BACKGROUND OF THE INVENTION
1. Field of the Invention
[0001] This invention relates to aqueous liquid detergent compositions containing a mercapto
end-capped hydrophilic polymer as a deflocculating agent.
2. Description of the Related Art
[0002] Heavy duty liquid detergents useful for machine washing of laundry are well known
materials which have been described in a number of patents and in the literature.
They are generally aqueous compositions comprising at least one or a compatible mixture
of two or more detergent active surfactants selected from anionic, cationic, nonionic,
zwitterionic and amphoteric species. Such compositions also generally contain detergency
builder components and/or sequestering agents such as inorganic phosphates or phosphonates,
alkali metal carbonates, alkali metal aminopolycarboxylates such as salts of nitrilotriacetic
acid and salts of ethylenediamine-tetraacetic acid, alkali metal silicates, aluminosilicates,
various zeolites and mixtures of two or more of these. Other components which may
be present in such compositions include a clay material such as bentonite present
as a fabric softener, optical brighteners, enzymes and their stabilizers, perfumes,
colorants, antifoaming agents, e.g. silicone compounds, preservatives and like known
additives.
[0003] A particular category of liquid detergents are the so called structured liquids comprising
lamellar droplets (micelles) dispersed in an aqueous electrolyte phase. The lamellar
droplets consist of an onion-like configuration of concentric bi-layers of surfactant
molecules between which layers are trapped water or electrolyte solution. Such liquids
may also contain suspended solids such as the water insoluble builders and clays referred
to above.
[0004] There is a trend in the industry to provide detergent compositions having a higher
concentration of active ingredients (payload), including surfactants. These include
detergent concentrates containing about 10 to 25% by weight of surfactant and super
concentrates containing from about 25 to 45% by weight surfactant. However, as the
level of surfactant is increased, the volume fraction of lamellar droplets suspended
is also increased, resulting in a diminished spacing between droplets. Contact of
the suspended lamellar droplets with one another can lead to a congealing or flocculation
phenomenon, resulting in a marked increase in the viscosity of the detergent composition
due to formation of a network throughout the liquid. Liquids containing flocculated
lamellar droplets are unacceptable because of phase separation and a difficulty in
pouring such liquids from their containers.
[0005] One approach to enhance the stability of such compositions is the inclusion of minor
amounts, e.g., 0.01 to 5% by weight, of a deflocculating polymer into the detergent
formulation. For example, U.S. Patent 5,147,576 discloses random interpolymers derived
from hydrophilic monomers, such as acrylic acid, and also containing one or more copolymerized
monomers having pendant hydrophobic side chains randomly dispersed along the polymer
chain. Use of these interpolymers in detergent compositions is disclosed to hinder
or prevent flocculation of lamellar surfactant droplets dispersed in the detergent,
and thus enhance stability.
[0006] Hydrophilic polymeric materials have also been used in liquid detergent compositions
as viscosity control agents. For example, U.S. Patent 4,715,969 and its counterpart
UK 2,168,717 disclose that the addition of less than about 0.5% by weight of a polyacrylate
polymer, e.g. sodium polyacrylate, having a molecular weight from about 1,000 to 5,000,
to aqueous detergent compositions containing primarily anionic surfactants will stabilize
the viscosity of the composition and prevent a major increase in viscosity after a
period of storage of the formulated composition. Also, EP-A-0 301,883 discloses similar
compositions containing from about 0.1 to 20% by weight of a viscosity reducing, water
soluble polymer such as polyethylene glycol, dextran or a dextran sulfonate.
[0007] EP-A-0 623 670 (published 9.11.1994) discloses aqueous based surfactant compositions
having surfactant micelles and containing a stabilizer. The stabilizer comprises a
hydrophilic polymeric chain of a certain size to reduce or prevent flocculation.
SUMMARY OF THE INVENTION
[0008] The present invention provides for concentrated, structured liquid detergent compositions
in the form of lamellar surfactant droplets dispersed in an aqueous electrolytic continuous
phase, comprising a mixture of:
a) from 10 to 45% by weight of a surfactant;
b) at least one detergent builder;
c) from 0.01 to 5% by weight of a deflocculating polymer composition having a weight
average molecular weight in the range of from 1500 to 50,000 and containing polymer
chains of the structure P-SR, where P represents a copolymer containing at least 50%
by weight of polymerized acrylic or methacrylic acid and less than 50% by weight of
polymerized maleic acid or maleic anhydride and SR represents a mercapto end-cap group,
R being an organic hydrophobic radical containing from 4 to 28 carbon atoms; and
d) water.
[0009] The presence of the deflocculating polymer in the composition both stabilizes the
detergent composition and retards the propensity of the lamellar droplets dispersed
in the aqueous electrolytic phase to flocculate, particularly where the droplets occupy
a higher volume ratio as the result of high concentrations of surfactant present in
the detergent.
[0010] The invention also provides both phosphate built and non-phosphate built detergent
compositions having a viscosity in the range of from about 500 to 20,000 mPa·s (500
to 20,000 cps), more preferably from 2,000 to 10,000 mPa·s (2,000 to 10,000 cps),
having improved flowability and stability.
DETAILED DESCRIPTION OF THE INVENTION
[0011] The detergent compositions of the invention contain one or a compatible mixture of
two or more detergent active surfactants which may be selected from anionic, cationic
nonionic, zwitterionic and amphoteric species.
[0012] Suitable anionic detergents include the water-soluble alkali metal salts having alkyl
radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used
to include the alkyl portion of higher acyl radicals. Examples of suitable synthetic
anionic detergent compounds are sodium and potassium alkyl sulphates, especially those
obtained by sulphating higher (C
8-C
18) alcohols produced, for example, from tallow or coconut oil; sodium and potassium
alkyl (C
9-C
20) benzene sulfonates, particularly sodium linear secondary alkyl (C
10-C
15) benzene sulfonates; sodium alkyl glycerol ether sulfates, especially those ethers
of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived
from petroleum; sodium coconut oil fatty monoglyceride sulfates and sulfonates; sodium
and potassium salts of sulfuric acid esters of higher (C
8-C
18) fatty alcohol-alkylene oxide, particularly ethylene oxide reaction products; the
reaction products of fatty acids such as coconut fatty acids esterified with isethionic
acid and neutralized with sodium hydroxide; sodium and potassium salts of fatty acid
amides of methyl taurine; alkane monosulfonates such as those derived from reacting
alpha-olefins (C
8-C
20) with sodium bisulfite and those derived from reacting paraffins with SO
2 and Cl
2 and then hydrolyzing with a base to produce a random sulfonate; and olefin sulfonates
which term is used to describe the material made by reacting olefins, particularly
C
10-C
20 alpha-olefins, with SO
3 and then neutralizing and hydrolyzing the reaction product. The preferred anionic
detergents are sodium (C
10-C
16) linear alkyl benzene sulfonates, (C
10-C
18) alkyl polyethoxy sulfates and mixtures thereof.
[0013] The more preferred anionic detergent is a mixture of linear or branched (preferably
linear) higher alkylbenzene sulfonate and alkyl polyethoxy sulfate. While other water
soluble linear higher alkylbenzene sulfonates may also be present in the formulas
of the present invention, such as potassium salts and in some instances the ammonium
and/or alkanolammonium salts, where appropriate, it has been found that the sodium
salt is highly preferred, which is also the case with respect to the alkyl polyethoxy
sulfate detergent component. The alkylbenzene sulfonate is one wherein the higher
alkyl group is of 10 to 16 carbon atoms, preferably 12 to 15, more preferably 12 to
13 carbon atoms. The alkyl polyethoxy sulfate, which also may be referred to as a
sulfated polyethoxylated higher linear alcohol or the sulfated condensation product
of a higher fatty alcohol and ethylene oxide or polyethylene glycol, is one wherein
the alkyl group is of 10 to 18 carbon atoms, preferably 12 to 15 carbon atoms, and
which includes 2 to 11 ethylene oxide groups, preferably 2 to 7, more preferably 3
to 5 and most preferably about 3 ethylene oxide groups.
[0014] The anionic detergent may be present in the composition at a level of from 10 to
45% by weight, more preferably from 15 to 40% by weight. Where mixtures of two or
more different anionic detergents are used, such as the sulfate and sulfonate mixtures
described above, they may be mixed in the relative proportions in the range of 5 to
95% by weight of each type.
[0015] The composition of this invention may also contain supplementary nonionic and amphoteric
surfactants. Suitable nonionic surfactants include, in particular, the reaction products
of compounds having a hydrophobic group and a reactive hydrogen atom, for example
aliphatic alcohols, acids, amides and alkyl phenols with alkylene oxides, especially
ethylene oxide, either alone or with propylene oxide. Specific nonionic detergent
compounds are alkyl (C
6-C
18) primary or secondary linear or branched alcohols with ethylene oxide, and products
made by condensation of ethylene oxide with the reaction products of propylene oxide
and ethylenediamine. Other so-called nonionic detergent compounds include long chain
tertiary amine oxides, long-chain tertiary phosphine oxides, dialkyl sulfoxides, fatty
(C
8-C
18) esters of glycerol, sorbitan and the like, alkyl polyglycosides, ethoxylated glycerol
esters, ethoxylated sorbitans and ethoxylated phosphate esters.
[0016] The preferred non-ionic detergent compounds are those of the ethoxylated and mixed
ethoxylated-propyloxylated (C
6-C
18) fatty alcohol type. The nonionic surfactants may be present in the composition at
a preferred level of from about 1 to 15% by weight.
[0017] It is also possible to include an alkali metal soap of a mono- or di-carboxylic acid,
especially a soap of an acid having from 12 to 18 carbon atoms, for example oleic
acid, ricinoleic acid, alk(en)yl succinate, for example dodecenyl succinate, and fatty
acids derived from castor oil, rapeseed oil, groundnut oil, coconut oil, palmkernel
oil or mixtures thereof. The sodium or potassium soaps of these acids can be used.
When used, the level of soap in compositions of the invention is from about 0.5 to
15% by weight of the composition.
[0018] Particularly preferred combinations of surfactants include:
1. A mixture which comprises 15 to 30% by wt. linear alkylbenzene sulfonate having
from 10 to 16 carbon atoms and 1 to 10% by wt. of alkyl polyethoxy sulfate wherein
the alkyl is of 10 to 18 carbon atoms and the polyethoxy is of 2 to 7 ethylene oxide
groups.
2. A mixture which comprises one or both of the anionic surfactants listed in 1 above
and a nonionic ethoxylated fatty alcohol wherein the fatty alcohol is of 8 to 18 carbon
atoms and the polyethoxy is of 2 to 7 oxide groups. The anionic to nonionic surfactant
ratio is from 1:4 to 10:1.
[0019] A more detailed illustration of the various detergents and classes of detergents
mentioned may be found in the text
Surface Active Agents, Vol. II, by Schwartz, Perry and Berch (Interscience Publishers, 1958), in a series
of annual publications entitled
McCutcheon's Detergents and Emulsifiers, issued in 1969, or in
Tensid-Taschenbuch, H. Stache, 2nd Edn. Carl Hanser Verlag, Munich and Vienna, 1981.
[0020] The composition of this invention also includes at least one detergency builder.
Suitable builders include phosphorous-containing inorganic salts, organic builders
and non-phosphorous-containing builders. The prime function of the builder is to complex
with hard water cations which form salts insoluble in water, for example calcium and
magnesium cations, through the mechanism of sequestration or cation exchange.
[0021] Examples of phosphorous-containing inorganic detergency builders include the water-soluble
salts, especially alkali metalpyrophosphates, orthophosphates, polyphosphates and
phosphonates. Specific examples of inorganic phosphate builders include sodium and
potassium tripolyphosphates, phosphates and hexametaphosphates. Phosphonate sequestrant
builders may also be used. Examples of organic detergency builders which may be used
include the alkali metal, ammonium and substituted ammonium polyacetates, carboxylates,
polycarboxylates, polyacetyl carboxylates and polyhydroxysulphonates. Specific examples
include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic
acid, nitrilotriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic
acids, tartrate mono succinate, tartrate di succinate, alk(en)yl succinates and citric
acid. Other organic detergency builders include water-soluble alkali metal carbonates
and bicarbonates, as well as mixtures thereof with phosphates, e.g., a mixture of
sodium carbonate and sodium tripolyphosphate.
[0022] In one embodiment of this invention, the liquid detergent is free of phosphorous-containing
builders. Preferred builders for use in phosphorous-free compositions include alkali
metal silicates in finely divided form, and particularly cation-exchanged amorphous
or crystalline aluminosilicates (zeolites) of natural or synthetic origin. Suitable
aluminosilicate zeolites include "zeolite A", "zeolite B", "zeolite X", "zeolite Y"
and "zeolite HS". The more preferred zeolite is crystalline sodium silicoaluminate
zeolite A. Preferably, the zeolite should be in a finely divided state with the ultimate
particle diameters being up to 20 microns, e.g., 0.005 to 20 microns, preferably from
0.01 to 15 microns and more preferably of 0.01 to 8 microns mean particle size, e.g.
3 to 7 microns, if crystalline, and 0.01 to 0.1 microns if amorphous. Although the
ultimate particle sizes are much lower, usually the zeolite particles will be of sizes
within the range of 100 to 400 mesh, preferably 140 to 325 mesh. Zeolites of smaller
sizes will often become objectionably dusty and those of larger sizes may not be sufficiently
and satisfactorily suspended.
[0023] In another embodiment of the invention where phosphorous-free builders are used,
the builder may comprise water soluble non-phosphorous containing compounds which
dissolve in the aqueous phase of the composition forming an electrolyte solution.
Examples of such builders include the alkali metal carboxylates referred to above,
e.g., sodium citrate, used alone or in a mixture with water soluble alkali metal carbonates
or bicarbonates, e.g., sodium or potassium carbonate.
[0024] Mixtures containing two or more of the above described detergency builders may also
be employed. The builder or mixture of builders may be present in the composition
in the range of from about 5 to about 40% by weight of the composition, more preferably
from about 8 to about 30% by weight. Where the builder is a zeolite material, it is
normally present in the range of from about 5 to 30% by weight of the composition,
and may be used in combination with other compatible builder materials.
[0025] The key ingredient in the compositions of the present invention is the hydrophobically
modified deflocculating polymer which both stabilizes the detergent formulation and
decreases the viscosity of such formulations. The hydrophobic end groups present in
the otherwise hydrophilic polymer become enveloped in the lamellar droplets formed
by the surfactant phase, thereby both sterically and electrostatically inhibiting
flocculation of these droplets, even at relatively high concentrations. This results
in a stable, lower viscosity product.
[0026] Deflocculating polymers useful in accordance with this invention are characterized
as comprising a hydrophilic polymer chain segment (P) having a hydrophobic mercapto
moiety (SR) covalently attached to a terminal carbon atom present in at least some
of the hydrophilic chain segments.
[0027] These polymers may be generally characterized as containing the structure P-SR wherein
P represents the hydrophilic polymer and R is an organic hydrophobic radical containing
from about 4 to 28 carbon atoms, more preferably an alkyl radical containing from
about 6 to 18 carbon atoms.
[0028] Monomers which may be polymerized to form the hydrophilic polymer segment include
one or a mixture of water soluble monomers or a combination of water soluble and relatively
water insoluble monomers such that the resulting polymers are water soluble at ambient
temperatures to the extent of greater than about 10 grams per liter. Examples of suitable
such monomers include ethylenically unsaturated amides such as acrylamide, methacrylamide
and fumaramide and their N-substituted derivatives such as 2-acrylamido-2-methylpropane
sulfonic acid, N-(dimethylaminomethyl) acrylamide as well as N-(trimethylammoniummethyl)
acrylamide chloride and N-(trimethylammoniumpropyl) methacrylamide chloride; ethylenically
unsaturated carboxylic acids or dicarboxylic acids such as acrylic acid, maleic acid,
methacrylic acid, itaconic acid, fumaric acid, crotonic acid, aconitic acid and citraconic
acid; and other ethylenically unsaturated quaternary ammonium compounds such as vinyl-benzyl
trimethyl ammonium chloride; sulfoalkyl esters of unsaturated carboxylic acids such
as 2-sulfoethyl methacrylate; aminoalkyl esters of unsaturated carboxylic acids such
as 2-aminoethyl methacrylate, dimethyl aminoethyl (meth)acrylate, diethyl aminoethyl
(meth)acrylate, dimethyl aminomethyl (meth)acrylate, diethyl aminomethyl (meth)acrylate,
and their quaternary ammonium salts; vinyl or allyl amines such as vinyl pyridine
and vinyl morpholine or allylamine; diallyl amines and diallyl ammonium compounds
such as diallyl dimethyl ammonium chloride; vinyl heterocyclic amides such as vinyl
pyrrolidone; vinyl aryl sulfonates such as vinylbenzyl sulfonate; vinyl alcohol obtained
by the hydrolysis of vinyl acetate; acrolein; allyl alcohol; vinyl acetic acid; sodium
vinyl sulphonate; sodium allyl sulphonate, as well as the salts of the foregoing monomers.
These monomers may be used singly or as mixtures thereof.
[0029] Optionally, the hydrophilic polymer segment may contain small amounts of relatively
hydrophobic units, e.g., those derived from polymers having a solubility of less than
1 g/1 in water, provided that the overall solubility of the hydrophilic polymer still
satisfies the solubility requirements as specified above. Examples of relatively water
insoluble polymers are polyvinyl acetate, polymethyl methacrylate, polyethyl acrylate,
polyethylene, polypropylene, polystyrene, polybutylene oxide, polypropylene oxide
and polyhydroxypropyl acrylate.
[0030] Mercaptans from which the hydrophobic mercapto moiety is derived include mercaptans
having the structure RSH where R is an organic radical having from 4 to 28 carbon
atoms. R should be of sufficient chain length such that it exhibits oleophilic properties,
i.e., it is miscible with the oily lamellar droplet or micelle phase of the detergent
composition. Preferably, the mercaptans are alkyl or aralkyl mercaptans containing
about 6 to 18 carbon atoms such as hexyl mercaptan, decyl mercaptan, dodecylbenzyl
mercaptan, dodecyl mercaptan and octadecyl mercaptan.
[0031] The polymers may be prepared by free radical polymerization of the hydrophilic monomer
or monomer mixture in an aqueous or water/alcohol medium in the presence of a water
soluble free radical initiator and in the presence of an RSH mercaptan. The molar
ratio of monomer to mercaptan may generally range from about 10:1 to about 150:1 respectively,
more preferably from about 25:1 to about 100:1 respectively. Under free radical polymerization
conditions, a number of RS free radicals will be generated which may serve to initiate
polymerization of additional monomer or these radicals can couple with a growing polymer
chain, resulting in a mixed polymer product wherein at least some of the chains have
the structure P-SR as described above. The number of P and P-SR chains present in
the mixed polymer product will vary depending on polymerization conditions, average
molecular weight of the polymer and the quantity of mercaptan present in the polymerization
mixture. Preferably from about 25 up to about 95% of the polymer chains are end-capped
by the SR mercapto hydrophobe.
[0032] Polymerization may be conducted by the general procedures described in U.S. Patent
5,021,525, the complete disclosure of which is incorporated herein by reference. The
preferred aqueous polymerization medium comprises a mixture of at least 50% by weight
of water and miscible cosolvent such as a C
1 to C
4 alcohol, e.g., isopropanol, which tends to retard precipitation of the developing
end-capped polymer from solution. Polymerization initiators which may be used include
water soluble initiators such as hydrogen peroxide, persulfates, perborates and permanganates,
present in solution at levels generally in the range of from about 0.1 to 5% by weight.
[0033] Polymerization may be conducted by initially charging an initiator, e.g. sodium persulfate,
into an aqueous polymerization medium, followed by gradual introduction of a mixture
comprising monomer and mercaptan into the medium at a level of from about 10 to 55%
by weight of total reactants, and heating the mixture at a temperature in the range
of from about 70 to 99°C for a period of time sufficient to form polymer of the desired
molecular weight, generally from about 3 to 6 hours. Preferably, only a portion of
the monomer and initiator is added to the medium initially, followed by the addition
of remaining monomer and initiator later during the polymerization. The polymer may
then be recovered by stripping the cosolvent, e.g., isopropanol and at least part
of the water, followed by neutralization of the polymer with caustic, e.g., sodium
hydroxide.
[0034] Preferred deflocculating polymers useful for the purposes of this invention have
a weight average molecular weight, as measured by gel permeation chromatography using
polyacrylate standards, in the range of from about 1500 to 50,000, more preferably
from about 2,000 to 25,000 and most preferably from about 3,000 to 10,000. The most
preferred polymers are hydrophilic homopolymers such as polyacrylic or polymethacrylic
acid and copolymers of acrylic or methacrylic acid with less than 50 wt% of maleic
acid (anhydride), wherein the bulk of the polymer chains are end-capped with a single
hydrophobic segment derived from dodecyl mercaptan.
[0035] These polymers and their method of preparation are further disclosed in US-A-5 599
784, the complete disclosure of which is incorporated herein by reference.
[0036] The liquid detergent composition of the invention may also optionally contain a swelling
bentonite clay material as a fabric softening agent. These materials are colloidal
clays (aluminum silicate) containing montmorillonite, available as sodium bentonite
or calcium bentonite. These materials generally form a swellable colloidal suspension
when mixed with water, which property can also aid in maintaining insoluble particulate
materials, i.e., zeolites, suspended in the liquid medium. Where present in the composition,
the bentonite is added at level in the range from about 1 to about 15% by weight.
[0037] The aqueous phase of the liquid detergent is electrolytic and thus contains a water
soluble salt. Where the builder present in the detergent is itself a water soluble
salt, e.g., where the builder is an alkali metal carbonate or citrate, no additional
electrolyte need be added. Where the builder is water insoluble, e.g., a zeolite,
then alkali metal halides or sulfates may be included as necessary to form the aqueous
electrolyte solution.
[0038] The only other required component of the liquid detergent compositions in accordance
with the present invention is water, some of which is present as a diluent in some
formulation components, e.g., surfactants, and some of which is added when the formulation
is prepared. Normally the hardness content of such water will be less than about 400
ppm as CaCO
3. Sometimes it may be desirable to utilize deionized water although city water will
be satisfactory. While harder waters may be successfully employed in making the liquid
detergent compositions of the present invention, it is considered that soft waters
have less likelihood of producing some objectionable materials which could adversely
affect the appearance of the liquid detergent or which could deposit objectionably
on laundry during washing. The quantity of water present in the composition will generally
range from about 25 to 70% by weight water. In more highly concentrated compositions,
the quantity of water may range from about 25 to less than 60% by weight, more preferably
less than 50% by weight.
[0039] Various adjuvants, both aesthetic and functional, may be present in the liquid detergent
compositions of the present invention, such as fluorescent brighteners, perfumes and
colorants. The fluorescent brighteners include the well known stilbene derivatives,
including the cotton and nylon brighteners, such as those sold under the trademark
Tinopal©, e.g. 5BM. The perfumes that are employed usually include essential oils,
esters, aldehydes and/or alcohols, all of which are known in the perfumery art. The
colorants may include dyes and water dispersible pigments of various types, including
ultramarine blue. Titanium dioxide may be utilized to lighten the color of the product
further or to whiten it. Inorganic filler salts, such as sodium sulfate and sodium
chloride may be present, as may be antiredeposition agents, such as sodium carboxymethylcellulose;
enzymes, such as proteases, amylases and lipases; bleaches, such as sodium perborate
or percarbonate or chlorine-containing materials; bactericides; fungicides; anti-foam
agents, such as silicones; antisoiling agents, such as copolyesters; preservatives,
such as formalin; foam stabilizers, such as lauric myristic diethanolamide; and auxiliary
solvents, such as ethanol. Normally the individual proportions of such adjuvants will
be less than 3%, often less than 1% and sometimes even less than 0.5%, except for
any fillers and solvents, and additional detergents and builders, for which the proportions
may sometimes be as high as 10%. The total proportion of adjuvants, including non-designated
synthetic detergents and builders, will normally be no more than 20% of the product
and desirably will be less than 10% thereof, more desirably less than 5% thereof.
Of course, the adjuvants employed will be non-interfering with the washing and the
softening actions of the liquid detergent and will not promote instability of the
product on standing. Also, they will not cause the production of objectionable deposits
on the laundry.
[0040] The viscosity of the liquid detergent composition immediately after completion of
the formulation mixing procedure will generally range from about 500 to 20,000 mPa·s
(500 to 20,000 centipoises (cps)), measured using a Brookfield Viscosimeter Model
LVT-II at an angular velocity of 12 rpm and at 25°C. Spindle n° 3 is used to measure
viscosities below 10,000 cps and spindle n° 4 is used for viscosities above 10,000
cps. The more preferred viscosity will be in the range of from 2,000 to 10,000 mPa·s
(2,000 to 10,000 cps), most preferably in the range of 3,000 to 6,000 mPa·s (3,000
to 6,000 cps). The pH of the composition will generally be in the range of from about
7 to about 12, preferably 10 to 12, and pH may be adjusted if necessary by adding
appropriate amounts of a basic solution such as 50% KOH.
[0041] The components of the detergent may be mixed in any suitable order which will lead
to the development of a structured product. In a preferred procedure, water and builders
are first mixed using a suitable high shear mixer to form a slurry/solution. The surfactant(s)
are separately mixed to foam a surfactant slurry. The deflocculating polymer in the
form of an aqueous dispersion (solids content of 30 to 60%) may then be mixed with
either slurry, and both slurries then combined under high shear mixing conditions,
followed by the subsequent addition of perfumes, enzymes (if any) and other additives.
[0042] The following examples are illustrative of the invention. Unless otherwise indicated,
all parts are by weight of active ingredients.
Examples 1-7
[0043] A series of zeolite-built, phosphorous-free superconcentrated heavy duty liquid detergent
(SCHDL) formulations were prepared by mixing the components shown in Table 1 in the
order shown in cylindrical tank with stirring using a Lightening® mixer. Mixing time
was approximately 30 minutes. Example 7 is a control example which does not contain
the deflocculating polymer. The identity and characteristics of the various deflocculating
polymers used in all examples are as described below. In each case, the hydrophobe
end capping group is docecyl mercaptan.
Deflocculating Polymer Physical Characteristics |
Polymer Designation |
Polymer Type |
Molecular Weight |
Mole Ratio of Hydrophile:Hydrophobe |
A |
Acrylic-maleic |
4000 |
25:1 |
B |
Acrylic-maleic |
7000 |
25:1 |
C |
Acrylic |
4000 |
25:1 |
D |
Acrylic |
7000 |
100:1 |
Table 1
wt. % (Active Ingredient) |
Component |
Ex 1 |
Ex 2 |
Ex 3 |
Ex 4 |
Ex 5 |
Ex 6 |
Ex 7 (Cont) |
Water |
QS |
QS |
QS |
QS |
QS |
QS |
QS |
Colorant |
0.75 |
--- |
--- |
0.75 |
--- |
--- |
--- |
Sodium Citrate |
8.0 |
6.0 |
4.0 |
8.0 |
8.0 |
8.0 |
8.0 |
Sodium Carbonate |
3.0 |
2.0 |
7.0 |
3.0 |
3.0 |
5.0 |
3.0 |
Brightener |
0.5 |
0.15 |
0.5 |
0.5 |
0.5 |
0.5 |
0.5 |
Preservative |
0.03 |
0.03 |
0.03 |
0.03 |
0.03 |
0.03 |
0.03 |
Deflocculating Polymer |
1.0(D) |
0.5(B) |
1.0(C) |
1.0(C) |
1.0(C) |
1.0(C) |
--- |
Zeolite A |
17.0 |
17.0 |
15.0 |
17.0 |
17.0 |
15.0 |
17.0 |
Nonionic* Surfactant (Neodol 23-6.5) |
7.0 |
7.0 |
7.0 |
7.0 |
7.0 |
7.0 |
7.0 |
Anionic** Surfactant (LAS) |
23.0 |
23.0 |
23.0 |
20.7 |
18.4 |
23.0 |
23.0 |
Fragrance |
0.4 |
0.4 |
0.4 |
0.4 |
0.4 |
0.4 |
0.4 |
Viscosity (mPa·s) (cps) |
2320 |
6400 |
4660 |
3470 |
1280 |
2790 |
>50000 |
Separation at 43.3°C (110°F) after 4 weeks |
0% |
0% |
0% |
0% |
0% |
0% |
0% |
Note:
Neodol® 23-6.5 is a nonionic ethoxylated fatty alcohol (6.5EO, 12-13 carbon atoms) |
LAS is a linear alkylbenzene sulfonate (10-14 carbon atoms) |
[0044] Viscosity comparison results contained in Table 1 show that the formulation of Examples
1-6 were all stable and exhibited low viscosities in the range of about 1280-6400
cps. Control Example 7 which does not contain one of the deflocculating polymers of
the invention exhibited a viscosity in excess of 50,000 due to flocculation of the
surfactant droplets present in the detergent.
Examples 8-11
[0045] A series of citrate-built, phosphate-free, enzyme-containing SCHDL formulations were
prepared by mixing the components in Table 2 in the order shown by the procedure set
forth above.
TABLE 2
wt% (Active Ingredient) |
COMPONENT |
Ex 8 |
Ex 9 |
Ex 10 |
Ex 11(cont) |
Water |
QS |
QS |
QS |
QS |
LAS |
29.6 |
20.0 |
24.0 |
20.0 |
AEOS* |
|
5.5 |
4.0 |
5.5 |
Nonionic Surfactant (Neodol 23-6.5) |
14.8 |
10.0 |
12.0 |
10.0 |
Sodium Citrate |
10.0 |
10.0 |
10.0 |
10.0 |
Borax |
2.0 |
2.0 |
2.0 |
2.0 |
Glycerin |
4.0 |
4.0 |
4.0 |
4.0 |
Protease |
1.5 |
1.5 |
--- |
1.5 |
Deflocculating Polymer |
1.0(A) |
1.0(A) |
1.0(A) |
--- |
Brightener |
0.4 |
0.4 |
0.4 |
0.4 |
Colorant |
0.75 |
0.75 |
0.75 |
0.75 |
Preservative |
0.05 |
0.05 |
0.05 |
0.05 |
Fragrance |
0.40 |
0.40 |
0.40 |
0.40 |
Viscosity mPa·s (cps) |
2600 |
6700 |
2600 |
15000 |
Separation 43.3°C (110°F) after 4 weeks |
0% |
0% |
0% |
31% |
Note:
*AEOS is an alkyl ethoxylated sulfate (3 EO, 12-15 carbon atoms) |
[0046] The formulation of Example 11 (Control) which does not contain the deflocculating
polymer exhibited a higher viscosity than formulations of Examples 8-10. In addition,
the control formulation shows some phase separation after 4 weeks storage at 110°F,
whereas the other formulations remained stable.
Examples 12-16
[0047] A series of phosphate-built SCHDL formulations were prepared by mixing the components
shown in Table 3 in the order shown by the procedure set forth above.
TABLE 3
wt% (Active Ingredients) |
COMPONENT |
Ex 12 |
Ex 13 |
Ex 14 |
Ex 15 |
Ex 16(cont) |
Water |
QS |
QS |
QS |
QS |
QS |
LAS |
26.0 |
26.0 |
25.0 |
25.0 |
25.0 |
AEOS |
1.5 |
1.4 |
3.75 |
2.0 |
3.75 |
Nonionic Surfactant (Neodol 25-7)* |
---- |
2.0 |
---- |
---- |
---- |
Sodium TPP |
11.0 |
15.0 |
15.25 |
12.0 |
15.25 |
Potassium TPP |
12.0 |
12.0 |
5.0 |
11.0 |
5.0 |
Sodium Carbonate |
7.0 |
3.5 |
4.0 |
2.0 |
4.0 |
Potassium Carbonate |
---- |
---- |
4.5 |
---- |
4.5 |
Sesquicarbonate |
---- |
---- |
---- |
6.0 |
---- |
Deflocculatlng Polymer |
0.4(A) |
0.7(C) |
0.65(C) |
0.65(C) |
---- |
Brightener |
0.15 |
0.15 |
0.15 |
0.15 |
0.15 |
Colorant |
1.5 |
1.5 |
1.5 |
1.5 |
1.5 |
Preservative |
0.03 |
0.19 |
0.19 |
0.19 |
0.19 |
Fragrance |
0.33 |
0.33 |
0.35 |
0.33 |
0.35 |
Viscosity mPa·s (cps) |
5800 |
6500 |
5700 |
4800 |
>30000 |
Separation 43.3°C (110oF) after 4 weeks |
0% |
0% |
0% |
0% |
4% |
Neodol ® 25-7 is a nonionic ethoxylated fatty alcohol (7 EO, 12-15 carbon atoms). |
[0048] Formulations within the scope of the invention (Examples 12-15) all exhibited pourable
viscosities in the range of 4800-6500 cps, whereas control formulation 16 had an initial
viscosity in excess of 30,000 cps and showed some phase separation after 4 weeks storage.
1. A concentrated liquid detergent composition, characterized in that it comprises lamellar
surfactant droplets dispersed in an aqueous electrolytic continuous phase which phase
is formed by dissolving soluble compounds in an aqueous phase, said composition comprising
mixture of:
a) from 10 to 45% by weight of surfactant;
b) at least one detergent builder;
c) from 0.01 to 5% by weight of a deflocculating polymer composition having a weight
average molecular weight in the range of from 1500 to 50,000 and containing polymer
chains of the structure P-SR, wherein P represents a copolymer containing at least
50% by weight of polymerized acrylic or methacrylic acid and less than 50% by weight
of polymerized maleic acid or maleic anhydride and SR represents a mercapto end-cap
group, R being an organic radical containing from 4 to 28 carbon atoms which is sufficiently
hydrophobic to be miscible with said droplets; and
d) water
2. The composition of claim 1 wherein said surfactant comprises at least one anionic
detergent selected from an anionic sulfate or sulfonate.
3. The composition of claim 2 containing from 15 to 40% by weight of an alkyl benzene
sulfonate anionic detergent having from 9 to 20 alkyl carbon atoms.
4. The composition of claim 2 containing from 1 to 25% by weight of a sodium or potassium
alkyl polyethoxy sulfate anionic detergent wherein the alkyl group contains from 8
to 22 carbon atoms and the polyethoxy is of 2 to 7 ethylene oxide groups.
5. The composition of claim 3 wherein said ionic detergent comprises a mixture of said
alkyl benzene sulfonate and from 1 to 25% by weight of a sodium or potassium alkyl
polethoxy sulfate wherein the alkyl group contains from 8-22 carbon atoms and the
polyethoxy is of 2 to 7 ethylene oxide groups.
6. The composition of claim 3 or 5 further containing from 1 to 20% by weight of a nonionic
ethoxylated fatty alcohol wherein the fatty alcohol contains 8 to 18 carbon atoms.
7. The composition of claim 1 wherein said hydrophilic polymer chain segment P is polyacrylic
or polymethacrylic acid.
8. The composition of claim 1 or 7, wherein said polymer has a weight average molecular
weight in the range of from 2,000 to 25,000.
9. The composition of claim 8 wherein said polymer has a weight average molecular weight
in the range of from 3,000 to 10,000.
10. The composition of claim 1 wherein R is an alkyl group containg from 6 to 18 carbon
atoms.
11. The composition of claim 10 wherein R is dodecyl.
12. The composition of claim 1 wherein from 25 up to 95% of the hydrophilic polymer chains
present in said deflocculating polymer composition are end-capped by SR mercapto hydrophobe.
13. The composition of claim 1 wherein said detergent builder is present in said composition
at a level of from 5 to 40% by weight of said composition.
14. The composition of claim 13 wherein said detergent builder comprises one or more phosphates.
15. The composition of claim 13 wherein said detergent builder comprises a zeolite.
16. The composition of claim 13, wherein said detergent builder comprises an alkali metal
citrate.
17. The composition of claim 13 wherein said detergent builder comprises an alkali metal
carbonate.
18. The composition of claim 1 containing less than 60% by weight of water.
19. The composition of claim 1 containing less than 50% by weight of water.
20. The composition of claim 1 having a viscosity in the range of from 500 to 20,000 mPa.s
(500 to 20,000 cps).
1. Konzentrierte flüssige Reinigungsmittelzusammensetzung, dadurch gekennzeichnet, dass
sie lamellare Tensidtröpfchen dispergiert in einer wässrigen, elektrolytischen, kontinuierlichen
Phase umfasst, wobei die Phase durch Auflösung von löslichen Verbindungen in einer
wässrigen Phase gebildet worden sind, wobei die Zusammensetzung eine Mischung aus:
a) 10 bis 45 Gew.-% Tensid,
b) mindestens einen Reinigungsmittelbuilder,
c) 0,01 bis 5 Gew.-% einer Deflockulierungspolymerzusammensetzung mit einem durchschnittlichen
gewichtsmäßigen Molekulargewicht im Bereich von 1500 bis 50 000 und Polymerketten
mit der Struktur P-SR, wobei P ein Copolymer ist, das mindestens 50 Gew.-% polymerisierte
Acryl- oder Methacrylsäure und weniger als 50 Gew.-% polymerisierte Maleinsäure oder
polymerisiertes Maleinsäureanhydrid enthält, SR eine Mercaptoendverkappungsgruppe
ist, und R ein organischer Rest mit 4 bis 28 Kohlenstoffatomen ist, der ausreichend
hydrophob ist, um mit den Tröpfchen mischbar zu sein, und
d) Wasser umfasst.
2. Zusammensetzung nach Anspruch 1, bei der das Tensid mindestens ein anionisches Reinigungsmittel
ausgewählt aus anionischem Sulfat oder Sulfonat umfasst.
3. Zusammensetzung nach Anspruch 2, die 15 bis 40 Gew.-% anionisches Alkylbenzolsulfonat-Reinigungsmittel
mit 9 bis 20 Alkylkohlenstoffatomen enthält.
4. Zusammensetzung nach Anspruch 2, die 1 bis 25 Gew.-% eines anionischen Natrium- oder
Kaliumalkylpolyethoxysulfat-Reinigungsmittels enthält, bei dem die Alkylgruppe 8 bis
22 Kohlenstoffatome enthält und das Polyethoxy aus 2 bis 7 Ethylenoxidgruppen besteht.
5. Zusammensetzung nach Anspruch 3, bei der das ionische Reinigungsmittel eine Mischung
aus dem Alkylbenzolsulfonat und 1 bis 25 Gew.-% eines Natrium- oder Kaliumalkylpolyethoxysulfats
umfasst, in dem die Alkylgruppe 8 bis 22 Kohlenstoffatome enthält und das Polyethoxid
aus zwei bis 7 Ethylenoxidgruppen besteht.
6. Zusammensetzung nach Anspruch 3 oder 5, die ferner 1 bis 20 Gew.-% eines nichtionischen
ethoxylierten Fettalkohols enthält, wobei der Fettalkohol 8 bis 18 Kohlenstoffatome
enthält.
7. Zusammensetzung nach Anspruch 1, bei der das hydrophile Polymerkettensegment P Polyacryl-
oder Polymethacrylsäure ist.
8. Zusammensetzung nach Anspruch 1 oder 7, bei der das Polymer ein durchschnittliches
gewichtsmäßiges Molekulargewicht im Bereich von 2 000 bis 25 000 aufweist.
9. Zusammensetzung nach Anspruch 8, bei der das Polymer ein durchschnittliches gewichtsmäßiges
Molekulargewicht im Bereich von 3 000 bis 10 000 aufweist.
10. Zusammensetzung nach Anspruch 1, bei der R eine Alkylgruppe ist, die 6 bis 18 Kohlenstoffatome
enthält.
11. Zusammensetzung nach Anspruch 10, bei der R Dodecyl ist.
12. Zusammensetzung nach Anspruch 1, bei der 25 bis zu 95 % der hydrophilen Polymerketten,
die in der Deflockulierungspolymerzusammensetzung vorhanden sind, durch SR-Mercapto-Hydrophob
endverkappt sind.
13. Zusammensetzung nach Anspruch 1, bei der der Reinigungsmittelbuilder in der Zusammensetzung
in einer Menge von 5 bis 40 Gew.-% der Zusammensetzung vorhanden ist.
14. Zusammensetzung nach Anspruch 13, bei der der Reinigungsmittelbuilder ein oder mehrere
Phosphate umfasst.
15. Zusammensetzung nach Anspruch 13, bei der der Reinigungsmittelbuilder Zeolith umfasst.
16. Zusammensetzung nach Anspruch 13, bei der der Reinigungsmittelbuilder Alkalimetallcitrat
umfasst.
17. Zusammensetzung nach Anspruch 13, bei der der Reinigungsmittelbuilder Alkalimetallcarbonat
umfasst.
18. Zusammensetzung nach Anspruch 1, die weniger als 60 Gew.-% Wasser enthält.
19. Zusammensetzung nach Anspruch 1, die weniger als 50 Gew.-% Wasser enthält.
20. Zusammensetzung nach Anspruch 1 mit einer Viskosität im Bereich von 500 bis 20 000
mPa·s (500 bis 20 000 cPs).
1. Composition détergente liquide concentrée, caractérisée en ce qu'elle comprend des
gouttelettes d'un tensioactif lamellaire dispersées dans une phase continue électrolytique
aqueuse, laquelle phase est formée par dissolution de composés solubles dans une phase
aqueuse, ladite composition comprenant un mélange :
a) de 10 à 45% en poids d'un tensioactif ;
b) d'au moins un adjuvant de détergence ;
c) de 0,01 à 5% en poids d'une composition de déflocculation à base de polymère présentant
une masse moléculaire moyenne en poids dans la plage allant de 1500 à 50000 et contenant
des chaînes polymères de structure P-SR, où P représente un copolymère contenant au
moins 50% en poids d'acide acrylique ou méthacrylique polymérisé et moins de 50% en
poids d'anhydride maléique ou d'acide maléique polymérisé et SR représente un groupe
mercapto coiffant une extrémité, R étant un radical organique contenant de 4 à 28
atomes de carbone qui est suffisamment hydrophobe pour être miscible auxdites gouttelettes;
et
d) de l'eau.
2. Composition selon la revendication 1 dans laquelle ledit tensioactif comprend au moins
un détergent anionique choisi parmi un sulfate ou un sulfonate anionique.
3. Composition selon la revendication 2 contenant de 15 à 40% en poids d'un détergent
anionique de type alkylbenzènesultonate présentant de 9 à 20 atomes de carbone dans
le groupe alkyle.
4. Composition selon la revendication 2 contenant de 1 à 25% en poids d'un détergent
anionique de type alkyl polyéthoxy sulfate de sodium ou de potassium dans lequel le
groupe alkyle contient de 8 à 22 atomes de carbone et le groupe polyéthoxy est constitué
de 2 à 7 groupes oxyde d'éthylène.
5. Composition selon la revendication 3 dans laquelle ledit détergent ionique comprend
un mélange dudit alkylbenzènesulfonate et de 1 à 25% en poids d'un alkyl polyéthoxy
sulfate de sodium ou de potassium dans lequel le groupe alkyle contient de 8 à 22
atomes de carbone et le groupe polyéthoxy est constitué de 2 à 7 groupes oxyde d'éthylène.
6. Composition selon la revendication 3 ou la revendication 5 contenant en outre de 1
à 20% en poids d'un alcool gras éthoxylé non ionique dans lequel l'alcool gras contient
de 8 à 18 atomes de carbone.
7. Composition selon la revendication 1 dans laquelle le segment P de chaîne polymère
hydrophile est un acide polyacrylique ou polyméthacrylique.
8. Composition selon la revendication 1 ou la revendication 7 dans laquelle ledit polymère
présente une masse moléculaire moyenne en poids dans la plage allant de 2000 à 25000.
9. Composition selon la revendication 8 dans laquelle ledit polymère présente une masse
moléculaire moyenne en poids dans la plage allant de 3000 à 10000.
10. Composition selon la revendication 1 dans laquelle R est un groupe alkyle contenant
de 6 à 18 atomes de carbone.
11. Composition selon la revendication 10 dans laquelle R représente dodécyle.
12. Composition selon la revendication 1 dans laquelle de 25 jusqu'à 95% des chaînes polymères
hydrophiles présentes dans ladite composition de déflocculation à base de polymère
sont coiffés à leur extrémité par des groupes mercapto hydrophobes SR.
13. Composition selon la revendication 1 dans laquelle ledit adjuvant de détergence est
présent dans ladite composition à raison de 5 à 40% en poids de ladite composition.
14. Composition selon la revendication 13 dans laquelle ledit adjuvant de détergence comprend
un ou plusieurs phosphates.
15. Composition selon la revendication 13 dans laquelle ledit adjuvant de détergence comprend
une zéolite.
16. Composition selon la revendication 13 dans laquelle ledit adjuvant de détergence comprend
un citrate de métal alcalin.
17. Composition selon la revendication 13 dans laquelle ledit adjuvant de détergence comprend
un carbonate de métal alcalin.
18. Composition selon la revendication 1 contenant moins de 60% en poids d'eau.
19. Composition selon la revendication 1 contenant moins de 50% en poids d'eau.
20. Composition selon la revendication 1 présentant une viscosité dans la plage allant
de 500 à 20000 mPa.s (500 à 20000 cps).