JPS61151111A - Antimicrobial hair-treatment composition - Google Patents

Abstract

PURPOSE:To provide the titled stable composition containing an organic surfactant and an antibacterial agent prepared by treating fine particles of 2- mercaptopyridine-N-oxide polyvalent metal salt having a specific particle size distribution with a hydroxyalkyl cellulose and a nonionic surfactant. CONSTITUTION:The titled composition such as shampoo, rinse, etc. contains (A) an antibacterial agent prepared by treating (i) fine particles of 2- mercaptopyridine-N-oxide polyvalent metal salt (preferably zinc salt) wherein the particles of <=0.2mum diameter account for >=50wt% of the powder (preferably the contents of the particles having diameter of <=0.2mu, 0.5-1.0mu, and >=1.0mu are >=50wt%, <=15wt% and <=2wt%, respectively) with (ii) a water-soluble polymer compound selected from a hydroxyalkyl cellulose and its partial quaternarized product and (iii) a nonionic surfactant (e.g. hardened castor oil). EFFECT:It has extremely excellent dispersion stability and storage stability and gives excellent feeling to the skin.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention provides a method for converting fine particles of 2-mercaptopyridine-N-oxide polyvalent metal salt (hereinafter abbreviated as "MeptJ") having a specific particle size distribution into hydroxyalkyl The present invention relates to an antibacterial hair treatment composition containing cellulose or a quaternized product thereof, an antibacterial agent treated with a nonionic active agent, and an organic surfactant.

[Conventional technology]

Polyvalent metal salts of 2-mercaptopyridine-N-oxide are effective as disinfectants, and are widely used not only as general disinfectants but also as anti-dandruff agents added to shampoos, conditioners, and the like.

The polyvalent metal of Mept includes magnesium, barium, strontium, zinc, cadmium, tin, zirconium, etc. Among these, zinc salt is widely used.

However, these Mepts are all soluble in water, for example, the solubility of their zinc salt (hereinafter abbreviated as rZptJ) in water is 15 ppm at 25°C, and they cannot be used in shampoos, conditioners, etc. If they are to be blended, they must be used in the form of a dispersed system.

[Problem that the invention seeks to solve]

However, for example, the specific gravity of Zpt is 1.8, which is a large difference in specific gravity from the dispersion medium, so that Zpt tends to settle and separate over time, making it difficult to obtain a stable dispersion system.

Measures to prevent such sedimentation and separation of Mept include, for example: (1) Increasing the viscosity of the dispersion medium at rest to make sedimentation less likely to occur (1) Making the particle size of Mept extremely small to prevent Brownian motion. It is conceivable to make it dominant and make it difficult for sedimentation to occur.

Based on the idea of (1), for example,
As disclosed in Japanese Patent Publication No. 9-49117, a method of adding a thickening polymer such as a cross-linked polyacrylate; A method of adding a copolymer may be mentioned, but in such a method, Me
This method has the disadvantage that the types of surfactants that can be used to stably disperse PT are limited.

Furthermore, according to my approach, it is not easy to produce Mept with a very small particle size of 1, and a composition with good dispersion stability using Mept fine particles has not been obtained in fact.

Under such circumstances, the present inventor previously discovered that Mept (hereinafter referred to as "micronized Mept") has a very small particle size compared to Mept that is blended in conventional shampoos, conditioners, etc.
succeeded in manufacturing (referred to as J) (%gansho 58-1
No. 22845, No. 58-122846, No. 59-82
No. 690).

The present inventor further continued research to obtain a stable antibacterial agent suspension using this micronized Mept, and as a result, the composition of hair treatment agents such as shampoos and conditioners containing a surfactant that itself is an electrolyte. It has become clear that micronized Mept tends to agglomerate in a substance, making it difficult to maintain the original particle size distribution. Protective colloids made of water-soluble polymers are usually considered as a means to prevent such aggregation of micronized Mept. However, due to the increase in the number of particles and the decrease in the distance between particles due to micronization, the cellulose-based water-soluble polymer normally used as a protective colloid causes aggregation when forming a protective colloid adsorption layer. For example, JP-A-53-14
No. 710, No. 53-14711, No. 53-97010
As shown in No. 57-176906, if micronized Mept is added to an aqueous solution of hydroxyalkylcellulose or the like, the original particle size distribution disappears and the property of being resistant to sedimentation is lost. Therefore, conventional techniques mainly utilize the properties of cellulose-based water-soluble polymers as thickeners to increase the viscosity of the shampoo base and slow down the sedimentation rate of Mept.
Orui often contains swelling clay, pearling agents, etc. to give the system structural viscosity and prevent sedimentation.

Therefore, there are restrictions on the formulation, such as the type of active agent that can be used in the shampoo base and the viscosity of the shampoo base.

On the other hand, when Gept is added to rinses and conditioners, there is a viscosity limitation, and it is limited to highly viscous emulsified or gel-like bases. The inventor conducted further intensive research to improve this drawback, and found that particles with a particle size of 0.2 μm or less weighed 50 tons.
% or more of Mept in the coexistence of hydroxyl-alkyl cellulose or its quaternized product and a nonionic activator, the micronized xept can form a protective colloid without losing its original particle size distribution, and can be used as a low-viscosity material. The present invention was created based on the discovery that a long-lasting dispersion system can be obtained even in shampoos.

That is, the present invention provides 2-mercaptopyridine-N-oxide, which has particles having a particle size of 0.2 μm or less and weighs 50 or more by weight.
Microparticles of polyvalent metal salt are converted into hydroxya f゛.

From rukyl cellulose and a part thereof to quaternized products: tJ
Fiゎ, □□oei, 8□, oio7 i/& ,! 5
The present invention provides an antibacterial hair treatment composition containing nine antibacterial agents.

MeptFi used in the present invention is expressed by the following general formula.

↓ (In the formula, M represents a polyvalent metal atom, and X represents the valence of M.) Examples of M include magnesium, barium, strontium, zinc, cadmium, tin, and zirconium, among which 2 Zinc salts of -mercaptopyridine-N-oxide are preferred.

The Mept fine particles used in the present invention have a particle size distribution in which 50% or more have a particle size of 0.2μ or less, and 15% or less have a particle size of 0.5 to 1.0μ,
Particularly preferred are those with a diameter of 1.0 μ or more and 2 μ or less. Mept fine particles having such a particle size distribution are produced, for example, by any of the following methods.

(2) A method in which Mept and KMept are stirred together with a rigid media having a particle size of 0.5H or less, such as glass, and the resulting particles are atomized by the shearing force of the media (C% Application No. 122845/1984).

(2) A method in which a monovalent water bath salt of 2-mercaptopyridine-N-oxide and a water-soluble polyvalent metal salt are reacted at pH 3 to 7 in the presence of a water-soluble compound having basic nitrogen in the molecule. is a method in which this reaction is further carried out in the presence of a water-bathable hydroxyl group-containing compound at a temperature below 0°C ('?
? M No. 58-122846).

■ Mept dispersion liquid with an average molecular weight of 11,100,000 (
A method of stirring in the presence of a meth)acrylic acid-styrene sulfonic acid copolymer salt with rigid media having a particle size of 0.2 y or less (4!F Application No. 59-82690).

Hydroxyalkyl cell o- used in the present invention
For example, cationic cellulose derivatives which are quaternized products of cellulose, such as hydroxyethylcellulose, hydroxypropylcellulose, and hydroxypropylcellulose, are preferably those represented by the following formula.

(2) In the formula (2), A represents a residue of an anhydroglucose unit, t is an integer from 50 to 20,000, and each R1 represents a substituent represented by the following general formula (2).

1゜■ In the formula, R', R'': a fullylene group having 2 or 3 carbon atoms m
: Integer from 0 to 10 n : Integer from 0 to 3 p : Integer from 0 to 10 R'#: Fullylene group having 1 to 3 carbon atoms or dialkylene group in hydro R'l, Rct R-: Same or different In addition, a heterocycle may be formed by containing an alkyl group, an aryl group, an aralkyl group having up to 10 carbon atoms, or a nitrogen atom in the formula.

X: Contains anions (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methyl sulfate, phosphoric acid, nitric acid, etc.).

The degree of cation substitution of cationic cellulose is 0.01~
1, that is, the average value of 1 per anhydroglucose unit is preferably 0.01 to 1, preferably 0.02 to 0.5. Moreover, the sum of m + p is 1 to 3 on average. A degree of substitution of 0.01 or less is not sufficient, and a degree of substitution of 1 or more is acceptable, but from the viewpoint of reaction yield, 1 or less is preferable. The molecular weight of the cationic cellulose used here is about 100,000 to a
It is between ooooo.

Nonionic activators used in the present invention include (1) polyoxyethylene alkyl or flukenyl ether having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and to which 1 #20 mole of ethylene oxide is added;

■ It has an alkyl group with an average carbon number of 6 to 12, and 1 to 20
Polyoxyethylene ruphenyl ether in alcohol with mol of ethylene oxide added.

(Polyoxypropylene alkyl or ha alkenyl ether having an alkyl group or 7 alkenyl groups having an average carbon number of 10 to 20 and added with 1 to 20 moles of propylene oquinide.

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

(5) A nonionic surfactant (ethylene oxide The ratio of propylene oxide or butylene oxide is 0.1/9.9 to 9.910.1
).

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

In formula 4, R1 represents an alkyl group or alkenyl group having 7 to 21 carbon atoms, R1 represents a hydrogen atom or a methyl group, and n! represents an integer from 1 to 20, and s ml represents an integer from 0 to 20. )
and hydrogenated castor oil.

The treatment of the Mept fine particles of the present invention with a water-soluble polymer and a nonionic activator (formation of a protective colloid adsorption layer) is preferably carried out as follows.

That is, the following four ingredients: ■ 1 to 10% effective Mept content, ■ 5 weight or more of the water-soluble polymer compound Mept, ■ 5 weight or more of the nonionic activator water-soluble polymer compound, ■ Exchange water balance Using the following order, dissolve (1) uniformly in (1), then add (2), and then add (4) while stirring to mix uniformly.

Alternatively, uniformly dissolve ■ in #'i■, then add ■ and mix 1.
This is done by adding ① to the mixture and stirring until it is uniformly suspended. In this case, a general stirring and mixing device such as a propeller stirring device, a homomixer, a sand mill, etc. is used for mixing.

The antibacterial agent dispersion obtained in this way can be added at any time during the ordinary shampoo and conditioner manufacturing process, but the Mept active content in the hair treatment composition is generally 0.01 to 5%, preferably 0.05%. Add ~2%.

As the hair treatment agent base, any commonly used base can be used. Among hair treatment agents, shampoo and conditioner compositions are particularly suitable, and their bases include one or more of anionic surfactants, amphoteric surfactants, nonionic surfactants, and cationic surfactants. A mixture is used. Examples of these surfactants include the following.

Anionic surfactant: ω A straight or branched alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 16.

■ Polyoxyalkylene having a linear or branched alkyl group with an average carbon number of 8 to 20 and to which an average of 0.5 to 8 moles of terene oxide and/or prohylene or tky9-ide is added per molecule. Alkyl ether sulfate salt.

(J Alkyl sulfate salt having a straight or branched alkyl group having an average carbon number of 10 to 20.

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

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

(Fatty acid salt having a linear or branched saturated or unsaturated hydrocarbon chain with an average carbon number of 10 to 20.

(7> Alkylethoxycarboxylic acid salt 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.

(Ta) Alkyl or alkenyl succinic acid having an alkyl or alkenyl group having an average carbon number of 6 to 20 and partially neutralized salts thereof.

((to) the following formula, Ax -P OXI [During the ceremony, A! is R’40-f-CHzCHO mother-in-law or■ a% R.

(Here, RS is a linear or branched saturated or unsaturated hydrocarbon group, R2 is a hydrogen atom or a methyl group, m is O-6
, n represents a number from 1 to 6), B represents -OX or A, and Xl and X! each represents a hydrogen atom or a counter ion] A phosphate ester salt-based activator represented by:

(Xl) Amino acid system represented by the following formula % formula % (wherein, R represents an alkyl group or alkenyl group having 7 to 21 carbon atoms, and x4 and so each represent a hydrogen atom or a counter ion) surfactant.

αυ The following formula, (wherein, R1 represents a C7-21Q alkyl group or alkenyl group, R,, R7 and R represent amino acid side chains, and n
1 represents a number from 1 to 6, and represents a hydrogen atom or a counter ion.) An acylated polypeptide surfactant represented by:

The counter ions represented by X1 to Xi of these anionic surfactants are usually alkali metal ions such as sodium potassium; alkaline earth metal ions such as magnesium; ammonium ions and, for example, monoethanolamine, jetanolamine, triethanolamine,
Examples include alkanolamine bases having 1 to 3 alkanol groups having 2 to 3 carbon atoms, such as triinpropylamine.

Amphoteric surfactant: C13 alkylamine oxide (
I) and amidoamine oxide (If).

R1・R, -N-so (I) ll R1g+ R@-CONH(CHt) ml -N40
(II) (wherein R-o is an alkyl group or alkenyl group having 10 to 20 carbon atoms, and R1 and R11 are the same or different and represent an alkyl group having 1 to 3 carbon atoms,
ml represents an integer of 1 to 4) Examples of nonionic surfactants include the following: 0 having an alkyl or alkenyl group with an average carbon number lθ to 20, and 1 to 20 mol Polyoxyethylene alkyl or alkenyl ether with ethylene oxide added.

R4 has an alkyl group with an average carbon number of 6 to 12, and 1 to 20
Polyoxyethylene alkylphenyl ether with moles of ethylene oxide added.

α9 Polyoxypropylene alkenyl ether having an alkyl or alkenyl group having an average carbon number of 10 to 20 and to which 1 to 20 moles of propylene oxide is added.

ae A polyoxybutylene alkyl or alkenyl ether having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and to which 1 to 20 moles of butylene oxide is added.

αη A nonionic surfactant having an alkyl group or an alkenyl group having an average carbon number of 10 to 20, to which a total of 1 to 30 moles of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide are added. (The ratio of ethylene oxide to propylene oxide or butylene oxide is 0.1/9.9 to 9.910.
1) En Higher fatty acid alkanolamide or its alkylene oxide adduct represented by the following formula.

IM! aSS 1 In the formula, aSS represents an alkyl group or alkenyl group having 7 to 21 carbon atoms, and %all represents a hydrogen atom or a methyl group,'
? (represents an integer of 1 to 3, ml represents an integer of 0 to 3) α9 Sucrose fatty acid ester consisting of a fatty acid having an average carbon number of 10 to 20 and sucrose.

■ Fatty acid glycerin monoester consisting of a fatty acid with an average carbon number of 10 to 20 and glycerin.

Further, the cationic surfactant is not particularly limited, and a quaternary ammonium salt represented by the following formula (1) is particularly preferred.

In formula 1, 1 of R14* ats t ats and aty
~2 represent a straight chain or branched alkyl group or hydroxyalkyl group having 8 to 22 carbon atoms, and the remaining are 1 to 3 carbon atoms
represents an alkyl group, a hydroxyalkyl group, a benzyl group, or a polyoxyethylene group with a total addition mole a of 10 or less, and X represents a halogen atom or an alkyl sulfate group having 1 to 2 carbon atoms) Furthermore, among these quaternary ammonium salts, , especially distearyldimethylammonium chloride, stearyltrimethylammonium methosulfate, stearyltrimethylammonium chloride, stearyldimethylbenzylammonium chloride, docosaryltrimethylammonium methosulfate, docosaryltrimethylammonium chloride, docosaryldimethylbenzylammonium chloride, distearyldimethylammonium chloride , lauryldiethylbenzylammonium chloride, lauryltrimethylammonium bromide, distearylmethylhydroxymethyl chloride, cetyltrimethylammonium chloride, N-stearyl-N,N.

Preferred are N-)su(polyoxyethylene)ammonium chloride (addition of 3 moles in total), cetyltriethylammonium bromide, stearyldimethylammonium chloride, and the like.

Further, the higher alcohol is an alcohol having a linear or branched alkyl or alkenyl group having 12 to 26 carbon atoms, and preferable specific examples include stearyl alcohol, cetyl alcohol, arachine alcohol,
Examples include behenyl alcohol, caranervir alcohol, and seryl alcohol. Glycerin monofatty acid ester has the following general formula (If), CM Xue 0 COR 1 CHOH (II) ■ CM Tom OH 1 In the formula, atS is a saturated or unsaturated linear or branched hydrocarbon having 11 to 23 carbon atoms. Preferred specific examples include those whose main components are oleic acid monoglyceride, palmitic acid monoglyceride, instearic acid monoglyceride, stearic acid monoglyceride, and behenic acid monoglyceride.

〔Effect of the invention〕

Conventionally, shampoo spears/spice containing Mept have been provided on the market, but in order to stably incorporate Mept into the composition, it has been necessary to increase the viscosity or to incorporate special polymers and clay minerals. Ta.

Therefore, in terms of product performance, for example, in the case of shampoo, there were drawbacks such as poor foaming properties and poor feel after shampooing.

The present invention improves the viscosity of such a dispersion medium to obtain Mept.
Unlike the conventional method of stabilizing the dispersion of Mept, this method utilizes the unique dispersibility of micronized Mept by treating it with hydrocosyl alkylcellulose or its quaternized product and a nonionic activator. Therefore this Mep
The antibacterial hair treatment composition containing T-fine particles has extremely good dispersion stability and storage stability, and has an excellent feeling of use.

In addition to the above-mentioned essential ingredients, the antibacterial hair treatment composition may contain optional ingredients that are commonly used. These optional components include #-i, for example, dissolving agents such as propylene glycol, glycerin, and urea; viscosity modifiers such as ethyl alcohol, inpropyl alcohol, and droxyethyl cellulose, methyl cellulose, and higher alcohols; antimicrobial substances; Seborrheic substances; keratolytic or keratin softening substances such as sulfur, salicylic acid, and enzymes; deodorants, pearlizing agents, lotion agents, fragrances, pigments, ultraviolet absorbers, antioxidants, preservatives, etc. Can be mentioned.

[Effect]

Although the mechanism of action of hydroxyalkyl cellulose or its quaternized product and nonionic activator on Mept microparticles in the present invention is not clear, the aqueous solution forms a protective colloid adsorption layer of Mept microparticles and prevents their aggregation. It is thought that this has been prevented.

〔Example〕

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

The particle size distribution of Zpt in the following reference examples or examples was measured using a centrifugal automatic particle size distribution analyzer CAPA-500 (manufactured by Horiba, Ltd.). Note that water is used as the dispersion medium,
The density was 1, the viscosity was 0.8 cp (30° C.), and the density of the Zpt particles was 1.78.

Reference Example 1 A mixed solution of 99.32% of zinc sulfate heptahydrate and 1% bolyte (water, ethanol, 65/35) was placed in a reaction vessel, cooled to -25°C, and 2-mercapto was added to the reaction vessel. Pyridine-N-oxide sodium salt aqueous solution (40%) 0.759 was added instantly and reacted. Stirring was continued for another minute at the same temperature, and then the precipitated fine particles of zpt were collected.

The particle size distribution of this fine particulate zpt was as shown in Table 1.

Table 1 Reference Example 2 Commercially available Zpt dispersion (commercial product A 5 Q wt
long-term active ingredient) 70d and 44-63μ glass beads (media) 13o*7 (media/dispersion liquid volume ratio = s
s/35)L, sand grinder with internal volume of 400-
Igarashi Machinery Manufacturing) for 3 hours at a circumferential speed of 5m/
Rotate in seconds. The temperature inside the sand grinder is 20~
The temperature is 25°C. Furthermore, when this is filtered under pressure, micronized Zpt 31 d is obtained. The particle size distribution of this micronized Zpt was as shown in Table 2.

The following is an all-white Table 2 Reference Example 3 Commercially available Zpt powder 23F1 water-soluble copolymer salt represented by the formula (the molecular weight of the compound of the above formula is 680,000) 4.5 f, water 63 and 0.1 −
Mix 187 tons of 0.2 m glass beads (media) (media/dispersion liquid volume ratio = 63/37) L, internal volume 4
In the 00- sand grinder (manufactured by Igarashi Kikai),
The disk is rotated for 12 hours at a circumferential speed of 6 m and 7 seconds.

The temperature inside the sand grinder is 20-25°C. Furthermore, when this is filtered under pressure, micronized ZPT dispersion liquid 40
1 is obtained. Furthermore, by washing the media twice with water 702, 98% of Zpt can be recovered. This micronized Zpt
The particle size distribution was determined as shown in Table 3.

Table 3 Excellent Example 1 An antibacterial agent dispersion of micronized Zpt was prepared with the following composition, diluted with exchanged water, and the particle size distribution was measured by centrifugal sedimentation. The results are shown in Figure 1.

(Composition 3 droxyethyl cellulose 1.2% monoethanolamide exchanged water Balance amount *i
Daicel Chemical Industries, Ltd. HEC Unicel QP.

400H *2 Shukai Fine Chemical Co., Ltd. Amizet 5C (v
4 Production Method Hydroxyethyl cellulose was dissolved in exchanged water by heating, cooled to room temperature, and then polyoxyethylene coconut oil fatty acid monoethanolamide was added and mixed uniformly. Next, while stirring, the fine particle Zpt dispersion of Reference Example 2 was added and further stirred to mix uniformly.

Example 2 Shampoo composition: (Composition) ■ Antibacterial agent dispersion of Example 1 25% (contains Amizet 5 C0.6%) ■ Lauryl sulfate triethanolamine salt 40% (active content 40%) ■ Jetanol laurate Amide 3% ■ Phosphoric acid appropriate amount ■ Pigment
Trace amount ■Fragrance
0.5 inch ethanol
Appropriate amount ■ Replacement water Balance (manufacturing method) Add ■ to the homogeneous solution of ■■ under stirring and mix uniformly. Next, add ■■■ and mix uniformly, then add an appropriate amount of ■■ and adjust the pH.
An anti-7 poppy composition with a viscosity of 200 cp (B-type viscometer) was obtained. It showed good dispersion for 2 weeks at 40C.

Example 3 Hair rinse composition: (Composition) ■Antibacterial agent dispersion of Example 1 12.5 t (containing Amizet C0.6%) ■Stearyltrimethylammonium chloride 3 t
Polyoxyethylene cether ether 2% (EO
5) ■Fluid paraffin 0.5% ■Instearin m o, s% ■Fragrance 0.5chi ■Pigment
Small amount ■ Replacement water Balance (manufacturing method) Add ■ to the homogeneous solution of ■■ under stirring, and stir further to mix uniformly. Next, ■■■■■ was added and mixed uniformly to obtain an anti-dandruff composition. It showed good dispersion for 2 weeks at 40°C.

Examples 4 to 11 Shampoo compositions shown in Table 1 were obtained in the same manner as in Examples 1 and 2. These did not show a good dispersion state after being stored at 40°C for 2 weeks.

Comparative Examples 1 to 5 Those not treated with water-soluble polymer/nonionic activator caused flocculation and sedimentation. Microparticle Zpt treated only with a water-soluble polymer without using a nonionic activator and commercially available Zpt treated with a water-soluble polymer/nonionic activator showed free sedimentation. Methyl cellulose/nonionic activator treated microparticles Zpt
li free sedimentation.

Microparticles Zpt treated with carboxymethylcellulose/nonionic activator flocculated and sedimented.

Margin below

[Brief explanation of drawings]

FIG. 1 is a graph showing the relationship between the micronized 2.10 particle size and the concentration of Amizet 5C. that's all

Claims (1)

[Scope of Claims] 1. Fine particles of 2-mercaptopyridine-N-oxide/polyvalent metal salt containing 50% by weight or more of particles with a particle size of 0.2 μm or less are mixed with hydroxyalkyl celluloses and a portion thereof. An antibacterial hair treatment composition containing a water-soluble polymer compound selected from graded products, an antibacterial agent treated with a nonionic active agent, and an organic surfactant. 2. Micronized 2-mercaptopyridine-N-oxide
The particle size distribution of polyvalent metal salts is 50% by weight or more of polyvalent metal salts with a particle size of 0.2μ or less, 15% by weight or less of particles with a particle size of 0.5 to 1.0μ, and 2% by weight of polyvalent metal salts with a particle size of 1.0μ or more. % or less, the antibacterial hair treatment composition according to claim 1. 3. The antibacterial hair treatment composition according to claim 1 or 2, wherein the polyvalent metal salt of 3,2-mercaptopyridine-N-oxide is a zinc salt. 4. Claims 1 to 3 in which the water-soluble polymer compound is at least one type of hydroxyethyl cellulose, hydroxypropyl cellulose, or a product obtained by reacting these with glycidyltrimethylammonium chloride.
The hair treatment composition according to any one of Items 1 to 9. 5. The nonionic activator has a linear or branched alkyl group or alkenyl group having an average of 10 to 20 carbon atoms, and has 2 carbon atoms.
polyoxyalkylene alkyl or alkenyl ether to which 1 to 20 moles of the alkylene oxide of ~4 are added,
The hair treatment composition according to any one of claims 1 to 4, which is at least one of polyoxyalkylene alkylphenyl ether, alkylene oxide adduct of higher fatty acid alkanolamide, and hydrogenated castor oil. 6. The hair treatment composition according to any one of claims 1 to 5, wherein the hair treatment composition is a shampoo or a conditioner.