JPH0449224A - Cleaning agent composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a detergent composition in which water-insoluble fine powder is stably dispersed.

[Prior art and problems to be solved by the invention] 2-Mercaptopyridine-N-oxide, which is useful as an anti-dandruff agent, a pearlizing agent, etc., is a typical example of a water-insoluble fine powder that is incorporated into hair and skin cleansers. polyvalent metal salt (hereinafter referred to as rMep
). Examples of the polyvalent metal of Mept include magnesium, barium, strontium, zinc, cadmium, tin, and zirconium, among which zinc salts are widely used.

By the way, for example, these Mepts have a solubility in water of the zinc salt (hereinafter abbreviated as "rZpt") of 25
Both of them are poorly soluble in water, with a concentration of 15 ppm at °C, and when these are added to detergents such as shampoo, the specific gravity of Zpt is 1.8, which is a large difference in specific gravity from the dispersion medium, so it becomes difficult to dissolve over time. Therefore, precipitation and separation of Zpt tended to occur, making it difficult to obtain a stable dispersion system.

As a means to prevent sedimentation and separation of water-insoluble fine powder such as Mept, for example, (1) increasing the viscosity of the dispersion medium at rest to make sedimentation less likely to occur, and (ii) adjusting the particle size of the water-soluble antibacterial particles. It is conceivable to make it very small so that Brownian motion becomes dominant, making it difficult for sedimentation to occur.

Methods based on the concept (i) include, for example, a method of adding a thickening polymer such as a cross-linked polyacrylate (Japanese Patent Publication No. 49-49117) and a method of adding an acrylic acid/acrylic acid ester copolymer. (Tokuko Showa 54-1
No. 6951), etc., but this method has the disadvantage that the types of surfactants that can be used to stably disperse the water-insoluble fine powder are limited.

Also, based on the idea of (u), the conventional Me
Mept (referred to as "microparticle MeptJ" in JJ), which has a very small particle size compared to pt, has been reported (Japanese Patent Publication Nos. 61-35186, 64-3193, and 4H
No. 60224676). However, this micronized Mep
t also easily aggregates due to mixing with salts such as surfactants, freezing, heating, etc., and the dispersion stability in detergents is still not fully satisfactory.

Furthermore, since there is a demand for cleaning agents for bacteria that are less irritating to the hair and skin, it is necessary to incorporate hypoallergenic surfactants and combinations of multiple anionic surfactants and nonionic surfactants. Although the systems of detergent compositions for use in combination are becoming more and more complex, the above-mentioned dispersion techniques have not been able to stably disperse water-insoluble fine powders in these complex systems.

Therefore, regardless of the type of anionic surfactant or nonionic surfactant that is frequently used as a cleaning agent component,
It has been desired to develop a cleaning composition in which water-insoluble fine powder can be stably dispersed.

[A means of promise to solve problems]

Therefore, the present inventors conducted extensive research to solve the above problems, and found that if water-insoluble fine powder is dispersed using an amphoteric polymer and a specific anionic copolymer, stable cleaning can be achieved even after long-term storage. The present invention was completed based on the discovery that a drug composition can be obtained.

That is, the present invention comprises the following components (a) to (6) (a) anionic surfactant and/or nonionic surfactant (b) water-insoluble fine powder (c) amphoteric polymer (d) carboxy group or sulfuric acid Detergent compositions containing anionic copolymers having groups are provided.

Examples of the anionic surfactant used as component (a) in the cleaning composition of the present invention include the following (1) to 0
Examples include those indicated by υ.

(1) Straight chain or branched chain alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 16.

(2) Polyoxyalkylene alkyl ether sulfate having a linear or branched alkyl group with an average carbon number of 8 to 20 and an average of 0.5 to 8 moles of ethylene oxide and/or propylene oxide added to each molecule. salt.

(3) An alkyl sulfate ester salt having a straight or branched alkyl group having an average carbon number of 10 to 20.

(4) Olefin sulfonate having an average of 10 to 20 carbon atoms in one molecule.

(5) Alkanesulfonate having an average of 10 to 20 carbon atoms in one molecule.

(6) A fatty acid salt having a linear or branched saturated or unsaturated hydrocarbon chain having an average carbon number of 10 to 20.

(7) An alkyl ethoxycarboxylate having a linear or branched alkyl group having an average carbon number of 10 to 20 and having an average of 0.5 to 8 moles of ethylene oxide added to each molecule.

(8) The following general formula (I> or (II>) with blank space R'-C-C1f-CH2-C-OM'
(1) So, M'1i'-C-CI42~C1(-C-[IM'
(II')SO,M' [In the formula, R1 represents R'-0-C)I2C)IOtr- or R'C0NHfcH=cHOt7-, (R' is a straight chain or branched chain having 8 to 22 carbon atoms P is the same or different and represents a hydrogen or methyl group, R4 represents a straight or branched alkyl group or alkenyl group having 7 to 21 carbon atoms, and ! is a number of 0 to 20. ), Ml represents a hydrogen atom or a cation that forms a water-soluble salt selected from alkali metals, alkaline earth metals, ammonium and organic ammonium].

(9) The following general formula (III) ^-P-OX' (II[) [in the formula,
A is R50 blue [:H2CH Kanoi or R5CONH Yun C1
(, CHO?-(Here, R5 is a linear or branched saturated or unsaturated hydrocarbon group, R3 is a hydrogen atom or a methyl group, m is a number from 0 to 6, and n is a number from 1 to 6. A phosphoric acid ester salt-based activator represented by the following formula: B represents 10X' or 8, and X' and x2 each represent a hydrogen atom or a counter ion.

Amino acid-based surfactant represented by the following formula % Formula %: [In the formula, R4 represents an alkyl group or alkenyl group having 7 to 21 carbon atoms, and x1 and x2 each represent a hydrogen atom or a counter ion] agent.

(b) The following formula % formula % [In the formula, R4 represents an alkyl group or alkenyl group having 7 to 21 carbon atoms, R6, R7 and R8 represent amino acid side chains,
n represents a number from 1 to 6, and Xl represents a hydrogen atom or a counter ion.] An acylated polypeptide surfactant represented by the following.

The counter ions represented by xl and Examples include alkanolamine bases having 1 to 3 alkanol groups having 2 to 3 carbon atoms, such as triethanolamine and triisopropylamine.

Among these anionic surfactants, (1), (2) or (8) are particularly preferred.

Examples of nonionic surfactants include the following (1) to (1).
Examples include those shown in 1.

(1) Polyoxyethylene alkyl or alkenyl ether having an alkyl group or alkenyl group having an average carbon number of 10 to 2 o and to which 1 to 20 moles of ethylene oxide is added.

(2) It has an alkyl group with an average carbon number of 6 to 12, and 1 to
Polyoxyethylene alkylphenyl ether with 20 moles of ethylene oxide added.

(3) A polyoxypropylene alkyl or alkenyl ether having an alkyl group or alkenyl group having an average carbon number of 10 to 2 o and to which 1 to 20 mol of propylene oxide is added.

(4) Poliocybuterene alkyl or alkenyl ether having an alkyl group or alkenyl group having an average carbon number of 10 to 2 o and to which 1 to 20 mol of butylene oxide is added.

(5) A nonionic surfactant having an alkyl group or an alganyl group with an average carbon number of 10 to 2 o and adding a total of 1 to 30 moles of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide (ethylene oxide and propylene oxide). oxide or butylene oxide is 0.1/9.9 to 9.910.1).

(6) Higher fatty acid alkanolamide or its alkylene oxide adduct represented by the following formula.

In formula c, R4 has the above-described meaning, R3 represents a hydrogen atom or a methyl group, 0 represents an integer of 1 to 3, and p represents an integer of 0 to 3.] (7) Average carbon number 5 to 20 Sucrose fatty acid ester consisting of fatty acid and sucrose.

(8) Fatty acid glycerin monoester consisting of a fatty acid having an average carbon number of 10 to 20 and glycerin.

(9) An alkyl glycoside having a straight or branched alkyl, alkenyl or alkylphenyl group having an average carbon number of 6 to 20.

A sugar amide surfactant having a straight or branched alkynovalkenyl or alkylphenyl group having 5 to 17 carbon atoms.

Among these nonionic surfactants, (1), (7) or (9) are particularly preferred.

Further, the anionic surfactant and the nonionic surfactant may be used alone or in combination. When an anionic surfactant and a nonionic surfactant are used in combination, the mixing ratio is preferably 1/9 to 9/1. In addition, component (a)
is preferably blended in the detergent composition in an amount of 5 to 30% by weight (hereinafter simply expressed as %).

The water-insoluble fine powder of component (b) is distilled water at 25°C.
Those having a solubility in 0d of 0.18 or less, specifically those that are blended into cleaning agents as disinfectants, abrasives, pigments, etc., such as Mept, titanium oxide, calcium carbonate,
Examples include fish scales, fatty acid glycol esters, and diatomaceous earth. Among these fine powders, Mept is particularly preferred, and its average particle size is preferably 5μ or less, and its particle size distribution is preferably 50% or more of particles with a particle size of 0.2μ or less, and more preferably a particle size of 0.5μ or less. ~1.0μ 15% or less, 1.
Particularly preferred are those with a particle size of 0μ or more and 2% or less.

The blending amount of these components (b) is preferably 0.01 to 10%.

These fine powders have various effects, for example, for hair washing,
It is added to prevent dandruff, itching, etc., to add flexibility and retention to the hair, or to give a pearl tone to improve the appearance.

Examples of the amphoteric polymer of component (c) include an amphoteric polymer having both a quaternary ammonium group as a cationic group and a carboxyl group as an anionic group, and the average molecular weight thereof is 500 to 6,000.000. It is preferable that Particularly preferred are amphoteric polymers having the following structural units and an average molecular weight of 110.000 to 1,000.000.

R’　　　　　　　R -t-CI1. C-10-2 CH2C.

0-Rl2-N-R14-Co.

[In the formula, R9 and R each represent a hydrogen atom or a methyl group, R10 represents a straight chain or branched alkyl group having 1 to 18 carbon atoms, and R12 and R14 represent an alkylene group having 1 to 4 carbon atoms. R13 represents a hydrogen atom, a methyl group, or an ethyl group, and q and r represent numbers that make the average molecular weight of the amphoteric polymer 10.000 to 1.000.000. However, r=o is not true. ] A particularly preferred commercially available amphoteric polymer is Yukaformer (Mitsubishi Yuka). Component (c) is 0.01 to 0 with respect to water-insoluble fine powder (b).
．． It is preferable to use 1 times the amount by weight.

The anionic copolymer of component (d) has a molecular weight of 5
00 to 6.000.000, such as homopolymers or copolymers of acrylic acid, methacrylic acid or crotonic acid; carboxypolyacrylamide:
Polymer of polyhydroxycarboxylic acid; unsaturated α selected from maleic acid, fumaric acid, itaconic acid, citraconic acid, phenylmaleic acid, benzylmaleic acid, dibenzylmaleic acid, ethylmaleic acid, and acid anhydrides thereof
, polymers of β-dicarboxylic acids; ethylene, vinyl esters, allyl esters, methallyl esters, vinyl ethers, vinyl halides, phenylvinyl derivatives, acrylic acid or its esters, methacrylic acid or its esters, cinnamic acid esters, Examples include half-ester and half-acids obtained by polymerization or copolymerization of compounds containing >C=Ct+ groups selected from the group consisting of acrylamide or methacrylamide, α-olefins, and N-vinylpyrrolidone, which may be polymerized. Among these, acrylic acid, methacrylic acid, or copolymers of esters thereof are particularly preferred. These components (d) are water-insoluble fine powders (b
) is preferably used in an amount of 0.01 to 10 times by weight.

Further, in addition to the above-mentioned essential components, the cleaning composition of the present invention may contain optional components that are commonly used.

These optional ingredients include, for example, solubilizing agents such as propylene glycol, glycerin, and urea; viscosity modifiers such as ethyl alcohol, ifpropyl alcohol, hydroxyethyl cellulose, methyl cellulose, and higher alcohols; antibiotics; antiseborrheic substances; sulfur , salicylic acid, enzymes, and other keratolytic or keratin softening substances; deodorants, lotion agents, fragrances, pigments, ultraviolet absorbers, antioxidants, preservatives, and the like.

The cleaning composition of the present invention can be prepared by a conventional method, but first, component (b) is treated with component (c), then this is treated with component (d), and the resulting product ( Preferably, it is prepared by adding component (a) to a polymer-coated powder and dispersing it. All components (a) to (d) are preferably used as an aqueous solution or an aqueous mixture.

The detergent composition of the present invention thus obtained has water-insoluble fine powder stably dispersed therein, and therefore can be used as shampoo, body shampoo, dishwashing detergent, etc.

[Effect of ribbing]

The present invention makes it possible to stably disperse water-insoluble fine powder such as Mept for a long period of time in cleaning agents with a wide range of applications, such as anionic surfactants, nonionic surfactants, and mixtures thereof, which have been frequently used in recent years. It has become possible.

〔Example〕

Next, the present invention will be explained with reference to Examples.

Example 1 A cleaning composition having the composition shown in Table 1 was prepared and heated at 40°C.
After storage for 2 weeks, dispersion stability was evaluated by visual observation. The results are shown in Table 1. The manufacturing method and evaluation criteria for the cleaning composition are as follows.

(Manufacturing method) Zinc pyrithione was dispersed in a 20% aqueous solution of an amphoteric polymer, and this was added to a 50% aqueous solution of an anionic copolymer. Next, this was added to a 25-30% surfactant aqueous solution without stirring, and a fragrance, a pigment, and a pH adjuster were added.

(Evaluation criteria) ○: Uniformly dispersed ×: Precipitation is observed Below margin Example 2 (Composition) Shampoo (%) ■Polyoxyethylene (2,5) uralyl ether sulfate Na salt ■Coconut oil fatty acid jetanolamide■ Zinc pyrithione (same as in Example 1, as a 50 wt% dispersion) The dispersion stability of fine particles was good for Zinc Pyrithione.

Example 3 Shampoo (composition) Good anti-dandruff effect (%) ■Ethylene glycol monostearate■Fragrance
0.5 ■
Pigment Trace amount■Citric acid Trace amount■Water
Balance (manufacturing method) ■ was dispersed in the aqueous solution of ■, and this was added to the aqueous solution of ■. Next, this dispersion liquid was added to a homogeneous solution consisting of ■, ■, and ■ with stirring, and ■, ■, and ■ were further added,
Got shampoo. This color material ■ Citric acid ■ Water (manufacturing method) ■ was dispersed in the aqueous solution of (1), and 0.5 trace amount of this was added to the aqueous solution of (2). Next, this dispersion liquid was added to a homogeneous mixed solution of (1), (2), (2), and (2) under stirring, and (1), (2), and (2) were further added to obtain a shampoo.

Example 4 Shampoo (group F&) (%
2) was dispersed in the aqueous solution of 2, and this was added to the aqueous solution of 2. Next, this dispersion liquid was added to a homogeneous mixed solution of (1), (2), (2) and (2) under stirring, and then (1), (2) and (2) were added to obtain a shampoo. This shampoo also had good dispersion stability of zinc pyrithione, was mild, and had excellent anti-dandruff effects.

that's all ■Amino lauric acid dopropyl betaine

Claims (1)

[Claims] 1. The following components (a) to (d) (a) Anionic surfactant and/or nonionic surfactant (b) Water-insoluble fine powder (c) Ampholytic polymer (d) Carboxylic acid A cleaning composition containing an anionic copolymer having a sulfuric acid group or a sulfate group. 2. The cleaning composition according to claim 1, wherein the water-insoluble fine powder is a polyvalent metal salt of 2-mercaptopyridine-N-oxide. 3. Treat the water-insoluble fine powder (b) with an amphoteric polymer (c), then treat it with an anionic copolymer (d) having a carboxy group or a sulfate group, and add anions to the resulting polymer-coated powder. The cleaning composition according to claim 1, which is prepared by adding and dispersing a surfactant and/or a nonionic surfactant (a).