JP3081049B2 - Hair composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hair composition which imparts excellent gloss and smooth feel to hair.

[0002]

BACKGROUND OF THE INVENTION Conventionally, oils such as silicone oils, ester oils and hydrocarbon oils have been used in hair compositions for solubilizing, emulsifying and dissolving in order to impart gloss and smoothness to the hair. ing. In particular, silicone oil has a low surface tension, is excellent in the familiarity of hair, has good gloss, and is widely used in recent years. However, there is a limit to oil content, and there is a disadvantage that hair is greasy when used in large quantities or used for a long time by consumers. Also, cationic surfactants are often used for the purpose of imparting smoothness, but they do not give satisfactory gloss, and there is a drawback that if they are blended in a large amount, safety is not preferable. In addition, hair is generally damaged and deteriorated when hair is frequently washed and washed, brushing, heat treatment with a dryer, hair coloring, bleaches, etc. is frequently repeated. It is well known to cause an increase in hair loss and the like and a decrease in strength.

[0003] Therefore, for the purpose of protecting and repairing hair against the above-mentioned hair damage, a hair composition contains various raw materials extracted from natural products as bases, for example, proteins, polysaccharides, extracted extracts, natural polymers or these. Or an oligo-body, such as an amino acid or a peptide, which constitutes the above. In addition, for the purpose of preventing hair damage while giving gloss and smoothness to hair, as disclosed in JP-A-63-183517 and JP-A-63-243018, high-molecular-weight dimethylpolysiloxane or A technique using a high molecular weight methylphenylpolysiloxane is known. However, the effect of preventing hair damage is not sufficient with natural raw materials, and it is not satisfactory in terms of feel such as smoothness after use, and high molecular weight dimethylpolysiloxane and high molecular weight methylphenylpolysiloxane prevent hair damage. Although it has a certain effect on the effect and on imparting gloss and smoothness to the hair after use, it is not satisfactory in terms of the persistence of the effect by brushing or drying.

On the other hand, hair compositions having a so-called rinsing effect of imparting smoothness and gloss to hair and improving combability are generally commercially available under the names of hair rinse, hair treatment, hair conditioner and the like. These hair compositions usually contain a quaternary ammonium salt, and it is known that the above-mentioned so-called rinsing effect is provided by the adsorption of the quaternary ammonium salt to the hair. Furthermore, for the purpose of improving the feeling after use such as smoothness, gloss and moistness, for example, higher alcohols, glycerin mono fatty acid esters, higher fatty acids, liquid paraffin,
Oils such as solid paraffin, ester oil, and silicone oil having a polymerization degree of 3 to 650 are added. These components are variously blended in order to obtain a hair composition that imparts smoothness to hair without making the hair sticky. For example,
JP-A-63-222109 discloses a hair treatment agent containing a quaternary ammonium salt and a high-molecular-weight silicone belonging to the category of silicone gum in a specific ratio, and teaches that it has excellent washing resistance. doing. The above prior arts have all been improved to a certain extent as hair compositions. For example, in Japanese Patent Application Laid-Open No. 63-222109,
It can be seen that the cosmetic has an improved washing resistance and exhibits a certain flexibility, smoothness, and glossing effect on hair.
However, this further increases hair smoothness,
This does not mean that there is no need for a hair composition with enhanced flexibility and shine. For example, at the time of application and rinsing of the composition for hair, even if it is possible to impart smoothness without sticking the hair, when the hair is dried or thereafter, it does not necessarily show satisfactory properties. .

[0005] Further, as for a cleaning agent such as a shampoo, a quaternary nitrogen-containing water-soluble polymer has been widely used as a conditioning component of a hair cleaning agent.
It is excellent in suppressing tangling and snagging of hair during hair washing and giving a smooth feel. However, these can improve the smoothness during rinsing, but after towel drying and when drying, the effect of improving hair smoothness and suppleness is not recognized, and conversely, these large amounts of In such cases, there is a tendency to lead to hair crackling, hair fly, etc., and improvement thereof is desired. We have:
In view of such conventional circumstances, it gives hair excellent sheen, gives a smooth feel, prevents hair damage, protects hair from chemical or mechanical treatment, and has a long lasting effect. As a result of intensive studies to obtain a long-lasting hair cosmetic, it has been found that the above object can be achieved if a specific amino-modified or ammonium-modified polymer silicone is used, and based on this finding, the present invention has been completed. Was.

[0006]

That is, the first aspect of the present invention is as follows.
Is the general formula 1:

Embedded image [In the formula, R ¹ represents a methyl group or a part thereof is a phenyl group, and R ² represents the same as R ³ or a methyl group or a hydroxyl group. R ³ is wherein R ⁴ Z {R ⁴ represents a divalent alkylene group having carbon atoms of 3 to 6, Z is _{^{-NR 5 2, -N + R 5}} 3
_{^{A -, -NR 5 (CH 2}} ) a NR 5 2, -NR 5 (CH 2) a N +
R ⁵ ₃ A ^- and _{^{-NR 5 (CH 2) a N}} (R 5) C = O
(R ⁶ ) (R ⁵ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, R ⁶ represents an alkyl group having 1 to 4 carbon atoms, A represents Cl, Br or I;
Is an integer from 2 to 6. 1) selected from the group consisting of
Represents a valence group. Represents a substituent having an amino group or an ammonium group represented by｝, m and n are each a positive integer, m + n is an integer of 3,000 to 20,000, and n / m is 1/500 to 1 / 10,000. ]
A hair composition comprising one or more amino- or ammonium-modified high molecular silicones represented by the formula:

A second aspect of the present invention is to provide an amino-modified or ammonium-modified high molecular silicone represented by the above general formula 1 with 0.1 to 10% by weight of a general formula 2:

Embedded image (Wherein, R ⁷ represents an alkyl group having 14 to 22 carbon atoms or a hydroxyalkyl group, and R ⁸ , R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group or a benzyl group. X represents a halogen atom or an alkyl sulfate group having 1 to 2 carbon atoms.)
It is a hair composition characterized in that it is incorporated in an amount of up to 5.0% by weight.

The third aspect of the present invention is that (I) one or more of anionic surfactants, amphoteric surfactants and nonionic surfactants is contained in an amount of 5 to 40% by weight; One or more of the amino-modified or ammonium-modified high molecular silicone represented by Formula 1 is blended, and (II) /
A hair composition characterized in that the weight ratio of (I) is from 1/2000 to 1/10.

Hereinafter, the configuration of the present invention will be described in detail. The polymer silicone m + of the present invention represented by the above general formula 1
n is from 3,000 to 20,000, preferably
4,000 to 10,000. If it is less than 3,000, it is oily and the effect of preventing hair damage is insufficient.
If it exceeds 0, it will be difficult to dissolve in other raw materials such as silicone oil, and it will be difficult to mix it into cosmetics or detergents.
That is, according to JP-A-58-210005, m +
It is already known to incorporate silicones having an amino group and an ammonium group in which n is from 1 to 2,000 into hair cosmetics. However, these silicones are oily and have insufficient hair damage preventing effect. Further, n / m is 1/500 to 1 / 10,000, preferably 1/500 to 1/2000. 1
If it exceeds / 500, the content of amino groups or ammonium groups in the silicone increases, which is not preferable from the viewpoint of a cross-linking reaction or the like during production, or from the viewpoint of raw material odor. 1/1
If it is less than 000, the interaction with the hair becomes insufficient, and the durability of the hair damage preventing effect becomes poor.

The amino-modified or ammonium-modified high-molecular silicone of the present invention can be produced by the same production method as general amino-modified or ammonium-modified silicone. For example, it can be produced by performing a polycondensation reaction between γ-aminopropylmethyldiethoxysilane, cyclic dimethylpolysiloxane and hexamethyldisiloxane in the presence of an alkali catalyst. The amino-modified or ammonium-modified high-molecular silicone used in the present invention is in the form of a soft rubber, has no stickiness of the hair and scalp even when used in a large amount or is continuously used for a long time, gives excellent gloss, and gives a smooth feel. An extremely excellent hair composition that can prevent hair damage can be obtained.

The compounding amount of the amino-modified or ammonium-modified high molecular silicone in the present invention is 0.1 to 50% by weight, preferably 2 to 30% by weight based on the total amount of the composition. If the content is less than 0.1% by weight, a sufficient effect cannot be obtained.
If the content is more than the weight%, it becomes difficult to dissolve. In particular, when this composition is used as a rinse effect agent, the amount is 0.1 to 10% by weight, preferably 0.2 to 8% by weight, based on the total weight of the hair composition. If the amount is less than 0.1% by weight, a sufficient effect cannot be obtained, while if it exceeds 10% by weight, the solubility of the high molecular silicone becomes poor.

When the silicone of the present invention is compounded in a composition, it is preferable to dissolve it in a liquid oil and mix it. Of course, they may be separately blended in the hair composition and dissolved in the system. Examples of the liquid oil include a chain silicone, a cyclic silicone, and an isoparaffin hydrocarbon. The chain silicone can be represented by the following general formula.

Embedded image (In the formula, m represents an integer of 0 to 650.) As such a chain silicone oil, for example, dimethylpolysiloxane (viscosity 0.65 to 5 cSt / 25 ° C.)
And the like. The cyclic silicone is represented by the following general formula.

Embedded image (In the formula, p represents an integer of 3 to 7.)

Specific examples of these compounds include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and tetradecamethylcyclohexasiloxane, which are called by the following general names. Examples of the isoparaffinic hydrocarbon include isoparaffinic hydrocarbons having a boiling point in the range of 60 to 260 ° C. at normal pressure. For example, Isopar A (registered trademark) manufactured by Exxon, C, D, and D E, G, H, K, L, M, Shell, Solsol 71 (registered trademark), Phillip's Soltor 100 (registered trademark) or 130, 220, and the like. Any one or more of the above low-boiling oils can be used, and the total amount thereof is 1 to high molecular weight silicone.
It is preferably from 50 to 50 times (weight), and 1 in the total amount of the hair composition.
It is preferable to select from 0 to 80% by weight. When used as a cleaning agent, the content is preferably within 20% by weight.

When the composition of the present invention is used as a rinsing effect agent, the quaternary ammonium salt is a group represented by the general formula 2
⁷ is an alkyl group having 14 to 22 carbon atoms, for example, a cetyl group,
And stearyl and behenyl. Carbon number 1 of the group R ⁷
Examples of the 4 to 22 hydroxyalkyl groups include a 12-hydroxystearyl group. The group R ^7, preferably an alkyl group having 16 to 22 carbon atoms and a stearyl group and a behenyl group as particularly preferred.
The groups R ⁸ , R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. Preferred groups include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group and a hydroxyethyl group. Is mentioned. The groups R ⁸ , R ⁹ and R ¹⁰ can be the same or different. The halogen atom of the group X is preferably a chlorine atom or a bromine atom.

Examples of the quaternary ammonium salt represented by the general formula 2 include cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, behenyldimethylhydroxyethylammonium chloride, stearyldimethylbenzylammonium chloride, and cetyl Triethylammonium methyl sulfate and the like can be mentioned.
Among them, particularly preferred are stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, stearyldimethylbenzylammonium chloride and a mixture thereof. The component amount of one or more of the quaternary ammonium salts represented by the formula 2 is in the range of 0.1 to 5.0% by weight of the whole hair composition.
Preferably, it is in the range of 0.6 to 3.0% by weight. 0.1
If the amount is less than 10% by weight, a sufficient rinsing effect as a hair composition cannot be obtained. If the amount exceeds 5.0% by weight, the viscosity of the hair composition becomes too high, which is not preferable.

When the composition of the present invention is used as a detergent, the anionic surfactants include fatty acid soaps, α-acyl sulfonates, alkyl sulfonates, alkyl allyl and alkyl naphthalene sulfonates, and alkyl sulfates. , Polyoxyethylene alkyl ether sulfate, alkyl amide sulfate, alkyl phosphate, alkyl amide phosphate, alkylloyl alkyl taurate,
N-long chain acyl amino acid salts and the like. As the nonionic surfactant used in the present invention, polyoxyethylene alkyl ether, alkyl allyl polyoxyethylene ether, alkylolamide, alkyl glycerin ether type polyoxyethylene ether, propylene glycol ester polyoxyethylene ether,
Polyoxyethylene fatty acid ester, polyoxyethylene ether of glycerin and fatty acid ester, polyoxyethylene ether of sorbitan ester of fatty acid, fatty acid ester of sorbitol polyoxyethylene, sucrose ester, polyoxyethylene fatty acid amide, polyoxyethylene alkylamine And the like. Examples of the amphoteric surfactant used in the present invention include betaine type (carboxybetaine and sulfobetaine), amidobetaine type, aminocarboxylate type, and imidazoline derivative type.

In the hair cleansing composition of the present invention,
The compounding ratio of the amino-modified or ammonium-modified polymer silicone to the anionic surfactant, nonionic surfactant and amphoteric surfactant is from 1/2000 to 1/10.
And particularly preferably 1/500
~ 1/15. If it is less than 1/2000, the effect of the present invention is not exhibited, and if it exceeds 1/10, the function as a detergent such as foaming and detergency is impaired. Further, the compounding amount of the anionic surfactant, the nonionic surfactant and the amphoteric surfactant is 5 to the total amount.
40% by weight.

In addition to the above essential components, the hair composition of the present invention may further comprise liquid paraffin, squalane, a lanolin derivative, and the like, within a quantitative and qualitative range according to the purpose, without impairing the effects of the present invention. Higher alcohols, various ester oils, avocado oil, palm oil, tallow, jojoba oil, silicone oil, polyalkylene glycol polyethers and their carboxylic acid oligoester compounds, oils such as terpene hydrocarbon oils, ethylene glycol, propylene glycol, 1 , 3-butylene glycol, glycerin, sorbitol, water-soluble polyhydric alcohols such as polyethylene glycol, humectants such as hyaluronic acid, chondroitin sulfate, and pyrrolidone carboxylate, ultraviolet absorbers, ultraviolet scattering agents, acrylic resins, silicone resins, Resins such as polyvinylpyrrolidone, Bean protein, gelatin, collagen, silk fibroin, protein or protein hydrolyzate, such as elastin, ethyl paraben, preservatives such as butyl paraben, various amino acids, biotin, activators such as pantothenic acid derivatives, .gamma.-oryzanol, sodium dextran sulfate,
Blood circulation promoters such as vitamin E derivatives and nicotinic acid derivatives,
Antiseborrheic agents such as sulfur and thianthol, diluents such as ethanol, isopropanol and tetrachlorodifluoroethane, thickeners such as carboxyvinyl polymer, chemicals, fragrances, coloring agents and the like may be optionally blended. .

In particular, cationic high-molecular substances, for example, cation-modified cellulose ether derivatives (Polymer JR (U.S. Pat.
C. C), etc.), quaternary ammonium polyvinylpyrrolidone derivatives (Guffcoat (GAF), etc.), diallyldimethylammonium chloride polymers (Mercoat (Mercoat)
k) etc.), quaternary ammonium polyacrylic acid derivative (C
artex (National Starch) etc.),
Polyamide derivative quaternary ammonium (Sandoz)
Etc.) and blending a polyoxyethylene polyalkylene polyamine (such as polycoat (HENKEL)) in an amount that does not impair the effects of the present invention (to the extent that it does not cause stiffness or hair frying), thereby imparting smoothness when rinsing the detergent. The effect is additively improved in addition to the effect according to the present invention.

The dosage form of the present invention is optional, and may be any of three types: a solubilizing system, an emulsifying system, a powder dispersing system, an oil-water two-layer system, and an oil-water-powder.
Any of a layer system and the like may be used. In the case of an emulsifying system, an oil phase containing an amino-modified or ammonium-modified high molecular silicone is emulsified with an emulsifier, for example, a nonionic surfactant, a cationic surfactant, an anionic surfactant or a mixture thereof. Also, when emulsifying, dissolving an emulsifier in a water-soluble polyhydric alcohol, adding an oil containing high molecular silicone, emulsifying to make an emulsified composition, and diluting the composition with water to make an emulsified product. Can also.

Emulsifiers used in this case include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene cholesteryl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glyceryl fatty acid ester, and polyoxyethylene hydrogenated castor oil. Nonionic activators such as polyethylene glycol fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyether-modified silicone, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium chloride, behenyltrimethylammonium chloride, cetylpyridinium chloride And other cationic activators, sodium cetyl sulfate, polyoxyethylene lauryl ether Sodium, sodium lauryl sulfate, potassium coconut oil fatty acids, anionic surfactants, such as coconut oil fatty acid methyl taurine sodium. Examples of the water-soluble polyhydric alcohol include ethylel glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, dipropylene glycol, glycerin, diglycerin, triglycerin, tetraglycerin, glucose, maltose, and the like. Maltitol, sucrose, fructose, xylitol, sorbitol, maltotriose, threitol, erythritol, starch, degraded sugar-reduced alcohol, hyaluronic acid, etc., and one or more of these are used.

[0022]

The present invention will be described in more detail with reference to the following examples. The present invention is not limited by these. All amounts are by weight. Examples as Hair Restoratives Example 1 (Hair Oil) (1) Light Liquid Isoparaffin (C _11-13 ) 70.0% (2) Dimethyl Polysiloxane (5 cSt / 25 ° C.) 20.0 (3) Amino Modified polymer silicone 10.0 (R ¹ and R ^{2 in} Formula 1 are methyl groups, R ³ is — (CH ₂ ) ₃ N (CH ₃ ) ₂ , m = 5,000, n = 5) ( 4) Perfume Appropriate amount (1) to (4) are stirred and dissolved at 70 to 80 ° C. and mixed.
A viscous and transparent liquid oil having a viscosity of 500 cps was obtained.

Example 2 (Azole type hair damage preventive and repairing agent) (1) Light liquid isoparaffin (C _12-15 ) 22.0% (2) Amino-modified polymer silicone 3.0 (in general formula 1) R ¹ and R ² are methyl groups, R ³ is — (CH ₂ ) ₃ N (CH ₃ ) (CH ₂ ) ₂ N (CH ₃ ) ₂ , m = 10,000, n = 5) (3) propylene glycol 6.0 (4) Polyoxyethylene (80 mol) hydrogenated castor oil ester 2.0 (5) Cationized cellulose polymer JR-400 0.2 (manufactured by UCC) (6) Water-soluble elastin 0 (7) Deionized water 46.8 (8) Dimethyl ether 4.0 (9) Dichlorodifluoromethane 6.0 A mixture of (1) and (2) in a mixture of (3) and (4) And emulsify. The solutions (5) to (7) are added to this, and mixed and stirred to obtain a stock solution. This stock solution was filled in an aerosol can, and then the propellant gas of (8) or (9) was filled to obtain an aerosol-type hair damage preventing / restoring agent.

Comparative Example 1 (Hair oil) (1) Light liquid isoparaffin (C _11-13 ) 70.0% (2) Dimethyl polysiloxane (5 cSt / 25 ° C.) 30.0 (3) Appropriate amount of fragrance (1) to ( 3) was mixed to obtain a liquid hair oil.

Comparative Example 2 (Hair oil) (1) Light liquid isoparaffin (C _11-13 ) 70.0% (2) Dimethyl polysiloxane (5 cSt / 25 ° C.) 20.0 (3) High molecular weight dimethyl polysiloxane 0 (degree of polymerization n = 7,000) (4) Appropriate amount of fragrance (1) to (4) were mixed to obtain a liquid hair oil.

With respect to Examples 1 and 2, and Comparative Examples 1 and 2, the smoothness of the hair, the effect of preventing the generation of split ends and the effect of repairing split ends were measured. Test Example 1 Measurement of Smoothness of Hair A hair bundle was formed from hair collected from the same person, the following samples were applied to each hair bundle, and the friction coefficient of the hair was measured by a friction measuring machine. After that, shampoo each hair bundle
And washed thoroughly with water, and then dried with a drier to measure the friction coefficient of the hair. Table 1 shows the results.

[0027]

[Table 1] ─────────────────────────── Shampoo immediately after sample application-Friction coefficient of Friction coefficient 後──────────────────── Example 1 0.2 0.25 Example 2 0.25 0.3 Comparative Example 1 0.35 0.5 Comparative Example 2 0.3 0.4 Uncoated 0.5 0.5 摩擦 By using the product of the present invention, friction It can be seen that the coefficient was significantly reduced and the hair remained smooth after shampooing.

Test Example 2 Measurement of Effect of Preventing Split Hair Generation A hair bundle was made from hair collected from the same person, the following sample was applied to each hair bundle, and one brushing was performed mechanically.
The number of split ends generated after 10,000 times was counted. Each hair bundle is 13
It consists of 00 hair. Table 2 shows the results.

[0029]

[Table 2] The product of the present invention had a remarkable effect in preventing split ends.

Test Example 3 Measurement of the effect of repairing split ends Four of the panels having many split ends used the hair oil of Example 1 to determine the effect of split ends. As a result, in each of the panels, the split ends became inconspicuous, and the repair effect of the product of the present invention was confirmed.

Example 3 (Hair Blow) (1) Decamethylcyclopentasiloxane 5.0% (2) Ammonium-modified polymer silicone 1.0 (In the general formula 1, 10% of R ¹ is a phenyl group remaining. Is a methyl group, R ² is a methyl group, R ³ is — (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₃ Cl ⁻ , m = 10,000, n = 2) (3) 1,3-butylene glycol 2.0 (4) Polyethylene (60) hydrogenated castor oil ester 2.0 (5) Ethyl alcohol 95% 15.0 (6) Purified water 75.0 (7) Perfume suitable amount (4) Dissolve (4) in (3) Then, (1) and (2) are added, emulsified, and mixed with (5), (6) and (7). Fill in a dispenser container and spray in mist on the hair.

Example 4 (Hair Mousse) (1) Decamethylcyclopentasiloxane 20.0% (2) Amino-modified polymer silicone 5.0 (In the general formula 1, R ¹ is a methyl group, R ² is Hydroxyl group, R ³ is — (CH ₂ ) ₃ N (CH ₃ ) ₂ , m = 3,000, n = 6) (3) dipropylene glycol 5.0 (4) polyoxyethylene-modified dimethylpolysiloxane 3 0.0 (EO 50 wt%, viscosity 100 cSt / 25 ° C.) (5) Ethanol 10.0 (6) Ion-exchanged water 51.0 (7) Appropriate amount of perfume (8) Butane 4.0 (9) Dimethyl ether 2 0.0 Dissolve (2) in (1), add to the mixture of (3) and (4) and emulsify. The emulsion is added to a solution obtained by mixing (5) to (7), and the emulsion is put in an aerosol solution, and after a valve is attached, (8) and (9) are filled.

Example 5 (Hair Cream) (1) Isosol 400 10.0% (Nippon Petrochemical Co., Ltd., low boiling point isoparaffinic hydrocarbon) (2) Ammonium-modified polymer silicone 3.0 ( In the general formula 1, R ¹ is a methyl group, R ² is a hydroxyl group, R ³ is — (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₃ Cl ⁻ , m = 18,000, n = 2) (3) Dimethylpolysiloxane (2OcSt / 25 ° C.) 5.0 (4) Glycerin tri-2-ethylhexanoate 8.0 (5) Vaseline 5.0 (6) Stearyl alcohol 2.0 (7) Sorbitan monooleate 2 2.0 (8) Polyoxyethylene (40 mol) 2.0 Hardened castor oil ester (9) Glycerin 5.0 (10) Hyaluronic acid 5.0 (11) Preservatives Appropriate amount (12) Deionized water residue (1) ~ (8) to 70 In a stirred solution, (9) - (1
2) is added to the dissolved substance and emulsified to obtain a hair cream.

Example 6 (Hair lotion) (1) Shellsol 71 15.0% (manufactured by Shell Co., low boiling point isoparaffin hydrocarbon) (2) Amino-modified polymer silicone 3.0 (general formula) 1, R ¹ and R ² are methyl groups, R ³ is — (CH ₂ ) ₃ N (CH ₃ ) ₂ , m = 8,000, n = 10) (3) 1,3-butylene glycol 0 (4) Polyoxyethylene (60 mol) 2.0 Hydrogenated castor oil ester (5) Titanium oxide sol (Neosample W-10, manufactured by Catalyst Kasei Kogyo) 10.0 (6) Ethanol 15.0 (7 ) Ion-exchanged water 53.0 (8) Appropriate amount of perfume (2) dissolved in (1), added to the mixture of (3) and (4) and emulsified, The mixture was dissolved in the lysate to obtain a hair lotion.

Example 7 (Hair spray) (1) Light liquid isoparaffin (C _12-15 ) 40.0 (2) Amino-modified polymer silicone 0.5 (In the general formula 1, R ¹ and R ² are methyl Group, R ³ is — (CH ₂ ) ₃ N (CH ₃ ) (CH ₂ ) ₂ N (CH ₃ ) C 2O (C ₂ H ₅ ), m = 15,000, n = 4) (3) ethanol 2.0 (4) Isopropyl alcohol 10.0 (5) Appropriate amount of perfume (6) Propane 7.0 (7) Dimethyl ether 3.0 (1) to (5) are mixed and dissolved. After filling in an aerosol can and attaching a valve, the propellant of (6) and (7) was filled to obtain a hair spray.

Example as Hair Rinse Effect Agent Example 8 A hair rinse was produced according to the composition shown in Table 3 according to a conventional method. Table 3 also shows the results of the evaluation of each product by the following method. (1) Hair protection effect 1 g of each sample is applied to a hair bundle of 500 cm to 600 hairs each having a length of 15 cm, and the hair bundle is dried by shaking and rinsing (100 cycles) twice in 300 ml of hot water at 40 ° C., and then the hair bundle is dried. Let it. The hair bundle is repeatedly brushed with a constant force and brushed 20,000 times, and the number of split ends and cut ends generated is counted, and the split ends and cut end incidences with respect to the total number of hairs are calculated. The incidence Y% of each sample treated hair was compared with the incidence X% of split ends and cut hairs of the untreated hair, and evaluated by the value of Y / X as follows. Y / X evaluation Y / X <0.5 A hair protection effect large 0.5 ≦ Y / X <0.8 B hair protection effect medium 0.8 ≦ Y / X <1.0 ·・ ・ C Hair protection effect small 1.0 ≦ Y / X ・ ・ ・ D Hair protection effect None

(2) Measurement of Adsorption Amount on Hair 2 g of each sample was applied to 4 g of the hair bundle after complete degreasing, and the hair was rinsed (100 cycles) twice in 1 l of warm water (40 ° C.). Dry the bundle. Soxhlet extraction (dichloromethane / methanol = 92/8 vol%, 5 hr extraction) of the adsorbed material from each hair bundle,
The amount of sample adsorbed per gram of hair was calculated from the weight.
The adsorptivity of each sample to hair was evaluated as follows. Evaluation of sample adsorption amount per 1g hair 30mg or more… A Adsorption to hair Large 10-30mg ・ ・ ・ B Adsorption to hair Medium 10mg or less ・ ・ ・ C Adsorption to hair Small

(3) Effect of imparting gloss to hair 1 g of each sample is applied to a bundle of 500 to 600 hairs each having a length of 15 cm and is subjected to shaking and rinsing (100 cycles) twice in 300 ml of warm water at 40 ° C. The hair bundle is dried. Ten hairs are arbitrarily selected from the hair bundle, and the reflected light distribution of the hairs with respect to the incident light is measured by a goniophotometer GP-IR (manufactured by Murakami Color Research Laboratory Co., Ltd.), and the glossiness (gloss) ) Was determined by the following equation. G = s / d (G: glossiness, s: specular reflection light quantity, d: diffuse reflection light quantity) The gloss effect of each sample on hair was evaluated by the glossiness G obtained by the above method as follows. .

(4) Uniform Coatability The uniform coatability was evaluated from a scanning electron microscope (SEM) photograph of a hair sample prepared in the same manner as in measuring the gloss of hair. SEM pictures of hair treated with each sample (400-
1000 times) by 15 judges, SE of untreated hair
Uniform coatability is "good""comparable" compared to M-photo
Was evaluated in two stages. Evaluation was made as follows from the results of the determination. Judgment result evaluation All 15 people answered "good" ... A 8 to 14 out of 15 people answered "good" B 7 out of 15 answered "good" What ... C

(5) Smoothness after Drying (Sensory Evaluation of Effect on Hair) As test subjects, 15 women aged 19 to 36 years old were selected. Each test subject applied 12 g of each sample to the hair after washing with a commercially available hair shampoo (normal alkyl sulfate ester shampoo), rinsed with water at about 40 ° C., and then dried with a dryer. The feel of the hair was measured using a control sample (stearyltrimethylammonium chloride 2.0).
%, 3.0% of cetostearyl alcohol, 5.0% of propylene glycol and 90% of water), markedly excellent, "good", "same as" and "poor". It was evaluated on a scale. Evaluation was made as follows from the results of the determination. Of the 15 evaluation results , 12 or more answered “significantly good” or “good” A out of 15, 8 to 11 answered “notably good” or “good” B out of 15 4 to 7 persons answered "significantly good" or "good" C 15 out of 15 persons answered "significantly good" or "good" D

[0041]

[Table 3]

As can be seen from Table 3, the hair cosmetic composition of the present invention has a hair protection effect, smoothness after drying, absorptivity to hair, a gloss imparting effect to hair, and a uniform coatability as compared with Comparative Examples. It was excellent.

Example 9 A hair rinse having the following formulation was prepared and evaluated in the same manner as in Example 8. Ingredient Weight% cetyltrimethylammonium chloride 0.6 cetostearyl alcohol (C16 / C18 = 6/4 ) 2.0 Amino-modified silicone polymer 3.0 (R ¹ and R ² are methyl, R ³ is - (CH ₂ ) ₃ N (CH ₃ ) (CH ₂ ) ₂ N (CH ₃ ) ₂ m = 10,000, n = 5) Cyclic Silicon Pentamer 15.0 Glycerol Monostearate 1.0 Stearic Acid 0.5 Glycerin 5 5.0 Propylene glycol 5.0 Yellow-4 (dye) Suitable amount Perfume Suitable amount Methylparaben Suitable amount EDTA-3Na (Chelating agent) Suitable amount Ion-exchanged water residue This hair rinse is excellent in stability and has never before been excellent in sensory test evaluation. It exhibited smoothness and provided an excellent protective effect to the hair.

Example 10 A hair treatment cream having the following formulation was prepared and evaluated in the same manner as in each of the above examples. Ingredient Weight% Behenyltrimethylammonium 3.0 cetostearyl alcohol chloride (C16 / C18 = 7/3 ) 6.5 behenyl 2.0 Dimethyl polysiloxane 5cs 20.0 ammonium-modified silicone polymer 6.0 (R ¹ is a methyl group , R ² is a hydroxyl group, R ³ is — (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₃ Cl ⁻ , m = 18,000, n = 2) 2-octyldodecanol 2.0 polyoxyethylene hydrogenated castor oil derivative 0.3 (Ethylene oxide 60 mol adduct) Polyoxyethylene stearyl ether 1.0 (Ethylene oxide 4 mol adduct) Soybean lecithin 0.5 Glycerin 10.0 Dipropylene glycol 5.0 Yellow-4 (pigment) Appropriate amount Perfume Appropriate amount Methylparaben qs EDTA-3Na (chelating agent) qs ion-exchanged water residue Instrument cream, compared especially damaged hair, provides excellent smoothness, it was having good hair protective effect.

Example as a Detergent Example 11 A shampoo composition was prepared according to a conventional method using the composition shown in Table 4. Table 4 also shows the results of the evaluation of each composition by the following method. (1) Smoothness of Hair after Hair Washing The tester actually washed hair, and organoleptically evaluated the smoothness of hair after rinsing and after natural drying. ：: Smooth △: Slightly smooth ×: Not smooth (2) Ease of combing the hair after shampoo The tester actually washed the hair, and sensory evaluated the easiness of combing the hair after rinsing and drying. ○: Comb is easy to pass △: Slightly difficult to pass ×: Scratch is difficult to pass

(3) Foaming Test Method 400 ml of a 1% sample concentration solution was prepared with 70 ppm of artificial hard water of CaCO _3, and the foaming amount was measured at 40 ° C. using a cylindrical cylinder with a stirrer. . ：: good foaming foam amount 2,000 ml or more △: normal foaming foam amount 1,500 ml or more 2,000
Less than 1 ml ×: Poor foaming Foam amount less than 1,500 ml (4) Detergency test method CaO / MgO = 3/1, 5% DH An artificial sebum was prepared by preparing a 1% solution in artificial hard water and using wool surge. The contaminated cloth was washed. Washing was performed using a targotometer (JIS K-3371) at a temperature of 40 ° C., and the washing effect was determined from the reflectance before and after washing. Washing efficiency _{(%) = (R W -R} S / R O -R S) × 100 R O: reflectance R _S of the original cloth (wool serge): reflectance R _W of stained cloth: after washing of soiled cloth Reflectivity ○: Good washability Washing efficiency 80% or more △: Normal washability 60% or more, less than 80% ×: Poor washability Washing efficiency less than 60%

[0047]

[Table 4] 試 料 Comparative sample Sample of the present invention Sample number ─ ──── ──────────── 1 2 1 2 3 4 ────────────────────────────ナ ト リ ウ ム Sodium dodecyl sulfate 20 20 20 20 20 20 Amino-modified high polymer silicone ^{* 1} 0 3.0 0.05 0.1 0.5 1.0 Dimethyl polysiloxane 3.0 4.5 0.075 0.15 0.75 1.5 (5cs) Water Residual Residual Residual Residual Residue ─髪 After shampoo Smoothness After rinsing × ○ ○ ○ ○ ○ After drying × ○ ○ ○ ○ ○ After combing Rinse × ○ ○ ○ ○ ○ After drying × ○ ○ ○ ○ ○ ───────────────────────── ─────────── Foaming × ○ ○ ○ ○ cleaning of ○ × ○ ○ ○ ○ ──────────────────────────────────── ^{* 1} : R ¹ is a methyl group, R ² is a hydroxyl group, R ³ is — (CH ₂ ) ₃ N (CH ₃ ) ₂ , m = 3,000, n = 6

As is evident from Table 4, the composition for hair of the present invention, when used as a shampoo, has excellent smoothness and combability after rinsing and drying, and also has good foaming and cleaning properties. It turns out that it is excellent. Example 12 Shampoo compositions shown in Table 5 below were prepared and evaluated.

[0049]

[Table 5] 試 料 Comparative sample Sample of the present invention Sample number ─ ─────── ２ 1 2 3 1 2 3 ─────────────────────────── ───────── Surfactant Lauroylmethyltaurine-Na 20--20--(Anionic surfactant) N-lauryldimethylamino betaine acetate-15--15-Imidazolium betaine--20- -20 (Amphoteric surfactant) Amino-modified polymer silicone ^{* 2} 0 0 0 1 1 1 Cyclic silicone pentamer 2 2 2 2 2 2 Water Residue Residue Residue Residue Residue ───────────髪 After shampooing Smoothness After rinsing × × × ○ ○ ○ After drying × × × ○ ○ ○ Comb rinse After × × × ○ ○ ○ After drying × × × ○ ○ ○ ──────────────────────────────────── Foaming property ○ ○ ○ ○ ○ ○ Washability ○ ○ ○ ○ ○ ○ ──────────────────────────────────── ^{* 2} : R ¹ and R ² are methyl groups, R ³ is — (CH ₂ ) ₃ N (CH ₃ ) ₂ m = 8,000, n = 10

As is clear from Table 5, the hair composition of the present invention is excellent in smoothness and combability after rinsing and drying when used as a shampoo, and also excellent in foaming and washing properties. You can see that it is.

Example 13 A shampoo having the following composition was prepared. Isosol 400 (Nippon Petrochemicals Co., Ltd.) 4.0 ammonium modified silicone polymer 0.5 (R ¹ is methyl, R ² is a hydroxyl group, R ³ is ^{_{- (CH 2) 3 N +}} (CH 3) 3 Cl - , M = 18,000, n = 2) Cocoyl methyl taurine-Na 8.0 Cocoyl propyl amide betaine 12.0 Palm fatty acid diethanolamide 4.0 Glycerin 2.0 Fragrance 0.3 Water Residue This shampoo has a foaming property. It was excellent in washability, smoothness after rinsing and drying, and excellent combability.

[0052]

Industrial Applicability The composition for hair of the present invention gives rich gloss and smoothness to hair, prevents damage to hair such as split ends and cut hair, and repairs split ends that have occurred. It is a hair composition having an effect of making it less noticeable. Also, when the composition of the present invention is used as a hair rinse effect agent containing a water rinsing step of a hair rinse, a hair treatment, a hair pack, etc., it does not stick the hair and can impart excellent smoothness and luster to the hair. Thus, a hair composition having a high effect of protecting hair from physical stimuli such as brushing can be obtained. Furthermore, when the composition of the present invention is used as a shampoo composition, in addition to the smoothness when rinsing the detergent, even after complete drying, it can smooth and moisten the hair. .

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-338317 (JP, A) JP-A-2-160712 (JP, A) JP-A 1-132509 (JP, A) JP-A-1-132509 106811 (JP, A) JP-A-63-222109 (JP, A) JP-A-55-66506 (JP, A) JP-A-4-270209 (JP, A) JP-A-63-131714 (JP, A) JP-A-4-230615 (JP, A) JP-A-3-287519 (JP, A) JP-A-1-110611 (JP, A) JP-A-61-109707 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) A61K 7/06 A61K 7/08

Claims (8)

(57) [Claims] 1. A compound of the general formula: [In the formula, R ¹ represents a methyl group or a part thereof is a phenyl group, and R ² represents the same as R ³ or a methyl group or a hydroxyl group. R ³ is wherein R ⁴ Z {R ⁴ represents a divalent alkylene group having carbon atoms of 3 to 6, Z is _{^{-NR 5 2, -N + R 5}} 3
_{^{A -, -NR 5 (CH 2}} ) a NR 5 2, -NR 5 (CH 2) a N +
R ⁵ ₃ A ^- and _{^{-NR 5 (CH 2) a N}} (R 5) C = O
(R ⁶ ) (R ⁵ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, R ⁶ represents an alkyl group having 1 to 4 carbon atoms, A represents Cl, Br or I, a
Is an integer from 2 to 6. 1) selected from the group consisting of
Represents a valence group. Represents a substituent having an amino group or an ammonium group represented by｝, m and n are each a positive integer, m + n is an integer of 3,000 to 20,000, and n / m is 1/500 to 1 / 10,000. ]
A hair composition comprising one or more amino-modified or ammonium-modified high molecular silicone represented by the formula: 2. An amount of one or more of the amino-modified or ammonium-modified high molecular silicones according to claim 1 in an amount of 0.1 to 10% by weight and a general formula: (Wherein, R ⁷ represents an alkyl group having 14 to 22 carbon atoms or a hydroxyalkyl group, and R ⁸ , R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group or a benzyl group. X represents a halogen atom or an alkyl sulfate group having 1 to 2 carbon atoms.)
A composition for hair, which is contained in an amount of up to 5.0% by weight. 3. An amount of one or more of (I) an anionic surfactant, an amphoteric surfactant, and a nonionic surfactant in an amount of 5 to 40% by weight; Mix one or more of ammonium-modified high molecular silicone,
A hair composition, wherein the weight ratio of (II) / (I) is 1/2000 to 1/10. 4. The hair composition according to claim 1, wherein an amino-modified or ammonium-modified high molecular weight silicone is dissolved in a liquid cyclic silicone. 5. The hair composition according to claim 1, wherein an amino-modified or ammonium-modified high molecular weight silicone is dissolved in a liquid chain silicone. 6. The hair composition according to claim 1, wherein an amino-modified or ammonium-modified high-molecular-weight silicone is dissolved in a liquid isoparaffinic hydrocarbon. 7. An emulsion-type hair composition obtained by emulsifying the amino-modified or ammonium-modified polymer silicone solution according to any one of claims 4 to 6 with an emulsifier. 8. The emulsion type emulsion according to claim 7, wherein, during the emulsification, an amino-modified or ammonium-modified polymer silicone solution is added to a solution obtained by dissolving an emulsifier in a water-soluble polyhydric alcohol to emulsify. Hair composition.