JPH05262626A - Detergent composition - Google Patents

Abstract

PURPOSE:To provide a detergent composition capable of stably keeping the dispersed state of water-insoluble fine powder of an antibacterial agent, etc., over a long period, having excellent dandruff-suppressing effect, deodorant effect and conditioning effect, exhibiting low stimulation and giving excellent feeling. CONSTITUTION:The objective detergent composition stably storable over a long period, exhibiting excellent cleaning power, frothing power and feeling and having high antibacterial activity and low stimulation can be produced by using a detergent composition containing (A) a sugar-based nonionic surfactant, (B) one or more surfactants selected from anionic surfactant, amphosteric surfactant and nonionic surfactant and (C) water-insoluble fine powder and compounding the detergent composition with (D) a water-soluble polymer having cellulosic skeleton and (E) a nonionic surfactant having an aliphatic alkylolamide structure as a dispersing agent for the fine powder C. The composition is preferably prepared by dispersing the component C in a mixture of the components D and E, adding the obtained polymer dispersion liquid to an aqueous solution containing homoeneousl dissolved components A and B and mixing and dispersing the components.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a detergent composition, more specifically, a water-insoluble fine powder that can be stably dispersed therein, has low irritation to the skin, and contains an antibacterial substance as the water-insoluble fine powder. The present invention relates to a detergent composition having excellent antibacterial activity when used, and particularly showing a mild cleansing feeling with high anti-dandruff effect, deodorant effect and conditioning effect when used for scalp / hair washing.

[0002]

2. Description of the Related Art As the current trend, the tendency toward cleanliness is generally increasing regardless of age and sex. Therefore, scalp and hair cleansing agents are required to have a bactericidal effect and a deodorant effect. It started to come out. Also,
As the number of times the hair is washed increases, the demand for products that are mild and less irritating to the skin and hair that can be used everyday is also increasing.

That is, a cleaning agent having both antibacterial properties and low irritation is desired, but up to now, there is a cleaning agent having both of these two points and having excellent stability. Hard to say. Usually, the main active agents used as detergents are synthetic anionic surfactants such as alkyl sulphates and ethoxylated alkyl sulphates, but these synthetic anionic surfactants have a detergency and foaming effect. Although excellent in strength and the like, it has a drawback that it may affect the skin and hair depending on the conditions of use and the person using it.

Therefore, in recent years, as a detergent for solving such a drawback, for example, Japanese Patent Laid-Open Publication No. 3-127717 discloses a sugar-based nonionic surfactant and an antibacterial agent which are mild to skin and hair. Disclosed is a detergent composition which is used in combination with low skin irritation and excellent antibacterial activity. However, the sugar-based nonionic surfactant used here has a property of low irritation, but has a problem of poor stability and cleaning performance. In particular, a technique for stably dispersing water-insoluble fine powder such as an antibacterial agent using this surfactant has not been established yet.

Generally, as a typical example of the water-insoluble fine powder to be blended in the detergent for hair and skin, a pearling agent and 2-mercaptopyridine-N-oxide useful as an anti-dandruff agent (hereinafter referred to as "Mept"). ) Polyvalent metal salts, selenium disulfide and the like can be mentioned. Among these, as the polyvalent metal salt of Mept, there are magnesium, barium, strontium, zinc, cadmium, tin, zirconium salts and the like, but among these, the zinc salt is most widely used.

However, all of these Mept are sparingly soluble in water, for example, the solubility of zinc salt (hereinafter referred to as "Zpt") in water is 15 ppm at 25 ° C., and these Mept are shampooed. When blended with a cleaning agent such as Zpt, the specific gravity of Zpt is 1.8 and the difference in specific gravity from the dispersion medium is large, so that precipitation and separation of Zpt tend to occur over time, making it difficult to obtain a stable dispersion system. Met.

As means for preventing the settling / separation of the water-insoluble fine powder, for example, the following methods (1) to (3) can be considered. (1) The particle size of the water-insoluble fine powder is made extremely small so that Brownian motion control is more dominant than gravity control,
Make sedimentation less likely. (2) The viscosity of the dispersion medium at rest is increased to prevent sedimentation. (3) Other substances are adsorbed on the surface of the water-insoluble fine powder to impart a steric or electrostatic repulsive force to prevent aggregation.

Based on the idea of (1), Mept having a very small particle size as compared with the conventional Mept.
(Hereinafter, referred to as "fine particle Mept") has been reported (Japanese Patent Publication Nos. 61-35186, 64-3193 and 60-224676). However, this fine particle Mept is also mixed with salts such as a surfactant,
Aggregation easily occurred due to freezing, heating, etc., and the dispersion stability in the detergent was not yet sufficiently satisfactory.

Based on the idea of (2), for example, a method of adding a thickening polymer such as cross-linked polyacrylic acid (Japanese Patent Publication No. 49-119117) and an acrylic acid / acrylic acid ester copolymer are used. Examples thereof include a method of adding (Japanese Patent Publication No. 54-16951) and the like. In this method, the type of surfactant that can be used to stably disperse the water-insoluble fine powder is limited, and sugar-based nonionic It was not readily applicable in the activator system.

As a method based on the idea of (3), for example, a method of adding polyvinyl alcohol (Japanese Patent Laid-Open No. 63-297315) and the like can be mentioned, which is also a sugar-based nonionic activator-based method. Was not suitable for.

Therefore, it has been desired to develop a detergent composition which has stable dispersibility of the water-insoluble fine powder, has low irritation, and is excellent in usability and detergency.

[0012]

Under the circumstances, the inventors of the present invention have conducted diligent research to solve the above-mentioned problems, and as a result, as a result, a sugar-based nonionic surfactant, an anionic surfactant and an amphoteric interface have been obtained. In a mixed system of one or more surfactants selected from the group consisting of surfactants and cationic surfactants, a water-soluble polymer having a cellulose skeleton and a nonionic surfactant having a fatty acid alkylolamide structure When used as a dispersant for water-insoluble fine powder when used in combination with an agent, it is stable even after long-term storage, has excellent detergency, foaming power, and feeling of use, and has both antibacterial and hypoallergenic properties. It was found that a detergent composition can be obtained, and the present invention was completed.

That is, the present invention comprises the following components (a)-
(E) (a) Sugar-based nonionic surfactant (b) One or more surfactants selected from the group consisting of anionic surfactants, amphoteric surfactants and cationic surfactants. (C) Water-insoluble fine powder (d) Water-soluble polymer having a cellulose skeleton (e) A detergent composition containing a nonionic surfactant having a fatty acid alkylolamide structure.

In the detergent composition of the present invention, the component (a)
As the sugar-based nonionic surfactant used as
For example, the following alkyl saccharide-based surfactants, sugar amide-based surfactants, sucrose fatty acid ester-based surfactants and the like can be mentioned.

(A-1) An alkyl saccharide-based surfactant represented by the following general formula (1). R ¹ —O— (R ² O) _a —G _b (1) (In the formula, R ¹ represents a linear or branched alkyl, alkenyl or alkylphenyl group having 6 to 18 carbon atoms, and R ²
Represents an alkylene group having 2 to 4 carbon atoms, G represents a reducing sugar having 5 to 6 carbon atoms, a represents a number of 0 to 10 and b represents a number of 1 to 10).

In the formula (1), R ¹ is a linear or branched alkyl, alkenyl or alkylphenyl group having 6 to 18 carbon atoms, and particularly a linear or branched alkyl group having 9 to 14 carbon atoms. (Decyl group, lauryl group, myristyl group, etc.)
Is preferable from the viewpoint of cleaning characteristics such as foamability. R ² represents an ethylene group, a propylene group, a trimethylene group, a butylene group or the like. The average degree of polymerization a of the alkylene oxide is 0 to 1
A value of 0 is shown, but from the viewpoint of cleaning characteristics such as foaming property, 0 to 3 is preferable, and 0 is particularly preferable. Further, the saccharide moiety (G in the formula (1)) which is a hydrophilic group has a reducing sugar having 5 to 6 carbon atoms as a basic unit, and the reducing sugar is preferably glucose, galactose or fructose. The average degree of polymerization b of the saccharide is 1 to 10, but b = 1 to 4
Is preferably 80% or more, and particularly low in average degree of polymerization, that is, 1 to 1.4. Further, both the average degree of polymerization and the group R ¹ are compounds (1)
Considering the influence on the characteristics of R ¹ , R ¹ has 8 to ¹ carbon atoms.
When 1, b has ¹ to 1.4 and R ¹ has 12 carbon atoms
When it is -14, b is preferably 1.5-4.0.

(A-2) A sugar amide-based surfactant represented by the following general formula (2).

[0018]

[Chemical 1]

In the formula (2), R ³ represents a linear or branched alkyl, alkenyl or alkylphenyl group having 5 to 17 carbon atoms. Among them, R ³ —CO— is capric acid, caprylic acid or lauric acid. Acid, myristic acid, palmitic acid,
Those derived from stearic acid, isostearic acid and oleic acid are preferable, and those derived from capric acid and lauric acid are particularly preferable. Specific examples of R ⁴ include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, octyl group, 2-ethylhexyl group, decyl group,
Examples thereof include dodecyl group, stearyl group, isostearyl group, polyethylene glycol group having a polymerization degree of 2 to 10, polypropylene glycol group, 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, and the like. , Methyl group, ethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group and 3-hydroxypropyl group are preferred. X represents a polyhydroxyalkyl group consisting of a sugar residue having 4 to 30 carbon atoms, but even a polyhydroxyalkyl group having 4 to 7 carbon atoms which is glycosidic bonded to a mono-, di- or oligosaccharide group. good.

(A-3) A sucrose fatty acid ester-based surfactant represented by the following general formula (3).

[0021]

[Chemical 2]

(In the formula, R ⁶ , R ⁷ and R ⁸ may be the same or different, and at least one is a linear or branched saturated or unsaturated C 8-24 acyl group, And the rest represent hydrogen atoms) and the like, and generally consist of a mixture of mono-, di-, and triacyl compounds. In the formula, R ⁶ , R ⁷ and R ⁸ each represent an acyl group having 6 to 24 carbon atoms, particularly preferably an acyl group having 10 to 18 carbon atoms, and the ratio of mono / di or tri is 70/30. ~ 30/7
0 is preferred.

In the present invention, the sugar-based nonionic surfactant as the component (a) is preferably an alkyl saccharide-based surfactant represented by the above general formula (1). The sugar-based nonionic surfactants may be used singly or in combination of two or more kinds, and the blending amount thereof is 0.1 to 95% by weight (hereinafter, simply referred to as%) in the total amount of the composition. ), Especially 1 to 15% is preferable.

Examples of the anionic surfactant used as the component (b) in the detergent composition of the present invention include those represented by the following (1) to (11). (1) Polyoxyalkylene alkyl ether sulfuric acid ester having a linear or branched alkyl group having an average carbon number of 8 to 20 and having an average of 0.5 to 8 mol of ethylene oxide and / or propylene oxide added per molecule. salt. (2) An alkyl sulfate ester salt having a linear or branched alkyl group having an average carbon number of 10 to 20. (3) α having an average of 10 to 20 carbon atoms in one molecule
-Olefin sulfonate. (4) An alkanesulfonate having an average of 10 to 20 carbon atoms in one molecule. (5) A fatty acid salt having a linear or branched saturated or unsaturated hydrocarbon chain having an average carbon number of 10 to 20. (6) An alkylethoxycarboxylic acid salt having a linear or branched alkyl group having an average carbon number of 10 to 20, to which an average of 0.5 to 8 mol of ethylene oxide is added per molecule. (7) The following general formula (4) or (5)

[0025]

[Chemical 3]

(R ¹⁰ is a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, R ¹¹ is the same or different and is a hydrogen atom or a methyl group, and R ¹² is 7 to 7 carbon atoms. 21 represents a linear or branched alkyl group or alkenyl group, d represents a number of 0 to 20), M ¹ is a hydrogen atom or a water-soluble selected from alkali metal, alkaline earth metal, ammonium and organic ammonium. Which represents a cation which forms a salt]. (8) The following general formula (6)

[0027]

[Chemical 4]

(Wherein R ¹³ is a linear or branched saturated or unsaturated hydrocarbon group, R ¹⁴ is a hydrogen atom or a methyl group, e is a number of 0 to 6 and f is 1 to 6). The number is shown), B represents -OX ² or A, and X ¹ and X ² each represent a hydrogen atom or a counter ion].

(9) The following general formula (7) or (8)

[0030]

[Chemical 5]

[Wherein R ¹⁵ represents an alkyl group or an alkenyl group having 7 to 21 carbon atoms, and X ³ and X ⁴ each represent a hydrogen atom or a counter ion]. (10) The following equation (9)

[0032]

[Chemical 6]

[Wherein R ¹⁶ represents an alkyl or alkenyl group having 7 to 19 carbon atoms, R ¹⁷ represents a lower alkyl group having 1 to 3 carbon atoms, and X ⁵ represents a counter ion]. System surfactant. (11) The following equation (10)

[0034]

[Chemical 7]

[In the formula, R ¹⁸ represents an alkyl group or an alkenyl group having 7 to ²¹ carbon atoms, R ¹⁹ , R ²⁰ and R ²¹ represent an amino acid side chain, g is a number of 1 to 6, and X ⁶ is Represents a hydrogen atom or a counter ion].

X ^{1 to} X ^{6 of} these anionic surfactants
The counter ion represented by is usually an alkali metal ion such as sodium and potassium; an alkaline earth metal ion such as magnesium; an ammonium ion and, for example, monoethanolamine, diethanolamine, triethanolamine, triisopropylamine and the like having 2 carbon atoms. And alkanolamine bases having 1 to 3 alkanol groups of 3 to 3.

Examples of the amphoteric surfactant used as the component (b) in the present invention include the following (12)
And those shown by (13). (12) An α-position addition type, secondary amide type or tertiary amide type imidazoline-based amphoteric surfactant having an alkyl group, an alkenyl group or an acyl group having 6 to 24 carbon atoms. (13) Carbobetaine-based, amidobetaine-based, sulfobetaine-based, hydroxysulfobetaine-based or amidosulfobetaine-based amphoteric surfactants having an alkyl group, an alkenyl group, or an acyl group having 8 to 24 carbon atoms.

Furthermore, examples of the cationic surfactant used as the component (b) in the present invention include those represented by the following (14) and (15). (14) The following general formula (11)

[0039]

[Chemical 8]

[0040] wherein one or two straight or branched chain alkyl group having a carbon number of 8 to 28 of the R ²² to R ^25, a hydroxyalkyl group, or _{^{R 26 - (CH 2 CH 2}} O) _h- (R
²⁶ represents an alkyl group or a hydroxyalkyl group having 8 to 24 carbon atoms, h represents a number of 1 to 10), and the remainder represents a benzyl group, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, X ⁻ represents a halogen ion or an organic anion]. (15) An alkylpyridinium salt having an alkyl group having an average carbon number of 10 to 18.

In the present invention, each of the above-mentioned component (b) surfactants may be used alone or in combination of two or more kinds, but it is preferable to use an anionic surfactant, particularly preferably The anionic surfactant of (1), (2) or (7) is preferable.

In the present invention, the total amount of the component (b) surfactants is 0.1 to 95 in the total amount of the composition.
%, Particularly 1 to 30% is preferable. Further, it is preferable that the mixing ratio of the component (a) and the component (b) is such that the weight ratio is (a) / (b) = 1/9 to 9/1.

The water-insoluble fine powder of the component (c) in the detergent composition of the present invention has a solubility of 20 ppm or less in distilled water at 25 ° C., and specifically, a bactericide in the detergent,
Compounds such as abrasives and pigments, eg Mep
t, titanium oxide, calcium carbonate, fish scales, pearlizing agents such as fatty acid glycol esters, diatomaceous earth and the like. Of these fine powders, Mept is particularly preferable, and as the polyvalent metal thereof, magnesium, barium, strontium, zinc, cadmium, tin, zirconium and the like can be mentioned, and among these, zinc is particularly preferable. Also,
The shape of the fine powder may be granular or plate-like, but if it is plate-like, its major axis is preferably 5 μm, and if it is granular, its average particle size is preferably 5 μm or less. Those having a diameter of 0.2 μm or less are preferably 50% or more, more preferably those having a particle size of 0.5 to 1.0 μm are 15% or less, and those having a particle size of 1.0 μm or more are 2% or less.

In the present invention, these components (c) may be used alone or in combination of two or more kinds,
The blending amount thereof is preferably 0.01 to 10% in the total amount of the composition. These fine powders have various effects, for example, in the case of washing hair, the effect of preventing dandruff and itch, the effect of softening hair,
It is added for the effect of giving a pearl tone for improving the appearance.

In the detergent composition of the present invention, the component (d)
As the water-soluble polymer having a cellulose skeleton, for example, methyl cellulose, carboxymethyl cellulose,
Examples thereof include hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose and the like. These are polymers obtained by reacting cellulose with caustic soda to give alkali cellulose, and then reacting with methyl chloride, monochloroacetic acid, ethylene oxide, propylene oxide or the like to replace the hydroxyl groups of the cellulose, and the average degree of substitution is 0 to 0. It is 3. The average molecular weight is preferably 200,000 to 3,000,000. Of these components (d), hydroxyethyl cellulose is particularly preferable, and those having an average degree of substitution of 0.5 to 2.0 and an average molecular weight of 500,000 to 2,000,000 are preferable.

In the present invention, the polymer having a cellulose skeleton as the component (d) may be used alone or in combination of two or more kinds, and the blending amount thereof is 0.01 to 0 in the total amount of the composition. 0.2%, especially 0.1-0.2% is preferable.

Examples of the nonionic surfactant having a fatty acid alkylolamide structure of the component (e) in the detergent composition of the present invention include, for example, fatty acid monoethanolamide, fatty acid monoethanolamide ethylene oxide adduct, fatty acid monoester. Examples thereof include ethanolamide ethoxylate, fatty acid monoisopropanolamide, and fatty acid diethanolamide. In addition, examples of the fatty acid here include coconut oil fatty acid, tallow fatty acid, stearic acid,
Examples include lauric acid and myristic acid.

Of these, coconut oil fatty acid monoethanolamide ethylene oxide adducts are particularly preferable in the present invention. This is a nonionic surfactant prepared by adding ethylene oxide to coconut oil fatty acid alkylolamide, and among them, particularly preferred is one having an addition mole number of ethylene oxide of 1 to 15.

In the present invention, the nonionic surfactant having a fatty acid alkylolamide structure of the component (e) is
Each may be used alone or in combination of two or more kinds, and the blending amount thereof is preferably 0.01 to 1%, particularly preferably 0.1 to 0.2% in the total amount of the composition.

In the detergent composition of the present invention, the water-soluble polymer having a cellulose skeleton as the component (d) and the nonionic surfactant having a fatty acid alkylolamide structure as the component (e) are used in combination, It is possible to stabilize the dispersion of the water-insoluble fine powder of the component (c) and improve the feeling in use.

In addition to the above-mentioned essential components, the cleaning composition of the present invention may contain optional components that are generally incorporated. Examples of these optional components include solubilizers such as propylene glycol and glycerin; viscosity modifiers such as ethyl alcohol, isopropyl alcohol, methyl cellulose, and higher alcohols; antiseborrheic substances; antibiotics;
Examples thereof include keratolytic or keratin softening substances such as sulfur, salicylic acid, and enzymes; deodorants, lotions, fragrances, dyes, ultraviolet absorbers, antioxidants, preservatives and the like.

The detergent composition of the present invention can be prepared by a conventional method. First, the component (d) and the component (e) are mixed and the component (c) is dispersed in the aqueous mixture solution. Then, it is preferable that the obtained polymer dispersion is added to an aqueous solution in which the component (a) and the component (b) are uniformly dissolved, and mixed and dispersed to prepare the polymer dispersion.

[0053]

EFFECT OF THE INVENTION The detergent composition of the present invention can stably disperse water-insoluble fine powder such as an antibacterial agent for a long period of time, is excellent in anti-dandruff effect, deodorant effect, conditioning effect, and is used with low irritation. It has a good feel and is extremely useful.

[0054]

The present invention will be further described with reference to examples, but the present invention is not limited thereto.

Example 1 A detergent composition having the composition shown in Table 1 was prepared, and this was prepared at 40 ° C.
After storing for 1 week in, the dispersion stability was evaluated by visual observation. The results are shown in Table 1. The production method and evaluation criteria of the cleaning composition are as follows.

(Production method) Inventive product 1: Component (d), component (e) and part of water were mixed to prepare a uniform aqueous solution, and component (c) was dispersed therein. Then, this is added to an aqueous solution obtained by mixing the component (a), the component (b) and the remaining water with stirring, and further,
A pH adjuster was added. Comparative product 1: Component (d) and a part of water were mixed to prepare a uniform aqueous solution, and component (c) was dispersed therein. Then, this was added under stirring to an aqueous solution obtained by mixing the component (a), the component (b) and the remaining water, and a pH adjusting agent was further added. Comparative product 2: Component (e) and a part of water were mixed to prepare a uniform aqueous solution, and component (c) was dispersed therein. Then, this was added under stirring to an aqueous solution obtained by mixing the component (a), the component (b) and the remaining water, and a pH adjusting agent was further added. Comparative product 3: Component (c) was added with stirring to an aqueous solution obtained by mixing component (a), component (b) and water, and a pH adjuster was further added. (Evaluation Criteria) O: Dispersed uniformly. X: Separated.

[0057]

[Table 1]

As is clear from the results shown in Table 1, the detergent composition of the present invention has excellent dispersion stability of zinc pyrithione which is a water-insoluble fine powder.

Example 2 Shampoo Composition (Composition) (%) (1) Alkyl glucoside ^{* 4} 5.0 (2) Polyoxyethylene (2.5) Lauryl ether sulfate sodium salt 13.0 (3) Zinc pyrithione 1.0 (4) Hydroxypropyl methylcellulose ^{* 5} 0.2 (5) Coconut oil fatty acid diethanolamide ^{* 6} 0.2 (6) Fragrance 0.3 (7) Dye trace amount (8) Water balance * 4: R in formula (1) ¹ = dodecyl group, G = glucose a = 0, b (average value) = 3.0 * 5: Metroses 60SH-4000 (Shin-Etsu Chemical Co., Ltd.) * 6: Amycol CDE-2 (Miyoshi fats and oils) (Production method) (4) Is dissolved in a part of (8), and (5) is added to the resulting aqueous solution to uniformly dissolve. Next, (3) is dispersed in this aqueous solution, and the resulting dispersions are (1), (2),
A shampoo was obtained by adding to a homogeneous solution consisting of (6), (7) and the rest of (8) with stirring and thoroughly mixing. This shampoo composition has excellent shampoo performance such as foam amount and feel,
Furthermore, the anti-dandruff / itch effect was high, the skin irritation was low, and the dispersion stability of the water-insoluble fine particles was good.

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area C11D 1:68 3: 382)

Claims (2)

[Claims] 1. A group consisting of the following components (a) to (e) (a) sugar-based nonionic surfactant (b) anionic surfactant, amphoteric surfactant and cationic surfactant: One or more surfactants selected from (c) water-insoluble fine powder (d) water-soluble polymer having a cellulose skeleton (e) detergent containing a nonionic surfactant having a fatty acid alkylolamide structure Composition. 2. A water-soluble polymer (d) having a cellulose skeleton and a nonionic surfactant (e) having a fatty acid alkylolamide structure are mixed, and a water-insoluble fine powder (c) is dispersed in an aqueous solution of the mixture. The polymer dispersion thus obtained is used as one or two kinds selected from the group consisting of a sugar-based nonionic surfactant (a), an anionic surfactant, an amphoteric surfactant and a cationic surfactant. The cleaning composition according to claim 1, which is obtained by adding, mixing and dispersing the above-mentioned surfactant (b) to an aqueous solution in which it is uniformly dissolved.