Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
b 2 1 2 ~; 7 1 9
-- CASE 4941
STABLE, POU M BLE AQUEOUS LIQUID LAUNDRY DETERGENT
COMPOSITIONS WITH PEROXYACID BLEACH
AND HIGH NONIONIC SURFACTANT
TECHNICAL FIELD
This relates to stable, pourable aqueous liquid laundry
detergents containing solid, substantially water-insoluble organic
peroxyacid, C8-20 alkyl ethoxylate, fatty acid, agar or xanthan
polysaccharide, and a pH jump system.
BACKGROUND OF THE INVENT~ON
U. S. Patents 4,992,194 and 5,073,285, both Liberati et al,
issued February 12, 1991 and December 17,1991, respectively,
describe aqueous structured heavy duty liquid detergent
formulations which contain solid, particulate, substantially
water-insoluble organic peroxyacid, surfactant combinations, pH
adjusting systems, and selected decoupling polymers.
U. S. Patent 4,879,057, Dankowski et al, issued November 7,
1989 discloses aqueous bleaching suspensions including
peroxycarboxylic acid suspended in a carrier liquid in the
presence of an organic thickening agent and of an acidifying
agent. The suspensions contain agar or xanthan polysaccharide as
thickening agent, and a hydrate-forming neutral salt.
Aqueous liquid laundry detergent products which contain
suspended solids such as solid, substantially water-insoluble
peroxyacid can have phase stability problems, particularly across
the varying environmental temperatures to which such products may
be exposed.
A further problem is product and wash pH, since low product
pH is required for bleach stability while alkaline wash pH is
advantageous for cleaning and bleaching efficacy (see U.S. Patent
4,259,201, Cockrell).
Lastly, when product detergent surfactant levels are
increased in such compositions for better cleaning and bleaching
2 1 2 ~ 7 1 9
-
- 2 -
performance, product viscosity often increases to unacceptable
levels.
It has now been found that a stable, pourable aqueous liquid
laundry detergent composition can be formulated by including from
about 0.05 to about 2 weight % of xanthan polysaccharide for phase
stability, along with a specific pH jump system for cleaning
performance and product bleach stability, in a peroxyacid-
containing suspension. This is accomplished without the use of a
stability enhancing polymer which is a copolymer of a hydrophobic
and a hydrophilic monomer.
It has also been found that for improved cleaning performance
without adversely affecting product viscosity, ethoxylated
nonionic surfactant can be added (to the above composition
containing peroxyacid and xanthan polysaccharide) in an amount
greater than or equal to the amount of anionic surfactant to
achieve a stable, pourable aqueous liquid detergent composition
which cleans and bleaches quite well (even in the absence of
enzymes and an effective amount of detergency builder). In this
second type of high nonionic composition with product stability
and good detergency, certain low levels of fatty acid are also
included for phase stability.
SUMMARY OF THE INVENTION
This relates to a stable, pourable aqueous liquid laundry
detergent composition, comprising, by weight of the composition:
a. from about 1 to about 30% of solid, substantially
water-insoluble organic peroxyacid;
b. from about 10 to about 40% of C8-20 alcohol which has been
ethoxylated with an average of from about 2 to about 20 moles of
ethylene oxide per mole of alcohol;
c. from O to about 10% of bleach-compatible anionic
surfactant; and
d. from about 2 to about 40% of a pH jump system which
produces a pH in the composition of between about 3 and about 6,
and upon dilution of the composition produces a pH of between
about 7 and about 10;
~ ~ - 3 - ~ 7 ~ ~
- e. from about 0.05 to about 2% of agar or xanthan
polysaccharide; and
f. from about 0.5 to about 3% of C10-14 fatty acid.
DESCR~PTION OF THE INVENTION
The compositions according to the present invention are
aqueous and preferably comprise, by weight of the composition,
from about 30 to about 70%, preferably from about 40 to about 60%,
of water, preferably distilled and deionized, and from about 30 to
about 70%, preferably from about'40 to about 60%, of active
ingredients.
A. Peroxyacid
Compositions of the present invention comprise from about 0.5
to about 30%, preferably from about 1 to about 20~o~ most
preferably from about 1.5 to about 570, by weight of the
composition, of solid, substantially water-insoluble organic
peroxyacid.
The organic peroxyacid should be evenly suspended throughout
the liquid detergent composition.
The following organic peroxyacids (IUPAC names) are
preferred: 4-nonylamino-4-oxoperoxybutyric acid ("NAPSA");
6-nonylamino-6-oxoperoxyhexanoic acid ("NAPAA")i 1,12-diperoxy-
dodecanedioic acid, (nDPDA~); heptyl sulfonylperpropionic acid;
decylsulphonyl perpropionic acid; heptyl-, octyl-, nonyl-, and
decyl-sulphonylperbutyric acid; and phthaloyl aminoperoxycaproic
acid.
~ Of the organic peroxyacids, amidoperoxyacids (amide
substituted peroxycarboxylic acids) are preferred. Suitable
amidoperoxyacids for use herein are described in U.S. Patents
4,634,551 and 4,686,063, both Burns et al, issued January 6, 1987
and August 11, 1987, respectively. Suitable amidoperoxyacids are of
the formula:
R1 - NH - C - R2 - C - OOH or R1-C-NH-R2-C-OOH
'11 11 11 11
0 0 0 0
wherein R1 is an alkyl group containing from about 6 to about 12
carbon atoms, and R2 js an alkylene containing from 1 to about 6
2 5 7 ~ ~
- 4 -
carbon atoms. Preferably, R1 is an alkyl group containing from
~ about 8 to about 10 carbon atoms, and R2 is an alkylene group
containing from about 2 to about 4.
Also preferred are peroxyfumarates, which are described in
U.S. Patent 4,852,989, Burns et al., issued August 1, 1989, and
sulfone peroxyacids (sulfone peroxycarboxylic acids), which are
described in U.S. Patents 4,758,369, 4,824,591, and 5,004,558,
all Dryoff et al., issued July 19, 1988, April 25, 1989, and
April 2, 1991, respectively.
The most preferred amidoperoxyacids are monononylamido
peroxyadipic acid (NAPM; most preferred), monononylamido
peroxysuccinic acid (NAPSA), and 1,12-diperoxy-dodecanedioic acid
(DPDA).
Another name for NAPM is 6-(nonylamino)-6-oxo-caproic acid.
The chemical formula for NAPM is:
~0 0
l 11 11
CH3(CH2)gN C(CH2)4COOH
The molecular weight of NAPM is 287.4.
Example I of U.S. Patent 4,686,063 contains one description
of the synthesis of NAPSA, from Column 8, line 40 to Column 9, line
5, and NAPM, from Column 9, line 15 to Column 9, line 65. At the
end of the amidoperoxyacid synthesis, the reaction is quenched with
water, filtered, washed with water to remove some excess sulfuric
acid (or other strong acid with which the peroxyacid was made), and
filtered again.
The amidoperoxyacid wet cake thus obtained can be contacted
with a phosphate buffer solution at a pH between about 3.5 and 6,
preferably between about 4 and 5, according to U.S. Patent
4,909,953, Sadlowski et al., issued March 20, 1990, U.S. Patent
5,055,218, Getty et al., issued October 8, 1991. describes bleach
granules containing amidoperoxyacid.
CA 0212~719 1998-03-27
NAPM filter cake herein is preferably washed twice in phosphate
buffer. It has been found that two successive phosphate buffer washes
lend optimal stability to NAPM .
NAPM can be prepared by, for example, first reacting NMM
(monononyl amide of adipic acid), sulfuric acid, and hydrogen peroxide.
The reaction product is quenched by addition to ice water followed by
filtration, washing with distilled water, and final suction filtration
to recover the wet cake. Washing can be continued until the pH of the
filtrate is neutral.
Preferred NAPM is thermally annealed (or thermally
agglomerated), meaning that it has been heated up to 70~C and then
quenched and filtered.
Al so sui table for use herein are phthaloyl aminoperoxycaproic
acids (" PAP " ), which are described in U.S. Patent 5,073,285, Liberati
et al, issued December 17, 1991.
Particulate (solid), organic peroxyacids with a theoretical AvO
(available oxygen) of between about 3 and about 15, most preferably
between 5 and 12, are preferred.
B. Deterqent Surfactant
The present composition comprises, by weight of the composition,
from about 5 to about 50X, preferably from about 10 to about 40X, most
preferably from about 15 to about 30X, of detergent surfactant,
preferably nonionic and/or anionic surfactant.
Preferred compositions for the second, high nonionic surfactant
type of composition with phase stability comprise from about 10 to about
40X, preferably from about 12 to about 30X, most preferably from about
15 to about 20X, by weight of the composition, of C8-C20 alcohol which
has been ethoxylated with an average of from about 2 to about 20 moles
of ethylene oxide per mole of alcohol; and from 0 to about 10%,
preferably from about 5 to about 8%, of bleach-compatible anionic
surfactant.
More preferred is C1O_C18 alcohol which has been ethoxylated with
an average of from about 4 to about 15, more preferably from about 6 to
about 12, moles of ethylene oxide per mole of alcohol. Blends of C10-Cl8
alkyl ethoxylates and C10-Cl8 alkyl ethoxylates
2125719
_ 6
with additional detergent surfactants, are also included herein.
Most preferred is C12-15 alkylethoxylate (E6-9), which is C12-15
alcohol which has been ethoxylated with an average of 6-9 moles of
ethylene oxide per mole of alcohol. The most preferred anionic
surfactant is C12 linear alkylbenzene sulfonic acid.
Preferably, the present compositions comprise ethoxylated
nonionic surfactant:anionic surfactant in a ratio of between about
1:1 and about 30:1, preferably between about 2:1 and about 20:1,
most preferably between about 2:1 and about 4:1.
lo These are preferably selected from the group consisting of
c9-2o linear alkylbenzene sulfonate, C8-l8 alkenyl
carboxysulfonate, E2 20 ethoxylated C10-2o alcohols, polyhydroxy
fatty acid amide, and mixtures thereof. More preferred are
C10 14 linear alkylbenzene sulfonate (most preferred), and E2 5
ethoxylated C12 18 alcohols.
1. Anionic Surfactant
Anionic surfactants useful for detersive purposes are
included in the compositions hereof. These can include salts of
soap, Cg-C20 linear alkylbenzenesulphonates, Cg-C22 primary or
secondary alkanesulphonates, Cg-C24 olefinsulphonates, sulphonated
polycarboxylic acids prepared by sulphonation of the pyrolyzed
product of alkaline earth metal citrates, e.g., as described in
British Patent Specification No. 1,082,179, alkyl glycerol
sulfonates, fatty acyl glycerol sulfonates, paraffin sulfonates,
alkyl phosphates, isothionates such as the acyl isothionates,
N-acyl taurates, fatty acid amides of methyl tauride, alkyl
succinamates and sulfosuccinates, monoesters of sulfosuccinate
(especially saturated and unsaturated C12-Clg monoesters) diesters
of sulfosuccinate (especially saturated and unsaturated C6-C14
diesters), N-acyl sarcosinates (the nonionic nonsulfated compounds
being described below), branched primary alkyl sulfates, alkyl
polyethoxy carboxylates such as those of the formula
RO(CH2CH20)kCH2C00-M+ wherein R is a Cg-C22 alkyl, k is an integer
from 0 to 10, and M is a soluble salt-forming cation, and fatty
acids esterified with isothionic acid and neutralized with sodium
hydroxide. Resin acids and hydrogenated resin acids are also
suitable, such as rosin, hydrogenated rosin, and resin acids and
5 7 ~ ~ ~
- 7 -
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). A
variety of such surfactants are also generally disclosed in U.S.
Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at
Column 23. line 58 through Column 29, line 23.
One type of anionic surfactant preferred for use in liquid
detergent compositions herein is alkyl ester sulfonates, which is
preferably
alkyl ester sulfonate surfactant of the structural formula:
o
~ Il
R3---CH---C---oR4
I
S03M
wherein R3 is a Cg-C20 hydrocarbyl, preferably an alkyl, or
combination thereof, R4 is a C1-C6 hydrocarbyl, preferably an
alkyl, or combination thereof, and M is a soluble salt-forming
cation. Suitable salts include metal salts such as sodium,
potassium, and lithium salts. Preferably, R3 is C10-cl6 alkyl,
and R4 is methyl, ethyl or isopropyl. Especially preferred are
the methyl ester sulfonates wherein R3 is C14-C16 alkyl.
Preferred for use in liquid detergent compositions herein is
Cg-C20 linear alkylbenzene sulfonate (preferably sodium salts).
Preferably the nonionic surfactant is the condensation
product of C1o-C20 alcohol and between about 2 and about 20 moles
of ethylene oxide per mole of alcohol (nE2 20 ethoxylated C10-2o
alcohol~).
2. Nonionic Surfactant
Suitable nonionic detergent surfactants are generally
disclosed in U.S. Patent 3,g29,678, Laughlin et al., issued
December 30, 1975, at column 13, line 14 through column 16, line
6. Exemplary non-limiting classes of useful nonionic surfactants are
listed below.
1. The polyethylene, polypropylene, and polybutylene oxide
condensates of alkyl phenols.
~ .,~
- 212S719
- 8 -
2. The condensation products of aliphatic alcohols with from
about 1 to about 25 moles of ethylene oxide. The alkyl chain of
the aliphatic alcohol can either be straight or branched, primary
or secondary, and generally contains from about 8 to about 22
carbon atoms.
3. The condensation products of ethylene oxide with a
hydrophobic base formed by the condensation of propylene oxide
with propylene glycol.
4. The condensation products of ethylene oxide with the
o product resulting from the reaction of propylene oxide and
ethylenediamine.
5. Semi-polar nonionic surfactants are a special category
of nonionic surfactants which include water-soluble amine oxides
containing one alkyl moiety of from about 10 to about 18 carbon
atoms and 2 moieties selected from the group consisting of alkyl
groups and hydroxyalkyl groups containing from about 1 to about 3
carbon atoms; water-soluble phosphine oxides containing one alkyl
moiety of from about 10 to about 18 carbon atoms and 2 moieties
selected from the group consisting of alkyl groups and
hydroxyalkyl groups containing from about 1 to about 3 carbon
atoms; and water-soluble sulfoxides containing one alkyl moiety of
from about 10 to about 18 carbon atoms and a moiety selected from
the group consisting of alkyl and hydroxyalkyl moieties of from
about 1 to about 3 carbon atoms.
6. Alkylpolysaccharides 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.
7. Fatty acid amide surfactants having the formula:
o
Il
R6 - C - N(R7)2
wherein R6 is an alkyl group containing from about 7 to about 21
(preferably from about 9 to about 17) carbon atoms and each R7 is
212~719
_ g
selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4
hydroxyalkyl, and -(C2H40)XH where x varies from about 1 to about
The polyhydroxy fatty acid amide surfactant component
comprises compounds of the structural formula:
o R1
Il I
(I) R2 - C - N - Z
wherein: R1 is C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy
propyl, or a mixture thereof, preferably C1-C4 alkyl, more
0 preferably C1 or C2 alkyl, most preferably Cl alkyl (i.e.,
methyl); and R2 is a Cs-C31 hydrocarbyl, preferably straight chain
C7-C1g alkyl or alkenyl, more preferably straight chain Cg-C17
alkyl or alkenyl, most preferably straight chain C11-C1s alkyl or
alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl
having a linear hydrocarbyl chain with at least 3 hydroxyls
directly connected to the chain, or an alkoxylated derivative
(preferably ethoxylated or propoxylated) thereof. Z preferably
will be derived from a reducing sugar in a reductive amination
reaction; more preferably Z will be a glycityl. Suitable reducing
sugars include glucose, fructose, maltose, lactose, galactose,
mannose, and xylose. Z preferably will be selected from the group
consisting of -CH2-(CHOH)n-CH20H, -CH(CH20H)-(CHOH)n 1-CH20H,
-CH2-(CHOH)2(CHOR')(CHOH)-CH20H, and alkoxylated derivatives
thereof, where n is an integer from 3 to 5, inclusive, and R' is H
or a cyclic or aliphatic monosaccharide. Most preferred are
glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH20H.
C. DH JumD Svstem
Solid, substantially water-insoluble peroxyacids are more
stable at acidic pHs while cleaning and bleaching effectiveness of
liquid laundry detergents in the wash is better at alkaline pHs.
Incorporation of peroxyacid bleaches in liquid laundry detergents,
particularly heavy duty liquids, was therefore thought to be
impractical. Attaining these different pH requirements in product
and in the wash is accomplished by using a pH jump (i.e.
adjusting) system to maintain product pH between about 3 and about
6 and to achieve a pH in the wash (i.e. on dilution) of between
about 7 and about 10.
~12~719
-- - 10 -
The present composition comprises from about 2 to about 40%,
preferably from about 5 to about 30%, most preferably from about
10 to about 25%, by weight of the composition, of a pH jump system
which produces a pH in the composition of between about 3 and
about 6, preferably from about 3.5 to about 5, most preferably
from about 4 to about 4.5, and upon dilution of the composition
produces a pH of between about 7 and about 10, preferably from
about 7.5 to about 9, in the dilute solution.
1. Borate/PolYol pH Jump SYstem
lo Preferably, compositions of the present invention comprise
from about 2 to about 40%, preferably from about 5 to about 30%,
most preferably from about 10 to about 25%, by weight of the
composition, of a pH jump system comprising:
1. a borate and;
2. a polyol wherein the polyol is a cis 1,2 polyol
capable of forming a complex with the borate when the composition
is in a concentrated form to cause a reduction in pH of the
composition to a value of about 3-6 and the complex being capable
upon dilution of the composition, of dissociating in dilute
solution to liberate the borate to cause an increase in pH in the
solution to a value of about 7-9, the polyol to borate weight
ratio being 1:1 to 10:1.
The present compositions most preferably comprise from about
1 to about 20%, preferably from about 2 to about 10%, by weight of
the composition, of a boron compound such as borax (preferred),
boric oxide, or sodium ortho- or pyro-borate; and from about 1 to
about 20X, preferably from about 5 to about 15%, by weight of the
composition, of a polyol such as sorbitol, dulcitol, xylitol,
fructose, arabitol, mannitol, galactitol, catechol, pinacol,
glucose and polyhydroxy fatty acid amide. Preferred polyols for
use herein are sorbitol, xylitol and dulcitol. Most preferred
compositions comprise from about 4 to about 6%, by weight of the
composition, of borax and from about 10 to about 15%, by weight of
the composition, of sorbitol.
Preferably, the polyol is dissolved in part of the water to
be added to the formula, followed by the addition to this mixture
of any salt or electrolytes in the formula. Last, the boron
212~
.,_ - 11 -
compound is mixed into this pre-mix. This clear pH jump solution
is added to the remainder of the formula after the surfactants.
The mechanism of action of this borate-polyol system is
believed to be the formation of an acidic borate-polyol complex in
concentrated solution. Upon dilution, the complex dissociates and
yields borate ions, which have a buffered pH of about 9.
2. Other DH JumD SYstems
Other pH jump systems aside from borate/polyol can be useful
herein. These may include insoluble alkaline salts in product
which dissolve in the wash for a more alkaline pH. These may
include sodium carbonate, sodium bicarbonate, sodium silicate,
sodium pyrophosphate and orthophosphate.
D. Xanthan wlYsaccharide
Compositions of the present invention comprise from about
0-05 to about 2%, preferably from about 0.1 to about lX, most
preferably from about 0.1 to about 0.15%, by weight of the
composition, of agar or xanthan polysaccharide, which is also
called xanthan gum. Xanthan gum is produced by fermentation and
extraction of the naturally occurring plant bacteria, Xanthomonas
camDestrias.
E. FattY Acid
Preferred compositions for the second type of high nonionic
surfactant composition comprise from about 0.5 to about 3.5%,
preferably from about 1 to about 3X, most preferably from about
1.5 to about 2.5%, by weight of the composition, of C10-16,
preferably C10-12, fatty acid. Preferred are lauric acid,
myristic acid, palmitic acid, and stearic acid. Most preferred is
lauric acid. These low levels of fatty acid are included for
product phase stability.
F. Other Parameters
The present aqueous laundry detergent compositions do not
comprise a stability enhancing polymer which is a copolymer of a
hydrophobic and a hydrophilic monomer. The second type of
composition (high nonionic surfactantJ preferably does not include
such a copolymer. Stability enhancing polymers in general need
not be included herein.
212S~lg
- 12 -
The following are preferably not included in the present
compositions: enzymes, an effective amount of detergency builder,
urea, and glycerol. An effective amount of detergency builder is
preferably more than about 4X and less than about 30%, by weight
of the composition (to exclude the above-described low fatty acid
levels).
The compositions herein preferably have a viscosity of from
about 100 to about 3000, most preferably from about 300 to about
1000, most preferably from about 400 to about 900, centipoise
O (cps) at 20-C when measured with an RVT Brookfield Viscometer,
using a No. 3 spindle and a setting of 100 rpm. This viscosity is
desirable for convenient pouring from a container by a liquid
laundry detergent user.
G. Optional Inqredients
The ingredients herein should be combined in any manner which
will evenly disperse or dissolve them in the composition, and
which does not interfere with their action. The preferred order
of addition is: surfactant, lauric acid, pH jump, electrolytes,
chelant, peroxyacid, xanthan gum, polyacrylate, brightener,
polyvinyl pyrrolidone and water to balance.
Optional and preferred ingredients include from about 0.5 to
about 5, preferably from 1 to 2, % by weight of the composition of
polyvinyl pyrrolidone (preferred) and/or polyvinyl alcohol. The
PVP, which includes substituted and unsubstituted vinyl
pyrrolidone polymerization products, and PVA have a molecular
weight between about 4,000 and about 200,000, preferably between
about 5,000 and about 100,000, most preferably between 10,000 and
30,000. A combination of PVPs and/or PVAs of different molecular
weights could also be used.
Another optional and preferred ingredient is from about 0.05
to about 2, preferably from about 0.1 to 1, % by weight of the
composition of bleach-stable, stilbene fluorescent whitening agent
(nFWAn). This preferably has the following structural formula:
- 13 - ~ ~ 2 ~ j ~ 9 ~ ~
.~
(503M)n
~ CH--~CH
Rl R2 Rl R2
m
wherein Rl is hydrogen, halogen, alkyl, alkoxy or phenyl;
R2 is hydrogen or alkyl;
M is hydrogen, an alkali metal or ammanium ion;
10n ~ 0-2, but the formula must contain at least one S03M
group; and
m - 1-2 and when m-1, the substituent on the linkage carbon
is hydrogen.
Suitable stilbene F~As for use herein, if they are
15bleach-stable, are as described in U.S. Patents 4,309,316 and
4,298,490, Lange et al, issued January 5, 198Z and November 3,
1981 respectively and U.S. Patent 5.035.825. Eckhardt et al.. issued
July 30. 1991.
The most preferred stilbene F~A for use herein, because it is
20bleach-stable, is Tinopal~ CBS-%, which is benzenesulfon~c acid,
2,2'-((I,I'-biphenyl)-4,4'-dtyldl-2,1-ethenedtyl~bis-, disodium
salt (CA Index Ha~e). The for~ula for Tinopal~ CBS-X is:
S03Na+
CH~ ~ ~3-Na+
A suffkient a~ount of sodiu~ hydroxide (0.4N) is added
(usually 2-5 weight %) just before balancing with water to bring
the pH of the composition at 20-C to a preferred pH of 4.5.
30Hydrotropes such as sodium and potassium xylene sulfonate.
sodium and potassium toluene sulfonate, sodium and potassium sulfonate.
and mixtures thereof. and related compounds (as disclosed in U.S.
Patent 3,915,~03, can be utilized in the compositions of the present
2125719
_ - 14 -
invention. They may be present at levels of from about 0.5% to
about 10%, preferably from about 1% to about 5%, by weight.
Examples of suitable chelants for use herein are:
carboxylates, such as ethylene diamine tetraacetate (EDTA) and
diethylene triamine pentaacetate (~TPA); polyphosphates, such as
sodium acid pyrophosphate (SAPP), tetrasodium pyrophosphate
(TSPP), and sodium tripolyphosphate (STPP); phosphonates, such as
ethylhydroxydiphosphonate (Dequest~ 2010 (1-hydroxyethylidene)
bisphosphonic acid) and other sequestering agents sold under the
Dequest~ trade name; and combinations of the above. Other
sequestering agents for use herein are 2,6-pyridinedicarboxylic
acid (dipicolinic acid), picolinic acid, and 8-hydroxyquinoline,
and combinations thereof. From about 0.05 to about 0.5% of
ethylhydroxydiphosphonate and dipicolinic acid, alone or combined;
are preferred chelants.
The compositions herein may further contain magnesium
sulfate, which is commercially available in the heptahydrate form.
(If anhydrous magnesium sulfate is used, the above levels should
be adjusted accordingly.)
The compositions may further contain sodium sulfate or
potassium sulfate.
This invention further provides a method for cleaning and
bleaching fabrics in the wash by contacting the fabrics with
effective amounts of an aqueous liquid detergent composition
comprising, by weight of the composition:
a. from about 1 to about 30% of solid, substantially
water-insoluble organic peroxyacid;
b. from about 5 to about 50X of detergent surfactant;
c. fro~ about 2 to about 40X of a pH jump system which
produces a pH in the composition of between about 3 and about 6,
and upon dilution of the composition produces a pH of between
about 7 and about 10 in the dilute solution; and
d. from about 0.05 to about 2% of agar or xanthan
polysaccharide; and which laundry detergent composition does not
- 212~71~
- 15 -
comprise a stability enhancing polymer which is a copolymer of a
hydrophobic and a hydrophilic monomer.
Also provided is a method for cleaning and bleaching fabrics
in the wash by contacting the fabrics with effective amounts of an
aqueous liquid laundry detergent composition comprising, by weight
of the composition:
a. from about 1 to about 30% of solid, substantially
water-insoluble organic peroxyacid;
b. from about 10 to about 40% of C8-20 alcohol which has been
ethoxylated with an average of from about 2 to about 20 moles of
ethylene oxide per mole of alcohol;
c. from 0 to about 10% of bleach-compatible anionic
surfactant; and
d. from about 2 to about 40% of a pH jump system whic~
produces a pH in the composition of between about 3 and about 6,
and upon dilution of the composition produces a pH of between
about 7 and about 10 in the dilute solution;
e. from about 0.05 to about 2% of agar or xanthan
polysaccharide; and
f. from about 0.5 to about 3% of C10-14 fatty acid.
The following examples illustrate the compositions of the
present invention. All parts, percentages and ratios used herein
are by weight unless otherwise specified.
EXAMPLE I
A composition of the present invention is as follows.
Inqredient Active %
C12- 15 alkylethoxylate (E9) 5. 2
C12-13 linear alkylbenzene sulfonic acid 12.1
30 Monononylamido peroxyadipic acid 1.6
Ethylhydroxydiphosphonate 0. 2
Magnesium sulfate heptahydrate 2.25
Sodium sulfate 2.25
Sorbitol 10.5
35 Borax 3.8
Xanthan gum 0.10
Sodium polyacrylate (MW 10,000) 0.15
- 212~719
- 16 -
Fluorescent whitening agent ("FWA") 0.30
Sodium hydroxide (4N) to pH 4.5
Water Balance
TOTAL 100
Viscosity: 800 centipoise (cps)--pourable
pH jump: 4.38 (product); 8.00 (wash solution)
The procedure for the preparation of the above composition
lo containing peroxyacid bleach is as follows:
1. Xanthan gum is dissolved in enough water to make a 1%
solution.
2. A pH jump premix is prepared by dissolving the sorbitol
and borax in an equal amount of water. If any
electrolytes are in the composition, they can also be
dissolved in the pH jump premix.
3. The composition is prepared in an appropriate size
beaker (typically a 2-liter beaker). First charge the
beaker with the linear alkyl benzene sulfonic acid,
alkylethoxylate and, if present, lauric acid, and mix to
dissolve.
4. The pH jump premix is added to the stirring surfactant
mix.
5. The chelant is added with agitation.
6. The desired amount of solid peroxyacid (e.g. NAPM ) is
added and dispersed.
7. The xanthan gum solution is added.
8. Next the sodium polyacrylate is added.
9. Then the fluorescent whitening agent, and PVP, if
present, is added.
10. The resulting mix is homogenized on a homogenizer at low
speed for about 1 minute.
11. The pH of the composition is adjusted to 4.5 with a 4N
sodium hydroxide solution.
- 35 The resulting product is a pourable, creamy suspension. The
pH jump capability of the composition is checked by diluting 1.5
gm. of the composition into 1,000 gms. of water.
21257i9
- 17 -
In the above formula, other peroxyacids can be substituted
for the monononylamido peroxyadipic acid, such as 1,12-diperoxy-
dodecanedioic acid or sulfone peroxyacid or phthaloyl amino-
peroxycaproic acid. Agar polysaccharide can be substituted for
the xanthan polysaccharide. Other detergent surfactants can be
substituted for the above. Water can replace magnesium sulfate
heptahydrate and sodium sulfate in the above formula.
EXAMPLE II
A composition of the present invention containing
1,12-diperoxydodecanedioic acid as the peroxyacid is as follows.
The procedure for preparation is as described in Example I.
Inqredient Active %
C12-13 alkylethoxylate (E6.5) 12.1
15 C12 linear alkylbenzene sulfonic acid 5.2
1,12-Diperoxydodecanedioic acid 2
Dipicolinic acid 0.3
Magnesium sulfate heptahydrate 6.8
Sodium sulfate 5.38
20 Sorbitol 10.6
Borax 2.4
Lauric acid 2.5
Xanthan gum 0.12
Sodium polyacrylate (MW 10,000) 0.1
25 FWA 0.1
Polyvinyl pyrrolidone (MW 10,000) 1.0
Sodium hydroxide (4N) 2.0
Water Balance
TOTAL 100
Viscosity: 430 centipoise
pH jump: 4.5 (product) to 7.78 (wash)
In the above formula, other peroxyacids can be substituted
for the 1,12-diperoxydodecanedioic acid, such as monononylamido
peroxyadipic acid or sulfone peroxyacid or phthaloyl amino-
peroxycaproic acid. Agar polysaccharide can be substituted for
21'~5719
- 18 -
the xanthan gum. Other detergent surfactants can be substituted
for the above. Water can replace magnesium sulfate heptahydrate
and sodium sulfate in the above formula.
EXAMPLE III
A composition of the present (high nonionic surfactant)
invention containing 1,12-diperoxydodecanedioic acid as the
peroxyacid is as follows.
Inqredient Active %
0 C12-13 alkylethoxylate (E6-5) 15
Linear alkylbenzene sulfonic acid 5.2
1,12-Diperoxydodecanedioic acid 2
Dipicolinic acid 0.3
Magnesium sulfate heptahydrate 4.2
Sorbitol
Borax 5.1
Lauric acid 2.0
Xanthan gum 0.12
Sodium polyacrylate 0.25
FWA 0.20
Polyvinyl pyrrolidone (MW 4,500) 1.0
Sodium hydroxide (4N) to pH 4.5
Water Balance
TOTAL 100
Viscosity: 660 centipoise
pH jump: 4.5 (product) to 7.85 (wash)
In the above formula, other peroxyacids can be substituted
for the 1,12-diperoxydodecanedioic acid, such as monononylamido
peroxyadipic acid or sulfone peroxyacid or phthaloyl amino-
peroxycaproic acid. Agar polysaccharide can be substituted for
the xanthan gum. Water can replace magnesium sulfate heptahydrate
and sodium sulfate in the above formula.
- 212~719
19 -
EXAMPLE IV
A composition of the present invention (high nonionic
surfactant) is as follows. The procedure for preparation is as
described in Example I.
Inqredient Active %
C12-15 alkylethoxylate (E9) 15
C12 linear alkylbenzene sulfonic acid 6.4
Monononylamido peroxyadipic acid 2
Ethylhydroxydiphosphonate 0. 2
10 Magnesium sulfate heptahydrate 6.0
Sorbitol 20
Borax 5.0
Lauric acid 2 . 0
Xanthan gum 0.15
Sodium polyacrylate (MW 4,500) 0.20
FWA 0.20
Sodium hydroxide (4N) to pH 4.5
Water Balance
TOTAL 100
Viscosity: 910 centipoise (cps)
pH Jump: 4.5 (product) to 7.95 (wash)
WHAT IS CLAIMED IS:
