Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
W0 96106149 ~ ~ ~ ~ ~ ~ ~ PCT/US951095R5
1
DETERGENT COMPOSITIONS
Technical Field of the Invention
The present invention relates to detergent compositions, far use in
cleaning processes comprising alkyl alkoxylated sulphates and essentially
no alkyl benzene sulphanate.
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
performance, especially on greasy and oily stains over a wide range of
temperatures and conditions.
W096l06t44 PGTlUS9510955_i
2
The detergent industry is however continually seeking surfactant
systems with improved environmental profiles. 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 generally
have a low overall level of anionic surfactant which may result in a lower
soil suspension capacity and less effective whiteness and colour brightness
maintenance in the presence of high level of soils and cationic fabric
conditioner residues.
The art also describes the use of anionic surfactant based detergent
compositions, preferably alkyl sulphate, comprising low levels of LAS.
Far example GB 1 39996h discloses detergent compositions camprising
primary alcohol sulphate (PAS) and nonionic surfactants. EP-A 342 917
discloses detergent compositions comprising PAS having a range of chain
lengths to improve the cleaning performance at lower temperatures.
However, it has been observed that such detergent compositions do not
exhibit the same cleaning performance as the corresponding LAS
compositions.
It is therefore an object of the present invention to replace the alkyl
benzene sulphonate in surfactant systems with an anionic surfactant
system which provides similar averall performance over a range of
temperatures compared with the alkyl benzene sulphonate surfactant
systems. In addition, another object of the present invention is to develop
a surfactant system which is readily biodegradable.
It has now been found that these objectives can be reached by the
use of a anionic surfactant system comprising an alkyl alkoxylated
sulphate having an average alkoxylation degree of from 0.1 to 10, having
certain ratios of alkyl monoalkoxylated sulphate, alkyl dialkoxylated
sulphate and alkyl alkoxylated sulphates with 3 or more aikoxyl groups
per alkyl group.
It has been found that said alkyl alkoxyIated sulphates in
combination with other surfactants provide excellent cleaning benefits
over a wide range of temperatures. Indeed, it has been found that specific
combinations of ratios of the alkyl alkoxylated sulphates of the present
CA 02198093 2000-O1-28
3
invention have been found to give superior cleaning performance in comparison
with alkyl alkoxylated sulphates having a similar average alkoxylation degree
but
having different ratios of mono-, di- and trialkoxylated sulphates, which are
derived from mixtures of alkyl sulphates and alkyl alkoxylated sulphates.
An additional advantage of the surfactant system of the present invention
is that it exhibits increased solubility over alkyl sulphates, which are the
currently
preferred substitutes for alkyl benzene sulphonate.
Another advantage of the surfactant system of the present invention is the
excellent wetting properties, which is a highly desirable property in
detergent
compositions.
Furthermore, the surfactant system of the present invention is particularly
efficient in the removal of sebum, a major constituent of body soils.
Alkyl ethoxy sulphates (referred to herein as AES) 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,
preferably from 0.5 to 3. EP-A 4671894 discloses liquid detergent compositions
comprising LAS and AES with a preferred average degree of ethoxylation of 0.8
to 2. WO 93/18124 discloses granular detergent compositions comprising alkyl
sulphates and alkyl ethoxy sulphates having an average of 1 to 7 ethoxy groups
per mole.
However, none of the identified art recognises the performance benefits
associated with anionic surfactant systems comprising alkyl alkoxylated
sulphates
having specific ratios of mono-, di- and trialkoxylated sulphates having
specific
ratios as in the present invention.
CA 02198093 2000-O1-28
4
Summar~r of the Invention
The present invention is directed to a detergent composition, comprising
(a) from 1% to 90% of an anionic surfactant comprising at least 30% of alkyl
alkoxylated sulphate having an average degree of alkoxylation of from 0.1 to
3,
and a balance of anionic surfactant other than alkyl alkoxylated sulphate,
wherein the ratio of the combined weight of alkyl monoalkoxylated sulphate and
alkyl dialkoxylated sulphate to the total weight of the anionic surfactant is
from
0.2 to 1, and the ratio of the combined weight of the alkyl monoalkoxylated
sulphate and the alkyl dialkoxylated sulphate to the total weight of alkyl
alkoxylated sulphate having 3 or more alkoxy groups per alkyl group is at
least 1,
and (b) at least one builder or chelant, or a mixture thereof.
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 from 1% to
90% of an anionic surfactant system said system comprising at least 30% of an
alkyl alkoxylated sulphate. Said surfactant system delivers excellent cleaning
performance on greasy and oily soils over a broad temperature range.
Thus an essential component of the present invention is an alkyl
alkoxylated sulphate. According to the present invention said alkyl
alkoxylated
sulphates are represented by the formula Rl(CmH2",O)"S03M, wherein Rl is a
C10-C24~ preferably a C12-CAB, more preferably a C~4-Cis linear or branched
hydrocarbyl, m is from 1 to 4, preferably 2 to 4, most preferably 2, n is from
0.1
to 10, most preferably from 1 to 3 and M is an alkali metal, an alkaline earth
metal, alkanol amine or ammonium and mixtures thereof.
According to the present invention the alkyl alkoxylated sulphates
have an average degree of alkoxylation of from 0.1 to 10, preferably from
WO 96106149 ~ ~ ~ ~ ~ ~ ~ PCTIUS95/09585
0.S 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 total weight of anionic surfactant is at least 0.2
to l, preferably 0.25 to 1, most preferably 0.3 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 present invention comprises more than 30% , preferably more
than 50% , more preferably more than 70% of said alkyl alkoxylated
sulphates by weight of the total anionic surfactant system.
Anionic surfactant s~rstem
According to the present invention the anionic surfactant system may
comprise any other anionic surfactants. Suitable anionic surfactants
include anionic sulphate, sulphonate, carboxylate surfactant or acyl-N-
(alkyl) glucamine sulphate. The detergent compositions of the present
invention comprise from 1% to 90~, preferably from 1 to 70~, most
preferably from 5 % to 60 k of said anionic surfactant system.
Anionic sulphate surfactants
The anionic sulphate surfactant may be any organic sulphate
surfactant other than the alkoxylated sulphates of the present invention,
preferably a Clp-Clg 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-C17
acyl-N-(C1-C4 alkyl) glucamine sulphates, fatty oleyl glycerol sulphates,
alkyl phenol ethylene oxide ether sulphates, N-acyl C6_20 sarcosinates,
sulphates of alkylpolysaccharides such as the sulphates of C1~20
alkylpolyglucoside
W096/OG149 ~ ~ r~ ~ ~ ~.~ PC1'lUS951G95135
Anionic sulphonate surfactants suitable for use herein include, far
example, the salts (e.g. alkali metal salts) of Cg-C20 linear alkylbenzene
sulphonates, Cg-C~2 primary or secondary alkane sulphonates, Cg-C~4
olefin sulphonates, sulphonated polycarboxyIic acids, alkyl glycerol
sulphonates, fatty acyl glycerol sulphonates, fatty oleyl glycerol
sulphonates, paraffin sulphonates, and any mixtures thereof. According
to the present invention the anionic surfactant system preferably
comprises less than 40'T, more 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.
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 C1? 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
201, preferably less than 15%, most preferably Iess 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 10l , the average x is from 2 to
4 when the average R is C13 or less, and the average x is from 3 to 6
when the average R is greater than C13, 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 alkyl nol, ev thox~polvcarboxylate surfactant
Alkyl polyethoxy polycarboxylate surfactants suitable for use herein
include those having the formula:
R-0-(CH-CH-O)x-R3
R~ R2
w0 96106149 ~ ~ ~ ~ ~ ~ ~ PC1'/US95I09585
wherein R is a C6 to Clg alkyl group, x is from 1 to 25, RI and R~ are
selected from the group consisting of hydrogen, methyl acid radical,
succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof,
wherein at least one R1 or R2 is a succinic acid radical or
hydroxysuccinic acid radical, and R3 is selected from the group
consisting of hydrogen, substituted or unsubstituted hydrocarbon having
between 1 and 8 carbon atoms, and mixtures thereof.
Anionic secnndar,~p 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 (or 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-LOOM,
wherein RS is C~-C1~, preferably C8-C9, 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.)
w0 96/06149 ~ ,~ PCTlU895l09585
8
C. Still another class of secondary soaps comprises secondary
carboxyl compounds of the formula CH3(CHR)k-(CH2)m-(CHR)n-
CH(COOhI)(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 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-solubilizing, counterion, e.g., H, alkali
metal, alkaline earth metal, ammonium, alkanolammonium, di- and tri-
alkanolammonium, and C1-CS alkyl substituted ammonium. Sodium is
convenient, as is diethanolammonium.
Preferred secondary soap surfactants for use herein are water-
soluble members selected from the group consisting of the water-soluble
salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-
nonanoic acid, 2-butyl-1-octanoic acid, 2-pentyl-1-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,
acyi alkyl taurines, fatty acid amides of methyl tauride, alkyl succinates
and sulphosuccinates, monoesters of sulphosuccinate (especially saturated
and unsaturated C12-Clg monoesters) diesters of sulphosuecinate
(especially saturated and unsaturated C(-Clq. 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).
WO 96!06149 2 ~ ~ r~ ~ ~ ~ PCT/US95/09585
9
According to the present invention the compositions may
additionally comprise as optional ingredients from 1 % to 20% of other
surfactants such cationic, nonionic, zwitterionic and amphoteric
surfactants.
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 IS% of said nonionic surfactants.
Nonionic conden atec of alkyl phenols
The polyethylene, polypropylene, and polybutylene oxide
condensates of alkyl phenols are suitable for use herein. In general, the
polyethylene oxide condensates are preferred. These compounds include
the condensation products of alkyl phenols having an alkyl group
containing from about 6 to about 12 carbon atoms in either a straight
chain or branched chain configuration with the alkylene oxide.
Nonionic ethoxylated 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
TergitolTM 15-S-9 (the condensatioli product of C11-C15 linear alcohol
with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the
CA 02198093 2000-O1-28
10
condensation product of C 12-C 14 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-C15 linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-
6.5 (the condensation product of C 12-C 13 linear alcohol with 6.54 moles
of ethylene oxide), NeodoITM 45-7 (the condensation product of C 14-
C15 linear alcohol with 7 moles of ethylene oxide), NeodolTM 45-4 (the
condensation product of C14-C15 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 Lial
111 marketed by Enichem.
Nonionic EO/PO condensatet with ronJrlene 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 "propylene oxide/eth, l ~ .P
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.
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,
WO 9bI06149 ~ , (~ ~ ~ ~ 7 PCTIUS95IU9585
11
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, mast 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-, andJor 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, hydraxyalkylphenyl, 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, x is from 0 to 10 preferably from about 1.3 to about 3,
most preferably from about 1.3 to about 2.7 and t is from 0 to 10. The
glycosyl is preferably derived from glucose.
Nonionic fatty acid amide surfactant
Fatty acid amide surfactants suitable for use herein are those
having the formula:
O R1
R2-CI -N-Z
wherein Rl is H or a C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy
propyl and R2 is a CS-C31 hydrocarbyl and Z is a
polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3
hydroxy 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
W0 96f06149 P(."rIUS95109i85
12
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:
Z Z
I I
N-X-N
I I
0=G C=O
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 twa 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 unsaricrated (e.g., oleoyl) and mixtures thereof.
Preferred X groups are selected from substituted or unsubstituted,
branched or linear alkyl, ether alkyl, amino alkyC, or amido alkyl moieties
having from about 2 to about 15 carbon atoms. Preferred alkyl moieties
are unsubstituted, linear alkyl moieties having the formula -(CH~jn-,
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 andlor aryl
moieties (preferably ethyl, propyt or combinations thereof) and m is an
integer from 1 to about ~. X may also be unsubstituted, branched or linear
amino andlor 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
WO 96lOG 149 2 '~ Cl ~ ~ ~ ~z~ PCT/US95/09585
13
thereof), m is an integer from 1 to about 5, and R3 is selected from
hydrogen, CI-Cg alkyl, and -C(O)R4-, wherein R4 is CI-C21 alkyl,
including -C(O}R. The X moiety may be derived from commercially
available amine compounds such as, for example, JeffaminesR (supplied by
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)S-, -(CH2)6-~ -CH2CH(CH3)CCH2)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-, -(CHZ)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)_
(CH2)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 5, inclusive, and R1 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.
w0 96106149 ~ PCTlUS95/09585
14
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 Cg-C11 alkyl or aikenyl, most
preferably straight chain C$-C9 alkyl or alkenyl, or mixtures thereof. R-
CO-N G 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(CHOH)4CH20H)-(CH2)~-
[CH2(CHOH)4CH20H]NC(O)(CH2)6CH3;
CH3(CH2)gC(O)N[CH2(CHOH)4CH~OH]-(CH~2-
[CH~(CHOH)4CH20H]NC(O)(CH2)gCH3;
CH3{CHI) IpC(O)N(CH2(CHOE3)4CH~OH)-(CH2)2-
[CHZ(CHOH)4CH20H]NC(O){CH~) 1 pCH3;
CH3(CH2)8C(O)N[CH2(CHOH)4CH20H]-(CH2)2-O-(CH2)2-O-{CH2)2-
(CHI,(CHOH)4CH20H]NC(O)(CH2)gCH3;
CH3(CH2)8C(O)N[CH2(CHOH)4CH20H)-CH~CH(CH3)(CH~)3-
(CH2(CHOH}4CH20H]NC(O)(CH2)gCH3;
CHg(CH2)8C(O)N(CH2(CHOH}4CH20H)-(CH2)3-O-(CH2)2-O-(CH2)3-
(CH2(CHOH)4CH20H]NC(O)(CH~)gCHg;
CHg(CH2)3CH(CH~CHg)C(O)N[CH2(CHOH)4CH20H]-(CH2)2-
[CH2(CHOH)4CH20H]NC(O)GH(CH2CHg)(CH~)gCH3;
CH3(CH2)6C(Q)NLCH2(CHOH)4CH20H]-(CH2)3-O-(CH2)2-~(CH~)3-
[CH2(CHOH)4CH20H]NC(O)(CH2)~CH3;
CH3(CHZ)4C(O)N[CHZ(CHOH)4CH20H]-(CH2)~-O-(CH2)2-O-(CH2)3-
[CH2(CHOH)4CHZOH)NC(O)((~H2)gCH3;
C6HgC(O)N(CH2{CHOH)4CH20H]-(CH2)3-O-(CH~)2-O-(CH2)3-
[CH2(CHOH)4CH20H]NC(O}C6Hg;
CH3(CH2)4C(O)N[CH2(CHOH)4CH20H]-(CHZ)~-
(CH~(CHOH)4CH20H]NC(O){CHZ)gCH3.
These compounds can be readily synthesized from the following
disugar diamines: HN[CH2(CHOH)4CH20H]-(CHZ)2-
[CH~(CHOH)4CHZOH]NH; HN[CH~(CHOH)4CH20H]-
CH2CH(CH3)(CH2)3-[CH2(CHOH)4CH20H]NH;
HN[CHZ(CHOH)4CH20H]-(CH2)2-O-(GH2)2-O-(CH2)2-
W096/06149 ~ ~ ~ ~ ~ ~ ~ PCT/US95109585
[CH2(CHOH)q.CH20H]NH; HN[CH~(CHOH)q.CH20H]-(CH2)g-O-
(CH2)2-O-(CH2)3-[CH2(CHOH)q.CH20H]NH; and
HN[CHI(CHOH)4CH20H]-(CH2)3-[CH2(CHOH)4CH20H]NH.
Amphoteric surfactant
Suitable amphoteric surfactants for use herein include the alkyl
amphocarboxylic acids of the formula:
w0 9GIOG l49 ~ ~ ~ ~ ~ ~ '~ PC1'/US951Q9585
16
O
RC-NHCH2CH2Ri
wherein R is a Cg-Clg alkyl group, and Ri is of the general formula:
(CI-i~ )xC00-M (CH2)xC00 -M
i,: f
N or N~+ CH2CHZOH
v.,.,.,R1 ,.vR1
wherein Rl 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 C10 to C14 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. xide surfactant
According to the present invention amine oxides useful as
amphoteric surfactants may be used herein. Such optional but highly
preferred amine oxides suitable for use have the formula:
0
R6R7NR$
wherein R6 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl
and alkyl phenyl group, or mixtures thereof, containing from 6 to 20
carbon atoms, preferably I2 to 14 carbon atoms; and R7 and Rg are
independently CI_3 alkyl or C2_3 hydyroxyalkyl groups, or a
w0 96/06149 ~ ~ 9 ~ PCT1US95/09585
17
polyethylene oxide group containing from 1 to 3, preferable 1, ethylene
oxide groups. These amine oxide surfactants in particular include CIO-
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 C12-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 inventian the compositions may thus
comprise betaines. The betaines useful as zwitterionic surfactants, in the
present invention are those compounds having the formula
R(RI)2N+R2C00- wherein R is a C6-Clg hydrocarbyl group,
preferably a Clp-C16 alkyl group or Clp-16 acylamido alkyl group, each
RI is typically CI-C3 alkyl, preferably methyl, and R2 is a CI-CS
hydrocarbyl group, preferably a CI-Cg alkylene group, more preferably a
CI-C2 alkylene group. Examples of suitable betaines include cocanut
acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; C12-14
acylamidopropylbetaine; Cg_14 acylamidohexyldiethyl betaine; 4[C14-16
acylmethylamidodiethylammonio]-I -carboxybutane; C I 6-18
acylamidodimethylbetaine; Ch-16 acylamidopentanediethyl-betaine;[C12-
16 acylmethylamidodimethylbetaine. Preferred betaines are C12-18
dimethyl-ammonio hexanoate and the CIO-18 acylamidopropane (or
ethane) dimethyl {or diethyl) betaines.
The complex betaines suitable for use herein have the formula:
R - {A)n ~ - {CHRI)xly N - Q {1)
B B
WO 9CrI06149 PCTlU595109585
21~~~9~
is
wherein R is a hydrocarbon group having from 7 to 22 carbon atoms,
preferably 12 to I4 carbon atoms, A is the group (C(O)), n is 0 or 1, RI
is hydrogen or a lower alkyl group, x is 2 ar 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°r~, preferably from 0% to 5%a of said betaines.
ltaines
The sultaines useful in the present invention are those compounds
having the formula (R(R1)2N+R2S03- wherein R is a C6-CIg
hydroc:arbyl group, preferably a C10-C16 alkyl group, more preferably a
C12-C13 alkyl group, each Rl is typically C1-C3 alkyl, preferably
methyl, and R2 is a CI-C6 hydrocarbyl group, preferably a C1-Cg
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 hydrocarbyi group. Examples of such cationic surfactants
include the ammonium surfactants such as alkyldimethylammonium
halogenides and surfactants having the formula:
[R~(OR3)y)[RQ(OR3)yl2R5N'1'X-
wherein R2 is an alkyl or alkyl benzyl group having from about $ to about
18 carbon atoms in the alkyl chain, each R3 is selected from the group
consisting of CH2CH2-, -CH~CH(CHg)-, -CH2CH(CH20H)-, -
CH2CH2CH2-, and mixtures thereof; each R4 is selcted from the group
consisting of C1-Cø alkyl, C1-C4 hydroxyalkyl, benzyl ring structures
PCTJUS95109585
WO 96f06149
19
formed by joining the two R4 groups, -CH2CHOH-
CHOHCOR6CHOHCH20H wherein R6 is any hexose or hexose polymer
having a molecular weight less than about 1000 and hydrogen when y is
nat 0; RS is the same as R4 or is an alkyl chain wherein the total number
of carbon atoms of R2 plus R$ is not more than about 18; each y is from
about 0 to about 10 and the sum of the y values is from 0 to about 13; and
X is any compatible anion.
Preferred cationic surfactants are the water soluble quaternary
amonium compounds useful in the present composition have the formula:
R 1 R2R3~N+X_
wherein Rl is a Cg-Clb alkyl, each of R2 R3 and R4 is independently
Cl-C4 alkyl, C1-C4 hydroxy alkyl, benzyl and (C2H40)xH where x has
a value of from 1 to 5 and X is an anion. Nat more than one of the R2,
R3 or R4 should be benzyl.
The preferred alkyl chain length for R1 is from C12-C15.
particularly where the alkyl group is a mixture of chain lengths derived
from coconut or palm kernel fat or is derived from synthetically by olefin
build up or OXO alcohols synthesis. Preferred groups for the R2R3 and
R4 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-CIS dimethyl hydroxyethyl ammonium chloride or
broimde; coconut dimethyl hydroxyethyl ammonium chloride or bromide;
myristyl trimethyl ammonium methyl sulphate; lauryl dimethyl benzyl
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
w0 9G/06149 ~ ~ ~ PCI'/US95/09585
compositions of the present invention typically comprise from 0.5°I to
about 5~ by weight of said cationic surfactants.
According to the present invention the compositions may also
comprise optional ingredients such as builders, antiredeposition agents,
polymeric soil release agents, chelating agents, dispersing agents and suds
supressors or enhancers. Preferably the detergent composition of the
present invention comprises from 15 J to 50% of a detergent adjunct
selected from builders, chelants and mixtures thereof.
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 about 1 °!o builder.
Liquid
formulations typically comprise from about 5 % to about SO l , 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 IS l 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 meta-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
W096/06149 ~ ~ ~ ~ f~ ~ PCT/US95109585
a ~
21
"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, 19$7 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-Na2Si20~ morphology farm 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-11, as the alpha, beta and gamma farms.
As noted above, the delta-Na2Si205 (NaSKS-6 form) is most preferred
for use herein. Other silicates may also be useful such as for example
magnesium silicate, which can serve as a crispening agent in granular
formulations, as a stabilizing agent for oxygen bleaches, and as a
component of suds control systems.
Examples of carbonate builders are the alkaline earth and alkali
metal carbonates as disclosed in German Patent Application No.
2,321,001 published on November 15, 1973.
Aluminosilicate builders are useful in the present invention.
Aluminosilicate builders are of great importance in most currently
marketed heavy duty granular detergent compositions, and can also be a
significant builder ingredient in liquid detergent formulations.
Aluminosilicate builders include those having the empirical formula:
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.
w0 96!06149 PCT/U595f09585
22
Useful aluminosiIicate ion exchange materials are commercially
available. These aluminosilicates can be crystalline or amorphous in
structure and can,be naturally-occurring aluminosilicates or synthetically
derived. A method for producing aluminosilicate ion exchange materials
is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12,
1976. Preferred synthetic crystalline 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) 12l ~ xH20
wherein x is from about 20 to about 30, especially about 27. This material
is known as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used
herein. Preferably, the aiuminosilicate 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 ta, a wide variety of
poiycarboxylate 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 polycarbaxylate
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 "TMS/TDS" huilders 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 thane
described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874
and 4,102,903.
W09GIOG149 ~ ~ ~ ~ ~ ~ ~ PCT/lJS95lp9585
23
Other useful detergency builders include the. ether
hydroxypolycarboxylates, copolymers of malefic anhydride with ethylene
or vinyl methyl ether, I, 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 used in granular compositions, especially in combination with
aeoIite andlor 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 C$-C20 alkyl and alkenyl
succinic acids and salts thereof. A particularly preferred compound of this
type is dodecenylsuccinic acid. Specific examples of succinate builders
include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-
dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.
Laurylsuccinates are the preferred builders of this group, and are
described in European Patent Application 86200690.5!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.
w0 9G/OG t49 PCTYUS95I09585
?1 ~~~09~
24
Fatty acids, e.g., C12-C18 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 accaunt 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.
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
CA 02198093 2000-O1-28
25
phosphonates include ethylenediaminetetrakis (methylenephosphonates),
nitrilotris (methylenephosphonates) and diethylenetriaminepentakis
(methylenephosphonates) as DEQUESTTM ("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 3 812 044. Preferred
compounds of this type in acid form are dihydroxydisuphobenzenes such
as 1,2-dihydroxy-3,5-disulphobenzene.
A preferred biodegradable chelator for use herein is
ethylenediamine disuccinate ("EDDS") especially the s,s form as
described in U.S. patent 4 704 233.
Polymeric Soil Release Ascent
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
terethphalate: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
CA 02198093 2000-O1-28
26
degree of polymerisation of at least 2, or (iv) Cl-C4 alkyl ether or C4
hydroxyalkyl ether substituents or mixtures thereof, wherein said
subsituents are present in the form of Cl-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 Cl-C4 alkyl ether and/or C4 hydroxyalkyl ether units to deposit upon
conventional polyester synthetic fibre surfaces and retain a su~cient 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
esters, preferably polyvinyl acetate) grafted onto polyalkylene oxide
backbones, such as polyethylene oxide backbones. Commercially
available materials of this kind include Sokalanmarketed by BASF.
Polymeric Disnersing,~~Pnr~
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 soil release
peptitization and anti-redeposition.
Polymeric polycarboxylate materials can be prepared by
polymerising or copolymerising 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
W096106149 ~ ~ ~ PCi'IUS951O958i
27
acid. The presence in the polymeric polycarboxylates herein of
monomeric segments containing no carboxylate radicals such as
vinylmethyl ether styrene, ethylene etc. is suitable provided that such
segments da 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 10 000, more preferably from about 4000 to
7000 and most preferably from about 4000 to 5000. Water salable 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 dispersinglantiredeposition agent. Such materials
include the. water soluble salts of copolymers of acrylic acid and malefic
acid. The average molecular weight of such copolymers in the acid form
preferably ranges from about 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
Application 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/antirepositian 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 10 000.
Polyaspartate and polyglutamate dispersing agents (mol. wt. about
10000) may also be used especially in conjunction with zeolite builders.
PCTIUS95109595
wQ 96/06149
28
Suds sup ro essor
Compounds for 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 suppressers, and
suds suppressers are well known to those skilled in the art. See, for
example, Kirk Othmer Encyclapedia of Chemical Technology, Third
Edition, Valume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One
category of suds suppresser of particular interest encompasses
monocarboxylic 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 suppresser
typically have hydrocarbyl 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
alkanolammonium salts.
The detergent compositions herein may also contain non-surfactant
suds suppressers. 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-C4p
ketones (e.g., stearone), etc. Other suds inhibitors include N-alkylated
amino triazines such as tri- to hexa-alkylmeiamines 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 monestearyl 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. 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
1I0°C
CA 02198093 2000-O1-28
29
(atmospheric pressure). It is also known to utilize waxy hydrocarbons,
preferably having a melting point below about 100°C. The hydrocarbons
constitute a preferred category of suds suppresser for detergent
compositions. Hydrocarbon suds suppressers 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 "para~n," as used in this suds
suppresser discussion, is intended to include mixtures of true paraffins
and cyclic hydrocarbons.
Another preferred category of non-surfactant suds suppressers
comprises silicone suds suppressers. 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 suppressers 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
Application 354,016, published February 7, 1990, by Starch, M. S.
Other silicone suds suppressers 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 suppresser for use herein is a
suds suppressing amount of a suds controlling agent consisting essentially
of:
w0 96106149 ~ ~ ~ '~~, t~ ~ PCTIUS95109585
(i) palydimethylsiloxane fluid having a viscosity of from about 20
cs. to about 1,500 cs. at 25°C;
(ii) from about 5 to about 50 parts per 100 parts by weight of (i) of
siloxane resin composed of (CH3)35101/2 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 I of said silicone suds
suppresser, which comprises (1) a nonaqueous emulsion of a primary
antifoam agent which is a mixture of (a) a palyorganosiloxane, (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 (e), to farm 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 46 through column 4, line 35.
The silicone suds suppresser herein preferably comprises
polyethylene glycol and a copolymer of polyethylene
glycollpolypropylene glycol, all having an average molecular weight of
less than about 1,000, preferably between about 100 and 800. The
CA 02198093 2000-O1-28
31
polyethylene glycol and polyethylene/polypropylene copolymers herein
have a solubility in water at room temperature of more than about 2
weight ~ , preferably more than about S weight °6 .
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 I2.
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.
WO 96JIj6149 ~ ~ ~ ~ ~ ~ ~ PCTIUS95H195fiS
32
The compositions herein will generally comprise from 0% to about
5% of suds suppresser. When utilized as suds suppressers,
monocarboxyIic 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 monoearboxylate suds
suppresser is utilized. Silicone suds suppressers 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 suppresser 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 suppressers are.
generally utilized in amounts ranging from about 0.1 % to about 2%, by
weight, of the composition. Hydrocarbon suds suppressers are typically
utilized in amounts ranging from about 0.01 % to about 5.0%, although
higher levels can be used. The alcohol suds suppressers are typically used
at 0.2%-3% by weight of the finished compositions.
bleaching agents
The detergent compositions herein may optionally contain bleaching
agents or bleaching compositions containing a bleaching agent and one or
more bleach activators. When present, bleaching agents will typically he
at levels of from about I % 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 0.5'7 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.
CA 02198093 2000-O1-28
33
Perborate bleaches, e.g., sodium perborate (e.g., mono- or tetra-hydrate)
can be used herein.
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., OXONETM, 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% 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
CA 02198093 2000-O1-28
34
corresponding to the bleach activator. Various nonlimiting examples of
activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990
to Mao et al, and U.S. Patent 4,412,934. The 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(RS)C(O)R2C(O)L or R1C(O)N(RS)R2C(O)L
wherein R1 is an alkyl group containing from about 6 to about 12 carbon
atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms, RS
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:
O
II
~~0
N~ O
Still another class of preferred bleach activators includes the acyl
lactam activators, especially acyl caprolactams and acyl valerolactams of
the formulae:
CA 02198093 2000-O1-28
35
O O
O C-CH2-CH \ O C-CH2-CH2
R6-C-N~ ~C H2 Rs-C-N~
C H2-C H2 C H - ~ 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, octanoyI caprolactarn, 3,5,5-
trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl
caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl
valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl
valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof.
See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985,
which discloses acyl caprolactams, 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
1.25 % , 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,
Mn~II2(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, MnuIMnN~
(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 96106149 ~ ~ ~ ~ ~ PGTIU595t09585
36
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 States Patents: 4,728,455; 5,284,944;
5,246,612;5,256,779; 5,280,117; 5,274,147; 5,153,161; 5,227,084;
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 purposes.
WO 9b106t49 ~ ~ ~ ~~ ~ g ? PC1YUS95J09585
37
Examples
The invention will now be described in more detail in the following non-
limiting examples.
Examples lto 5
Examples 1 to 5 illustrate the soil removal performance of the alkyl
alkaxylated sulphates of the present invention.
Soil removal testing, using an Atlas launder-Ometer, was carried out in a
wash solution containing 1000ppm anionic surfactant, SOOppm zeolite,
SOOppm SKS-6, SOOppm carbonate, 100ppm suds-suppressor. The water
hardness of the wash solution was either SdH (Clark) or 25 dH (Clark).
The temperature of the wash solution was either 20°C or 60°C.
The
wash cycle time was 4S minutes. The stain was on WFK sebum stain on
cotton fabric. Differences in greasy soil removal performance are
recorded in panel scare units (psu), positive having a better performance
than the reference product. The following grading scale (psu grading)
was used:
0 = equal
1 = I pink this one is better
2 = I know this one is a little better
3 = This one is a lot better
4 = This one is a whole lot better
Grading is done under controlled light conditions by expert graders. The
number of replicates used in this test was eight.
- 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 6% AEXS
(with x >_ 3.0).
WO 96/061d9 ~ ~ (~ ~ ~ ~ ~ PGTfUS95109585
38
- Example 2: wash solution B contains an alkyl ethaxylated sulphate with
a Clq.-C15 chain-length, an average of 3 moles ethylene oxide per mole
of surfactant.
- Example 3: wash solution C contains an alkyl ethoxylated sulphate with
a C14-C15 chain-length, an average of 0.6 moles ethylene oxide per mole
of surfactants, containing 2°~ AE1S, 3~ AE2S and 12°k AEXS,
(with x>_
3.0).
- Example 4: wash solution D contains an alkyl sulphate with a wide
chain-length distribution (ie C12-CIq./C16-C18)~
- Example 5: wash solution E contains an C14-CI5 alkyl sulphate.
The wash solution in example 1 contains a detergent composition covered
by the invention.
Soil removal performance of A versus B, C, D, E (psu):
B_ ~ ~ E
20C, 5dH +2.88 +1.63 +3.38 +1.25
20C, 25dH +2.88 -0.88 +1.25 +0.75
60C, SdH +2.88 +1.13 +2.63 +2.75
60C, 25dH +2.50 +0.38 +2.50 +0.75
The detergent compositions described in example 1 has an excellent
greasy sail removal performance across a wide range of temperatures and
water hardness.
Examples 6 to 11
Soil removal testing as described in examples 1 to 5 was carried out with
a wash solution containing 700ppm anionic surfactant, 300ppm nonionic
surfactant (either C 12-C 15 AE3 or C 14-C 15 AE7), 500ppm zeolite,
500ppm SKS-6, SOOppm carbonate, 100ppm suds-suppressor. The
temperature of the wash solution was either 20°C or 60°C. The
water
hardness was 5dH (Clark).
W ~ 96106149 ~ , ~7 ~ ~ ~ ~ PCT/Cr595109585
39
- Example 6: as example and withC12-Clg AE3 nonionic:wash
1
solution F
- Example 7: as example and withClq.-ClgAE7 nonionic:wash
1
solution G
Example 8: as example and withC12-C15 AE3 nonionic:wash
Z
solution H
- Example 9: as example and withC14-C15 AE7 nonionic:wash
2
solution I
- Example 10: as example and withC12-C15 AE3 nonionic:wash
3
solution J
- Example 11: as example 3 and with Clq.-C15 AE7 nonionic: wash
solution K
The wash solutions in Examples 6 & 7 comprise a detergent composition
of the invention.
Soil removal performance of F versus H and J (psu).
Ii J_
20°C +1.63 +0.5
60°C +2.06 +0.5
Soil removal performance of G versus I and K (psu)
_I
20°C +2.25 +0.5
60°C + 1.3$ +0.13
Examples 12 to 13
The examples 12 to 13 illustrate the wetting properties of the present
invention.
Wash solutions A, B, C, D, E were prepared as in examples 1 to 5.
WO 9bJ061.19 ~ ~ ~ ~ ~ 9 ~ PCCIITS95JiN3585
4.0
Example 12
The wetting time of untreated wool by solution A-E was measured
Y
_A B_ _C _D _E
Wetting
time (sec) 6.5 11.5 12.5 8.0 7.0
Example 13
The wetting time of wool pretreated with fabric conditioners.
A B_ ~ ~7 E
Wetting
time (sec) 3.5 6.0 4.0 4.3 4.3
Wash solution A which comprises specific alkyl ethoxylated sulphates of
the present invention has improved wetting properties.
Examples 14-17
The following granular detergent compositions were prepared by mixing
the listed ingredients in the amounts specified.
Detergent com osition: ~_4 ~ ~ ~7
Linear Alkyl Sulphate - 3.6 - -
Alkyl Ethoxylated Sulphate AExS
with x = 0 6.6 0.5 5.4 7.2
with x = 1 2.5 3.8 2.I 2.8
with x = ? 1.1 0.5 1.8 1.'?
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
W096/06149 ~~ ~ PCT/US95109585
41
Percarbonate 22 - I? _
N,N.N,N-tetra acetyl ethylene 6 - 5
diamine
S.S-Ethylene diamine-di-succinic acid 0.4 0.7 0.2 0.2
Enzymes (e.g. lipase, cellulose,
protease, amylase) 1.0 0.? 0.8 1.4
Aluminasilicate (zeolite A) 14 IS 10 8
Layered silicate/citric acid 12 _ _ _
Sodium citrate 5 _ _ _
sodium carbonate 8 8 6 6
sodium silicate _ _ -
sulphate - - - ll
sodium malefic ~ acrylic acid j 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 - -
PEG - 0.~ - _
brighteners, suds suppressors 0.3 - 0.2 0?
Example 18
A liquid detergent composition according to the present invention was
prepared containing the following ingredients:
by weight of the detergent composition
AExS with x = 0 15.6
x = 1 6.0
x = ' 2.6
x - 3 1.8
C12-C14 N-methyl glucamide 6.5
C 12-C 14 fatty alcohol ethoxylate 6.5
C 12-C 16 ~~Y acid ?
Citric acid anhydrous 6.0
Diethylene triamine penta methylene phosphonic 1.0
acid
Monoethanolamine 13.2
WO 96106149 PCTIUS95109585
" 42
Propanediol 12.7
Ethanol 1.8
Enzymes (e.g. lipase, protease, cellulase, amylase)0.9
Terephthalate-based polymer 0.5
Boric acid 2.4
Minors and water
