Note: Descriptions are shown in the official language in which they were submitted.
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NON-AQUEOUS, PARTICULATE-CONTAINING
DETERGENT COMPOSITIONS CONTAINING
s BLEACH PRECURSOR COMPOSITIONS
FIELD OF THE INVENTION
This invention relates to non-aqueous laundry detergent products
io which are in the form of a liquid and which are in the form of stable
dispersions of particulate material such as bleaching agents and bleach
precursor.
is BACKGROUND OF THE INVENTION
Detergent products in the form of a liquid are often considered to be
more convenient to use than are dry powdered or particulate detergent
products. Said detergents have therefore found substantial favor with
2o consumers. Such detergent products are readily measurable, speedily
dissolved in the wash water, capable of being easily applied in concentrated
solutions or dispersions to soiled areas on garments to be laundered and are
non-dusting. They also usually occupy less storage space than granular
products. Additionally, such detergents may have incorporated in their
2s formulations materials which could not withstand drying operations without
deterioration, which operations are often employed in the manufacture of
particulate or granular detergent products.
Although said detergents have a number of advantages over granular
3o detergent products, they also inherently possess several disadvantages. In
particular, detergent composition components which may be compatible with
each other in granular products may tend to interact or react with each other.
Thus such components as enzymes, surfactants, perfumes, brighteners,
solvents and especially bleaches and bleach activators can be especially
3s difficult to incorporate into liquid detergent products which then have an
acceptable degree of chemical stability.
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One approach for enhancing the chemical compatibility of detergent
composition components in detergent products has been to formulate non-
aqueous (or anhydrous) detergent compositions. In such non-aqueous
products, at least some of the normally solid detergent composition
s components tend to remain insoluble in the liquid product and hence are less
reactive with each other than if they had been dissolved in the liquid matrix.
Non-aqueous liquid detergent compositions, including those which contain
reactive materials such as peroxygen bleaching agents, have been disclosed
for example, in Hepworth et al., U.S. Patent 4,615,820, Issued October 17,
io 1986; Schultz et al., U.S. Patent 4,929,380, Issued May 29, 1990; Schultz
et
al., U.S. Patent 5,008,031, Issued April 16, 1991; Elder et al., EP-A-030,096,
Published June 10, 1981; Hall et al., WO 92/09678, Published June 11,
1992 and Sanderson et al., EP-A-565,017, Published October 13, 1993.
is A particular problem that has been observed with the incorporation of
bleach precursor in non-aqueous detergents, include the chemical stability of
the bleach precursor. EP 339 995 describes a non-aqueous liquid detergent
composition comprising a persalt bleach and a precursor therefore, the
composition containing a capped alkoxylated nonionic surfactant.
2o EP 540 090 proposes to use a bleach precursor which is relatively insoluble
in the non aqueous liquid phase of the liquid detergent composition.
A difficulty associated with the improvement of chemical stability of
bleach precursor is that, upon dilution in the wash liquor, the bleach
2s precursors still need to have a certain degree of solubility high enough to
be
effective as a bleaching species in the wash liquor.
Given the foregoing, there is clearly a continuing need to identify and
provide non-aqueous, bleach precursor containing detergent compositions in
3o the form of liquid products that have a high degree of chemical stability
in the
concentrate along with an efficient bleaching performance in the wash liquor.
Accordingly, it is an object of the present invention to provide a non-
aqueous detergent composition wherein the bleach precursors have
3s improved chemical stability in the concentrate, while at the same time
still
being effective as bleach species in the wash liquor.
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According to the present invention, there is provided a non-aqueous
detergent composition which is in the form of a liquid, containing a bleaching
agent and a bleach precursor composition.
s SUMMARY OF THE INVENTION
The present invention provides a non-aqueous heavy-duty detergent
composition which is in the form of a liquid, said composition comprising a
bleaching agent and a bleach precursor composition.
io
DETAILED DESCRIPTION OF THE INVENTION
Bleach precursor composition
is According to the present invention, the bleach precursor composition
comprises
a) a bleach precursor; and
b) a surfactant system; and
c) salt of an organic acid,
According to a preferred embodiment of the present invention, the
bleach precursor composition comprises
a) a bleach precursor; and
b) a surfactant system comprising a non-ethoxylated anionic surfactant
Zs andlor a nonionic surfactant; and
c) salt of an organic acid,
wherein said surfactant, said precursor and said organic acid are in the form
of an agglomerate, granule or extrudate in which said precursor, said
surfactant system and the salt of the organic acid are optionally coated in
3o intimate admixture;
a) Bleach precursor
An essential component of the invention is a bleach precursor. Bleach
3s precursors for inclusion in the composition in accordance with the
invention
typically contain one or more N- or O- acyl groups, which precursors can be
selected from a wide range of classes. Suitable classes include anhydrides,
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esters, imides, nitrites and acylated derivatives of imidazoles and aximes,
and examples of useful materials within these classes are disclosed in GB-
A-1586789.
Suitable esters are disclosed in GB-A-836988, 864798, 1147871,
2143231 and EP-A-0170386. The acylation products of sorbitol, glucose and
all saccharides with benzoylating agents and acetylating agents are also
suitable.
to Specific O-acylated precursor compounds include 3,5,5-tri-methyl hexanoyl
oxybenzene sulfonates, benzoyl oxybenzene sulfonates, cationic derivatives
of the benzoyl oxybenzene sulfonates, nonanoyl-6-amino caproyl
oxybenzene sulfonates, monobenzoyltetraacetyl glucose and pentaacetyl
glucose. Phtalic anhydride is a suitable anhydride type precursor. Useful N-
is acyl compounds are disclosed in GB-A-855735, 907356 and GB-A-1246338.
Preferred precursor compounds of the imide type include N-benzoyl
succinimide, tetrabenzoyl ethylene diamine, N-benzoyl substituted ureas
and the N,N-N'N' tetra acetylated alkylene diamines wherein the alkylene
2o group contains from 1 to 6 carbon atoms, particularly those compounds in
which the alkylene group contains 1, 2 and 6 carbon atoms. A most
preferred precursor compound is N,N-N',N' tetra acetyl ethylene diamine
(TAED).
2s N-acylated precursor compounds of the lactam class are disclosed
generally in GB-A-955735. Whilst the broadest aspect of the invention
contemplates the use of any lactam useful as a peroxyacid precursor,
preferred materials comprise the caprolactams and valerolactams.
Suitable caprolactam bleach precursors are of the formula:
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s
O
p C CH2 CH2
CH2
R1 C N
CH2 CH2
wherein R1 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from
1 to 12 carbon atoms, preferably from 6 to 12 carbon atoms.
s
Suitable valero lactams have the formula:
0
O C CH2 CH2
R1 C -- N
CH2 CH2
io wherein R1 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing
from
1 to 12 carbon atoms, preferably from 6 to 12 carbon atoms. In highly
preferred embodiments, R1 is selected from phenyl, heptyl, octyl, nonyl,
2,4,4-trimethylpentyl, decenyl and mixtures thereof.
is The most preferred materials are those which are normally solid at
<30°C, particularly the phenyl derivatives, ie. benzoyl valerolactam,
benzoyl
caprolactam and their substituted benzoyl analogues such as chloro, amino,
nitro, alkyl, alkyl, aryl and alkyoxy derivatives.
ao Caprolactam and vaferolactam precursor materials wherein the R1
moiety contains at least 6, preferably from 6 to about 12, carbon atoms
provide peroxyacids on perhydrolysis of a hydrophobic character which
afford nucleophilic and body soil clean-up. Precursor compounds wherein
R1 comprises from 1 to 6 carbon atoms provide hydrophilic bleaching
2s species which are particularly efficient for bleaching beverage stains.
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Mixtures of 'hydrophobic' and 'hydrophilic' caprolactams and valero lactams,
typically at weight ratios of 1:5 to 5:1, preferably 1:1, can be used herein
for
mixed stain removal benefits.
s Another preferred class of bleach precursor materials include the
cationic bleach activators, derived from the valerolactam and acyl
caprolactam compounds, of formula:
R'
R~~ ~ R
X- N O
CH2\ O C - (CH2)X - C; 2
~//\\.',
C_N~ /CH2
CH2 - CH2
wherein x is 0 or 1, substituents R, R' and R" are each C1-C10 alkyl or C2-
C4 hydroxy alkyl groups, or [(CyH2y)O]n-R"' wherein y=2-4, n=1-20 and R"'
is a C1-C4 alkyl group or hydrogen and X is an anion.
is Suitable imidazoles include N-benzoyl imidazole and N-benzoyl
benzimidazole and other useful N-acyf group-containing peroxyacid
precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl
pyroglutamic acid.
2o Another preferred class of bleach activator compounds are the amide
substituted compounds of the following general formulae:
R1 N{R5)C(O}R2C(O)L or R1 C(O)N(R5)R2C(O)L
2s wherein R1 is an al~~ rl, alkylene, aryl or alkaryl group with from about 1
to
about 14 carbon ai.~ ~s, R2 is an alkylene, arylene, and alkarylene group
containing from about 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl, or
alkaryl group containing 1 to 10 carbon atoms and L can be essentially any
leaving group. R1 preferably contains from about 6 to 12 carbon atoms. R2
3o preferably contains from about 4 to 8 carbon atoms. R1 may be straight
chain or branched alkyl, substituted aryl or alkylaryl containing branching,
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substitution, or both and may be sourced from either synthetic sourEes ~or
natural sources including for example, tallow fat. Analogous structural
variations are permissible for R2. The substitution can include alkyl; aryl,
halogen, nitrogen, sulphur and other typical substituent groups or organic
s compounds. R5 is preferably H or methyl. R1 and R5 should preferably not
contain more than 18 carbon atoms total. Preferred examples of bleach
precursors of the above formulae include amide substituted peroxyacid
precursor compounds selected from (fi-octanamido-
caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxy benzene
io sulfonate, (6-decanamido-caproyl) oxybenzene-sulfonate, and mixtures
thereof as described in EP-A-01703$6.
Also suitable are precursor compounds of the benzoxazin-type, as
disclosed for example in EP-A-332,294 and EP-A-4$2,$07, particularly those
is having the formula:
O
II
CEO
I
N C-R~
including the substituted benzoxazins of the type
R2 O
R3 ~O
C-R~
R4 N
Rs
wherein R1 is H, alkyl, alkaryl, aryl, arylalkyl, secondary or tertiary amines
and wherein R2, R3, R4, and R5 may be the same or different substituents
selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino,
alkyl
2s amino, COORO (wherein R6 is H or an alkyl group) and carbonyl functions.
An especially preferred precursor of the benzoxazin-type is:
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O -
I I
I
~C
N
The particles of particulate bleach activator component preferably
have a particle size of from 250 micrometers to 2000 micrometers.
s
These bleach precursors can be partially replaced by preformed
peracids such as N,N phthaloylaminoperoxy acid (PAP), nonyl amide of
peroxyadipic acid (NAPAA), 1,2 diperoxydodecanedioic acid (DPDA) and
trimethyl ammonium propenyl imidoperoxy mellitic acid (TAPIMA).
to
More preferred among the above described bleach precursors are the
amide substituted bleach precursor compounds. Most preferably, the bleach
precursors are the amide substituted bleach precursor compounds selected
from (6-octanamido-caproyl)oxybenzenesulfonate, (6-
ls nonanamidocaproyl)oxy benzene sulfonate, (6-decanamido-
caproyl)oxybenzenesulfonate, and mixtures thereof.
The bleach precursors are normally incorporated at a level of from
20% to 95% preferably 50% to 90% by weight of the bleach activator
2o component and most preferably at least 60% by weight thereof.
b) Surfactant system
Surfactants are useful in the bleaching precursor compositions of the
2s present invention in particular as solubilising agents. Anionic, nonionic,
cationic, amphoteric and/or zwitterionic surfactants are useful. Nonlimiting
examples of surfactants useful herein include the conventional C11-C18
alkyl benzene sulphonates ("LAS") and primary, branched-chain and random
C10-C20 alkyl sulphates ("AS"), the C10-C18 secondary (2,3) alkyl
3o sulphates of the formula CH3(CH2)x(CHOS03- M+) CH3 and
CH3(CH2)y(CHOS03- M+) CH2CH3 where x and (y+1 ) are integers of at
least 7, preferably at least about 9, and M is a water-solubilising cation,
especially sodium, unsaturated sulphates such as oleyl sulphate, the C10-
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C18 alkyl alkoxy sulphates ("AExS"; especially EO 1-7 ethoxy sulphates),
C10-C18 alkyl alkoxy carboxylates (especially EO 1-7 ethoxy carboxylates),
the C10-C18 glycerol ethers, the C10-C18 alkyl polyglycosides and their
corresponding sulphated polyglycosides, the C12-C18 alpha-sulphonated
s fatty acid esters, methyl ester sulphonate {"MES") and oleoyl sarcosinate.
A preferred embodiment of the present invention is a surfactant
system comprising an anionic surfactant and/or a nonionic surfactant. The
surfactant system will typically be present in amount of 0.1 % to 50% by
io weight of the precursor composition, more preferably in an amount of 5-
15%.
Preferred anionic surfactants are non-ethoxylated anionic surfactants.
These can include salts (including, for example, sodium, potassium,
is ammonium, and substituted ammonium salts such as mono-, di- and
triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and
sarcosinate surfactants.
Other anionic surfactants include the isethionates such as the acyl
2o isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl
succinates and sulfosuccinates, monoesters of sulfosuccinate (especially
saturated and unsaturated C12-C18 monoesters) diesters of sulfosuccinate
(especially saturated and unsaturated C6 C14 diesters), N-acyl
sarcosinates. Resin acids and hydrogenated resin acids are also suitable,
2s such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin
acids present in or derived from tallow oil.
Anionic sulfate surfactants suitable for use herein include the linear
and branched primary alkyl sulfates, fatty oleyl glycerol sulfates, the C5-C17
3o acyl-N-{C1-Cq, alkyl) and -N-(C1-C2 hydroxyalkyl) glucamine sulfates, and
sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside
(the nonionic nonsulfated compounds being described herein).
Alkyl sulfate surfactants are preferably selected from the group
3s consisting of branched-chain and random C10-C20 alkyl sulphates ("AS"),
the C10-C18 secondary (2,3) alkyl sulphates of the formula
CH3(CH2)x(CHOS03- M+) CH3 and CH3(CH2)y(CHOS03- M+) CH2CH3
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where x and (y+1 ) are integers of at least 7, preferably at feast about-9,
and
M is a water-solubilising cation, especially sodium, unsaturated sulphates
such as oleyl sulphate.
s Anionic sulfonate surfactants suitable for use herein include the salts
of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, Cg-C22
primary or secondary alkane sulfonates, C6-C24 olefin sulfonates,
sulfonated polycarboxyfic acids, alkyl glycerol sulfonates, fatty acyl
glycerol
sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
to
Anionic carboxylate surfactants suitable for use herein include the
soaps ('alkyl carboxyls'), especially certain secondary soaps as described
herein.
is Preferred soap surfactants are secondary soap surfactants which
contain a carboxyl unit connected to a secondary carbon. The secondary
carbon can be in a ring structure, e.g. as in p-octyl benzoic acid, or as in
alkyl-substituted cyclohexyl carboxylates. The secondary soap surfactants
should preferably contain no ether linkages, no ester linkages and no
2o hydroxyl groups. There should preferably 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 preferred secondary soap surfactants:
2s A. A highly preferred class of secondary soaps 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 0 or an integer from 1
to 4, x is an integer from 4 to 10 and the sum of (x + y) is 6-10, preferably
7-
9, most preferably 8.
3o B. Another preferred class of secondary soaps comprises those carboxyl
compounds wherein the carhoxyl substituent is orr 'a ring hydrocarbyl unit,
i.e., secondary soaps of the ;ormu3a R5-R8-COOP~d r herein R~ is C7-C10,
preferably C8-C9, alkyl or alkenyl and R6 is a ring structure, such as
benzene, cyclopentane and cyclohexane. (Note: R5 can be in the ortho;
3s meta or para position relative to the carboxyl on the ring.)C. Still
another
preferred class of secondary soaps comprises secondary carboxyl
compounds of the formula
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CHg(CHR)k-(CHZ)m-{CHR)n-CH(COOM)(CHR)o-(CH2)p-(CHR)q-CHg,
wherein each R is C1-Cq, alkyl, wherein k, n, o, q are integers in the range
of
s 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.
Especially preferred secondary soap surfactants for use herein are
to 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 and 2-pentyl-1-heptanoic
acid.
is Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R-CON (R1 ) CH2 COOM, wherein R is a C5-C17 linear or branched
alkyl or alkenyl group, R1 is a C1-C4 alkyl group and M is an alkali metal
ion.
Preferred examples are the myristyl and oleyl methyl sarcosinates in the
form of their sodium salts.
Among the above described non-ethoxylated anionic surfactants, the
anionic sulfate surfactants, anionic sulfonate surfactants, or mixtures
thereof
are preferred. More preferably, the anionic surfactant is selected from salts
2s of C12-C15 {AS), C5-C20 linear alkylbenzene sulfonates and mixtures
thereof, and most preferably is the salt of C5-C2p linear alkylbenzene
sulfonate.
3o Preferably the anionic surfactant is present in an amount of 1-25%,
more preferably 5-15%.
Nonionic surfactant
3s Essentially any nonionic surfactants useful for detersive purposes can
be included in the compositions such as polyhydroxy fatty acid amide
surfactants, condensates of alkyl phenols, ethoxylated alcohol surfactants,
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ethoxylated/propoxylated fatty alcohol surfactant, ethylene oxidelpropylene
oxide condensates with propylene glycol, ethylene oxide condensation
products with propylene oxide/ethylene diamine adducts,
alkylpolysaccharide surfactants, fatty acid amide surfactants and mixtures
s thereof. Exemplary, non-limiting classes of useful nonionic surfactants are
listed below.
Polyhydroxy fatty acid amides suitable for use herein are those
having the structural formula R2CONR1Z wherein : R1 is H, C1-Cq.
to hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof,
preferable C1-C4 alkyl, more preferably C1 or C2 alkyl, most preferably C1
alkyl (i.e., methyl); and R2 is a Cb-C31 hydrocarbyl, preferably straight-
chain
Cb-C1 g alkyl or alkenyl, more preferably straight-chain Cg-C17 alkyl or
alkenyl, most preferably straight-chain C11-C17 alkyl or alkenyl, or mixture
is thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl
chain
with at least 3 hydroxyls directly connected to the chain, or an alkoxylated
derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will
be derived from a reducing sugar in a reductive amination reaction; more
preferably Z is a glycityl.
The polyethylene, polypropylene, and polybutylene oxide
condensates of alkyl phenols are suitable for use herein. In general, the
polyethylene oxide condensates are preferred. These compounds include
the condensation products of alkyl phenols having an alkyl group containing
2s from about 6 to about 18 carbon atoms in either a straight chain or
branched
chain configuration with the alkylene oxide.
The alkyl ethoxylate condensation products of aliphatic alcohols with
from about 1 to about 25 moles of ethylene oxide are suitable for use herein.
3o The alkyl chain of the aliphatic alcohol can either be straight or
branched,
primary or secondary, and gener~!ly contains from 6 to 22 carbon atoms.
Particularly preferred are the cone-~nsation products of alcohols having an
alkyl group containing from 8 to 20 carbon atoms with from about 2 to about
10 moles of ethylene oxide per mole of alcohol.
As ethoxylated/propoxylated fatty alcohol surfactants, the ethoxylated
Cg-C1 g fatty alcohols and Cg-C1 g mixed ethoxylated/propoxylated fatty
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alcohols are suitable surfactants for use herein, particularly wheror water
soluble. Preferably the ethoxylated fatty alcohols are the C1p-C18
ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50, most
preferably these are the C12-C1 g ethoxylated fatty alcohols with a degree of
s ethoxylation from 3 to 40. Preferably the mixed ethoxylated/propoxylated
fatty alcohols have an alkyl chain length of from 10 to 18 carbon atoms, a
degree of ethoxylation of from 3 to 30 and a degree of propoxylation of from
1 to 10.
to The condensation products of ethylene oxide with a hydrophobic
base formed by the condensation of propylene oxide with propylene glycol
are suitable for use herein. The hydrophobic portion of these compounds
preferably has a molecular weight of from about 1500 to about 1800 and
exhibits water insolubility. Examples of compounds of this type include
is certain of the commercially-available PluronicTM surfactants, marketed by
BASF.
The condensation products of ethylene oxide with the product
resulting from the reaction of propylene oxide and ethylenediamine are
2o suitable for use herein. The hydrophobic moiety of these products consists
of the reaction product of ethylenediamine and excess propylene oxide, and
generally has a molecular weight of from about 2500 to about 3000.
Examples of this type of nonionic surfactant include certain of the
commercially available TetronicTM compounds, marketed by BASF.
2s
Suitable alkylpolysaccharides for use herein are disclosed in U.S.
Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic
group containing from about 6 to about 30 carbon atoms, preferably from
about 10 to about 16 carbon atoms and a polysaccharide, e.g., a
3o polyglycoside, hydrophilic group containing from about 1.3 to about 10,
preferably from about 1.3 to about 3, most preferably from about 1.3 to
about 2.7 saccharide units. Any reducing saccharide containing 5 or 6
carbon atoms can be used, e.g., glucose, galactose and gaiactosyl moieties
can be substituted for the glucosyl moieties. (Optionally the hydrophobic
3s 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
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units and the 2-, 3-, 4-, and/or fi- positions on the preceding saccharide
units.
s The preferred alkylpolyglycosides have the formula
R20(CnH2n0)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alkylphenyl,
to hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl
groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2
or 3; t is from 0 to 10, preferably 0, and X is from 1.3 to 8, preferably from
1.3 to 3, most preferably from 1.3 to 2.7. The glycosyl is preferably derived
from glucose.
is
Fatty acid amide surfactants suitable for use herein are those having
the formula: R6CON(R7)2 wherein R6 is an alkyl group containing from 7 to
21, preferably from 9 to 17 carbon atoms and each R7 is selected from the
2o group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -
{C2H40)xH, where x is in the range of from 1 to 3.
Preferred among the above described nonionic surfactants are the
2s ethoxylated surfactants, preferably selected from ethoxylated alcohol
surfactants, ethoxylated/propoxylated fatty alcohol surfactant, ethylene
oxide/propylene oxide condensates with propylene glycol, ethylene oxide
condensation products with propylene oxide/ethylene diamine adducts and
mixtures thereof, more preferably the ethoxylated alcohol surfactants.
3o Most preferred ethoxylated alcohol surfactants are the condensation
products of alcohols having an alkyl group containing from 8 to 20 carbon
atoms with frorrr 2 to 10 moles of ethylene oxide per mole of alcohol, in
particular the linear primary alcohol (C12/C14) condensed with an average
of 3 moles of ethylene oxide.
c) Organic acid or salt thereof
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Organic acid compounds suitable for the purposes of the present
invention comprise aliphatic or aromatic monomeric or oligomeric
carboxylates and preferably comprise monomeric aliphatic carboxylic acids.
Examples of such aliphatic acid compounds are glycolic, glutamic,
s citraconic, succinic, 1-lactic and citric acids. Citric acid is a
particularly
preferred surface treating agent.
Typical levels of such acids are from 1-30%, preferably from 2-20%,
most preferably from 5-15% by weight of the bleach precursor composition.
to It has been surprisingly found that the salt of the organic acid enhances
the
chemical stability of the bleach precursor in the non-aqueous liquid
detergent and reduces the tendency for the bleach activator to solubilize in
the matrix. In addition, the rheological stability of the product is improved.
is Form of the bleach precursor composition
The bleach precursor composition may be in any known suitable
particulate form for incorporation in a detergent composition, such as
agglomerate, granule, extrudate or spheronised extrudate. Preferably, the
2o bleach precursor composition is in a form of a spheronised extrudate.
Preferably, the process for the manufacture of the bleach activator
spheronised extrudate comprises the steps of:
{i) preparing a mix of solids, and optionally liquids, comprising the
2s bleach activator;
(ii) extruding the mix through a die under pressure to form an
extrudate, the pressure being less than 25 bar; and
{iii) breaking the extrudate to form the spheronised extrudate.
3o Preferably, the mixing step (i) is carried out using a a Loedige~ mixer,
the extrusion step {ii) by using a dome extruder such as a Fuji Paudal Model
DGL-1, most preferably having a die with orifices < 1 mm and extruded at a
pressure of about 20 bar. Step (iii) is preferably carried using a a rotating
disc spheroniser such as a Fuji Paudal QJ-400 where the extrudate are
3s broken down into short lengths and formed into substantially spherical
particles.
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Preferably, the non-ethoxylated anionic surfactant is mixed in-step(i)
with the bleach precursor component. ,
The non-aqueous liquid detergent compositions incorporating the
s peroxy acid bleach precursor particulates will normally contain from 1 % to
25% of the precursor particulates, more frequently from 1 % to 20% and
most preferably from 1 % to 15%, on a composition weight basis.
Surprisingly, it has now been found that the bleach precursors of the
to present invention are physically and chemically stable in the concentrate
(the
non-aqueous liquid detergent), while at the same time being more effective
as a bleach species in the wash liquor.
The non-aqueous detergent compositions of this invention may further
is comprise a surfactant- and low-polarity solvent-containing liquid phase
having dispersed therein the bleach precursor composition. The components
of the liquid and solid phases of the detergent compositions herein, as well
as composition form, preparation and use, are described in greater detail as
follows:
2o All concentrations and ratios are on a weight basis unless otherwise
specified.
Surfactant
2s The amount of the surfactant mixture component of the non-aqueous
liquid detergent compositions herein can vary depending upon the nature
and amount of other composition components and depending upon the
desired rheological properties of the ultimately formed composition.
Generally, this surfactant mixture will be used in an amount comprising from
3o about 10% to 90% by weight of the composition. More preferably, the
surfactant mixture will comprise from about 15% to 50% by weight of the
composition.
A typical listing of anionic, nonionic, ampholytic and zwitterionic
3s classes, and species of these surfactants, is given in US Patent 3,664,961
issued to Norris on May 23, 1972.
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Highly anionic preferred surfactants are the linear alkyl benzene
sulfonate (LAS) materials. Such surfactants and their preparation are
described for example in U.S. Patents 2,220,099 and 2,477,383,
incorporated herein by reference. Especially preferred are the sodium and
s potassium linear straight chain alkylbenzene sulfonates in which the average
number of carbon atoms in the alkyl group is from about 11 to 14. Sodium
C11-C14, e~9~~ C12~ LAS is especially preferred.
Preferred anionic surfactants include the alkyl sulfate surfactants
1o hereof are water soluble salts or acids of the formula ROS03M wherein R
preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl
having a C10-C18 alkyl component, more preferably a C12-C15 alkyl or
hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g.
sodium,
potassium, lithium), or ammonium or substituted ammonium (quaternary
1s ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium
cations).
Highly preferred anionic surfactants include alkyl alkoxylated sulfate
surfactants hereof are water soluble salts or acids of the formula
2o RO(A)mS03M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl
group having a C10-C24 alkyl component, preferably a C12-C1g alkyl or
hydroxyalkyl, more preferably C12-C15 alkyl or hydroxyalkyl, A is an ethoxy
or propoxy unit, m is greater than zero, typically between about 0.5 and
about 6, more preferably between about 0.5 and about 3, and M is H or a
2s cation which can be, for example, a metal cation {e.g., sodium, potassium,
lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium
cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are
contemplated herein. Specific examples of substituted ammonium cations
include quaternary ammonium cations such as tetramethyl-ammonium and
3o dimethyl piperdinium cations Exemplary surfactants are C12-C15 alkyl
polyethoxylate {1.0) sulfate (C12-C15E(1.0)M), C12-C15 alkyl polyethoxylate
(2.25) sulfate {C12-C15E(2.25)M), C12-C15 alkyl polyethoxylate (3.0) sulfate
(C12-C15E(3.0)M), and C12-C15 alkyl polyethoxylate (4.0) sulfate (C12
C15E(4.0)M), wherein M is conveniently selected from sodium and
3s potassium.
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Other suitable anionic surfactants to be used are alkyl ester sulfonate
surfactants including linear esters of Cg-C20 carboxylic acids (i.e., fatty
acids) which are sulfonated with gaseous S03 according to "The Journal of
the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable
s starting materials would include natural fatty substances as derived from
tallow, palm oil, etc.
The preferred alkyl ester sulfonate surfactant, especially for laundry
applications, comprise alkyl ester sulfonate surfactants of the structural
to formula:
O
(I
R3 - CH - C - OR4
is 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
2o thereof, and M is a cation which forms a water soluble salt with the alkyl
ester sulfonate. Suitable salt-forming cations include metals such as sodium,
potassium, and lithium, and substituted or unsubstituted ammonium cations.
Preferably, R3 is C1p-C1g alkyl, and R4 is methyl, ethyl or isopropyl.
Especially preferred are the methyl ester sulfonates wherein R3 is C10-C16
2s alkyl.
Other anionic surfactants useful for detersive purposes can also be
included in the laundry detergent compositions of the present invention.
These can include salts (including, for example, sodium, potassium,
3o ammonium, and substituted ammonium salts such as mono-, di- and
triethanolamine salts) of soap, Cg-C20 linear alkylbenzenesulfonates, Cg-
C22 primary of secondary alkanesulfonates, Cg-C24 olefinsulfonates,
sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed
product of alkaline earth metal citrates, e.g., as described in British patent
3s specification No. 1,082,179, Cg-C24 alkylpolyglycolethersulfates
{containing
up to 90 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl
glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene
oxide
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ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates sucfa as-
the
acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates,
monoesters of sulfosuccinates (especially saturated and unsaturated C12-
C1g monoesters) and diesters of sulfosuccinates (especially saturated and
s unsaturated Cg-C12 diesters), sulfates of alkylpolysaccharides such as the
sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being
described below), and alkyl polyethoxy carboxylates such as those of the
formula RO(CH2CH20)k-CH2C00-M+ wherein R is a Cg-C22 alkyl, k is an
integer from 1 to 10, and M is a soluble salt-forming cation. Resin acids and
to 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 described 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
is December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column
29, line 23 (herein incorporated by reference).
When included therein, the detergent compositions of the present
invention typically comprise from about 1 % to about 40%, preferably from
2o about 5% to about 25% by weight of such anionic surfactants.
One class of nonionic surfactants useful in the present invention are
condensates of ethylene oxide with a hydrophobic moiety to provide a
surfactant having an average hydrophilic-lipophilic balance (HLB) in the
2s range from 8 to 17, preferably from 9.5 to 14, more preferably from 12 to
14.
The hydrophobic {lipophilic) moiety may be aliphatic or aromatic in nature
and the length of the polyoxyethylene group which is condensed with any
particular hydrophobic group can be readily adjusted to yield a water-soluble
compound having the desired degree of balance between hydrophilic and
3o hydrophobic elements.
Especially preferred nonionic surfactants of this type are the Cg-C15
primary alcohol ethoxylates containing 3-12 moles of ethylene oxide per
mole of alcohol, particularly the C12-C15 primary alcohols containing 5-8
3s moles of ethylene oxide per mole of alcohol.
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Another class of nonionic surfactants comprises alkyl polyglucoside
compounds of general formula
RO (CnH2n0)tZx
s
wherein Z is a moiety derived from glucose; R is a saturated hydrophobic
alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n
is 2 or 3; x is from 1.3 to 4, the compounds including less than 10%
unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
io Compounds of this type and their use in detergent are disclosed in EP-B 0
070 077, 0 075 996 and
0 094 118.
Also suitable as nonionic surfactants are poly hydroxy fatty acid amide
is surfactants of the formula
R2-C-N-Z,
O R1
wherein R1 is H, or R1 is C1~ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy
propyl or a mixture thereof, R2 is C5_31 hydrocarbyl, and Z is a
polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at feast 3
hydroxyls directly connected to the chain, or an alkoxylated derivative
2s thereof. Preferably, R1 is methyl, R2 is a straight C11-15 alkyl or alkenyl
chain such as coconut alkyl or mixtures thereof, and Z is derived from a
reducing sugar such as glucose, fructose, maltose, lactose, in a reductive
amination reaction.
3o Non-aqueous Liquid Diluent
To form the liquid phase of the detergent compositions, the
hereinbefore described surfactant (mixture) may be combined with a non
aqueous liquid difuent such as a liquid alcohol alkoxylate material or a non
3s aqueous, low-polarity organic solvent.
Alcohol Alkoxylates
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One component of the liquid diluent suitable to form the compositions
herein comprises an alkoxylated fatty alcohol material. Such materials are
themselves also nonionic surfactants. Such materials correspond to the
s general formula:
R1 (CmH2m0)nOH
wherein R1 is a Cg - C15 alkyl group, m is from 2 to 4, and n ranges from
about 2 to 12. Preferably R1 is an alkyl group, which may be primary or
to secondary, that contains from about 9 to 15 carbon atoms, more preferably
from about 10 to 14 carbon atoms. Preferably also the alkoxylated fatty
alcohols will be ethoxylated materials that contain from about 2 to 12
ethylene oxide moieties per molecule, more preferably from about 3 to 10
ethylene oxide moieties per molecule.
The alkoxylated fatty alcohol component of the liquid diluent will
frequently have a hydrophilic-lipophilic balance (HLB) which ranges from
about 3 to 17. More preferably, the HLB of this material will range from
about 6 to 15, most preferably from about 8 to 15.
Examples of fatty alcohol alkoxylates useful as one of the essential
components of the non-aqueous liquid diluent in the compositions herein will
include those which are made from alcohols of 12 to 15 carbon atoms and
which contain about 7 moles of ethylene oxide. Such materials have been
zs commercially marketed under the trade names Neodol 25-7 and Neodol 23-
6.5 by Shell Chemical Company. Other useful Neodols include Neodol 1-5,
an ethoxylated fatty alcohol averaging 11 carbon atoms in its alkyl chain with
about 5 moles of ethylene oxide; Neodol 23-9, an ethoxylated primary C12 -
C13 alcohol having about 9 moles of ethylene oxide and Neodol 91-10, an
3o ethoxylated Cg - C11 primary alcohol having about 10 moles of ethylene
oxide. Alcohol ethoxylates of this type have also been marketed by Shell
Chemical Company under the Dobanol tradename. Dobanol 91-5 is an
ethoxylated Cg-C11 fatty alcohol with an average of 5 moles ethylene oxide
and Dobanol 25-7 is an ethoxylated C12-C15 fatty alcohol with an average
3s of 7 moles of ethylene oxide per mole of fatty alcohol.
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Other examples of suitable ethoxylated alcohols include Tergitol_15-S-7
and Tergitol 15-S-9 both of which are linear secondary alcohol ethoxylates
that have been commercially marketed by Union Carbide Corporation. The
former is a mixed ethoxylation product of C11 to C15 linear secondary
s alkanol with 7 moles of ethylene oxide and the latter is a similar product
but
with 9 moles of ethylene oxide being reacted.
Other types of alcohol ethoxylates useful in the present compositions
are higher molecular weight nonionics, such as Neodol 45-11, which are
io similar ethylene oxide condensation products of higher fatty alcohols, with
the higher fatty alcohol being of 14-15 carbon atoms and the number of
ethylene oxide groups per mole being about 11. Such products have also
been commercially marketed by Shell Chemical Company.
is The alcohol alkoxylate component when utilized as part of the liquid
diluent in the non-aqueous compositions herein will generally be present to
the extent of from about 1 % to 60% by weight of the composition. More
preferably, the alcohol alkoxylate component will comprise about 5% to 40%
by weight of the compositions herein. Most preferably, the alcohol alkoxylate
2o component will comprise from about 10% to 25% by weight of the detergent
compositions herein.
Non-aqueous Low-Polarity Organic Solvent
2s Another component of the liquid diluent which may form part of the
detergent compositions herein comprises non-aqueous, low-polarity organic
solvent(s). The term "solvent" is used herein to connote the non-surface
active carrier or diluent portion of the liquid phase of the composition.
While
some of the essential and/or optional components of the compositions herein
3o may actually dissolve in the "solvent"-containing phase, other components
will be present as particulate m:~terial dispersed within the "solvent"-
containing phase. Thus the term "solvent" is not meant to require that the
solvent material be capable of actually dissolving all of the detergent
composition components added thereto.
3s
The non-aqueous organic materials which are employed as solvents
herein are those which are liquids of low polarity. For purposes of this
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. invention, "low-polarity" liquids are those which have little, if any,
tendency to
dissolve one of the preferred types of particulate material used in the
compositions herein, i.e., the peroxygen bleaching agents, sodium perborate
or sodium percarbonate. Thus relatively polar solvents such as ethanol
s should not be utilized. Suitable types of low-polarity solvents useful in
the
non-aqueous liquid detergent compositions herein do include alkylene glycol
mono lower alkyl ethers, lower molecular weight polyethylene glycols, lower
molecular weight methyl esters and amides, and the like.
io A preferred type of non-aqueous, low-polarity solvent for use herein
comprises the mono-, di-, tri-, or tetra- C2-C3 alkylene glycol mono C2-Cg
alkyl ethers. The specific examples of such compounds include diethylene
glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropolyene
glycol monoethyl ether, and dipropylene glycol monobutyl ether. Diethylene
is glycol monobuty! ether and dipropylene glycol monobutyl ether are
especially preferred. Compounds of the type have been commercially
marketed under the tradenames Dowanol, Carbitol, and Cellosolve.
Another preferred type of non-aqueous, low-polarity organic solvent
2o useful herein comprises the lower molecular weight polyethylene giycols
(PEGs). Such materials are those having molecular weights of at least
about 150. PEGs of molecular weight ranging from about 200 to 600 are
most preferred.
2s Yet another preferred type of non-polar, non-aqueous solvent
comprises lower molecular weight methyl esters. Such materials are those
of the general formula: R1-C(O)-OCH3 wherein R1 ranges from 1 to about
18. Examples of suitable lower molecular weight methyl esters include
methyl acetate, methyl propionate, methyl octanoate, and methyl
3o dodecanoate.
The non-aqueous, low-polarity organic solvents) employed should, of
course, be compatible and non-reactive with other composition components,
e.g., bleach and/or activators, used in the liquid detergent compositions
3s herein. Such a solvent component will generally be utilized in an amount of
from about 1 % to 60% by weight of the composition. More preferably, the
non-aqueous, low-polarity organic solvent will comprise from about 5% to
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40% by weight of the composition, most preferably from about 10% to 25%
by weight of the composition.
Liquid Diluent Concentration
s
As with the concentration of the surfactant mixture, the amount of total
liquid diluent in the compositions herein will be determined by the type and
amounts of other composition components and by the desired composition
properties. Generally, the liquid diluent will comprise from about 20% to 95%
to by weight of the compositions herein. More preferably, the liquid diluent
will
comprise from about 50% to 70% by weight of the composition.
SOLID PHASE
is The non-aqueous detergent compositions herein may further comprise
a solid phase of particulate material which is dispersed and suspended
within the liquid phase. Generally such particulate material will range in
size
from about 0.1 to 1500 microns. More preferably such material will range in
size from about 5 to 500 microns.
The particulate material utilized herein can comprise one or more types
of detergent composition components which in particulate form are
substantially insoluble in the non-aqueous liquid phase of the composition.
The types of particulate materials which can be utilized are described in
2s detail as follows:
Hydroaen peroxide sources
Preferred particulate material which can be suspended are hydrogen
3o peroxide or a source thereof.
Preferred sources of h ~~gen peroxide include perhydrate bleaches.
The perhydrate is typically aorganic perhydrate bleach, normally it .ne
form of the sodium salt, as the source of alkaline hydrogen peroxide in the
wash liquor. This perhydrate is normally incorporated at a level of from 0.1
3s to 60%, preferably from 3% to 40% by weight, more preferably from 5% to
35% by weight and most preferably from 8% to 30% by weight of the
composition.
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The perhydrate may be any of the alkalimetal inorganic salts such as
perborate monohydrate or tetrahydrate, percarbonate, perphosphate and
persilicate salts but is conventionally an alkali metal perborate or
s percarbonate.
Sodium percarbonate is an addition compound having a formula
corresponding to 2Na2C03.3H202, and is available commercially as a
crystalline solid. Most commercially available material includes a low level
of
to a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene 1, 1-
diphosphonic acid (HEDP) or an amino-phosphonate, that is incorporated
during the manufacturing process. For the purposes of the detergent
composition aspect of the present invention, the percarbonate can be
incorporated into detergent compositions without additional protection, but
is preferred executions of such compositions utilise a coated form of the
material. A variety of coatings can be used including borate, boric acid and
citrate or sodium silicate of Si02:Na20 ratio from 1.6:1 to 3.4:1, preferably
2.8:1, applied as an aqueous solution to give a level of from 2% to 10%,
{normally from 3% to 5%} of silicate solids by weight of the percarbonate.
2o However the most preferred coating is a mixture of sodium carbonate and
sulphate or sodium chloride.
The particle size range of the crystalline percarbonate is from 350
micrometers to 1500 micrometers with a mean of approximately 500-1000
2s micrometers.
Surfactants
Another type of particulate material which can be suspended in the non-
3o aqueous liquid detergent compositions herein includes ancillary anionic
surfactants which are fully or partially insoluble in the non-aqueous liquid
phase. The most common type of anionic surfactant with such solubility
properties comprises primary or secondary alkyl sulfate anionic surfactants.
Such surfactants are those produced by the sulfation of higher Cg-C20 fatty
3s alcohols.
Conventional primary alkyl sulfate surfactants have the general formula
ROS03-M+
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wherein R is typically a linear Cg - C20 hydrocarbyl group, which may be
straight chain or branched chain, and M is a water-solubilizing cation.
Preferably R is a C10 - C14 alkyl, and M is alkali metal. Most preferably R is
s about C12 and M is sodium.
Conventional secondary alkyl sulfates may also be utilized as the
essential anionic surfactant component of the solid phase of the
compositions herein. Conventional secondary alkyl sulfate surfactants are
to those materials which have the sulfate moiety distributed randomly along
the
hydrocarbyl "backbone" of the molecule. Such materials may be depicted by
the structure
CH3(CH2)n(CHOSOg-M+) (CH2)mCH3
is
wherein m and n are integers of 2 or greater and the sum of m + n is typically
about 9 to 15, and M is a water-solubilizing cation.
If utilized as all or part of the requisite particulate material, ancillary
2o anionic surfactants such as alkyl sulfates will generally comprise from
about
1 % to 10% by weight of the composition, more preferably from about 1 % to
5% by weight of the composition. Alkyl sulfate used as all or part of the
particulate material is prepared and added to the compositions herein
separately from the unalkoxylated alkyl sulfate material which may form part
2s of the alkyl ether sulfate surfactant component essentially utilized as
part of
the liquid phase herein.
Organic Builder Material
3o Another possible type of particulate material which can be suspended in
the non-aqueous liquid detergent compositions herein comprises an organic
detergent builder material which serves to counteract the effects of calcium,
or other ion, water hardness encountered during laundering/bleaching use of
the compositions herein. Examples of such materials include the alkali
3s metal, citrates, succinates, malonates, fatty acids, carboxymethyl
succinates,
carboxylates, polycarboxylates and polyacetyl carboxylates. Specific
examples include sodium, potassium and lithium salts of oxydisuccinic acid,
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mellitic acid, benzene polycarboxylic acids and citric acid. Other examples
of organic phosphonate type sequestering agents such as those which have
been sold by Monsanto under the bequest tradename and alkanehydroxy
phosphonates. Citrate salts are highly preferred.
s
Other suitable organic builders include the higher molecular weight
polymers and copolymers known to have builder properties. For example,
such materials include appropriate polyacrylic acid, polymafeic acid, and
polyacryliclpolymaleic acid copolymers and their salts, such as those sold by
io BASF under the Sokalan trademark.
Another suitable type of organic builder comprises the water-soluble
salts of higher fatty acids, i.e., "soaps". These include alkali metal soaps
such as the sodium, potassium, ammonium, and alkyiolammonium salts of
is higher fatty acids containing from about 8 to about 24 carbon atoms, and
preferably from about 12 to about 18 carbon atoms. Soaps can be made by
direct saponification of fats and oils or by the neutralization of free fatty
acids. Particularly useful are the sodium and potassium salts of the mixtures
of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium
2o tallow and coconut soap.
If utilized as all or part of the requisite particulate material, insoluble
organic detergent builders can generally comprise from about 1 % to 20% by
weight of the compositions herein. More preferably, such builder material
2s can comprise from about 4% to 10% by weight of the composition.
Inorganic Aikalinity Sources
Another possible type of particulate material which can be suspended in
3o the non-aqueous liquid detergent compositions herein can comprise a
material which serves to render aqueous washing solutions formed from
such compositions generally alkaline in nature. Such materials may or may
not also act as detergent builders, i.e., as materials which counteract the
adverse effect of water hardness on detergency performance.
3s
Examples of suitable alkalinity sources include water-soluble alkali
metal carbonates, bicarbonates, borates, silicates and metasilicates.
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Although not preferred for ecological reasons, water-soluble phosphate salts
may also be utilized as alkalinity sources. These include alkali metal
pyrophosphates, orthophosphates, polyphosphates and phosphonates. Of
all of these alkalinity sources, alkali metal carbonates such as sodium
s carbonate are the most preferred.
The alkalinity source, if in the form of a hydratable salt, may also serve
as a desiccant in the non-aqueous liquid detergent compositions herein.
The presence of an alkalinity source which is also a desiccant may provide
io benefits in terms of chemically stabilizing those composition components
such as the peroxygen bleaching agent which may be susceptible to
deactivation by water.
If utilized as all or part of the particulate material component, the
is alkalinity source will generally comprise from about 1 % to 15% by weight
of
the compositions herein. More preferably, the alkalinity source can comprise
from about 2% to 10% by weight of the composition. Such materials, while
water-soluble, will generally be insoluble in the non-aqueous detergent
compositions herein. Thus such materials will generally be dispersed in the
2o non-aqueous liquid phase in the form of discrete particles.
OPTIONAL COMPOSITION COMPONENTS
2s In addition to the composition liquid and solid phase components as
hereinbefore described, the detergent compositions herein can, and
preferably will, contain various optional components. Such optional
components may be in either liquid or solid form. The optional components
may either dissolve in the liquid phase or may be dispersed within the liquid
3o phase in the form of fine particles or droplets. Some of the materials
which
may optionally be utilizeri in the compositions herein are described in
greater
detail as follows:
3s Optional organic additives
r
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The detergent compositions may contain an organic additiue. A
preferred organic additive is hydrogenated castor oil and its derivatives.
Hydrogenated castor oil is a commercially available commodity being
s sold, for example, in various grades under the trademark
CASTORWAX® by NL Industries, Inc., Highstown, New Jersey.Other
Suitable hydrogenated castor oil derivatives are Thixcin R, Thixcin E,
Thixatrol ST, Perchem R and Perchem ST. Especially preferred
hydrogenated castor oil is Thixatrol ST.
io
The castor oil can be added as a mixture with ,for example stereamide.
The organic additive will be partially dissolved in the non-aqueous
is liquid diluent. To form the structured liquid phase required for suitable
phase
stability and acceptable theology, the organic additive is generally present
to
the extent of from about 0.05% to 20% by weight of the liquid phase. More
preferably, the organic additive will comprise from about 0.1 % to 10% by
weight of the non-aqueous liquid phase of the compositions herein.
Optional Inorganic Detergent Builders
The detergent compositions herein may also optionally contain one or
more types of inorganic detergent builders beyond those listed hereinbefore
zs that also function as alkalinity sources. Such optional inorganic builders
can
include, for example, aluminosilicates such as zeolites. Aluminosilicate
zeolites, and their use as detergent builders are more fully discussed in
Corkill et al., U.S. Patent No. 4,605,509; Issued August 12, 1986, the
disclosure of which is incorporated herein by reference. Also crystalline
layered silicates, such as those discussed in this '509 U.S. patent, are also
suitable for use in the detergent compositions herein. If utilized, optional
inorganic detergent builders can comprise from about 2% to 15% by weight
of the compositions herein.
3s Optional Enzymes
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The detergent compositions herein may also optionally contain one -or
more types of detergent enzymes. Such enzymes can include proteases,
amylases, cellulases and lipases. Such materials are known in the art and
are commercially available. They may be incorporated into the non-aqueous
s liquid detergent compositions herein in the form of suspensions, "marumes"
or "prills". Another suitable type of enzyme comprises those in the form of
slurries of enzymes in nonionic surfactants. Enzymes in this form have been
commercially marketed, for example, by Novo Nordisk under the tradename
"LDP."
ZO
Enzymes added to the compositions herein in the form of conventional
enzyme prills are especially preferred for use herein. Such prills will
generally range in size from about 100 to 1,000 microns, more preferably
from about 200 to 800 microns and will be suspended throughout the non-
is aqueous liquid phase of the composition. Prills in the compositions of the
present invention have been found, in comparison with other enzyme forms,
to exhibit especially desirable enzyme stability in terms of retention of
enzymatic activity over time. Thus, compositions which utilize enzyme prills
need not contain conventional enzyme stabilizing such as must frequently be
2o used when enzymes are incorporated into aqueous liquid detergents.
if employed, enzymes will normally be incorporated into the non-
aqueous liquid compositions herein at levels sufficient to provide up to about
10 mg by weight, more typically from about 0.01 mg to about 5 mg, of active
2s enzyme per gram of the composition. Stated otherwise, the non-aqueous
liquid detergent compositions herein will typically comprise from about
0.001 % to 5%, preferably from about 0.01 % to 1 % by weight, of a
commercial enzyme preparation. Protease enzymes, for example, are
usually present in such commercial preparations at levels sufficient to
3o provide from 0.005 to 0.1 Anson units (AU) of activity per gram of
composition.
Optional Chelating Agents
3s The detergent compositions herein may also optionally contain a
chelating agent which serves to chelate metal ions, e.g., iron and/or
manganese, within the non-aqueous detergent compositions herein. Such
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chelating agents thus serve to form complexes with metal impurities ~n the
composition which would otherwise tend to deactivate composition
components such as the peroxygen bleaching agent. Useful chelating
agents can include amino carboxylates, phosphonates, amino
s phosphonates, polyfunctionally-substituted aromatic chelating agents and
mixtures thereof.
Amino carboxylates useful as optional chelating agents include
ethylenediaminetetraacetates, N-hydroxyethyl-ethylene-diaminetriacetates,
to nitrilotriacetates, ethylenediamine tetrapropionates, triethylenetetraamine-
hexacetates, diethylenetriaminepentaacetates, ethylenediamine-disuccinates
and ethanoldiglycines. The alkali metal salts of these materials are
preferred.
Amino phosphonates are also suitable for use as chelating agents in
is the compositions of this invention when at least low levels of total
phosphorus are permitted in detergent compositions, and include
ethylenediaminetetrakis (methylene-phosphonates) as DEQUEST.
Preferably, these amino phosphonates do not contain alkyl or alkenyl groups
with more than about 6 carbon atoms.
Preferred chelating agents include hydroxyethyl-diphosphonic acid
{HEDP), diethylene triamine penta acetic acid (DTPA), ethylenediamine
disuccinic acid (EDDS) and dipicolinic acid (DPA) and salts thereof. The
chelating agent may, of course, also act as a detergent builder during use of
2s the compositions herein for fabric laundering/ bleaching. The chelating
agent, if employed, can comprise from about 0.1 % to 4% by weight of the
compositions herein. More preferably, the chelating agent will comprise from
about 0.2% to 2% by weight of the detergent compositions herein.
3o Optional Thickening Viscosi~ Control and/or Dispersing A
The detergent compositions herein may also optionally contain a
polymeric material which serves to enhance the ability of the composition to
maintain its solid particulate components in suspension. Such materials may
3s thus act as thickeners, viscosity control agents and/or dispersing agents.
Such materials are frequently polymeric polycarboxylates but can include
other polymeric materials such as polyvinylpyrrolidone (PVP) and polymeric
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amine derivatives such as quaternized, ethoxylated hexametfaylene
diamines.
Polymeric polycarboxylate materials can be prepared by polymerizing
s or copolymerizing suitable unsaturated monomers, preferably in their acid
form. Unsaturated monomeric acids that can be polymerized to form
suitable polymeric polycarboxylates include acrylic acid, malefic acid (or
malefic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic
acid,
citraconic acid and methylenemalonic acid. The presence in the polymeric
io polycarboxylates herein of monomeric segments, containing no carboxylate
radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable
provided that such segments do not constitute more than about 40% by
weight of the polymer.
is 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 polymerized acrylic acid. The average molecular
weight of such polymers in the acid form preferably ranges from about 2,000
to 10,000, more preferably from about 4,000 to 7,000, and most preferably
2o from about 4,000 to 5,000. Water-soluble salts of such acrylic acid
polymers
can include, for example, the alkali metal, salts. Soluble polymers of this
type are known materials. Use of polyacrylates of this type in detergent
compositions has been disclosed, for example, Diehl, U.S. Patent 3,308,067,
issued March 7, 1967. Such materials may also perform a builder function.
2s
if utilized, the optional thickening, viscosity control and/or dispersing
agents should be present in the compositions herein to the extent of from
about 0.1 % to 4% by weight. More preferably, such materials can comprise
from about 0.5% to 2% by weight of the detergents compositions herein.
Optional Brighteners. Suds Suppressors andlor Perfumes
The detergent compositions herein may also optionally contain
conventional brighteners, suds suppressors, silicone oils, bleach catalysts,
3s and/or perfume materials. Such brighteners, suds suppressors, silicone
oils,
bleach catalysts, and perfumes must, of course, be compatible and non-
reactive with the other composition components in a non-aqueous
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environment. If present, brighteners, suds suppressors and/or perfumes will
typically comprise from about 0.01 % to 2% by weight of the compositions
herein.
s Suitable bleach catalysts include the manganese based complexes
disclosed in US 5,246,621, US 5,244,594, US 5,114,606 and US 5,114,611.
Especially preferred catalysts are the metallo-catalysts as described in co-
pending US Patent applications Serial No. 60/040,629, Serial No.
60/039,915, Serial No. 60/040,222, Serial No. 60/040,156, Serial No.
Io 60/040,115, Serial No. 60/038,714, Serial No. 60/039,920, filed on March 7,
1997.
The catalyst can be protected by dissolving the catalyst in a biopolymer.
Suitable biopolymers are disclosed in EP 672 104. A preferred biopolymer is
is starch.
COMPOSITION FORM
The particulate-containing liquid detergent compositions of this
Zo invention are substantially non-aqueous (or anhydrous) in character. While
very small amounts of water may be incorporated into such compositions as
an impurity in the essential or optional components, the amount of water
should in no event exceed about 5% by weight of the compositions herein.
More preferably, water content of the non-aqueous detergent compositions
2s herein will comprise less than about 1 % by weight.
The particulate-containing non-aqueous detergent compositions
herein will be in the form of a liquid.
3o COMPOSITION PREPARATION AND USE
The non-aqueous liquid detergent compositions herein can be
prepared by mixing non-aqueous liquid phase and by thereafter adding to
this phase the additional particulate components in any convenient order
3s and by mixing, e.g., agitating, the resulting component combination to form
the phase stable compositions herein. In a typical process for preparing
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such compositions, essential and certain preferred optional components will
be combined in a particular order and under certain conditions.
In a first step of a preferred preparation process, the anionic surfactant-
s containing liquid phase is prepared. This preparation step involves the
formation of an aqueous slurry containing from about 30 to 60% of one or
more alkali metal salts of linear C10-16 alkyl benzene sulfonic acid and from
about 2-15% of one or more diluent non-surfactant salts. In a subsequent
step, this slurry is dried to the extent necessary to form a solid material
to containing less than about 4% by weight of residual water.
After preparation of this solid anionic surfactant-containing material,
this material can be combined with one or more of the non-aqueous organic
diluents to form the surfactant-containing liquid phase of the detergent
is compositions herein. This is done by reducing the anionic surfactant-
containing material formed in the previously described pre-preparation step
to powdered form and by combining such powdered material with an
agitated liquid medium comprising one or more of the non-aqueous organic
diluents, either surfactant or non-surfactant or both as herein before
zo described. This combination is carried out under agitation conditions which
are sufficient to form a thoroughly mixed dispersion of particles of the
insoluble fraction of the co-dried LAS/salt material throughout a non-
aqueous organic liquid diluent.
2s Subsequently, particulate material to be used in the detergent
compositions herein can be added. Such components which can be added
under high shear agitation include any optional surfactant particles,
particles
of substantially all of an organic builder, e.g. citrate and/or fatty acid
and/or
alkalinity source, e.g. sodium carbonate, can be added while continuing to
3o maintain this admixture of composition components under shear agitation.
Ac: ::ion of the mixture is contir ~d, and if necessary, can be increased at
this point to form a uniform disf ~sion of insoluble solid phase particulates
within the liquid phase.
3s The non-aqueous liquid dispersion so prepared can be subjected to
milling or high shear agitation. Milling conditions will generally include
maintenance of a temperature between about 10 and 90°C, preferably
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between 20°C and 60°C. Suitable equipment for this purpose
includes:
stirred ball mills, co-ball mills (Fryma), colloid mills, high pressure
homogenizers, high shear mixers, and the like. The colloid mill and high
shear mixers are preferred for their high throughput and low capital and
s maintenance costs. The small particles produced in such equipment will
generally range in size from 0.4- 150 microns.
Agitation is then continued, and if necessary, can be increased at this
point to form a uniform dispersion of insoluble solid phase particles within
io the liquid phase.
In a second process step, the bleach precursor particles are mixed with
the ground suspension from the first mixing step in a second mixing step.
This mixture is then subjected to wet grinding so that the average particle
is size of the bleach precursor is less than 600 microns, preferably between
50
and 500 microns, most preferred between 100 and 400 microns.
After some or all of the foregoing solid materials have been added to
this agitated mixture, the particles of the highly preferred peroxygen
2o bleaching agent can be added to the composition, again while the mixture is
maintained under shear agitation.
In a third processing step, the activation of the organic additive is
obtained. The organic additives are subjected to wetting and dispersion
2s forces to reach a dispersed state. It is well within the ability of a
skilled
person to activate the organic additive. The activation can be done
according to that described by Rheox, in Rheology Handbook, A practical
guide to rheological additives. There are basically three distinct stages.
The first stage consists in adding the agglomerated powder in the solvent.
3o This combination is carried out under agitation conditions (shear, heat,
Stage 2) which are sufficient to lead to complete deagglomeration. With
continued shear and heat development over a period of time, the solvent-
swollen particles of the organic additive are reduced to their active state in
Stage 3.
In adding solid components to non-aqueous liquids in accordance with
the foregoing procedure, it is advantageous to maintain the free, unbound
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36
moisture content of these solid materials below certain limits. Free moisture
in such solid materials is frequently present at levels of 0.8% or greater
(see
method described below). By reducing free moisture content, e.g. by fluid
bed drying, of solid particulate materials to a free moisture level of 0.5% or
s lower prior to their incorporation into the detergent composition matrix,
significantly stability advantages for the resulting composition can be
realized.
Free and Total Water Determinations:
io
For the purpose of this patent application, and without wanting to be bound
by theory, we refer to "free water" as the amount of water that can be
detected after removal of the solid, undissolved components of the product,
whereas "total water" is referred to as the amount of water that is present in
Is the product as a whole, be it bound to solids (e.g. water of hydration),
dissolved in the liquid phase, or in any other form. A preferred method of
water determinations is the so-called "Karl Fischer titration". Other methods
than Karl Fischer titration, e. g. NMR, microwave, or IR spectroscopy, may
also be suited for the determination of water in the liquid part of the
product
2o and in the full product as described below.
The "free water" of a formulation is determined in the following way. At
least one day after preparation of the formula (to allow for equilibration), a
sample is centrifuged until a visually clear layer, free of solid components,
is
2s obtained. This clear layer is separated from the solids, and a weighed
sample is directly introduced into a coulometric Karl Fischer titration
vessel.
The water level determined in this way (mg water / kg clear layer) is referred
to as "free water" (in ppm).
3o The "total water" is determined by first extracting a weighed amount of
- finished product with an anhydrous, polar extra 'eon liquid. The
extra;:cf;~n
liquid is selected in such a way that interference Irom dissc: . ed solids are
minimized. In most cases, dry methanol is a preferred extraction liquid.
Usually, the extraction process reaches an equilibrium within a few hours -
3s this needs to be validated for different formulations - and can be
accelerated
by sonification (ultrasonic bath). After that time, a sample of the extract is
centrifuged or filtered to remove the solids, and a known aliqot then
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introduced into the (coulometric or volumetric) Karl Fischer titration cell.
The
value found in this way (mg water / kg product) is referred to as "total
water"
of the formulation.
s Preferably, the non-aqueous liquid detergent compositions of the
present invention comprise less than 5%, preferably less than 3%, most
preferred less than 1 % of free water.
Viscosity and yield measurements:
io
The particulate-containing non-aqueous liquid detergent compositions
herein will be relatively viscous and phase stable under conditions of
commercial marketing and use of such compositions. Frequently, the
viscosity of the compositions herein will range from about 300 to 10,000 cps,
is more preferably from about 500 to 3000 cps. The physical stability of such
formulations can also be determined by yield measurements. Frequently,
the yield of the compositions herein will range from about 1 to 20 Pa, more
preferably from about 1.5 to 10 Pa. For the purpose of this invention,
viscosity and yield are measured with a Carri-Med CSL2100 rheometer
2o according to the method described herein below.
Rheological properties were determined by means of a constant stress
rheometer (Carri-Med CSL2100) at 25°C. A parallel-plate configuration
with
a disk radius of 40 mm and a layer thickness of 2 mm was used. The shear
2s stress was varied between 0.1 Pa and 125 Pa. The reported viscosity was
the value measured at a shear rate of about 20 s 1. Yield stress was defined
as the stress above which motion of the disk was detected. This implies that
the shear rate was below 3 x 10'4 s-1.
3o The compositions of this invention, prepared as herein before
described, can be used to form aqueous washing solutions for use in the
laundering and bleaching of fabrics. Generally, an effective amount of such
compositions is added to water, preferably in a conventional fabric
laundering automatic washing machine, to form such aqueous
3s laundering/bleaching solutions. The aqueous washing/bleaching solution so
formed is then contacted, preferably under agitation, with the fabrics to be
laundered and bleached therewith.
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An effective amount of the liquid detergent compositions herein added
to water to form aqueous laundering/bleaching solutions can comprise
amounts sufficient to form from about 500 to 8,000 ppm of composition in
s aqueous solution. More preferably, from about 800 to 5,000 ppm of the
detergent compositions herein will be provided in aqueous
washing/bleaching solution.
The following examples illustrate the preparation and performance
Io advantages of non-aqueous liquid detergent compositions of the instant
invention. Such examples, however, are not necessarily meant to limit or
otherwise define the scope of the invention herein.
EXAMPLE I
is
Preparation of the bleach precursor composition
The following bleach precursor particles were made:
Example Example Example C
A B
NACA-OBS 65 65 65
TAED - - -
LAS 9.8 - 9.8
C12/14 AE3S - 9.8 -
AE3 0.3 0.3 0.3
Na citrate 11.3 11.3 11.3
AAM 6.2 6.2 -
Water to balance
to100%
NACA-OBS : (6-nonanamidocaproyl)oxy benzene sulfonate
TAED . Tetraacetyl ethylene diamine
LAS . Sodium linear C12 alkyl benzene sulphonate
2s AE3 . A C12-15 Predominantly linear primary
alcohol condensed with an average of 3
motes of ethylene oxide
C'2-C'4 AE3S: C12-C14 sodium alkyl sulphate condensed with
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an average of 3 moles of ethylene oxide
per mole
AAM . Acrylic acid/Maleic acid copolymers
s In each of examples A to D the bleach activator (i.e. NACA-OBS or
TAED) was premixed with sodium citrate (where present), LAS or AS and
an aqueous solution (40% active) of the AAM polymer in a Loedige~ FM
mixer. The premix was then fed into a dome extruder (Fuji Paudal Model
DGL-1 ) having a die with 0.7 mm orifices and extruded at a pressure of
io about 20 bar. The resulting extrudate was then fed into a rotating disc
spheroniser (Fuji Paudal QJ-400) where they were broken down into short
lengths and formed into substantially spherical particles. The particles were
then dried in a Niro vibrating fluid-bed dryer resulting in crisp, free-
flowing
dust free particles with a particle size range of from 0.25 mm to 2.00 mm.
is
EXAMPLE II
Preparation of Non-Aqueous L9uid Detergent Composition
1 ) Part of the Butoxy-propoxy-propanol (BPP) and a C» EO(5) ethoxylated
alcohol nonionic surfactant (Genapol 24/50) are mixed for a short time
(1-5 minutes) using a blade impeller in a mix tank into a single phase.
2s 2) LAS is added to the BPP/NI mixture after heating the BPP/NI mixture
up to 45°C.
3) If needed, liquid base (LAS/BPP/NI) is pumped out into drums.
Molecular sieves (type 3A, 4-8 mesh) are added to each drum at 10%
of the net weight of the liquid base. The molecular sieves are mixed
into the liquid base using both single blade turbine mixers and drum
rolling techniques. The mixing is done under nitrogen blanket to
prevent moisture pickup from the air. Total mix time is 2 hours, after
which 0.1-0.4% of the moisture in the liquid base is removed. Molecular
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sieves are removed by passing the liquid base through a 20-30-mesh
screen. Liquid base is returned to the mix tank.
4) Additional solid ingredients are prepared for addition to the
s composition. Such solid ingredients include the following:
Sodium carbonate (particle size 100 microns)
Sodium citrate dehydrate
Malefic-acrylic copolymer (BASF Sokolan)
Brightener (Tinopal PLC)
io Tetra sodium salt of hydroxyethylidene diphosphonic
acid (HEDP)
Sodium diethylene triamine penta methylene phosphonate
Ethylenediamine disuccinic acid (EDDS)
These solid materials, which are all millable, are added to the mix
is tank and mixed with the liquid base until smooth. This takes
approximately 1 hour after addition of the last powder. The tank is
blanketed with nitrogen after addition of the powders. No particular
order of addition for these powders is critical.
20 5) The batch is pumped once through a Fryma colloid mill, which is a
simple rotor-stator configuration in which a high-speed rotor spins
inside a stator which creates a zone of high shear. This reduces
particle size of all of the solids. This leads to an increase in yield value
(i.e. structure). The batch is then recharged to the mix tank after
Zs cooling.
6) The bleach precursor particles are mixed with the ground suspension
from the first mixing step in a second mixing step. This mixture is then
subjected to wet grinding so that the average particle size of the bleach
precursor is less than 600 microns, preferably between 50 and 500
3o microns, most preferred between 100 and 400 microns.
7) Other solid materials could be added after the first processing step.
These include the following
Sodium percarbonate (400-600 microns)
3s Protease, cellulase and amylase enzyme prills (400-800 microns,
specific density below 1.7 g/mL)
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Titanium dioxide particles (5 microns) _
Catalyst
These non-millable solid materials are then added to the mix tank
followed by liquid ingredients (perfume and silicone-based suds
s suppressor fatty acid/silicone). The batch is then mixed for one hour
(under nitrogen blanket).
The resulting composition has the formula set forth in Table I.
to The catalyst is prepared by adding an octenylsuccinate modified starch, to
water in the approximate ratio of 1:2. Then, the catalyst is added to the
solution and mixed to dissolve. The composition of the solution is
catalyst 5%
is starch 32% (the starch includes 4-6% bound water)
water 63%
The solution is then spray dried using a lab scale Niro Atomizer spray drier.
The inlet of the spray drier is set at 200°C, and the atomizing
air is
2o approximately 4 bar. The process air pressure drop is roughly 30-35 mm
water. The solution feed rate is set to get an outlet temperature of
100°C.
The powdered material is collected at the base of the spray drier.
The composition is
2s
catalyst 15%
starch (and bound water) 85%
The particle size is 15 to 100 um exiting the dryer.
TABLE I
Non-Aqueous Liquid Detergent Composition with Bleach
Component Wt % Active Wt % Active
LAS Na Salt 16 15
C11 EO=5 alcohol ethoxylate 21 20
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BPP 19 19 -
Sodium citrate 4 5
[4-[N-nonanoyl-6-aminohexanoyloxy]6 7
benzene sulfonate] Na salt
Chloride salt of methyl quarternized1.2 1
polyethoxylated hexamethylene
diamine
Ethyienediamine disuccinic acid 1 1
Sodium Carbonate 7 7
Malefic-acrylic copolymer 3 3
Protease Prills 0.40 0.4
Amylase Prills 0.8 0.8
Cellulase Prills 0.50 0.5
Sodium Percarbonate 16 -
Sodium Perborate - 15
Suds Suppressor 1.5 1.5
Perfume 0.5 0.5
Titanium Dioxide 0.5 0.5
Brightener 0.14 0.2
Thixatrol ST 0.1 0.1
Catalyst 0.03 0.03
Speckles 0.4 0.4
Miscellaneous up to 100%
The resulting Table I composition is a structured, stable, pourable
anhydrous heavy-duty liquid laundry detergent which provides excelient
stain and soil removal performance when used in normal fabric laundering
s operations. The chemical decomposition of the bleach precursor was
insignificant even after 6 weeks of storage at room temperature.
