JPH0657839B2 - Liquid detergent composition containing organofunctional polysiloxane - Google Patents

Abstract

Liquid detergent compositions containing additive levels of organo-functional polysiloxanes are disclosed. The siloxanes are derived from poly-di-short-alkyl siloxanes by substituting part of the alkyl moieties by specific organo-functional groups, preferably amino-groups, with the proviso that the degree of substitution is in the range from 0.01 - 0.07. The liquid compositions herein unexpectedly provide through-the-wash softening benefits comparable to what can be obtained from the utilization of conventional cationic rinse-softeners.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to liquid detergent compositions containing small amounts of certain organofunctional polydialkylsiloxanes. More specifically, the composition comprises conventional ingredients such as surfactants, liquid carriers and optionally incorporated ingredients such as detergent builders, enzymes and foam control agents, and small amounts of organofunctional polydishort chain alkyl siloxanes. Become. The latter component unexpectedly provides desirable through-the-wash fabric benefits such as softness. Preferred siloxanes include amino derivatives. The requisite siloxanes are further characterized by a degree of substitution in the range 0.01 to 0.7.

In addition to softening, the through-the-wash fabric benefits provided by the composition are often perceived by antistatic, ease of ironing and anti-wrinkle benefits. It has been established, on a modest basis, that at least, contrary to a fixed prejudice, the essential siloxane components do not adversely affect the general fabric cleaning compatibility of the composition. The liquid composition of the present invention is optionally a builder (mostly P).
It can be divided into an encapsulating composition and a substantially builder-free composition. Both types of compositions will yield fabric handling benefits. Selective preference can result from the combined use of the present siloxanes with anionic surfactants.

There is a wide variety of prior art relating to the wide range of silicon / polydialkylsiloxane fabric treatment applications. Such siloxanes have found widespread commercial application, for example, in detergent foam control function. Silicon polymers have also found widespread application in the textile industry, providing fibrous properties such as flexibility, waterproofness and ironability. With that in mind,
Silicon polymers are applied to the fabric (in the textile industry) either during the manufacture of the fabric or during the make-up, in the form of relatively thick dispersions or solutions by either padding or spraying. Often mixtures of organofunctional polydialkylsiloxanes are used, especially for long-lasting flexibility, waterproofing or other benefits. The fabric is then treated with a catalyst or heated to effect crosslinking or curing of the silicone polymer.

West German Patent No. 27 54 504 and U.S. Patent No. 4,247,5
No. 92 discloses a treating agent consisting of a polydimethylsiloxane containing diaminoalkyl groups which imparts flexibility to natural and synthetic fabrics.

JP-A-54-131096 relates to a treating agent composed of a mixture of a polydimethylsiloxane having an NHR group and a polydimethylsiloxane having a hydroxy end group, which imparts flexibility to an acrylic. The fabric is spray coated and then heat cured.

West German Patent No. 20 16 095 uses polydimethylsiloxanes containing pendant epoxy groups that impart flexibility and smoothness to synthetic organic fabrics.

EP 058 493 describes an organopolysiloxane containing a diaminoalkyl group and a polyoxyalkylene group and an organopolysiloxane containing a carboxylic ester group or an organopolysiloxane containing an epoxy group and a polyoxyalkylene group. Processing agent mixture. The mixture is added by spraying and processed to cure. It is said to give flexibility, anti-wrinkle and long lasting antistatic benefits.

West German patent application DOS 26 31 419 relates to a fabric rinse softening composition containing a fabric-adhering cation component and optionally an amino-substituted polydimethylsiloxane. The mixture is applied as an aqueous dispersion.

The use of polydimethylsiloxane foam control agents in liquid detergents is known from EP 0 028 865. U.S. Pat. No. 4,075,118 discloses the use of emulsified polydimethylsilicon for foam control purposes.

The possibility of using polydimethylsilicone for defoaming in granular detergents is known from DOS 23 38 468.

It is also known that the incorporation of polydimethylsiloxane foam control agents into detergents can adversely affect fabric cleaning benefits.

Certain organofunctional polydialkylsiloxanes, preferably amino-substituted compounds, are preferably incorporated into liquid detergents to provide generally significant benefits, such as through-the-wash softening and other fabric handling enhancements. Has now been found. The essential tools required to achieve these unexpected properties are described below.

SUMMARY OF THE INVENTION The present invention is based on the discovery that liquid detergent compositions containing two-component and organofunctional siloxanes can now be formulated that can simultaneously provide fabric handling benefits such as fiber cleaning and softness. .

In particular, the composition comprises: (a) 5 to 70% by weight of a surfactant selected from the group of anionic surfactants, nonionic surfactants, amphoteric surfactants, zwitterionic surfactants and mixtures thereof. , (B) a liquid carrier, and (c) if desired it contains conventional detergent additives such as detergent builders, enzymes and foam regulators, which are (d) of the general formula [In the formula, L is R or _Where R is C _1-4 alkyl, n is an integer from 1 to 6 and Z is (In the formula, X and Y are independently -H, -C _1-30 alkyl, -C ₆ aryl, -C _5-6 cycloalkyl, -C.
_1-6 —NH ₂ , selected from —CO—R),
However, nitrogen is quaternized Where W can be selected from X or Y, or Z is (Wherein, P and M are -COOH, a ^-CO-NR _{1 2} or -CO-OR ^1, and ^{R 1} is hydrogen or C
_{1 to 2} alkyl), provided that the degree of substitution, ie C
The molar ratio of silicon carrying a substituent other than _{1 to 4} alkyl groups to the total silicon is in the range of 0.01 to 0.7] 0.05 to 5 parts by weight of an organic functional poly-di C _{1 to 4} alkylsiloxane cloth treating agent % Is included.

Amino-substituted siloxanes having a degree of substitution in the range of 0.05 to 0.5 are especially preferred.

In one preferred formulation of the invention, the substituted siloxane is incorporated into a liquid detergent composition containing an inorganic builder salt such as (poly) phosphate.

In another preferred composition aspect of the invention, the siloxane is incorporated into a concentrated liquid composition that is substantially free of builders.

DETAILED DESCRIPTION OF THE INVENTION The present invention broadly relates to a liquid detergent composition comprising a surfactant, a liquid carrier, an organofunctional polydialkylsiloxane fabric treating agent, and, if desired, conventional detergent additives. These variations and other aspects of the invention are described below.

Unless otherwise specified, the “%” indication means “% by weight”.

Surfactant The first essential ingredient used in the composition of the present invention is an interface selected from the group of anionic surfactants, nonionic surfactants, amphoteric surfactants, zwitterionic surfactants and mixtures thereof. Represented by an activator. As used herein, the term nonionic surfactant includes semipolar nonionic surfactants.

Examples of suitable nonionic surfactants are described in European Patent Application No. 0028
No. 865, page 4, line 23 to page 5, line 10 and page 8, 1
It is disclosed from line 4 to page 9, line 4.

The disclosure of zwitterionic and amphoteric surfactants used in the present invention is also disclosed in European Patent Application No. 0028865, page 7, page 21.
Lines to page 8, line 13 may be found.

The anionic surfactants used in the present invention are represented by known synthetic and natural anionic surfactants that are known to be suitable for use in detergents and often find commercial application. Can be done. Suitable synthetic anionic surfactants are described in European Patent Application No. 0028865, page 5, lines 12-31. Examples of natural anionic surfactants used in the present invention have 10 carbon atoms in the alkyl chain.
It may be represented by saturated and unsaturated fatty acids having -20 or their alkali metal soaps, alkaline earth metal soaps and amine soaps or alkanolamine soaps. Preferred fatty acids / soaps have 12-18 carbons in the alkyl chain. Known examples of suitable fatty acid / soap for use in the present invention include natural coconut fatty acids contain most C ₁₂ acids and C ₁₄ acids,
And tallow fatty acids containing a mixture of saturated and unsaturated C ₁₆ and C ₁₈ fatty acids / soaps.

Surfactants are generally used in amounts of 5% to 70%. Surfactants can be varied over a wide range depending on the intended practical use of the composition and the quantitative, qualitative definition of the additional and optionally incorporated components, but two preferred formulations are (poly) It may be formulated depending on the presence of phosphate builder.

In the first preferred formulation of the present invention, a substantially builder-free liquid composition is contemplated. In this embodiment, the surfactant is often used in an amount of 25% to 55% and is a mixture of anionic and nonionic surfactants, more preferably anionic to nonionic surfactants. It is represented by a mixture of surfactants in a weight ratio of 4: 1 to 1: 4.

In a second preferred embodiment, the surfactant is 5% to 25%.
%, Preferably 5% to 15%, builder liquid detergent compositions are contemplated. The surfactant component is preferably represented by a mixture of anionic and nonionic surfactants, and the anionic surfactant is at least the sum of anionic and nonionic surfactants. 20% and represents at least 3% calculated on the detergent composition.

Such detergent compositions often contain from 5% to 30%, preferably 12% of detergent builders which can be represented by conventional detergent builders, many of which already find commercial application.
% To 25%. Well known examples of suitable builders are (poly) phosphates such as tripolyphosphoric acid, nitrilotriacetic acid (NTA), alkali metal salts of citric acid, often sodium salts and crystalline fully hydrated synthetically produced zeolites. It is a builder (particle size 0.1 to 10, preferably 0.1 to 4 μm). Suitable zeolite builders are zeolite A. X and P. Mixtures of detergent builders can also be used.

The composition may additionally contain a cationic surfactant as an optional ingredient. Cationic surfactant species suitable for use in the present invention are described in European Patent Application No.
No. 0028865, page 5, line 32 to page 7, line 21. Cationic surfactants can provide and / or enhance a wide range of fabric treatment benefits, such as cleaning, hand, and bactericidal benefits. These optionally incorporated cationic surfactants are added in amounts not exceeding 10% of the additive amount, for example the cumulative amount of anionic and nonionic surfactants as defined above, more preferably Used in amounts ranging from 1% to 5% of the detergent composition.

Liquid Carrier The composition further comprises a liquid carrier as another essential component,
It optionally contains a mixture of liquid carriers. The liquid carrier component can be represented by water and conventional liquid organic carriers. Non-limiting examples of such organic carriers include lower aliphatic alcohols having hydroxyl groups of 2 to about 6 and 1 to 3 carbon atoms; diethylene glycol and ethers of lower aliphatic monoalcohols having 1 to 4 carbon atoms and their It is a mixture.

Specific examples of liquid carriers are ethanol, n-propanol, isopropanol, butanol, 1,2-propanediol, 1,3-propanediol, n-hexanol; monomethyl ether, monoethyl ether, monopropyl ether and monobutyl ether and diethylene glycol. Is. Other organic solvents having relatively high boiling points and low vapor pressures can also be used provided they do not react with any of the other components present. The relative amount of liquid carrier required to guarantee the liquid state of the composition can vary depending on the qualitative and quantitative component parameters within a given composition. However, the appropriate choice of carrier is based on routine determination methods well known in the art.

Organofunctional Siloxane Essential organofunctional siloxane for use in the present invention is 0.
05% to 5%, preferably 0.1% to 3%, most preferably
It can be present in an amount of 0.15% to 1%. Use of less than 0.05% will no longer produce the benefits of the present invention to any significant extent, while formulation of more than 5% will not produce additional benefit commensurate (proportional) with volume increase. Will.

The organofunctional polydi C _1-4 alkyl siloxane component is stoichiometrically of the general formula [In the formula, L is R or _Where R is C _1-4 alkyl, n is an integer from 1 to 6 and Z is (In the formula, X and Y are independently -H, -C _1-30 alkyl, -C ₆ aryl, -C _5-6 cycloalkyl, -C.
_1-6 —NH ₂ , selected from —CO—R),
However, nitrogen is quaternized Where W can be selected from X and Y, or Z is (Wherein, P and M are -COOH, a ^-CO-NR _{1 2} or -CO-OR ^1, and ^{R 1} is hydrogen or C
_{1 to 2} alkyl), provided that the degree of substitution, ie C
The molar ratio of silicon carrying a substituent other than _{1 to 4} alkyl groups to total silicon is 0.01 to 0.7, preferably 0.02 to 0.3].
Get defined by

The siloxane component is preferably represented by an amino functional polydialkyl siloxane, which amino functional polydialkyl siloxane is often used in an amount of 0.1% to 3%, more preferably 0.15 to 1.0%.

The degree of substitution of preferred siloxanes, such as aminosiloxanes, can be expressed as the molar (partial) ratio of non-terminal silicon bearing substituents other than C _1-4 alkyl groups to total non-terminal silicon. The preferred substitution degree value of siloxane is 0.01 to 0.
It is in the range of 7, preferably 0.02 to 0.3. Although non-terminal substitution is preferred to enhance through-the-wash fiber adhesion, it is understood that siloxanes with substituted terminal silicon atoms can also be used.

In a preferred siloxane component of the present invention, n is 3 or 4, X and Y are independently _{hydrogen, -C 1 to 4 alkyl, -C 5 to 6} cycloalkyl and _-C 2 -NH
It is selected from ₂ .

Preferred organofunctional polydimethylsiloxanes are amino functional siloxanes such as:

Organofunctional siloxanes generally have a viscosity of 40 cSt to 100,000 cS
t, preferably 250 cSt to 2000 cSt. Of siloxane
Viscosity is based on Brookfield (BR
OOKFIELD ) Measured by viscometer (LV Digital)
It

Optional In addition to the essential ingredients, the composition may optionally contain a series of detergent ingredients for the purpose of improving the composition to allow for a particular application. These optionally formulated ingredients are in amounts technically established due to their known function,
It can be presented by virtually any substance known to be suitable for use in such compositions.

The builder-free composition or builder-containing composition of the present invention contains, in addition to the detergent builder, various sequestering agents having precipitation-inhibiting properties or anti-coating properties in various amounts, for example, 0.2% to 5%. Can be contained in an amount of%. Such further sequestrants include water-soluble copolymerization components such as polyacrylates, polymaleates and copolymerized carboxylates, such as unsaturated polyacids such as maleic acid or citraconic acid and methacrylic acid, acrylic acid, mesaconic acid. And obtained from copolymerization with a suitable polymerizable reaction partner such as methyl vinyl ether. Mixtures of such water-soluble detergent sequestrants can also be used.

Examples of other optional ingredients include detergent enzymes such as proteases, amylases, lipases and mixtures thereof, and stabilizers for such enzymes, soil suspending agents such as sodium carboxymethylcellulose and polyvinylpyrrolidone, Suds regulator, eg C
_16-22 fatty acids and methylated polysiloxanes, especially dimethylpolysiloxane. This silicon is preferably used in an amount of 0.01% to 0.4%.

Hydrotropes can also be used and are often desirable in builder compositions. Examples of suitable hydrotropes are water-soluble alkylaryl sulphonates having up to 3 carbon atoms in the alkyl radical, such as the sodium salts of xylene sulphonic acid, toluene sulphonic acid, ethylbenzene sulphonic acid and isopropylbenzene sulphonic acid.
Potassium salts, ammonium salts, and ethanolamine salts.

The composition may further contain brighteners, fragrances, dyes, bactericides, antioxidants, opacifiers, photoactive agents, fillers and the like.

Examples The following examples illustrate preferred formulations of the present invention and facilitate its understanding. Abbreviations for the individual components of the examples have the following meanings.

LAS: Sodium salt of linear dodecylbenzenesulfonic acid HLAS: Linear dodecylbenzenesulfonic acid TEAC _n AS: Triethanolamine coconut (C
_12-14) alcohol sulfates C _{x to y} EO _{n: C} ethoxylated with n moles of ethylene oxide _{x to y} alcohol DTPA: sodium salt of diethylenetriaminepentaacetic acid DETPMP: Diethylenetriamine penta methyl phosphonic acid C ₁₂ TMAC: dodecyltrimethylammonium chloride C _x-y (ED) _n S: sodium salt of C _x-y alcohol ethoxylated and sulfated with n moles of ethylene oxide DTMAC: ditallowdimethylammonium chloride TEPA-EO: ethoxylated with about 100 moles of ethylene oxide. tetra ethylene pentamine KTS: potassium toluene sulfonate STPP: sodium tripolyphosphate NTA: sodium salt C _n DEA of nitrilotriacetic acid: coconut diethanolamide following liquid detergent composition, following the following components It was prepared by mixing in a conventional manner. The amino-functional polysiloxane was incorporated directly into the liquid composition under agitation.

The compositions of Examples I and II were compared for through-the-wash flexibility with identical compositions A and B containing no amino-functional polydimethylsiloxane.

The test conditions were as follows.

Automatic drum washing machine MIELE423 1 washing cycle, heating up to 60 ° C, main washing only 3kg clean cotton load + test terry sample 1% product concentration in washing liquid Water hardness 0.308g / 1 (CaCO ₃ standard) washed and Line-dried terry swatches 9 points Scheff by a panel of two independent judges who work independently.
Compared by pairwise comparison technique using e-scale.
Differences were recorded in panel score units (psu) (positive is better performance) and the least significant difference (LS) with 95% confidence.
D) was also calculated.

The test results were as follows.

These results show the significant flexibility through the wash benefits that can be derived from the present compositions of Examples I and II vs. identical compositions A and B without aminofunctional polydimethylsiloxane.

A comparable fabric benefit is (N-cyclohexyl-4-amino-butyl-1) polydimethylsiloxane (Sil-
It can be ensured from said liquid detergent compositions I and II using the following proportions of the organofunctional siloxanes instead of I).

Yet another example of a substantially builder-free composition according to the present invention is as follows.

Examples of the builder-containing composition according to the present invention are as follows.

Claims (15)

[Claims] (A) 5 to 70% by weight of a surfactant selected from the group of anionic surfactants, nonionic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof. (B) a liquid carrier, and (c) in a liquid composition containing conventional detergent additives such as detergent builders, enzymes and foam control agents, if desired (d) a general formula [Wherein L is R or _Where R is C _1-4 alkyl, n is an integer from 1 to 6 and Z is (In the formula, X and Y are independently -H, -C _1-30 alkyl, -C ₆ aryl, -C _5-6 cycloalkyl, -C.
_1-6 —NH ₂ , selected from —CO—R), provided that the nitrogen is quaternized. Where W may be selected from X or Y, or Z is (Wherein, P and M are -COOH, a ^-CO-NR _{1 2} or -CO-OR ^1, and ^{R 1} is hydrogen or C
_{1 to 2} alkyl), provided that the degree of substitution, ie C
Organofunctional poly having a silicon to molar proportions of total silicon carrying a substituent other than _1-4 alkyl groups is in the range of 0.01 to 0.7] - di C _1-4 alkylsiloxane cloth treating agent A liquid detergent composition capable of providing desirable textile benefits such as softness, characterized in that it contains from 0.05 to 5% by weight. 2. A composition according to claim 1 wherein the siloxane is amino substituted. 3. A composition according to claim 1 in which the siloxane has a degree of substitution in the range 0.02-0.3. 4. A surfactant 25-55 selected from the group of (a) anionic surfactants, nonionic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof.
% By weight, (b) liquid carrier, and (c) conventional detergent additives such as enzymes and foam control agents, if desired, and (d) general formula [Wherein L is R or _Where R is C _1-4 alkyl, n is an integer from 1 to 6 and Z is (In the formula, X and Y are independently -H, -C _1-30 alkyl, -C ₆ aryl, -C _5-6 cycloalkyl, -C.
_1-6 —NH ₂ , selected from —CO—R),
However, nitrogen is quaternized Where W may be selected from X or Y, or Z is (Wherein, P and M are -COOH, a ^-CO-NR _{1 2} or -CO-OR ^1, and ^{R 1} is hydrogen or C
_{1 to 2} alkyl), provided that the degree of substitution, ie C
_1-4 alkyl molar ratio of silicon to total silicon carrying a substituent other than groups organofunctional Poriji C _1-4 alkylsiloxane cloth treating agent having a] in the range of 0.01 to 0.7 0. A substantially builder-free liquid detergent composition capable of providing desirable textile benefits such as softness, characterized in that it contains from 0 to 5% by weight. 5. A patent in which the surfactant is represented by a mixture of anionic and nonionic surfactants in a weight ratio of anionic surfactant to nonionic surfactant of 4: 1 to 1: 4. The composition according to claim 4. 6. A composition according to claim 4, wherein the siloxane is amino substituted. 7. A composition according to claim 4, wherein the siloxane has a degree of substitution in the range 0.02-0.3. 8. A siloxane having the following: n is 3 or 4, and X and Y are independently hydrogen, --C.
_1-4 alkyl, _-C5-6 cycloalkyl, _and-
A composition according to paragraph 4 claims characterized by being selected from C ₂ -NH _2. 9. The siloxane component is (N-cyclohexylamino-4-amino-butyl-1) polydimethylsiloxane, (ethylenediamino-N-butyl-1) polydimethylsiloxane, (N-dodecyl-4-amino-). Butyl-1-) polydimethylsiloxane, (4- (N, N-dimethylammonium) -butyl-1) polydimethylsiloxane, (5- (tallowamido) -4-carboxy-pentyl-1) polydimethylsiloxane The composition according to claim 4 or claim 5. 10. (a) 5 to 25% by weight of a surfactant selected from the group of anionic surfactants, nonionic surfactants, amphoteric surfactants, zwitterionic surfactants and mixtures thereof, b) a liquid carrier, (c) 5 to 30% by weight of a detergent builder, (d) if desired conventional detergent additives such as enzymes and suds modifiers, and (e) a general formula [Wherein L is R or _Where R is C _1-4 alkyl, n is an integer from 1 to 6 and Z is (In the formula, X and Y are independently -H, -C _1-30 alkyl, -C ₆ aryl, -C _5-6 cycloalkyl, -C.
_1-6 —NH ₂ , selected from —CO—R),
However, nitrogen is quaternized Where W may be selected from X or Y, or Z is (Wherein, P and M are -COOH, a ^-CO-NR _{1 2} or -CO-OR ^1, and ^{R 1} is hydrogen or C
_{1 to 2} alkyl), provided that the degree of substitution, ie C
_1-4 alkyl molar ratio of silicon to total silicon carrying a substituent other than groups organofunctional Poriji C _1-4 alkylsiloxane cloth treating agent having a] in the range of 0.01 to 0.7 0. A builder liquid detergent composition capable of providing desirable textile benefits such as softness, characterized in that it contains from 05 to 5% by weight. 11. The surfactant, which is 5 to 15% by weight, is represented by a mixture of anionic and nonionic surfactants, and the anionic surfactant is nonionic and nonionic. At least 20 in sum with ionic surfactants
A composition according to claim 10 which represents% by weight. 12. A composition according to claim 10 wherein the siloxane is amino substituted. 13. A detergent builder, which represents 12 to 25% by weight and is selected from alkali metal salts of polyphosphoric acid, citric acid and nitrilotriacetic acid and zeolites A, X and P having a particle size of 0.1 to 4 μm. The composition according to claim 10. 14. A siloxane having the following: n is 3 or 4, and X and Y are independently hydrogen, --C.
_1-4 alkyl, _-C5-6 cycloalkyl, _and-
A composition according to paragraph 10 claims characterized by being selected from C ₂ -NH _2. 15. The siloxane is (N-cyclohexylamino-4-amino-butyl-1) polydimethylsiloxane, (ethylenediamino-N-butyl-1) polydimethylsiloxane, (N-dodecyl-4-amino-butyl). −
Claims selected from 1) polydimethylsiloxane, (4- (N, N-dimethylammonium) -butyl-1) polydimethylsiloxane, (5- (tallowamido) -4-carboxy-pentyl-1) polydimethylsiloxane. 14. The composition according to paragraph 13 of the above.