferably, they will have a pH optimum of between 5 and 9.5.
Suitable
cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, issued
March 6,
1984, which discloses fungal cellulase produced from Humicola insolens and
Humicola strain DSM 1800 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 (Novo) is
especially useful.
Peroxidase enzymes are used in combination with oxygen sources, e.g.,
percarbonate,
perborate, persulfate, hydrogen peroxide, etc. They are used for "solution
bleaching,"
i.e. to prevent transfer of dyes or pigments removed from substrates during
wash
operations to other substrates in the wash solution. Peroxidase enzymes are
known in
the art, and include, for example, horseradish peroxidase, ligninase, and
haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-containing
detergent compositions are disclosed, for example, in PCT
CA 02198094 2000-02-04
23
International Application WO 89/099813, published October 19, 1989, by
O. Kirk, assigned to Novo Industries A/S.
A wide range of enzyme materials and means for their
incorporation into synthetic detergent compositions are also disclosed in
U.S. Patent 3,553,139, issued January 5, 1971 to McCarty et al.
Enzymes are further disclosed in U.S. Patent 4,101,457, Place et al,
issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued
March 26, 1985, both. Enzyme materials useful for liquid detergent
formulations, and their incorporation into such formulations, are disclosed
in U.S. Patent 4,261,868, Hora et al, issued April 14, 1981. Enzymes for
use in detergents can be stabilized by various techniques. Enzyme
stabilization techniques are disclosed and exemplified in U.S. Patent
3,600,319, issued August 17, 1971 to Gedge, et al, and European Patent
Application Publication No. 0 199 405, published October 29, 1986,
Venegas. Enzyme stabilization systems are also described, for example,
in U.S. Patent 3,SI9,570.
Enzyme Stabilizers
The optional enzymes incorporated in the detergent compositions of
the present invention are stabilized by the presence of water-soluble
sources of calcium and/or magnesium ions in the finished compositions
which provide such ions to the enzymes. (Calcium ions are generally
somewhat more effective than magnesium ions and are preferred herein if
only one type of cation is being used.) Additional stability can be
provided by the presence of various other art-disclosed stabilizers,
especially borate species: see Severson, U.S. 4,537,706. Typical
detergents, especially liquids, will comprise from about 1 to about 30,
preferably from about 2 to about 20, more preferably from about 5 to ,
about 15, and most preferably from about 8 to about 12, millimoles of
calcium ion per liter of finished composition. This can vary somewhat,
depending on the amount of enzyme present and its response to the
calcium or magnesium ions. The level of calcium or magnesium ions
should be selected so that there is always some minimum level available
for the enzyme, after allowing for complexation with builders, fatty acids,
etc., in the composition. Any water-soluble calcium or magnesium salt
ZI9~~94
w0 ~61OG148 PCT/US9510'3RS4
24
can be used as the source of calcium or m::-resium ions, including, but
not limited to, calcium chloride, calcium suuace. calcium malate, calcium
maleate, calcium hydroxide, calcium formate, and calcium acetate, and
the corresponding magnesium salts. A small amount of calcium ion,
generally from about 0.05 to about 0.4 millimoles per titer, is often also
present in the composition due to calcium in the enzyme slurry and
formula water. In solid detergent compositions the formulation may
include a sufficient quantity of a water-soluble calcium ion source to
provide such arnaunts in the laundry liquor. In the alternative, natural
water hardness may suffice.
It is to be understood that the foregoing levels of calcium andlar
magnesium ions are sufficient to provide enzyme stability. More calcium
and/or magnesium ions can be added to the compositions to provide an
additional measure of grease removal performance. Accordingly, as a
general proposition the compositions herein will typically comprise from
about 0.05% to about 2% by weight of a water-soluble source of calcium
or magnesium ions, or both. The amount can vary, of course, with the
amount and type of enzyme employed in the composition.
The compositions herein may also optionally, but preferably,
contain various additional stabilizers, especially borate-type stabilizers.
Typically, such stabilizers will be used at levels in the compositions from
about 0.25% to about 10%, preferably from about 0.5% to about 5%,
more preferably from about 0.75% to about 3%, by weight of boric acid
or other borate compound capable of forming boric acid in the
composition (calculated on the basis of boric acid). Boric acid is
preferred, although other compounds such as boric oxide, borax and other
alkali metal borates (e.g., sodium ortho-, meta- and pyroborate, and
sodium pentaborate) are suitable. Substituted boric acids (e.g.,
phenylboronic acid, butane boronic acid, and p-bromo phenylboronic
acid) can also be used in place of boric acid.
B i r
Detergent builders can optionally be included in the compositions
herein to assist in controlling mineral hardness. Inorganic as well as
WO 96106148 PCT/US95I09584
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 about 1 % builder. Liquid
formulations typically comprise from about 5 % to about SO% , more
typically about 5% to about 30%, by weight, of detergent builder.
Granular formulations typically comprise from about 10% to about 80%,
more typically from about 15% to about 50% by weight, of the detergent
builder. Lower or higher levels of builder, however, are not meant to be
excluded.
Inorganic or P-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 rneta-phosphates), phosphonates, phytic acid,
silicates, carbonates (including bicarbonates and sesquicarbonates),
sulphates, and aluminosilicates. However, non-phosphate builders are
required in some locales. Importantly, the compositions herein function
surprisingly well even 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 alkali metal silicates,
particularly those having a Si02:Na20 ratio in the range 1.6:1 to 3.2:1
and layered silicates, such as the layered sodium silicates described in
U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 is
the trademark for a crystalline layered silicate marketed by Hoechst
(commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the
Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the
delta-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'YH2o wherein M is sodium or hydrogen, x is a number
WO 96106148 ~ ~ ~ ~ ~ ~ ~' PCTN895109RA4
26
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-l I, as the alpha, beta and gamma forms.
As noted abave, the delta-Na2Si20g (NaSICS-6 form) is most preferred
for use herein. Qther silicates may also be useful such as for example
magnesium silicate, which can serve as a crispening agent in granular
formulations, as a stabilizing agent for oxygen bleaches, and as a
component of suds control systems.
Examples of carbonate builders are the alkaline earth and alkali
metal carbonates as disclosed in German Patent Application No.
2,321,001 published on November 15, I973.
Aluminosilicate builders are useful in the present invention.
Aluminosilicate builders are of great importance in most currently
marketed heavy duty granular detergent compositions, and can also be a
significant builder ingredient in liquid detergent formulations.
Aluminosilicate builders include those having the empirical formula:
Mz(zA102)y] ~ 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 about 0.5, and x is an integer from about 15 to
about 264.
Useful aluminosilicate ion exchange materials are commercially
available. These aluminosilicates can be crystalline or amorphous in
structure and can be naturally-occurring aluminosilicates or synthetically
derived. A method for producing aluminosilicate ion exchange materials
is disclosed in U.S. Patent 3,985,b69, Krummel, et aI, issued October 12,
1976. Preferred synthetic crystalline aluminosiiicate 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:
Na 12f(A102) 12(Si02) 121 ~ xH20
wherein x is from about 20 to about 30, especially about 27. This material
is known as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used
s ~ ~I~~o9~
WO 96106148 PC'TJUS95109584
27
herein. Preferably, the aluminosilicate has a particle size of about 0.1-10
microns in diameter.
Organic detergent builders suitable for the purposes of the present
invention include, but are not restricted to, a wide variety of
polycarboxylate compounds. As used herein, "polycarboxylate" refers to
compounds having a plurality of carboxylate groups, preferably at least 3
carboxylates. Polycarboxylate builder can generally be added to the
composition in acid form, but can also be added in the form of a
neutralized salt. When utilized in salt form, alkali metals, such as sodium,
potassium, and lithium, or alkanolammonium salts are preferred.
Included among the polycarboxylate builders are a variety of
categories of useful materials. One important category of polycarboxylate
builders encompasses the ether polycarboxylates, including
oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April
7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18,
1972. See also "TMSJTDS" builders of U.S. Patent 4,663,071, issued to
Bush et al, on May 5, 1987. 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, copolymers of malefic anhydride with ethylene
or vinyl methyl ether, 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
CA 02198094 2000-02-04
28
can also be used in granular compositions, especially in combination with
aeolite and/or layered silicate builders. Oxydisuccinates are also
especially useful in such compositions and combinations.
Also suitable in the detergent compositions of the present invention
are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds
disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986.
Useful ~ succinic acid builders include the CS-C2p alkyl and alkenyl
succinic acids and salts thereof. A particularly preferred compound of this
type is dodecenylsuccinic acid. Specific examples of succinate builders
include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-
dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.
Laurylsuccinates are the preferred builders of this group, and are
described in European Patent Application 0,200,263, published
November 5, 1986.
Other suitable polycarboxylates are disclosed in U.S. Patent
4,144,226, Crutchfield et al, issued March 13, 1979 and in U.S. Patent
3,308,067, Diehl, issued March 7, 1967. See also Diehl U.S. Patent
3,723,322.
Fatty acids, e.g. , 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 fatty 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.
WO 96I(16148 ~ ~ ~ ~ PCT/US95109584
29
Polymeric Soil lZelease Agent
According to the present invention the detergent compositions may
comprise a polymeric soil release agent. Polymeric soil release agents are
characterised by having a hydrophobic and hydrophilic segments.
Polymeric soil release agents for use herein have
a) 1 or more nonionic hydrophile components consisting of (i)
polyoxyethylene segments with a degree of polymerisation of at least 2,
or (ii) oxypropylene or polyoxypropylene segments with a polymerisation
degree of 2 to 10, wherein said hydrophile segment does not encompass
any oxypropylene unit unless bonded to adjacent moieties at each end by
ether linkages, or (iii) a mixture of oxyalkylene units comprising
oxyethylene and from 1 to 30 oxyoxypropylene units, or
b) 1 or more hydrophobe components comprising (i) C3 oxyalkylene
terephthalate segments, wherein, if said hydrophobe components also
comprise oxyethylene terephthalate, the ratio of oxyethylene
terethphaIate:C3 oxyalkylene terephthalate units is about 2:1 or lower, (ii)
C4-C6 alkylene or oxy C4-C6 alkylene segments, or mixtures therein,
(iii) poly (vinyl ester segments, preferably poly (vinyl acetate), having a
degree of polymerisation of at least 2, or (iv) CI-C4 alkyl ether or C4
hydroxyalkyl ether substituents or mixtures thereof, wherein said
subsituents are present in the form of CI-C4 alkyl ether or C4
hydroxyalkyl ether cellulose derivatives, or mixtures thereof and such
cellulose derivatives are amphiphilic, whereby they have a sufficient level
of C1-C4 alkyl ether and/or C4 hydroxyalkyl ether units to deposit upon
conventional polyester synthetic fibre surfaces and retain a sufficient level
of hydroxyls to increase fibre surface hydrophilicity, or a combination of
(a) and (b).
Typically the polyoxyethylene segments of (a)(i) have a degree of
polymerisation of 2 to 200, preferably 3 to 150, most preferably 6 to 100.
Suitable oxy C4-C6 alkylene hydrophobe segments include end caps of
polymeric soil release agents such as M03S(CH)nOCH2CH20-, where
M is sodium and n is an integer from 4 to 6.
Soil release agents characterised by polyvinyl ester) hydrophobe
segments include graft copolymers of polyvinyl ester), e.g. C1-C6 vinyl
CA 02198094 2000-02-04
esters, preferably polyvinyl acetate) grafted onto polyalkylene oxide
backbones, such as polyethylene oxide backbones. Commercially
available materials of this kind include SokalanTmarketed by BASF.
helating Ag .ntS
The compositions of the present invention may optionally contain
one or more chelating agents selected from the group consisting of amino
carboxylates, amino phosphonates, polyfunctionally-subsituted aromatic
chelating agents and mixtures thereof. 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 the formation of soluble
chelates.
Amino carboxylates useful as chelating agents include
ethylenediaminetetraacetates, N-hydroxyethylenediaminetriacetates,
nitrilo-acetates, ethylenediamine tetraproprionates, triethylene-
tetraaminehexaacetates, diethylenetriaminepentaacetates and
ethanoldiglycines, alkali metal ammonium and substitute ammonium salts
therein and mixtures therein.
Amino phosphonates are also suitable for use as chelating agents in
the compositions of the present invention, preferably in the presence of
low levels of total phosphorus in the detergent compositions. Suitable
phosphonates include ethylenediaminetetrakis (methylenephosphonates),
nitrilotris (methylenephosphonates) Mnd diethylenetriaminepentakis
(methylenephosphonates) as REQUEST ("DTPMP"). Preferably these
amino phosphonates do not contain alkyl or alkenyl groups with more
than about 6 carbon atoms. HEDP, 1-hydroxyethane diphosphonate is
also suitable and preferably combined with aminophosphonates or amino
carboxylates for use herein. .
Polyfunctionally-subsituted aromatic chelating agents are also useful
in the compositions herein. See U.S. patent ~ 812 044. Preferred
compounds of this type in acid form are dihydroxydisuphobenzenes such
as 1,2-dihydroxy-3,5-disulphobenzene.
WO 96t06I48 PCT/U5951U9584
31
A preferred biodegradable chelator for use herein is
ethylenediamine disuccinate ("EDDS") especially the s,s farm as
' described in U.S. patent 4 704 233.
Palymeric Dis er ing_Agents
Polymeric dispersing agents are suitable optional ingredients in the
detergent compositions of the present invention. Suitable polymeric
dispersing agents include for example polymeric polycarboxylates and
polyethylene glycols. It is believed that the polymeric dispersing agents
enhance overall detergent builder performance when used in combination
with other builders by crystal growth inhibition, particulate snil release
peptitization and anti-redeposition.
Polymeric polycarboxylate materials can be prepared by
polymerising or copoIymerising suitable unsaturated monomers,
preferably in their acid form. Unsaturated monomeric acids that can be
polymerised to form suitable polymeric polycarboxylates include acrylic
acid aconitic acid, mesaconic acid, citraconic acid and methylenemalonic
acid. The presence in the polymeric polycarboxylates herein of
monomeric segments containing no carboxylate radicals such as
vinylrnethyl ether styrene, ethylene etc. is suitable provided that such
segments do not constitute more than about 40% by weight.
Particularly suitable polymeric polycarboxylates can be derived
from acrylic acid. Such acrylic acid-based polymers which are useful
herein are the water soluble salts of polymerised acrylic acid. The
average molecular weight of such polymers in the acid form preferably
ranges from about 2000 to to 000, more preferably from about 4000 to
7000 and most preferably from about 4000 to 5000. Water soluble salts of
such acrylic acid polymers can include for example the alkali metal,
ammonium and substituted ammonium salts. Use of polyacrylates of this
type in detergent compositions has been described for example in U.S.
patent 3 308 067.
Acrylic malefic based copolymers may also be used as a preferred
component of the dispersing/antiredeposition agent. Such materials
SUBSTITUTE SHEET (RULE 26)
CA 02198094 2000-02-04
32
include the water soluble salts of copolymers of acrylic acid and malefic
acid. The average molecular weight of such copolymers in the acid form
preferably ranges from about 2000 to 100 000, more preferably from
5000 to 75 000, most preferably from 7000 to 70 000. The ratio of
acrylate to maleate segments in such copolymers will generally range
from about 10:1 to 2:1. water soluble salts such of such acrylic
acid/maleic acid copolymers can include for example the alkali metal,
ammonium, and substituted ammonium salts. Suitable acrylate/maleate
copolymers of this type are known materials described in European Patent
Publication Number 66915.
Another polymeric material which can be included is polyethylene
glycol (PEG). PEG can exhibit. dispersing agent performance as well as
act as a clay soil removal/antireposition agent. Typical molecular weight
ranges for these purposes range from about 500 to 100 000, preferably
from about 1000 to 50 000, more preferably from about 1500 to TO 000.
Polyaspartate and polyglutamate dispersing agents (mol. wt. about
10000) may also be used especially in conjunction with zeolite builders.
~~9~9~
WO 96106148 PCTIUS95109584
33
Sud super
Compounds far reducing or suppressing the formation of suds can
be incorporated into the compositions of the present invention. Suds
suppression can be of particular importance in the so-called "high
concentration cleaning process" and in front-loading European-style
washing machines.
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 (John Wiley & Sons, Inc., 1979). One
category of suds suppressor of particular interest encompasses
monocarbaxylic fatty acid and soluble salts therein. See U.S. Patent
2,954,347, issued September 27, 1960 to Wayne St. John. The
monocarboxylic fatty acids and salts thereof used as suds suppressor
typically have hydracarbyl chains of 10 to about 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
alkanolammanium 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 Clg-C40
ketones (e.g., stearone), etc. Other suds inhibitors include N-alkylated
amino triazines such as tri- to hexa-alkylmelamines or di- 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 manostearyl 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. The liquid
hydrocarbons will be liquid at room temperature and atmospheric
pressure, and will have a pour point in the range of about -40°C and
about 50°C, and a minimum boiling point not less than about
110°C
(atmospheric pressure). It is also known to utilize waxy hydrocarbons,
CA 02198094 2000-02-04
34
preferably having a melting point below about 100°C. The hydrocarbons
constitute a preferred category of suds suppressor for detergent
compositions. Hydrocarbon suds suppressors are described, for example,
in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. The
hydrocarbons, thus, include aliphatic, alicyclic, aromatic, and
heterocyclic saturated or unsaturated hydrocarbons having from about 12
to about 70 carbon atoms. The term "paraffin," as used in this suds
suppressor discussion, is intended to include mixtures of true paraffins
and cyclic hydrocarbons.
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 oil's 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. -Patent
4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent
Publication 354016, published February 7, 1990, by Starch, M. S.
Other silicone suds suppressors are disclosed in U.S. Patent
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 silanated 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. Patent 3,933,672, Bartolotta et al, and in U.S. Patent 4,652,392,
Baginski et al, issued March 24, 1987.
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 about 20
cs. to about 1,500 cs. at 25 °C;
W O 911106148 PCT/U595/09584
(ii) from about 5 to about 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 about 0.6:1 to about 1.2:1; and
(iii) from about 1 to about 20 parts per 100 parts by weight of (i) of
a solid silica gel.
In the preferred silicone suds suppresser 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
suppresser is branchedlcrosslinked and preferably not linear.
To illustrate this point further, typical liquid laundry detergent
compositions with controlled suds will optionally comprise from about
0.001 to about l, preferably from about 0.01 to about 0.7, most
preferably from about 0.05 to about 0.5, weight ~o of said silicone suds
suppresser, which comprises (1) a nonaqueous emulsion of a primary
antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a
resinous siloxane or a silicone resin-producing silicone compound, (c) a
finely divided filler material, and (d) a catalyst to promote the reaction of
mixture components (a), (b) and (c), to form silanolates; {2) at least one
nonionic silicone surfactant; and {3) polyethylene glycol or a copolymer
of polyethylene-polypropylene glycol having a solubility in water at room
temperature of more than about 2 weight ! ; and without polypropylene
glycol. Similar amounts can be used in granular compositions, gels, etc.
See also U.S. Patents 4,978,471, Starch, issued December 18, 1990, and
4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et al.,
issued February 22, 1994, and U.S. Patents 4,639,489 and 4,749,740,
Aizawa et al at column 1, line 4b through column 4, line 35.
The silicone suds suppresser herein preferably comprises
polyethylene glycol and a copolymer of polyethylene
glycol/polypropylene glycol, all having an average molecular weight of
less than about 1,000, preferably between about 100 and 800. The
polyethylene glycol and polyethylene/polypropylene copolymers herein
CA 02198094 2000-02-04
36
have a solubility in water at room temperature of more than about 2
weight %, preferably more than about S weight %.
The preferred solvent herein is polyethylene glycol having an
average molecular weight of less than about 1,000, more preferably
between about 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 about 1:1 and 1:10,
most preferably between 1:3 and 1:6, of polyethylene glycol: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 pLURONICTM L101.
Other suds suppressors useful herein comprise the secondary
alcohols (e.g., 2-alkyl alkanols) 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 alcohols 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.
The compositions herein will generally comprise from 0°~ to about
% of suds suppressor. When utilized as suds suppressors,
C 1 ~~~J94
WO 96106148
PCT/US95109584
37
monocarboxylic fatty acids, and salts therein, will be present typically in
amounts up to about 5 % , by weight, of the detergent composition.
Preferably, from about 0.5 % to about 3 % of fatty monocarboxylate suds
suppressor is utilized. Silicone suds suppressors are typically utilized in
amounts up to about 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 about 0.01 % to about 1 % of silicone suds suppressor is
used, more preferably from about 0.25% to about 0.5%. As used herein,
these weight percentage values include any silica that may be utilized in
combination with polyorganosiloxane, as well as any adjunct materials
that may be utilized. Monostearyl phosphate suds suppressors are
generally utilized in amounts ranging from about 0.1% to about 2%, by
weight, of the composition. Hydrocarbon suds suppressors are typically
utilized in amounts ranging from about 0.01 % to about 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.
1 a hing age
The detergent compositions herein may optionally contain bleaching
agents or bleaching compositions containing a bleaching agent and one or
mare bleach activators. When present, bleaching agents will typically be
at levels of from about 1 % to about 30%, more typically from about 5%
to about 20%, of the detergent composition, especially for fabric
laundering. If present, the amount of bleach activators will typically be
from about 0.1 % to about 60% , more typically from about 0.5 % to about
40% of the bleaching composition comprising the bleaching agent-plus-
bleach activator.
The bleaching agents used herein can be any of the bleaching
agents useful for detergent compositions in textile cleaning, hard surface
cleaning, or other cleaning purposes that are now known or become
known. These include oxygen bleaches as well as other bleaching agents.
Perborate bleaches, e.g., sodium perborate (e.g., mono- or tetra-hydrate)
CA 02198094 2000-02-04
38
can be used herein. the bleaches are selcted fro their compatibility with
lipase.
Another category of bleaching agent that can be used without
restriction encompasses percarboxylic acid bleaching agents and salts
thereof. Suitable examples of this class of agents include magnesium
monoperoxyphthalate hexahydrate, the magnesium salt of metachloro
perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and
diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S.
Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent
4,806,632, Burns et al, filed June 3, 1985, European Patent
Application 0,133,354, Banks et al, published February 20, 1985, and
U.S. Patent 4,412,934, Chung et al, issued November 1, 1983. Highly
preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic
acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to
Burns et al.
Peroxygen bleaching agents can also be used. Suitable peroxygen
bleaching compounds include sodium carbonate peroxyhydrate and
equivalent "percarbonate" bleaches, sodium pyrophosphate
peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate
bleach (e.g., OXONE~'~', manufactured commercially by DuPont) can also
be used.
A preferred percarbonate bleach comprises dry particles having an
average particle size in the range from about 500 micrometers to about
1,000 micrometers, not more than about 10 °b by weight of said
particles
being smaller than about 200 micrometers and not more than about 10°~
by weight of said particles being larger than about 1,250 micrometers.
Optionally, the percarbonate can be coated with silicate, borate or water-
soluble surfactants. Percarbonate is available from various commercial
sources such as FMC, Solvay and Tokai Denka.
Mixtures of bleaching agents can also be used. Peroxygen
bleaching agents, the perborates, the percarbonates, etc., are preferably
combined with bleach activators, which lead to the in situ production in
aqueous solution (i.e., during the washing process) of the peroxy acid
corresponding to the bleach activator. Various nonlimiting examples of
CA 02198094 2000-02-04
39
activators are disclosed in U.S. Patent 4,915,854, . ~:ed April 10, 1990
to Mao et al, and U.S. Patent 4,412,934. The nonanoyloxybenzene
sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are
typical, and mixtures thereof can also be used. See also U.S. 4,634,551
for other typical bleaches and activators useful herein.
Highly preferred amido=derived bleach activators are those of the
formulae:
R1N(R5)C(O)R2C(O)L or R1C(O)N(R5)R2C(0)L
wherein R1 is an alkyl group containing from about 6 to about 12 carbon
atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms, R5
is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon
atoms, and L is any suitable leaving group. A leaving group is any group
that is displaced from the bleach activator as a consequence of the
nucleophilic attack on the bleach activator by the perhydrolysis anion. A
preferred leaving group is phenyl sulfonate.
Preferred examples of bleach activators of the above ' formulae
include (6-octanamido-caproyl)oxybenzenesulfonate, (6-
nonanamidocaproyl)- oxybenzenesulfonate,
(6-decanamido-
caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S.
Patent 4,634,551.
Another class of bleach activators comprises the benzoxazin-type
activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued
October 30, 1990. A highly preferred activator of the benzoxazin-type is:
0
~~0
C
Still another class of preferred bleach activators includes the acyl
lactam activators, especially acyl caprolactams and acyl valerolactams of
the formulae:
CA 02198094 2000-02-04
40
I I
6-0 C-C HZ-C H2 O C-C Hz-C H2
R C-N~ CH R6-C-N
CHI-CH2 2 NCH - ~ H
2 2
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing
from 1 to about 12 carbon atoms. Highly preferred lactam activators
include benzoyl caprolactam, octanoyl caprolactam, 3,S,S-
trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl
caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl
valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl
valerolactam, 3,S,S-trimethylhexanoyl valerolactam and mixtures thereof.
See also U.S. Patent 4,S4S,784, issued to Sanderson, October 8, 1985,
which discloses acyl caprolactams, including benzoyl caprolactam,
adsorbed into sodium perborate.
Bleaching agents other than oxygen bleaching agents are also
known in the art and can be utilized herein. One type of non-oxygen
bleaching agent of particular interest includes photoactivated bleaching
agents such as the sulfonated zinc and/or aluminum phthalocyanines. See
U.S. Patent 4,033,718, issued July S, 1977 to Holcombe et al. If used,
detergent compositions will typically contain from about 0.025 % to about
1.2S % , by weight, of such bleaches, especially sulfonate zinc
phthalocyanine.
If desired, the bleaching compounds can be catalyzed by means of a
manganese compound. Such compounds are well known in the art and
include, for example, the manganese-based catalysts disclosed in U.S.
Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat.
5,114,606; and European Pat. App. Pub. Nos. 549,271A1, 549,272A1,
544,440A2, and 544,490A1; Preferred examples of these catalysts
include Mn~2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2,
MnIII2(u-O) 1 (u-OAc)2( 1,4,7-trimethyl-1,4,7-triazacyclononane)2-
(C104)2, Mn~4(u-O)6(1,4,7-triazacyclononane)4(C104)4, MnIIIMnNø
(u-O) 1 (u-OAc)2-( 1,4,7-trimethyl-1,4,7-triazacyclononane)2(C104)3,
Mn~(1,4,7-trimethyl-1,4,7-triazacyclononane)- (OCH3)3(PF6), and
mixtures thereof. Other metal-based bleach catalysts include those
WO 96/06148 ~ ~ ~ ~ ~ ,Q ~ PCTIUS95I09584
41
disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The use of
manganese with various complex ligands to enhance bleaching is also
reported in the following United Skates Patents: 4,728,455; 5,284,944;
5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; 5,227,084;
In its broadest aspect the present invention relates to detergent
compositions. These compositions may be in any form such as powder,
granules, liquid, paste, gel or solid bar. Each particular embodiment of
the present invention may additionally comprise optional ingredients such
as soil suspending agents, abrasives, bactericides, tarnish inhibitors,
colouring agents, corrosion inhibitors and perfumes, which are known in
the art and are required to formulate the particular composition.
The detergent compositions described herein are for use in cleaning
purposes, principally for fabric treatment.. However, the compositions
may also find utility for both manual and automatic dishwashing puposes.
WO 96It96148 PCTlU595J09584
42
Examples
The invention witt now be described in more detailed by the following
non-limiting examples.
I. The stability of Lipase (i.e. enzyme activity versus time) was
determined in a wash solution containing 1000 ppm anionic surfactant,
500 ppm zeolite, 500 ppm SKS-6, 500 ppm carbonate, 100 ppm
polydimethylsiloxane, Lipase (3.0 LU/mL). The water hardness of the
wash solution was S.OdH (Clark). The temperature of the wash solution
was 40°C. The Lipase activity was measured at 25°C versus time
using
a standard Analytical method (pH stat). The influence of different anionic
surfactant on lipase stahility was investigated:
Wash solutions in example 1, contains alkyl ethoxy sulphate salt,
according to the present invention, while examples 2 and 3 do not.
- Example 1 wash solution A contains an alkyl ethoxylated sulphonate
with a C14-C15 chain-length, an average of 0.6 moles ethylene oxide per
mole of surfactant, containing 23% AE1S, 10% AE2S and 5% AEXS
(with x >_3.0).
- Example 2 wash solution B contains CII-C15 Alkyl Sulphate as anionic
surfactant
- Example 3 wash solution C contains C16 secondary Alcohol Sulphate as
anionic surfactant
Lipase activity versus time;
time fmin) A B_
0 100.0 100.0 100.0
86.4 70.0 71.6
76.8 56.4 46.2
71.0 48.1 40.9
~ 1 ~8~JQ~
WO 96/06148 PCT/US95109584
43
40 61.6 44.7 32.2
50 58.4 38.2 23.7
60 53.9 34.2 20.7
II. The stability of lipase was also determined in hard water [25.0 dH
(Clark)]. The temperature of the wash solution was 45°C. The
composition of the wash formulation was identical to the one described
above. The lipase activity was measured at 23°C versus time using a
standard Analytical method (pH stat). The influence of different anionic
surfactant on lipase stability was investigated:
Wash solutions in example 4 contains alkyl ethoxy sulphate salt of the
present invention, while examples 5 and 6 do not.
Example 4 wash solution D contains an alkyl ethoxylated sulphonate
with a C14-CIS chain-length, an average of 0.6 moles ethylene oxide per
mole of surfactant, containing 239 AEIS, 10°k AE2S and 5~ AEXS
(with x >_3.0).
- Example 5 wash solution E contains C14-Clg Alkyl Sulphate as anionic
surfactant.
- Example 6 wash solution F contains C16 secondary Alcohol Sulphate as
anionic surfactant
Lipase activity versus time:
1~ min D
0 100.0 100.0 100.0
86.7 81.3 74.4
80.5 62.0 62.8
74.5 47.8 46.5
67.0 41.3 39.5
64.0 34.2 34.9
61.4 31.8 16.3
WO 96!116148 ~ ~ ~ ~ ~ ~ '~ PC'T/U595109584
44v
Wash solutions A and D containing alkyl ethoxy sulphates, are more
lipase compatible than wash solutions B, C, E, F at the same water
hardness.
examples 7-10
The following granular detergent compositions were prepared by mixing
the listed ingredients in the amounts specified.
7 $ ~ 10
Linear Alkyl Sulphate - 3.6 - -
Alkyl Ethoxylated Sulphate AExS
withx=0 6.6 0.5 5.4 7.2
with x = 1 2.5 3.8 2.1 2.8
with x = 2 1.1 0.5 1.8 1.2
with x = 3 0.8 0.8 0.6 0.8
Alkyl Ethoxylate 5 6 4 4
Alkyl-N-methyl Glucosamide 2 3 - -
Alkyl tri-methyl ammonium chloride- - 2 -
Perborate - - - 7
Percarbonate 22 - 17 -
N,N,N,N-tetra acetyl ethylene 6 - 5 2
diamine
S,S-Ethylene diamine-di-succinic0.4 0.7 0.2 0.2
acid
Enzymes {e.g. lipase, protease,
cellulose, amylase) i.0 0.7 0.8 1.2
Aluminosilicate (zeolite A) 14 15 10 8
Layered silicate/citric acid 12 - -
Sodium citrate 5 - - -
sodium carbonate 8 8 6 6
sodium silicate - - - 2
sulphate - - - 11
sodium malefic & acrylic acid 5 4 3 3
copolymer
Sodium carboxymethyl cellulose 0.4 0.3 0.3 0.3
Soil release polymer 0.3 0.2 0.3 0.3
polyvinyl-N-oxide 0.03 0.2 - -
2198094
WO 96/06148 PCTlU595109584
PEG - 0.5 - _
brighteners, suds suppressors 0.3 - 0.2 0.2
WO 96!06148 PCTfiJS95109584
46
Exam l
A liquid detergent composition according to the present invention was
prepared containing the following ingredients:
°l by weight of the detergent composition
AExS with x = 0 15.6
x = 1 6.0
x = 2 2.6
x=3 1.8
C12-C14 N-methyl glucamide 6.5
C12-C14 fatty alcohol ethoxylate 6.5
C 12-C 16 fatty acid 7
Citric acid anhydrous 6,0
Diethylene triamine penta methylene phosphonic 1.0
acid
Monoethanolamine 13.2
Propanediol 12.7
Ethanol 1.8
Enzymes (e.g. lipase, protease, cellulase) 0.9
Terephthalate-based polymer 0.5
Boric acid 2.4
Minors and water
