Note: Descriptions are shown in the official language in which they were submitted.
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NON-AQUEOUS LIQUID DETERGENT COMPOSITIONS
CONTAINING ENZYME PARTICLES
~ FIELD OF THE INVENTION
This invention relates to liquid laundry detergent products which are
non-aqueous in nature and which contain stabilized enzyme particles.
BACKGROUND OF THE INVENTION
Detergent products in the form of liquid are often considered to be
more convenient to use than are dry powdered or particulate ~ detergent
products. Said detergents have therefore found substantial favour with
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
2o products. Additionally, such detergents may have incorporated in their
formulations materials which could not withstand drying operations without
deterioration, which operations are often employed in the manufacture of
particulate or granular detergent products.
2s Although said detergents have a number of advantages over granular
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,
so brighteners, solvents and especially bleaches and bleach activators can be
especially difficult to incorporate into liquid detergent products which have
an acceptable degree of chemical stability.
35 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
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2
products, at least some of the normally solid detergent composition
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, 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,
o Published June 11, 1992 and Sanderson et al., EP-A-565,017, Published
October 13, 1993.
A particular problem that has been observed with the incorporation of
enzymes in non-aqueous detergents, containing bleaching agent and/or
bleach precursors includes the chemical stability of the enzymes upon
dilution in the wash liquor.
Given the foregoing, there is clearly a continuing need to identify and
provide said detergent compositions in the form of liquid products that have
2o an efficient enzymatic detergency performance in the wash liquor.
Accordingly, it is an object of the present invention to provide said
detergent composition wherein the enzymes are still effective in the wash
liquor.
SUMMARY OF THE INVENTION
3o According to the present invention, there is provided a liquid non-
aqueous detergent composition containing bleaching agent and/or bleach
precursor which is in the form of a liquid, containing an enzyme
characterized in that said compositions further comprise ethylenediamine-N-
N'disuccinic acid.
DETAILED DESCRIPTION OF THE INVENTION
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Enzyme particles - -
The enzyme particles suitable for the present invention comprise one or
- more enzymes which provide cleaning performance and/or fabric care
benefits.
Said enzymes include enzymes selected from cellulases,
hemicellulases, peroxidases, proteases, gluco-amylases, amylases,
xylanases, lipases, esterases, cutinases, pectinases, keratanases,
reductases, oxidases, phenoloxidases, lipoxygenases, ligninases,
pullulanases, tannases, pentosanases, rnalanases, f3-glucanases,
arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof.
A preferred combination is a cleaning composition having cocktail of
~ 5 conventional applicable enzymes like protease, amylase, lipase, cutinase
and/or cellulase in conjunction with one or more plant cell wall degrading
enzymes.
The cellulases usable in the present invention include both bacterial
20 or fungal cellulase. Preferably, they will have a pH optimum of between 5
and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307,
Barbesgoard et al, which discloses fungal cellulase produced from Humicola
insolens. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-
2.095.275 and DE-OS-2.247.832.
Examples of such cellulases are cellulases produced by a strain of
Humicola insolens (Humicola grisea var. thermoidea), particularly the
Humicola strain DSM 1800.
Other suitable cellulases are cellulases originated from Humicola
3o insolens having a molecular weight of about 50KDa, an isoelectric point of
5.5 and containing 415 amino acids. Especially suitable cellulases are the
cellulases having color care benefits. Examples of such cellulases are
cellulases described in European patent application No. 91202879.2, filed
November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A/S)
are especially useful. See also W091/17243.
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Peroxidase enzymes are used in combination with oxygen sources,
e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are
used for "solution bleaching", i.e. to prevent transfer of dyes or pigments
removed from substrates during wash operations to other substrates in the
s wash solution. Peroxidase enzymes are known in the art, and include, for
example, horseradish peroxidase, ligninase, laccase and haloperoxidase
such as chloro- and bromo-peroxidase. Peroxidase-containing detergent
compositions are disclosed, for example, in PCT International Application
WO 89/099813, W089/09813 and in European Patent application EP No.
91202882.6, fled on November 6, 1991 and EP No. 96870013.8, filed
February 20, 1996.
Preferred enhancers are substitued phenthiazine and phenoxasine
10-Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4-carboxylic
~ s acid {EPC), 10-phenoxazinepropionic acid {POP) and 10-
methylphenoxazine (described in WO 94/12621 ) and substitued syringates
(C3-C5 substitued alkyl syringates) and phenols. Sodium percarbonate or
perborate are preferred sources of hydrogen peroxide.
2o Said cellulases and/or peroxidases are normally incorporated in the
detergent composition at levels from 0.0001 % to 2% of active enzyme by
weight of the detergent composition.
Other preferred enzymes that can be included in the detergent
2s compositions of the present invention include lipases. Suitable lipase
enzymes for detergent usage include those produced by micro-organisms of
the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as
disclosed in British Patent 1,372,034. Suitable lipases include those which
show a positive immunological cross-reaction with the antibody of the lipase,
3o produced by the microorganism Pseudomonas fluorescent IAM 1057. This
lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan,
under the trade name Lipase P "Amano," hereinafter referred to as "Amano-
P". Other suitable commercial lipases include Amano-CES, lipases ex
Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum
ss NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum
lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The
Netherlands, and lipases ex Pseudomonas gladioli. Especially suitable
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lipases are lipases such as M1 LipaseR and LipomaxR (Gist-Brocades)~and
LipolaseR and Lipolase UItraR{Novo) which have found to be very effective
when used in combination with the compositions of the present invention.
5 Also suitable are cutinases [EC 3.1.1.50] which can be considered as
. a special kind of lipase, namely fipases which do not require interfacial
activation. Addition of cutinases to detergent compositions have been
described in e.g. WO-A-88/09367 (Genencor).
The lipases and/or cutinases are normally incorporated in the detergent
~o composition at levels from 0.0001% to 2% of active enzyme by weight of the
detergent composition.
Suitable proteases are the subtilisins which are obtained from
particular strains of B. subfilis and B. licheniformis (subtilisin BPN and
BPN').
One suitable protease is obtained from a strain of Bacillus, having maximum
activity throughout the pH range of 8-12, developed and sold as
ESPERASE~ by Novo Industries A/S of Denmark, hereinafter "Novo". The
preparation of this enzyme and analogous enzymes is described in GB
1,243,784 to Novo. Other suitable proteases include ALCALASE~,
2o DURAZYM~ and SAVINASE~ from Novo and MAXATASE~~ MAXACAL~,
PROPERASE~ and MAXAPEM~ (protein engineered Maxacal) from
International Bio-Synthetics, Inc., The Netherlands; as well as Protease A as
disclosed in EP 130,756 A, January 9, 1985 and Protease B as disclosed in
EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. See also
a high pH protease from Bacillus sp. NCIMB 40338 described in WO
93/18140 A to Novo. Enzymatic detergents comprising protease, one or
more other enzymes, and a reversible protease inhibitor are described in
WO 92/03529 A to Novo. Other prefen-ed proteases include those of WO
95/10591 A to Procter & Gamble. When desired, a protease having
3o decreased adsorption and increased hydrolysis is available as described in
WO 95/07791 to Procter & Gamble. A recombinant trypsin-like protease for
detergents suitable herein is described in WO 94/25583 to Novo.
In more detail, protease referred to as "Protease D" is a carbonyl
hydrolase variant having an amino acid sequence not found in nature, which
is derived from a precursor carbonyl hydrolase by substituting a different
amino acid for a plurality of amino acid residues at a position in said
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carbonyl hydrolase equivalent to position +76, preferably also in combination
with one or more amino acid residue positions equivalent to those selected
from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105,
+109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216,
+217, +218, +222, +260, +265, and/or +274 according to the numbering of
Bacillus amyloliquefaciens subtilisin, as described in W095/10591 and in
the patent application of C. Ghosh, et al, "Bleaching Compositions
Comprising Protease Enzymes" having US Serial No. 08/322,677, filed
October 13, 1994. Also suitable for the present invention are proteases
~o described in patent applications EP 251 446 and W091/06637.
Preferred protease for use in the present invention are SAVINASE~
and the proteases described in EP 215 446 and W095/10591 at a level of
from 0.001 % to 0.5%, preferably from 0.003% to 0.2%, more preferably from
0.01 % to 0.1 % pure enzyme by weight of total composition for liquid
detergent compositions and; SAVINASE~, ALCALASE~ and the proteases
described in W091 /06637 and W095110591 at a level of from 0.0001 % to
0.2%, preferably from 0.001 % to 0.1 %, more preferably 0.005% to 0.05%
pure enzyme by weight of total composition in granular detergent
2o compositions.
Highly preferred enzymes to be included are amylases. Amylases (a
andlor f3) can be included for removal of carbohydrate-based stains.
WOI94/02597, Novo Nordisk A/S published February 03, 1994, describes
cleaning compositions which incorporate mutant amylases. See also
W0/94/18314, Genencor, published August 18, 1994 and WOI95I10603,
Novo Nordisk A/S, published April 20,1995. Other amylases known for use
in cleaning compositions include both a- and ~i-amylases. a-Amylases are
known in the art and include those disclosed in US Pat. no. 5,003,257; EP
252,666; W0/91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP
368,341; and British Patent specification no. 1,296,839 (Novo). Other
suitable amylase are stability-enhanced amylases including Purafact Ox
AmR described in WO 94/18314, published August 18, 1994 and amylase
variants having additional modification in the immediate parent available
from Novo Nordisk A/S, disclosed in WO 95110603, published Apri! 95.
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Examples of commercial a-amylases products are Termamyl~, Ban~
Fungamyl~ and Duramyl~, all available from Novo Nordisk A/S Denmark.
W095/26397 describes other suitable amylases : a-amylases characterised
by having a specific activity at least 25% higher than the specific activity
of
s Termamyl0 at a temperature range of 25°C to 55°C and at a pH
value in the
range of 8 to 10, measured by the Phadebas~ a-amylase activity assay.
Other arnylolytic enzymes with improved properties with respect to the
activity level and the combination of thermostability and a higher activity
level are described in W095I35382.
The above-mentioned enzymes may be of any suitable origin, such
as vegetable, animal, bacterial, fungal and yeast origin. Said enzymes are
normally incorporated in the detergent composition at levels from 0.0001
to 2% of active enzyme by weight of the detergent composition. The
1s enzymes can be added as separate single ingredients (prills,
granulatescontaining one enzyme) or as mixtures of two or more enzymes
{e.g. cogranulates).
Other suitable detergent ingredients that can be added are enzyme
oxidation scavengers which are described in co-pending European Patent
application 92870018.6 filed on January 31, 1992. Examples of such
enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
A range of enzyme materials and means for their incorporation into
2s synthetic detergent compositions is also disclosed in WO 9307263 A and
WO 9307260 A to Genencor International, WO 8908694 A to Novo, and
U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further
disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and in U.S.
4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid
so detergent formulations, and their incorporation into such formulations, are
disclosed in U.S. 4,261,868, Hora et al, April 14, 1981. Enzymes for use in
detergents can be stabilised by various techniques. Enzyme stabilisation
techniques are disclosed and exemplified in U.S. 3,600,319, August 17,
1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986,
3s Venegas. Enzyme stabilisation systems are also described, for example, in
U.S. 3,519,570. A useful Bacillus, sp. AC13 giving proteases, xylanases
and cellulases, is described in WO 9401532 A to Novo.
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Preferred enzyme particles according to the present invention are
characterized by having a reduced average particle size less than 600
microns, preferably between 50 and 500 microns, most preferred between
s 100 and 400 microns. Stated particle sizes are the diameters of particles of
equal volume. Desirably, the particle size distribution is relatively narrow
so
that average particle sizes expressed as number average or weight average
sizes are similar. Particle sizes can be measured, for example, using
Coulter counters or laser particle size measuring equipment such as that
sold under the Malvern name.
The enzyme particles are prepared by grinding in a mill which will break
down the particles to diameters below 600 microns. The enzyme particles
will generally be supplied as much larger particles of above about 600
~ 5 microns diameter. If desired, the enzyme particle may be premixed with
other solids (e.g. builders, enzymes). Preferred mills are colloid mills.
Preferred enzyme particles have reduced particle size, since said
2o particles are physically and chemically stable in the concentrate, while at
the
same time being more effective in the wash liquor.
The compositions of the invention contain, as an essential component,
from about 0.01 % to about 10%, preferably from about 0.05% to about 2%,
2s of ethylenediamine-N, N'-disuccinic acid (EDDS) or the alkali metal,
alkaline
earth metal, ammonium, or substituted ammonium salts thereof, or mixtures
thereof. Preferred EDDS compounds for liquid detergent compositions are
the free acid form and sodium or potassium salts thereof. EDDS are
described in US patent 4,704,233.
According to the present invention, it has been found that EDDS
effectively improves the efficiency of enzymes, especially amylases, in liquid
non-aqueous detergent compositions upon dilution in the wash liquor.
Without being bound by theory, it is believed that ethylenediamine-N,
N'-disuccinic acid or its salts act to bind heavy metal ions thereby
preventing
that heavy metal ions bind at the active site of the enzyme. The binding of
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heavy metal ions at the active site of the enzyme results in generation of~OH
free radicals within the enzyme, resulting in destruction of the enzyme.
Chelatina Aqents - The liquid non-aqueous detergent compositions
s according to the present invention may also contain other chelating agents.
Such chelating agents can be selected from the group consisting of amino
carboxylates, amino phosphonates, polyfunctionally-substituted aromatic
chelating agents and mixtures therein, all as hereinafter defined. Without
intending to be bound by theory, it is believed that the benefit of these
~o materials is due in part to their exceptional ability to remove iron and
manganese ions from washing solutions by formation of soluble chelates.
Amino carboxylates useful as optional chelating agents include
ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,
nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetra-
aminehexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines,
alkali metal, ammonium, and substituted ammonium salts therein and
mixtures therein.
2o Amino phosphonates are also suitable for use as chelating agents in
the compositions of the invention when at lease low levels of total
phosphorus are permitted in detergent compositions, and include
ethylenediaminetetrakis (methylenephosphonates) as DEQUEST.
Preferred, these amino phosphonates to not contain alkyl or alkenyl groups
25 with more than about 6 carbon atoms.
Polyfunctionally-substituted aromatic chelating agents are also useful
in the compositions herein. See U.S. Patent 3,812,044, issued May 21,
1974, to Connor et al. Preferred compounds of this type in acid form are
3o dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
. The compositions herein may also contain water soluble methyl
glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder
useful with, for example, insoluble builders such as zeolites, layered
silicates
35 and the like.
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These chelating agents will generally comprise from about 0.1 % to
about 15% by weight of the detergent compositions herein. More preferably,
the chelating agents will comprise from about 0.1 % to about 3.0% by weight
of the non-aqueous liquid detergent composition.
5
The non-aqueous detergent compositions of this invention may further
comprise a surfactant- and low-polarity solvent-containing liquid gel phase
having dispersed therein the enzyme particles. The components of the liquid
and solid phases of the detergent compositions herein, as well as
1o composition form, preparation and use, are described in greater detail as
follows:
All concentrations and ratios are on a weight basis unless otherwise
specified.
Surfactant
The amount of the surfactant mixture component of the detergent
compositions herein can vary depending upon the nature and amount of
other composition components and depending upon the desired rheological
2o properties of the ultimately formed composition. Generally, this surfactant
mixture will be used in an amount comprising from 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 classes,
and species of these surfactants, is given in US Patent 3,664,961 issued to
Norris on May 23, 1972.
Highly anionic preferred surfactants are the linear alkyl benzene sulfonate
so (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 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.
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Other suitable surfactants include the alkyl sulfate surfactants hereofi~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-
. C1g 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 ammonium
cations such as tetramethyl-ammonium and dimethyl piperdinium cations).
Highly preferred anionic surfactants include alkyl alkoxylated sulfate
1o surfactants hereof are water soluble salts or acids of the formula
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
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
2o include quaternary ammonium cations such as tetramethyl-ammonium and
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
potassium.
Other suitable anionic surfactants to be used are alkyl ester sulfonate
surfactants including linear esters of Cg-C20 carboxylic acids (i.e., fatty
3o acids) which are sulfonated with gaseous S03 according to "The Journal of
the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable
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
formula:
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O
R3 - CH - C - OR4
S03M
wherein R3 is a Cg-C2p hydrocarbyl, preferably an alkyl, or combination
1o thereof, R4 is a C1-Cg hydrocarbyl, preferably an alkyl, or combination
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 C10-C1g alkyl, and R4 is methyl, ethyl or isopropyl.
Especially preferred are the methyl ester sulfonates wherein R3 is C10-C16
alkyl.
Other anionic surfactants useful for detersive purposes can also be
included in the laundry detergent compositions of the present invention.
2o These can include salts (including, for example, sodium, potassium,
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
specification No. 1,082,179, Cg-C24 alkylpolyglycolethersulfates (containing
up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl
glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene
oxide
ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as
the
3o 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
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
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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
s 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 (herein incorporated by reference).
When included therein, the detergent compositions of the present
invention typically comprise from about 1 % to about 40%, preferably from
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
~ s surfactant having an average hydrophilic-lipophilic balance (HLB) in the
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
2o compound having the desired degree of balance between hydrophilic and
hydrophobic elements.
Especially preferred nonionic surfactants of this type are the Cg-C15
primary alcohol ethoxylates containing 3-12 moles of ethylene oxide per
2s mole of alcohol, particularly the C12-C15 primary alcohols containing 5-8
moles of ethylene oxide per mole of alcohol.
Another class of nonionic surfactants comprises alkyl polyglucoside
compounds of general formula
30 RO (CnH2n0)tZx
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 O to 10 and n
is 2 or 3; x is from 1.3 to 4, the compounds including less than 10%
3s unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
Compounds of this type and their use in detergent are disclosed in EP-B 0
070 077, 0 075 996 and
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14
0 094 118. - -
Also suitable as nonionic surfactants are poly hydroxy fatty acid amide
surfactants of the formula
R2-C-N-Z,
() I
O R1
wherein R1 is H, or R1 is C1~ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy
1o propyl or a mixture thereof, R2 is C5-31 hydrocarbyl, and Z is a
polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3
hydroxyls directly connected to the chain, or an alkoxylated derivative
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
1 s reducing sugar such as glucose, fructose, maltose, lactose, in a reductive
amination reaction.
Non-aqueous Liquid Diluent
2o To form the liquid phase of the detergent compositions, the
hereinbefore described surfactant (mixture) may be combined with a non-
aqueous liquid diluent such as a liquid alcohol alkoxylate material or a non-
aqueous, low-polarity organic solvent.
2s Alcohol Alkoxylates
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
so general formula:
R1 (CmH2m0)nOH
wherein R1 is a Cg - C1 g 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
3s 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
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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
1o 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
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
ethoxylated Cg - C11 primary alcohol having about 10 moles of ethylene
oxide. Alcohol ethoxylates of this type have also been marketed by Shell
2o 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
of 7 moles of ethylene oxide per mole of fatty alcohol.
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
alkanol with 7 moles of ethylene oxide and the latter is a similar product but
3o 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
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.
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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
component will comprise from about 10% to 25% by weight of the detergent
compositions herein.
1o Non-aqueous Low-Polarity Organic Solvent
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
1s 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
may actually dissolve in the "solvent"-containing phase, other components
will be present as particulate material dispersed within the "solvent"-
containing phase. Thus the term "solvent" is not meant to require that the
2o solvent material be capable of actually dissolving all of the detergent
composition components added thereto.
The non-aqueous organic materials which are employed as solvents
herein are those which are liquids of low polarity. For purposes of this
25 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
should not be utilized. Suitable types of low-polarity solvents useful in the
3o 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.
A preferred type of non-aqueous, low=polarity solvent for use herein
3s comprises the mono-, di-, tri-, or tetra- C2-Cg alkylene glycol mono C2-Cg
alkyl ethers. The specific examples of such compounds include diethylene
glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropolyene
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glycol monoethyl ether, and dipropylene glycol monobutyi ether. Diethylene
glycol monobutyi ether and dipropylene glycol monobutyl ether are
especially preferred. Compounds of the type have been commercially
marketed under the tradenarnes Dowanol, Carbitol, and Cellosolve.
s
Another preferred type of non-aqueous, low-polarity organic solvent
useful herein comprises the lower molecular weight polyethylene glycols
(PEGs). Such materials are those having molecular weights of at least
about 150. PEGs of molecular weight ranging from about 200 to 600 are
1o most preferred.
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)-OCHg wherein R1 ranges from 1 to about
15 18. Examples of suitable lower molecular weight methyl esters include
methyl acetate, methyl propionate, methyl octanoate, and methyl
dodecanoate.
The non-aqueous, low-polarity organic solvents) employed should, of
2o course, be compatible and non-reactive with other composition components,
e.g., bleach and/or activators, used in the liquid detergent compositions
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
2s 40% by weight of the composition, most preferably from about 10% to 25%
by weight of the composition.
Licluid Diluent Concentration
3o 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%
by weight of the compositions herein. More preferably, the liquid diluent will
ss comprise from about 50% to 70% by weight of the composition.
SOLID PHASE
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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
1o substantially insoluble in the non-aqueous liquid phase of the composition.
The types of particulate materials which can be utilized are described in
detail as follows:
Peroxyaen Bleaching Agent With Optional Bleach Activators
The most preferred type of particulate material useful for forming the
solid phase of the detergent compositions herein comprises particles of a
peroxygen bleaching agent. Such peroxygen bleaching agents may be
organic or inorganic in nature. Inorganic peroxygen bleaching agents are
2o frequently utilized in combination with a bleach activator.
Useful organic peroxygen bleaching agents include percarboxylic acid
bleaching agents and salts thereof. Suitable examples of this class of
agents include magnesium monoperoxyphthalate hexahydrate, the
magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-
oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching
agents are disclosed in U.S. Patent 4,483,781, Hartman, Issued November
20, 1984; European Patent Application EP-A-133,354, Banks et al.,
Published February 20, 1985; and U.S. Patent 4,412,934, Chung et al.,
3o Issued November 1, 1983. Highly preferred bleaching agents also include
6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as described in U.S. Patent
4,634,551, Issued January 6, 1987 to Burns et al.
Inorganic peroxygen bleaching agents may also be used in particulate
form in the detergent compositions herein. Inorganic bleaching agents are
in fact preferred. Such inorganic peroxygen compounds include alkali metal
perborate and percarbonate materials, most preferably the percarbonates.
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For example, sodium perborate (e.g. mono- or tetra-hydrate) can be used.
Suitable inorganic bleaching agents can also include sodium or potassium
carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium
- pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
s Persulfate bleach {e.g., OXONE, manufactured commercially by DuPont)
can also be used. Frequently inorganic peroxygen bleaches will be coated
with silicate, borate, sulfate or water-soluble surfactants. For example,
coated percarbonate particles are available from various commercial
sources such as FMC, Solvay Interox, Tokai Denka and Degussa.
Inorganic peroxygen bleaching agents, e.g., the perborates, the
percarbonates, etc., are preferably combined with bleach activators, which
lead to the in situ production in aqueous solution (i.e., during use of the
compositions herein for fabric laundering/bfeaching) of the peroxy acid
1s corresponding to the bleach activator. Various non-limiting examples of
activators are disclosed in U.S. Patent 4,915,854, Issued April 10, 1990 to
Mao et al.; and U.S. Patent 4,412,934 Issued November 1, 1983 to Chung
et al. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene
diamine (TAED) activators are typical. Mixtures thereof can also be used.
2o See also the hereinbefore referenced U.S. 4,634,551 for other typical
bleaches and activators useful herein.
Other useful amido-derived bleach activators are those of the formulae:
25 R1 N(R5)C(O)R2C(O)L or R1 C(O)N{R5)R2C(O)L
wherein R1 is an alkyl group containing from about 6 to about 12 carbon
atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms, R5 is H
or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms,
3o and L is any suitable leaving group. A leaving group is any group that is
displaced from the bleach activator as a consequence of the nucleophilic
attack on the bleach activator by the perhydrolysis anion. A preferred
leaving group is phenol sulfonate.
35 Preferred examples of bleach activators of the above formulae include
{6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)
oxyben-zenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate and
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mixtures thereof as described in the hereinbefore referenced U.S. Pafent
4,634,551. Such mixtures are characterized herein as (6-Cg-C10 alkamido-
caproyl)oxybenzenesulfonate.
5 Another class of useful bleach activators comprises the benzoxazin-
type activators disclosed by Hodge et al. in U.S. Patent 4,966, 723, Issued
October 30, 1990, incorporated herein by reference. A highly preferred
activator of the benzoxazin-type is:
O
~I
C,O
I
'C
N
Still another class of useful bleach activators includes the acyl lactam
activators, especially acyl caprolactams and acyl valerolactams of the
formulae:
O O
~I ~I
O C-CH2-CH2 O C-CH2 CH2
C N ~ H2 R6 C N
\CH2-CH2~ \CHZ CH2
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing
from
1 to about 12 carbon atoms. Highly preferred lactam activators include
benzoyl caprolactam; octanoyl caprolactam, 3,5,5-trimethylhexanoyl
2o caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl
caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl
valerolactam, undecenoyl valerolactam, 3,5,5-trimethylhexanoyl
valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, Issued
to Sanderson, October 8, 1985, incorporated herein by reference, which
discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into
sodium perborate.
If peroxygen bleaching agents are used as all or part of the essentially
present particulate material, they will generally comprise from about 1 % to
30% by weight of the composition. More preferably, peroxygen bleaching
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agent will comprise from about 1 % to 20% by weight of the composition.
Most preferably, peroxygen bleaching agent will be present to the extent of
from about 3% to 15% by weight of the composition. If utilized, bleach
activators can comprise from about 0.5% to 20%, more preferably from
s about 1 % to 10%, by weight of the composition. Frequently, activators are
employed such that the molar ratio of bleaching agent to activator ranges
from about 1:1 to 10:1, more preferably from about 1.5:1 to 5:1.
In addition, it has been found that bleach activators, when
1o agglomerated with certain acids such as citric acid, are more chemically
stable.
Surfactants
15 A type of particulate material which can be suspended in the non-
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.
2o Such surfactants are those produced by the sulfation of higher Cg-C20 fatty
alcohols.
Conventional primary alkyl sulfate surfactants have the general formula
2s ROSOg-M+
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 - Clq, alkyl, and M is alkali metal. Most preferably R
is
3o 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
35 those materials which have the sulfate moiety distributed randomly along
the
hydrocarbyl "backbone" of the molecule. Such materials may be depicted by
the structure
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CHg(CH2)n(CHOSOg-M+) (CH2)mCH3
wherein m and n are integers of 2 or greater and the sum of m + n is typically
s about 9 to 15, and M is a water-solubilizing cation.
If utilized as all or part of the requisite particulate material, ancillary
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
of the alkyl ether sulfate surfactant component essentially utilized as part
of
the liquid phase herein.
Organic Builder Material
Another possible type of particulate material which can be suspended in
the non-aqueous liquid detergent compositions herein comprises an organic
2o 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
metal, citrates, succinates, malonates, fatty acids, carboxymethyl succinates,
carboxylates, polycarboxylates and poiyacetyl carboxylates. Specific
examples include sodium, potassium and lithium salts of oxydisuccinic acid,
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.
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, polymaleic acid, and
polyacryliclpofymaleic acid copolymers and their salts, such as those sold by
BASF under the Sokaian trademark.
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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 alkylolammonium salts of
higher fatty acids containing from about 8 to about 24 carbon atoms, and
s 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
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
can comprise from about 4% to 10% by weight of the composition.
Inorganic Alkalinity Sources
Another possible type of particulate material which can be suspended in
the non-aqueous liquid detergent compositions herein can comprise a
2o 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.
2s Examples of suitable alkalinity sources include water-soluble alkali
metal carbonates, bicarbonates, borates, silicates and metasilicates.
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
3o all of these alkalinity sources, alkali metal carbonates such as sodium
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.
3s The presence of an alkalinity source which is also a desiccant may provide
benefits in terms of chemically stabilizing those composition components
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such as the peroxygen bleaching .agent which may be susce_ ptible to
deactivation by water.
If utilized as all or part of the particulate material component, the
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
1o non-aqueous liquid phase in the form of discrete particles.
OPTIONAL COMPOSITION COMPONENTS
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
2o may either dissolve in the liquid phase or may be dispersed within the
liquid
phase in the form of fine particles or droplets. Some of the materials which
may optionally be utilized in the compositions herein are described in greater
detail as follows:
Optional organic additives
The detergent compositions may contain an organic additive. A
3o preferred organic additive is hydrogenated castor oil and its derivatives.
Hydrogenated castor oil is a commercially available commodity being
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.
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The castor oil can be added as a mixture with ,for example stereamide.
. The organic additive will be partially dissolved in the non-aqueous
5 liquid diluent. To form the structured liquid phase required for suitable
phase
. stability and acceptable rheology, 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 Inorg~~anic Detergent Builders
The detergent compositions herein may also optionally contain one or
more types of inorganic detergent builders beyond those listed hereinbefore
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
2o 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.
Optional Thickening. Viscosity Control and/or Dispersing Agents
The detergent compositions herein may also optionally contain a
3o polymeric material which serves to enhance the ability of the composition
to
maintain its solid particulate components in suspension. Such materials may
thus act as thickeners, viscosity control agents and/or dispersing agents.
Such materials are frequently polymeric polycarboxyiates but can include
other polymeric materials such as polyvinylpyrrolidone {PVP) and polymeric
amine derivatives such as quaternized, ethoxylated hexamethylene
diamines.
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Polymeric polycarboxylate materials can be prepared by polymerizing
or copolymerizing suitable unsaturated monomers, preferably in their acid
form. Unsaturated monomeric acids that can be polymerized to form
suitable polymeric polycarboxylates include acrylic acid, malefic acid (or
s malefic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic
acid,
citraconic acid and methylenemalonic acid. The presence in the polymeric
polycarboxylates herein of monomeric segments, containing no carboxylate
radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable
provided that such segments do not constitute more than about 40% by
o weight of the polymer.
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
~ 5 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
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
2o 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.
If utilized, the optional thickening, viscosity control and/or dispersing
agents should be present in the compositions herein to the extent of from
25 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 Briahteners. Suds Suppressors and/or Perfumes
3o The detergent compositions herein may also optionally contain
conventional brighteners, suds suppressors, silicone oils, bleach catalysts,
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
35 environment. If present, brighteners suds suppressors and/or perfumes will
typically comprise from about 0.01 % to 5% by weight of the compositions
herein.
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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-
y 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.
60/040,115, Serial No. 60/038,714, Serial No. 60/039,920, filed on March 7,
1997.
~o COMPOSITION FORM
The particulate-containing liquid detergent compositions of this
invention are substantially non-aqueous (or anhydrous) in character. While
very small amounts of water may be incorporated into such compositions as
~5 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
herein will comprise less than about 1 % by weight.
2o The particulate-containing non-aqueous detergent compositions
herein will be in the form of a liquid.
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
and by mixing, e.g., agitating, the resulting component combination to form
3o the stable compositions herein. In a typical process for preparing 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-
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
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28
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
containing less than about 4% by weight of residual water.
s 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
compositions herein. This is done by reducing the anionic surfactant-
containing material formed in the previously described pre-preparation step
~o to powdered form and by combining such powdered material with an
agitated liquid medium comprising one or more of the non-aqueous organic
diiuents, either surfactant or non-surfactant or both as herein before
described. This combination is carried out under agitation conditions which
are sufficient to form a thoroughly mixed dispersion of particles of the
~5 insoluble fraction of the co-dried LAS/salt material throughout a non-
aqueous organic liquid diluent.
In a subsequent processing step, particulate material to be used in the
detergent compositions herein can be added. Such components which can
2o 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 maintain this admixture of composition components
under shear agitation. Agitation of the mixture is continued, and if
2s necessary, can be increased at this point to form a uniform dispersion of
insoluble solid phase particulates within the liquid phase.
The non-aqueous liquid dispersion so prepared can be subjected to
milling or high shear agitation. Milling conditions will generally include
3o maintenance of a temperature between about 10 and 90°C, preferably
between 20°C and fi0°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
3s maintenance costs. The small particles produced in such equipment will
generally range in size from 0.4- 150 microns.
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Agitation is then continued, and if necessary, can be increased at this
point to form a uniform dispersion of insoluble solid phase particles within
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 gMnding so that the average particle
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
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
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
2o 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.
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
3o the foregoing procedure, it is advantageous to maintain the free, unbound
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
s5 lower prior to their incorporation into the detergent composition matrix,
significantly stability advantages for the resulting composition can be
realized.
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Free and Total Water Determinations:
For the purpose of this patent application, and without wanting to be bound
5 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
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
~o 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
and in the full product as described below.
15 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
obtained. This clear layer is separated from the solids, and a weighed
sample is directly introduced into a coulometric Karl Fischer titration
vessel.
2o The water level determined in this way (mg water / kg clear layer) is
referred
to as "free water" (in ppm).
The "total water" is determined by first extracting a weighed amount of
finished product with an anhydrous, polar extraction liquid. The extraction
25 liquid is selected in such a way that interferences from dissolved solids
are
minimized. In most cases, dry methanol is a preferred extraction Liquid.
Usually, the extraction process reaches an equilibrium within a few hours -
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
3o centrifuged or filtered to remove the solids, and a known aliqot then
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.
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.
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Viscosity and yield measurements:
~ 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,
1o 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
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
2o a disk radius of 40 mm and a layer thickness of 2 mm was used. The shear
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~ s''.
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
laundering/bleaching solutions. The aqueous washing/bteaching solution so
formed is then contacted, preferably under agitation, with the fabrics to be
laundered and bleached therewith.
An effective amount of the liquid detergent compositions herein added
to water to form aqueous laundering/bleaching solutions can comprise
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amounts sufficient to form from about 500 to 8,000 ppm of composition in
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
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
~5 Preparation of Non-Aqueous Liquid 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.
2) LAS is added to the BPP/NI mixture after heating the BPP/NI mixture
up to 45°C.
3) !f 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
3o which 0.1-0.4% of the moisture in the liquid base is removed. Molecular
sieves are removed by passing the liquid base through a 20-30 mesh
screen. Liquid base is returned to the mix tank.
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4) Additional solid ingredients are prepared for addition to -the
composition. Such solid ingredients include the following:
Sodium carbonate {particle size 100 microns)
Sodium citrate dihydrate
s Malefic-acrylic copolymer (BASF Sokolan)
. Brightener (Tinopal PLC)
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
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
~ 5 order of addition for these powders is critical.
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
2o 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
cooling.
6) The bleach precursor particles are mixed with the ground suspension
2s 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
microns, most preferred between 100 and 400 microns.
30 7) Other solid materials could be added after the first processing step.
These include the following
Sodium percarbonate (400-600 microns)
Protease, cellulase and amylase enzyme grills (400-800 microns,
specific density below 1.7 glmL)
35 Titanium dioxide particles (5 microns)
Catalyst
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These non-millable solid materials are then added to the mix tank
followed by liquid ingredients (perfume and silicone-based suds
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.
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
1o solution and mixed to dissolve. The composition of the solution is
catalyst 5%
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
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.
2o The powdered material is collected at the base of the spray drier.
The composition is
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
BPP 19 19
Sodium citrate 4 5
i,
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[4-[N-nonanoyl-6-aminohexanoyloxy) 6 7
benzene sulfonate] Na salt
Chloride salt of methyl quarternized 1.2 1
polyethoxylated hexamethylene diamine
Ethylenediamine disuccinic acid 1 1
Sodium Carbonate 7 7
Maieic-acrylic copolymer 3 3
Protease Prills 0.40 0.4
Amylase Priils 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 excellent
enzymatic stain and soil removal performance when used in normal fabric
laundering operations. The viscosity measurement at 25°C is about 2200
cps at shear rate 20 s', yield is about 8.9 Pa at 25°C.
