[0001] This invention relates to aqueous homogeneous liquid detergent compositions comprising
surface-active agents and a mixture, in additive level, of alkylcellulose and carboxymethylcellulose.
In more detail, the invention herein relates to concentrated homogeneous compositions
comprising a coacervate mixture of known anti-redeposition agents in combination with
high levels of anionic and nonionic surface-active agents. The mixture of anti-redeposition
agents is present as a coacervate capable of forming, in combination with the surfactants,
a network of loosely associated droplets. This tridimensional network provides means
for stably and homogeneously suspending detergent components/additives which otherwise
could not be incorporated, particularly ingredients which are substantially insoluble
in the liquid matrix. The compositions herein are especially beneficial in several
respects. First, the claimed compositions exhibit the benefits attached to the utilization
of anti-redeposition agents. As of yet, it was virtually impossible to effectively
incorporate the like agents in liquid detergent compositions. Secondly, the tridimensional
network provides a "honey comb-" or "wine cellar-" like structure, i.e, means for
incorporating desirable detergent additives which up to now could not be compatibly
incorporated into the like compositions because of phase separation, sedimentation,
flocculation, coalescence or other known phenomena which can destablize the like liquid
compositions. In addition the compositions herein do not require highly viscous and/or
thixotropic consistencies with a view to stabilize the cellulose ether coacervate.
[0002] The use of alkylcellulose and carboxymethylcellulose is well known in detergents
and has found widespread commercial application, particularly in granular detergents,
in an anti-redeposition functionality. However, it is also known that the incorporation
of these cellulose ethers in liquid detergents is subject to considerable difficulties.
The solubilization of anti-redeposition agents in liquid detergents is virtually impossible
in presence of anionic surface-active agents. In general, it was tried to incorporate
these agents via dispersion. However, stable cellulose ether dispersions require frequently
high product viscosities with or without thixotropic properties. It is understood
that product viscosity serves as a means to provide homogeneous dispersions as a result
of decreased phase separation.
[0003] The prior art use of partial solublization and/or dispersion techniques for incorporating
cellulose ethers frequently aims at the incorporation of one cellulose ether species,
i.e., anionic or nonionic.
[0004] Dispersion stability can allegedly also be obtained from using mixtures of anionic
and nonionic cellulose ethers. This approach, in fact, aims at providing equilibrium
between ascending and descending tendencies of the nonionic and anionic particles
respectively. The latter approach is disclosed in FR-A-1 192 968. Phosphate built,
highly alkaline, liquid detergent compositions are disclosed containing mixtures of
different cellulose ether derivatives. The '638 technology requires an excess of methylcellulose
over carboxymethylcellulose.
[0005] U.S. Patent 3,328,305, patented June 27, 1967, relates to a process for preparing
detergent formulations containing separately prewetted cellulose ethers. The prewetting
step is carried out with fatty acids which are liquid at ambient temperatures.
[0006] German Patent Application 24 02 225 discloses pourable, substantially non-aqueous,
fluid masses having plastic Bingham-properties. Dispersed particulate solids are suspended
in the fluid compositions with the aid of a fibrous tridimensional network. Fatty
acid soaps constitute the network structure which network can serve to suspend particulate
materials such as inorganic abrasives, or pigments.
[0007] Belgian Patent 758,553 and German Patent Application 19 55 556 also relate to suspending
particulate materials in liquid detergents.
[0008] US-Patent 3,523,088 pertains to an antiredeposition agent and detergent compositions
containing same. The antiredeposition agent is represented by a mixture of alkali
metal carboxymethylcellulose and hydroxypropylcellulose.
[0009] The prior art has, as of yet, not suggested means for effectively using mixtures
of anionic and nonionic cellulose ethers, having a coacervate network structure, in
liquid detergents. The art is non-suggestive of formulating stable liquid detergents
containing cellulose ethers having a low viscosity without thixotropic properties.
Moreover, the art is silent with respect to advantageously utilizing a cellulose ether
coacervate network structure for stably incorporating ingredients which otherwise
would be difficulty incorporatable, e.g., ingredients which are normally insoluble
in the matrix.
[0010] The standing prior art prejudice against the possibility of effectively incorporating
cellulose ethers, especially carboxymethylcellulose, into liquid detergents is based
on general knowledge and supported by e.g. the disclosures of U.S. Patent 4,127,495
assigned to Hercules Inc. This prejudice is said to be particularly damaging towards
using anionic surface-active agents in combination with cellulose ethers.
[0011] While the terms "coacervation" and "coacervate" are well-known in the technical community,
for the sake of common understanding these terms and the related term "coacervate
network" can be described as follows.
[0012] The separation into two liquid phases in colloid systems is called coacervation.
This separation results from a decrease in solubility of a lyophilic colloid. It leads
to one colloid-rich and one colloid-poor phase.
[0013] A coacervate is in general an aggregate of colloidal droplets, held together by basic
colloidal forces, frequently termed primary coacervate.
[0014] The term network herein stands for a coacervate network; it is a particular coacervate
wherein colloidal isotropic droplets, having generally a diameter below 10 microns,
are loosely associated into a three-dimensional network. The obtainment of a stable
"tridimensional coacervate network" requires the presence of anionic and nonionic
surface-active agents.
[0015] It is a major object of this invention to formulate homogeneous liquid detergent
compositions containing additive levels of anti-redeposition agents.
[0016] It is a further object of this invention to provide concentrated homogeneous liquid
detergents containing a mixture of anionic and nonionic cellulose ethers which compositions
exhibit excellent storage stability over prolonged periods of time.
[0017] It is yet another object of this invention to formulate substantially phosphate builder-free
concentrated neutral to mildly alkaline liquid detergent compositions containing stably
incorporated therein detergent additives which additives up to now could not be used
in liquid detergents.
[0018] The above and other advantages are now achieved with the aid of the composition and
the method of this invention as described in more detail hereinafter.
Summary of the invention
[0019] This invention relates to aqueous homogeneous concentrated liquid detergents containing
a coacervate of carboxymethyl cellulose and a mixture of anionic and nonionic surface-active
agents. The invention more specifically relates to homogeneous liquid detergent compositions
containing:-
from 0.1 % to 3% by weight of a coacervate of Cl-C4 alkyl, possibly hydroxylated, cellulose (AC) and carboxymethylcellulose (CMC) in
a wseight ratio of CMC:AC of from 6:1 to 1:4;
more than 20% by weight of a mixture of anionic and nonionic surface-active agents
whereby the nonionic surface-active agent represents more than 3% by weight and whereby
the weight ratio of anionic to nonionic is in the range from 1:1 to 8:1; and
more than 10% by weight of water, whereby the weight ratio of the total ingredients
to water is from 1:1 to 9:1.
[0020] Preferred compositions of this invention have a pH measured "as is" at 20°C of from
6.0-10. In another preferred aspect, the compositions herein comprise at least 5%
by weight, calculated on the total detergent composition, of non-soap anionic surface-active
agents.
[0021] The coacervate network provides storage stability and consequently an approch for
beneficially utilizing the known anti-redeposition properties of the AC and CMC in
liquid detergents. Additionally, the tridimensional coacervate network can serve to
stably incorporate all kinds of detergent additives which up to now could not be effectively
incorporated into the like composition because of known incompatibility to the general
liquid system.
[0022] The preferred alkylcellulose for use herein is methylcellulose.
[0023] Unless indicated to the contrary, the "%-indications" stand for ―% by weight―.
Detailed description of the invention
[0024] The compositions of this invention comprise as a first essential component from 0.1
% to 3%, preferably from 0.5% to 1.5%, of a coacervate of a nonionic C
i-C
4 alkyl, possibly hydroxylated, cellulose and an anionic carboxymethyl cellulose.
[0025] The nonionic C
1-C
4 alkyl, possibly hydroxylated, cellulose is represented by methylcellulose. The latter
ingredient has normally a degree of substitution (DS) ranging from 0.5 to 2.8, preferably
from 1.4 to 2.2. It is further characterized by a degree of polymerization (DP) between
50-1000, preferably between 150-300. Typical examples of suitable nonionic C
l-C
4 alkyl cellulose for use herein include: methylcellulose DS 1.7; DP 200; ethylcellulose
DS 1.5; DP 200; methylhydroxyethylcellulose DS 2.1; DP 200; and methylhydroxypropylcellulose
DS 1.7; DP 200.
[0026] The DS indicates the number of substituted alkyl groups per anhydro-glucose unit.
The DP expresses the number of anhydro-glucose units present in the polymer molecule.
[0027] The anionic carboxymethylcellulose is represented by one having a DS ranging from
0.3 to 1.5, preferably from 0.6 to 0.9, and a DP in the range from 50-1000, preferably
from 200-400. Carboxymethylcellulose is eminently well-known in the detergent art.
The carboxymethylcellulose is preferably used as a salt with conventional cation such
as sodium, potassium, amines, or substituted amines. A typical example of a suitable
carboxymethylcellulose is the sodium salt having a DS of 0.7 and a DP of 250.
[0028] The weight ratio of the alkylcellulose to carboxymethylcellulose is normally in the
range from 4:1 to 1:6, preferably from 1:1 to 1:3.
[0029] A second essential ingredient for use in the compositions herein is represented by
a mixture of anionic and nonionic surface-active agents. This mixture is used in an
amount of more than 20%, preferably in a level from 25% to 60%. The nonionic surface-active
agent represents more than 3% (of the total detergent composition) whereas the weight
ratio of anionic to nonionic surface-active agents is in the range from 1 to 1 to
8 to 1, preferably from 1:1 to 4:1. In a preferred embodiment, the non-soap anionic
surface-active agent shall represent at least 5%, preferably more than 8%, of the
total detergent composition.
[0030] Suitable anionic surface-active agents are usually selected from the group of sulfonates,
sulfates, and carboxylates/soaps. These anionic detergents are eminently well-known
in the detergent arts and have found wide-spread commercial application. Preferred
anionicwater-soluble sulfonate or sulfate surfactants have in their molecular structure
an alkyl radical containing from 8 to 22 carbon atoms. Examples of preferred anionic
surfactant are the reaction products obtained by sulfating C
8C
l8 fatty alcohols derived from tallow and coconut oil; alkylbenzene sulfonates wherein
the alkyl group contains from 8 to 15 carbon atoms; sodium alkylglyceryl ether sulfonates;
ether sulfates of fatty alcohols derived from tallow and coconut oils; coconut fatty
acid monoglyceride sulfates and sulfonates; and water-soluble salts of paraffin sulfonates
having from 8 to 22 carbon atoms in the alkyl chain. Sulfonated olefin surfactants
as more fully described in e.g. U.S. Patent Specification 3.332.880, incorporated
herein by reference, can also be used. The neutralizing cation for the anionic synthetic
sulfonates and/or sulfates is represented by conventional cations which are widely
used in detergent technology such as sodium, potassium, amines and substituted amines.
[0031] A preferred anionic surfactant component herein is represented by the water-soluble
salts of an alkylbenzene sulfonic acid having from 10 to 13 carbon atoms in the alkyl
group. Preferred are the sodium, potassium and substituted amine, such as triethanolamine,
salts. Another preferred anionic surface-active agent is a sulfated C
'2-C
'4 fatty alcohol, possibly with a degree of ethoxylation in the range from 1-4, in combination
with alkylbenzene sulfonates in a weight ratio of 3:1 to 1:3.
[0032] Still another preferred anionic surfactant is a paraffin sulfonate having from 12
to 20, preferably from 14 to 18 carbon atoms in the alkyl chain. The paraffin sulfonate
can beneficially be used in combination with C,,-C
13 alkylbenzene sulfonate in e.g. a weight ratio of 1:3 to 3:1.
[0033] The anionic surface-active agent is usually represented by the salts of fatty acids
having from 10 to 24, preferably 12 to 18, carbon atoms. Suitable soap surface-active
agents can originate from saturated and unsaturated fatty acids.
[0034] Examples of suitable saturated fatty acids for use in the compositions of this invention
include capric, lauric, myristic, palmitic, stearic, arachadic and behenic acid. Suitable
unsaturated fatty acid species include: palmitoleic, oleic, linoleic, linolenic and
ricinoleic acid. Highly preferred for use herein are fatty acids having from 16 to
18 carbon atoms and which are comprised of at least 30% of unsaturated species. Other
preferred fatty acids are represented by a mixture of saturated C
10―C
14 (coconut) fatty acids and oleic acid in a ratio (weight) of from 2:1 to 1:3.
[0035] The nonionic surface-active agents are frequently ethoxylated. All ethoxylated nonionic
surfactants which are known to be suitable for use in detergent application can be
used in the compositions of this invention. Examples of suitable nonionics include
polyethoxylates derived from primary and secondary aliphatic alcohols having from
8 to 24 carbon atoms, and having a HLB (hydrophilic-lipophilic balance) in the range
from 9 to 15. These ethoxylates frequently contain from 2 to 14 moles of ethylene
oxide per mole of hydrophobic moiety. The alkyl chain (hydrophobic moiety) can be
represented by linear or branched fatty alcohols.
[0036] A preferred class of nonionic ethoxylates is represented by the condensation product
of a fatty alcohol having from 12 to 15 carbon atoms and from 4 to 10 moles of ethylene
oxide per mole of fatty alcohol. Suitable species of this class of ethoxylates include:
the condensation product of C
'2-C
'5 oxo-alcohols and 7 moles of ethylene oxide per mole of alcohol; the condensation
product of narrow cut C
14―C
15 oxo-alcohols and 7 or 9 moles of ethylene oxide per mole of fatty (oxo) alcohol;
the condensation product of a narrow cut C
12―C
13 fatty (oxo) alcohol and 6.5 moles of ethylene oxide per mole of fatty alcohol; and
the conddensation products of a C
'O-C
'4 coconut fatty alcohol with a degree of ethoxylation (moles EO/mole fatty alcohol)
in the range from 5 to 8. The fatty oxo alcohols while mainly linar can have, depending
upon the processing conditions and raw material olefins, a certain degree of branching,
particularly short chain such as methyl branching. A degree of branching in the range
from 15% to 50% (weight %) is frequently found in commercial oxo-alcohols.
[0037] Preferred nonionic ethoxlated components can also be represented by a mixture of
2 separately ethoxylated nonionic surface-active-agents having a different degree
of ethoxylation. For example, the nonionic ethoxylate can be represented by mixtures
of a first ethoxylated surfactant containing from 3 to 7 moles of ethylene oxide per
mole of hydrophobic moiety and a second ethoxylated species having from 8 to 14 moles
of ethylene oxide per mole of hydrophobic moiety. A preferred nonionic ethoxylated
mixture contains a lower ethoxylate which is the condensation product of a C
12―C
15 oxo-alcohol, with up to 50% (wt) branching, and from about 3 to 7 moles of ethylene
oxide per mole of fatty oxo-alcohol, and a higher ethoxylate which is the condensation
product of a C
16―C
19 oxo-alcohol with more than 50% (wt) branching and from 8 to 14 moles of ethylene
oxide per mole of branched oxo-alcohol.
[0038] The presence of nonionic and anionic surface-active agents is essential with a view
to produce the coacervate network. It is believed that the anionic surfactant aids
in the formation of a primary coacervate whereas the mixed non-soap anionic+nonionic
surface-active agents promote the formation of a tridimensional network structure,
usually starting from the primary coacervate.
[0039] The formation of the coacervate network can easliy be ascertained e.g. by microscopic,
particularly dark-field, examination of the composition. The network can be seen as
a filamentous arrangement of aggregated droplets.
[0040] The coacervate network formation will occur provided water is used in a level in
the range of from 10% to 50%. This formulation parameter is expressed in the weight
ratio of the total ingredients to water as being in the range of from 1:1 to 9:1.
The term "total ingredient" stands for the sum of all substances inclusive of surface-active
agents, soaps, solvents, hydrotropes and organic and inorganic neutralizing agents.
[0041] The pH can have an adverse impact on the formation of the coacervate network. Under
highly alkaline conditions e.g. pH above 10 the network formation can become more
difficult, particularly if inorganic bases such as sodium or potassium hydroxide are
used for pH adjustment. The use of organic bases, such as amines or substituted amines,
is less damaging in this respect and some coacervate network formation can occur even
under conditions of high alkalinity e.g. around pH 11.
[0042] The preferred compositions of this invention have a pH, measured "as is" and at 20°C,
in the range from 6.0 to 10.
[0043] A preferred aspect of this invention relates to liquid detergent compositions which
are essentially free of conventional water-soluble polyphosphate builders, having
a pH in the range from 7 to 9 ("as is" -20°C). The term "water-soluble" qualifies
the dissolution of the particular polyphosphate in the total liquid detergent. More
than subadditive levels, e.g. above 2%, of composition-soluble polyphosphates can
inhibit the formation of the coacervate network because of excessive alkalinity and
increase of ionic strength. It is understood that composition-insoluble polyphosphate
salts can be stably incorporated with the aid of the wine cellar structure as explained
hereinafter.
[0044] The compositions of this invention can be prepared by a variety of mixing techniques
whereby the formation of the coacervate network can easily be ascertained. In a particularly
simple and easy mixing sequence, the non-soap anionic surface-active agents are added,
under mixing, to an aqueous solution of the nonionic and anionic cellulose ethers,
preferably at a temperature in the range from 15°C to 30°C. The resulting solution
contains the primary coacervate droplets. The remainder of the anionic surfactants
is thereafter added, under mixing, to the solution containing the primary coacervate.
The nonionic surface-active agents are subsequently added under mixing. The pH of
the solution throughout the mixing sequence shall be maintained above 6, usually in
the range from 7 to 9. pH adjustments are made at the end of the sequence.
[0045] Solvents, pH regulating agents and other additives and optional ingredients can be
added after the primary coacervate is formed or at the end of the mixing operation.
Conventional minor additives inclusive of dyes, perfumes, brightners, can frequently
be added at the end of the mixing process, i.e., after the addition of the nonionic
surface-active agents.
[0046] The compositions of this invention can contain, in addition to the essential ingredients
described hereinbefore, a series of conventional liquid detergent composition additives
in the art established levels for their known functionality.
[0047] These conventional liquid detergent additives are, unless indicated differently,
usually employed in levels below 5%. Examppes of the like additives which are well
compatible with the claimed compositions include: enzymes, polyacids, suds regulants,
opacifiers, anti-oxidants, bactericides, dyes, perfumes, brightneners, co-surfactants,
photoactivators, incrusation inhibitors, corrosion inhibitors, enzyme-stabilizers
or detergent builders.
[0048] Detergent enzymes generally aid and augment the removal of specific stains. Suitable
enzymes can be represented by proteases, amylases, lipases, glucose oxidases or mixtures
thereof. Proteases and/or amylases are preferred in the claimed liquid concentrated
compositions. They are frequently employed in a level from 0.01 % to 1 %. Mixtures
of proteases and amylases can usually contain from 0.05% to 0.8% proteases and from
0.001 % to 0.2% alpha-amylases.
[0049] Another preferred additive is represented by a polyacid or mixture of polyacids in
an amount from 0.05% to 2%.
[0050] Preferred polyacid species for use herein can be represented by organo-phosphonic
acids, particularly alkylenepolyamino-polyalkylene phosphonic acids such as-ethylene
diamine tetramethylenephosphonic acid, hexamethylene diaminetetramethylenephosphonic
acid, diethylene triaminepentamethylene-phosphonic acid, and aminotrimethylenephosphonic
acid or the salts thereof. These organophosphonic acids/salts are preferably used
in an amount from 0.1 %-0.8%. A non-phosphonated polyacid suitable for use include
ethylenediaminetetraacetic acid and diethylene triamine pentaacetic acid.
[0051] The beneficial utilization of the claimed compositions under various usage conditions
can require the utilization of a suds regulant. While generally all detergent suds
regulants can be utilized preferred for use herein are alkylated polysiloxanes, such
as dimethylpolysiloxane also frequently termed silicone, self emulsifiable silicones
as e.g. known from German Patent Application DE-OS 26 46 057. The silicones are frequently
used in a level not exceeding 0.5%, most preferably between 0.01 % and 0.2%.
[0052] It can also be desirable to utilise opacifiers inasmuch as they contribute to create
a uniform appearance of the concentrated liquid detergent compositions. Examples of
suitable opacifiers include: polystyrene commercially known as Lytron 621
0 manufactured by Monsanto Chemical Corporation. The opacifiers are frequently used
in an amount from 0.3% to 1.5%.
[0053] The compositions herein can also contain conventional antioxidants for their known
utility, frequently radical scavengers, in the art established levels i.e. 0.001%
to 0.25% (by reference to total composition). These antioxidants can be introduced
in conjunction with the fatty acid, especially the unsaturated fatty acid. While many
suitable antioxidants are readily known and available for that purpose especially
preferred for use in the compositions herein are: 2,6 ditertiary butyl-p-cresol, more
commonly known as butylated hydroxytoluene, BHT, and 2-tertiarybutyl-4-hydroxyanisole
or 3-tertiarybutyl-4-hydroxyanisole more commonly known as BHA or butylated hydroxyanisole.
Other suitable antioxidants are: 4,4'thiobis(6-tert-butyl-m-cresol) and 2-methyl-4,6-dinonyl
phenol.
[0054] In addition to the essential non-ionic/anionic surface-active mixture, the compositions
herein can comprise additive levels, usually below 5%, of co-surface-active agents
such as: nonionics other than ethoxylated species, zwitterionics, semipolar nonionics;
and cationic surface-active agents. Examples of suitable semipolar nonionics include
amine oxides, phosphone oxides and sulfoxides containing at least one C
12-C
14 alkyl group. Coconutalkyldimethyl amine oxide in a level of from 0.2 to 2% can be
particularly useful inasmuch as, in addition to detergency, it can provide soil release
properties. Cationic surfactants can also be utilized beneficially in the compositions
herein, usually in a level in the range from 0.5% to 4%. Suitable cationic surfactant
species include C
10―C
16 alkyl trimethylammonium salts.
[0055] The compositions herein can also contain as an optional ingredient from 0.0001% to
0.2% of a photoactivator. Suitable photoactivators are described in European Patent
No. 0 026 744, granted May 5, 1982.
[0056] Suitable incrustation/decrustation inhibitors can be added to improve the appearance
of used soiled textiles. They are frequently used in levels ranging from 0.5% to 2%.
A well-known example of such a "crustation" inhibitor is a copolymer containing maleic
acid and (meth)-acrylic acid monomers, as more fully described in European Patent
Application 82.200602.9.
[0057] The compositions herein can also contain additive levels (0.01%―0.3%) of particular
aminosilanes with a view to improve machine compatibility, particularly in relation
to enamel-coated surfaces. Suitable amino-silanes are disclosed in EP―A―0.075.988.
[0058] Suitable enzyme stablizers for use herein include short chain carboxylic acid, most
preferably salts of formic acid, in levels of 0.1% to 3%, and subadditive levels of
water-soluble Ca-salts. The utilization of these stabilizers is described in U.S.
Patent 4.287.082 of September 1, 1981.
[0059] The claimed compositions can further contain composition-soluble detergent builders.
Organic detergent, usually sequestering, builders are preferred although low levels
of inorganic builders can be used provided they are soluble in the total detergent.
Specific examples of suitable organic detergent builders include monomeric polycarboxylates
such as citric acid; carboxymethyloxysuccinic acid; nitrilotriacetic alkali metal,
salts thereof. Polymeric carboxylate builders inclusive of polyacrylate and polyhydroxyacrylate
can also be used. The optional builder component can be used in the claimed compositions
in levels from 2% to 10%.
[0060] Further, the claimed compositions can contain a series of useful detergent additives
which could up to now not be used effectively in the like liquid detergent compositions
because of insufficient storage stability, deactivation, flocculation, sedimentation
and other phenomena which were known to adversely affect their effectiveness. The
like additives are usually employed in levels of from 1 % to 10%, preferably 2%―6%.
[0061] It is believed that these further additives can be stably incorporated with the aid
of the tridimensional network obtained from the combiend use of the nonionic and anionic
cellulose ethers. This structure in fact resembles a fairly regular geometric arrangement
of void spaces which can be filled up with marginally compatible, usually composition-insoluble
ingredients. The network properties are such that the insoluble ingredients are kept
within the void spaces without being subject to phase separation, frequently as a
result of coagulation, sedimentation, creaming, etc.
[0062] Examples of ingredients which can be stably incorporated in the claimed compositions
with the aid of the coacervate network include water-insoluble ingredients and composition-insoluble
ingredients which have a non-negligible water-solubility. The terms "water-insoluble"
and "composition-insoluble" as used herein stand for solubilities below 0.1% in water
and the composition respectively. These ingredients shall have a particle size in
the range from 1 µ · meter to 100 u- meters preferably from 1-20 u- meters. Water-insoluble
ingredients can be represented by inorganic builders such as Zeolite A having the
formula Na
l2 (AlO
2·SiO
2)
12·27H
2O; Zeolite X: Na
86 (AlO
2)
86(SiO
2)
106 · 264H
20; and Zeolite P(B): Na
6(AlO
2)
6(SiO
2)
10 · 15H
20. These zeolites have frequently primary particle sizes of from 1-6 µ · meters.
[0063] Other examples of insoluble additives are suds depressors such as hydrophobic silica,
microcrystalline waxes, and fabric treatment/softening agents such as smectite clays.
[0064] Composition-insoluble ingredients can also include inorganic builders such as salts
of pyrophosphates, anti-corrosion agents e.g. sodium aluminate, particularly upon
use of this aluminate in neutral to mildly alkaline compositions, oxygen-bleach activators
such as tetra-acetylethylene diamine (TAED), oxygen bleaches, e.g., the alkaline earth
metal salts of perborates, antibactericides, immobilized enzymes and homopolymeric
and copolymeric additives such as polycarboxylates having sequestrant and anti-redeposition
functionalities.
[0065] Another class of composition-insoluble ingredients that can be stably incorporated
herein includes coated, especially micro-encapsulated, additives such as enzymes,
bactericidal agents, bleaches and activators therefore, perfumes, dyes, suds regulant
anti-corrosion agents and more in general any kind of desirable additives which heretofore
were not compatible with concentrated liquid detergent compositions.
[0066] The following liquid detergents were prepared by mixing the individual ingredients
in the listed proportions thereby using the method set forth in Claim 10.
[0067] These detergent compositions were evaluated in parallel, for coacervate network formation
ascertained by microscopic examination, and storage stability (room temperature, 1
week) with the following results.
[0068] The above results demonstrate the benefits derived from the compositions in accordance
with this invention vs. closely related prior art compositions. The results high-light
the claim criticalities -Composition A absence of AC; Composition B absence of nonionic
ethoxylate; Composition C ratio total ingredients: water below 1:1.
[0069] Additional liquid compositions of this invention having the listed formulae were
prepared thereby using the techniques of Examples I-V.
[0070] The above compositions which contain the coacervate network exhibit excellent storage
stability characteristics.
[0071] Additional liquid detergents were prepared having the compositions below.
Additives
(a) Hydrophobic silica: Quoso WR50® from Philadelphia Quartz Company-Particles size
mean average: 5 p - meters
(b) Zeolite A: Na12 (SiO2 · AlO2)12 · 27H20; particle size; 2―5 µ · meters
(c) Silicone oil: polydimethylsiloxane-DB 100® supplied by Dow-Corning-predispersed
in nonionic surfactant with droplet size 50 µ · meters
(d) Tetra-acetylenediamine: particle size mean of 60 µ · meters.
(e) Bentonite clay: particle size mean of 10 µ · meters
(f) Sodium aluminate powder: supplied by Dynamit Nobel, particle size: 50 µ · meters
(g) Tetrapotassium pyrophosphate: particle size mean of about 70 p - meters.
[0072] Identical levels of the listed insoluble additives were added to Composition XIII
of this invention, and to a substantially identical composition except that it did
not contain the coacervate forming mixture of CMC and AC, termed Reference D. Stability
readings (one week; room temperature) are summarized below.
[0073] These comparative results confirm the unusual benefits derivable from the inventive
compositions.
1. Eine wässerige, homogene, flüssige Reinigungsmittelzusammensetzung, enthaltend
anionische grenzflächenaktive Mittel, nichtionische grenzflächenaktive Mittel, Carboxymethylcellulose
und gegebenenfalls herkömmliche Bestandteile für derartige Zusammensetzungen, dadurch
gekennzeichnet, daß sie:-
0,1 Gew-% bis 3 Gew.-% eines Koazervats von gegebenenfalls hydroxylierter C1―C4-Alkylcellulose (AC) und Carboxymethylcellulose (CMC) in einem Gewichtsverhältnis
von CMC:AC von 6:1 bis 1:4;
mehr als 20 Gew.-% eines Gemisches der anionischen und der nichtionischen grenzflächenaktiven
Mittel, wobei das nichtionische grenzflächenaktive Mittel mehr als 3 Gew.-% darstellt,
und wobei das Gewichtsverhältnis von anionischem grenzflächenaktivem Mittel zu nichtionischem
grenzflächenaktivem Mittel im bereich von 1:1 bis 8:1 liegt; und
mehr als 10 Gew.-% Wasser enthält, wobei das Gewichtsverhältnis der gesamten Bestandteile
zu Wasser 1:1 bis 9:1 beträgt.
2. Die Zusammensetzung nach Anspruch 1, wobei das Gewichtsverhältnis von CMC zu AC
im Bereich von 3:1 bis 1:1 liegt.
3. Die Zusammensetzung nach Anspruch 1, welche einen pH-Wert, gemessen "so wie sie
ist" bei 20°C, von 6,0 bis 10 aufweist.
4. Die Zusammensetzung nach Anspruch 1, wobei das AC-CMC-Koazervat 0,5 Gew.-% bis
1,5 Gew.-% ausmacht.
5. Die Zusammensetzung nach Anspruch 1, wobei wenigstens 5 Gew.-%, berechnet auf Basis
der Reinigungsmittelzusammensetzung, des anionischen grenzflächenaktiven Mittels durch
ein anionisches Nichtseifen-grenzflächenaktives Mittel repräsentiert wird.
6. Die Zusammensetzung nach Anspruch 1, wobei das Verhältnis der anionischen zu nichtionischen
grenzflächenaktiven Mitteln im Verhältnisbereich von 1:1 bis 4:1 liegt.
7. Die Zusammensetzung nach den Ansprüchen 1 und 5, wobei das Gemisch der anionischen
und der nichtionischen grenzflächenaktiven Mittel 25 Gew.-% bis 60 Gew.-% darstellt,
und wobei das nichtionische grenzflächenaktive Mittel ein ethoxyliertes, nichtionisches
grenzflächenaktives Mittel ist, das eine Hydrophil-Lipophil-Bilanz (HLB) im Bereich
von 9 bis 15 hat, und das anionische Nichtseifengrenzflächenaktive Mittel ein C,o-C,3-Alkylbenzolsulfonat ist.
8. Die Zusammensetzung nach Anspruch 1, enthaltend ein dreidimensionales Koazervatnetzwerk
und 1 Gew.-% bis 10 Gew.-% von in der Zusammensetzung unlöslichen Reinigungsmittelzusätzen
mit einer Teilchengröße im Bereich von 1 um bis 100 um.
9. Die Zusammensetzung nach Anspruch 1, enthaltend zusätzlich:
0,01 Gew.-% bis 1 Gew.-% eines Gemisches von Proteasen und a-Amylasen;
0,05 Gew.-% bis 2 Gew.-% einer Polysäure;
bis zu 5 Gew.-% an nichtionischen, semipolaren nichtionischen und kationischen kogrenzflächenaktiven
Mitteln; und
0,1 Gew.-% bis 3 Gew.-% an Salzen der Ameisensäure.
10. Ein Verfahren zur Herstellung der wässerigen, homogenen, flüssigen Reinigungsmittelzusammensetzung
nach den Ansprüchen 1, 5 und 8, umfassend die folgenden Stufen:-
Zugeben des anionischen Nichtseifen-grenzflächenaktiven Mittels zu einer wässerigen
Lösung des Gemisches aus gegebenenfalls hydroxylierter C1-C4-Alkylcellulose und Carboxymethylcellulose, um dabei unter Mischen ein primäres Koazervat
zu bilden; gefolgt vom
Zugeben der übrigen anionischen grenzflächenaktiven Mittel unter Mischen; und anschließend
Zugeben der nichtionischen grenzflächenaktiven Mittel unter Mischen, um dabei ein
Koazervatnetzwerk zu bilden; mit der weiteren Maßgabe, daß während der Mischvorgänge
der pH-Wert über 6,0 gehalten wird.
1. Composition détergente liquide homogène et aqueuse contenant des agents tensioactifs
anioniques, des agents tensioactifs non ioniques, de la carboxyméthylcellulose et
des ingrédients classiques facultutatifs pour ces compositions, caractérisée en ce
qu'elle contient:-
de 0,1 % à 3% en poids d'un coacervat d'alkyl(en C1―C4)-cellulose (AC), éventuellement hydroxylée, et de carboxyméthylcellulose (CMC), en
un rapport pondéral (CMC:AC) d'environ 6:1 à 1:4;
plus de 20% en poids d'un mélange des agents tensioactifs anioniques et non ioniques,
dans lequel l'agent tensioactif non ionique représente plus de 3% en poids et dans
lequel le rapport pondéral de l'agent anionique à l'agent non ionique est dans l'intervalle
de 1:1 à 8:1; et
plus de 10% en poids d'eau, le rapport pondéral de l'ensemble des ingrédients à l'eau
étant de 1:1 à 9:1.
2. Composition selon la revendication 1, dans laquelle le rapport pondéral de la CMC
à l'AC est dans l'intervalle de 3:1 à 1:1.
3. Composition selon la revendication 1, dont le pH, mesuré "tel quel" à 20°C, est
de 6,0 à 10.
4. Composition selon la revendication 1, dans laquelle le coacervat AC-CMC représente
de 0,5% à 1,5% en poids.
5. Composition selon la revendication 1, dans laquelle au moins 5% en poids, par rapport
à la composition détergente de l'agent tensioactif anionique sont représentés par
un agent tensioactif anionique non saponacé.
6. Composition selon la revendication 1, dans laquelle le rapport de l'agent tensioactif
anionique à l'agent tensioactif non ionique est dans l'intervalle de 1:1 à 4:1.
7. Composition selon les revendications 1 et 5, dans laquelle le mélange des agents
tensioactifs anioniques et non ioniques représente de 25% à 60% en poids, et dans
laquelle l'agent tensioactif non ionique est un agent tensioactif non ionique étoxylé
ayant une balance hydrophile-lipophile (HLB) dans l'intervalle de 9 à 15 et l'agent
tensioactif anionique non saponacé est un alkyl(en C10―C13)benzène-sulfonate.
8. Composition selon la revendication 1, contenant un réseau de coacervat tridimensionnel
et de 1 % à 10% en poids d'additifs détergents insolubles dans la composition ayant
une granulométrie dans l'intervalle de 1 pm à 100 pm.
9. Composition selon la revendication 1, contenant en outre:-
de 0,01 % à 1% en poids d'un mélange de protéases et d'a-amylases;
de 0,05% à 2% en poids d'un polyacide;
jusqu'à 5% en poids d'agents co-tensioactifs non ioniques semi-polaires non ioniques
et cationiques; et
de 0,1 % à 3% en poids de sels d'acide formique.
10. Procédé de préparation de la composition détergente liquide homogène et aqueuse
selon les revendications 1, 5 et 8, comprenant les étapes suivantes:
l'addition de l'agent tensioactif anionique non saponacé à une solution aqueuse du
mélange d'alkyl(en Ci-C4)cellulose, éventuellement hydroxylée, et de carboxyméthylcellulose, pour former ainsi,
sous agitation, un coacervat primaire; suivie de
l'addition, sous agitation, du reste des agents tensioactifs anioniques; et ensuite
de
l'addition, sous agitation, des agents tensioactifs non ioniques, pour former ainsi
un réseau de coacervat, à condition que, en outre, pendant les opérations de mélange,
le pH soit maintenu à une valeur supérieure à 6,0.