JP4889089B2 - Hair cosmetics - Google Patents

Description

  The present invention has a very good smoothness when applied to hair cosmetics, especially when applied to hair, and gives a moist and dry feeling to the hair after drying. The present invention relates to a hair cosmetic that is excellent in hair conditioning and has improved hair condition and smoothness.

After washing hair with shampoo or the like, gloss and fingering generally deteriorate, and thus treatment agents such as hair conditioners have been used after shampooing.
Such a treatment agent (hereinafter sometimes simply referred to as a hair conditioner) is usually mixed with a quaternary ammonium salt type cationic surfactant. Cationic surfactants are highly effective in imparting flexibility and antistatic properties to hair, and are therefore incorporated into various hair cosmetics including treatment agents, but lack gloss and smoothness.
Examples of hair cosmetics that give glossiness and a smooth feel include, for example, hair cosmetics containing high molecular weight silicone (Japanese Patent Laid-Open No. 63-183517), and hair cosmetics containing amino-modified silicone (Japanese Patent Laid-Open No. Hei 4-4-1). No. 338317) is disclosed.
JP 63-183517 A JP-A-4-338317

  However, hair cosmetics containing the above-described high molecular weight silicone are not sufficiently satisfactory in terms of sustainability of the hair protection effect due to insufficient adsorptivity to hair. In addition, since the hair cosmetic containing the amino-modified silicone uses a low molecular weight (low polymerization degree) amino-modified silicone, a smooth finish cannot be obtained. Moreover, the stability of the compound itself was poor, and problems such as odor were liable to occur.

  The present invention has been made in view of the above-mentioned problems of the prior art, and its purpose is to be familiar with hair during use, smoothness and rinsing when rinsing, gloss in finish after drying, smoothness, softness, An object of the present invention is to provide a hair cosmetic that exhibits a good effect in a smooth and moist feeling.

As a result of intensive studies by the present inventors in order to solve the above-mentioned problems, synergistically excellent effects are exhibited by blending a specific amino-modified or ammonium-modified silicone with a specific hydroxy ether amine. As a result, the present invention has been completed.
That is, the hair cosmetic according to the present invention is a hair cosmetic characterized by containing the following components (A) and (B).
(A) Amino-modified or ammonium-modified silicone represented by the following general formula (I).

［式（Ｉ）中、Ｒ¹はそれぞれ独立してメチル基、フェニル基又は水酸基である。
Ｒ²はそれぞれ独立して式−Ｒ⁴Ｚで表される基であり、Ｒ⁴は炭素数３〜６のアルキレン基、Ｚは窒素含有基であり、下記式：

[In formula (I), each R ¹ independently represents a methyl group, a phenyl group or a hydroxyl group.
R ² is independently a group represented by the formula —R ⁴ Z, R ⁴ is an alkylene group having 3 to 6 carbon atoms, Z is a nitrogen-containing group, and the following formula:

（Ｒ⁵はそれぞれ独立して水素原子又は炭素数１〜３０のアルキル基、Ｒ⁶は炭素数１〜３０のアルキル基、Ａは塩素原子又は臭素原子又はヨウ素原子、ｂは２〜６の整数である。）で表される基である。
ａは０〜３の整数であり、ｍ及びｎはそれぞれ正の整数で、ｍ＋ｎの平均値は４０００〜６０００、ｎ／ｍの平均値は０．００５〜０．０３である。］

(R ⁵ is independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, R ⁶ is an alkyl group having 1 to 30 carbon atoms, A is a chlorine atom, bromine atom or iodine atom, b is an integer of 2 to 6) It is a group represented by.
a is an integer of 0 to 3, m and n are each a positive integer, the average value of m + n is 4000 to 6000, and the average value of n / m is 0.005 to 0.03. ]

［式（II）中、Ｒ^１、Ｒ^２はそれぞれ炭素数１〜３のアルキル基あるいはヒドロキシアルキル基あるいは下記一般式（III）で示される基であるが、Ｒ^１、Ｒ^２の少なくとも一方／又は両方は前記一般式（III）で示される基である。Ｒ^３は炭素数１〜３のアルキル基あるいはヒドロキシアルキル基である。

（式（III）中、Ｒは直鎖又は分岐した炭素数６〜２４のアルキル基、アルケニル基あるいはヒドロキシアルキル基であり、ｎは１〜５の整数である。）］ (B) A hydroxy ether amine compound represented by the following general formula (II).

[In the formula (II), R ¹ and R ² are each an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group or a group represented by the following general formula (III), but at least one of R ¹ and R ² / Or both are groups represented by the general formula (III). R ³ is an alkyl group having 1 to ³ carbon atoms or a hydroxyalkyl group.

(In the formula (III), R is a linear or branched alkyl group having 6 to 24 carbon atoms, an alkenyl group or a hydroxyalkyl group, and n is an integer of 1 to 5)]

In the hair cosmetic composition of the present invention, it is preferable that the blending amount of each component in the hair cosmetic composition is in the following range.
(A) 0.01-10.0 mass%.
(B) 0.01-10.0 mass%.
The hair cosmetic composition of the present invention preferably further contains a reactive silicone block copolymer represented by the following general formula (IV).

[式（IV）中、Ｒ^１は脂肪族不飽和を含まない１価の炭化水素基である。
Ｘは

の何れかで示される反応性官能基である。
Ｒ^２はＲ^１またはＸで定義された何れかの基を表す。
ｎは２〜４の整数である。
ａは少なくとも２の整数であり、ｂは少なくとも１の整数であり、ｃは少なくとも４の整数であり、ｄは少なくとも２の整数である。
Ｙは炭素−珪素によって隣接珪素原子に、そして酸素原子によってポリオキシアルキレンブロックに結合している２価の有機基を表し、−Ｒ ^４ −，−Ｒ ^４ −ＣＯ−，−Ｒ ^４ −ＮＨＣＯ−，−Ｒ ^４ −ＮＨＣＯＮＨＲ ^５ −ＮＨＣＯ−または−Ｒ ^４ −ＯＯＣＮＨ−Ｒ ^５ −ＮＨＣＯ−で示される基である（Ｒ ^４ はエチレン基、プロピレン基、ブチレン基から選ばれる２価のアルキレン基、Ｒ ^５ はＲ ^４ として例示した２価のアルキレン基または−Ｃ _６ Ｈ _４ −、−Ｃ _６ Ｈ _４ −Ｃ _６ Ｈ _４ −、−Ｃ _６ Ｈ _４ −ＣＨ _２ −Ｃ _６ Ｈ _４ −、−Ｃ _６ Ｈ _４ −ＣＨ（ＣＨ _３ ）−Ｃ _６ Ｈ _４ −から選ばれる２価のアリレン基である）。
シロキサンブロックの平均分子量は２５０〜１０，０００であり、各ポリオキシアルキレンブロックの平均分子量は２００〜１０，０００であり、シロキサンブロックは共重合体の２５〜９５質量％を構成し、ブロック共重合体は少なくとも１，０００の平均分子量を有する。]
また、本発明にかかる毛髪化粧料がヘアコンディショナー組成物であることが好適である。

[In the formula (IV), R ¹ is a monovalent hydrocarbon group containing no aliphatic unsaturation.
X is

It is a reactive functional group shown by either .
R ² represents any group defined by R ¹ or X.
n is an integer of 2-4.
a is an integer of at least 2, b is an integer of at least 1, c is an integer of at least 4, and d is an integer of at least 2.
Y is carbon - Represents a divalent organic group bonded to the polyoxyalkylene block in the adjacent silicon atom by a silicon, and by oxygen ^{atoms, -R 4 -, - R 4} -CO -, - R 4 -NHCO —, —R ⁴ —NHCONHR ⁵ —NHCO— or —R ⁴ —OOCNH—R ⁵ —NHCO— (R ⁴ is a divalent alkylene group selected from an ethylene group, a propylene group and a butylene group, R ⁵ represents the divalent alkylene group exemplified as R ⁴ , or —C ₆ H ₄ —, —C ₆ H ₄ —C ₆ H ₄ —, —C ₆ H ₄ —CH ₂ —C ₆ H ₄ —, —C ₆ H ₄ —CH (CH ₃ ) —C ₆ H ₄ — is a divalent arylene group) .
The average molecular weight of the siloxane block is 250 to 10,000 , the average molecular weight of each polyoxyalkylene block is 200 to 10,000 , and the siloxane block constitutes 25 to 95% by mass of the copolymer . The coalescence has an average molecular weight of at least 1,000. ]
In addition, the hair cosmetic composition according to the present invention is preferably a hair conditioner composition.

  The hair cosmetic composition of the present invention is a combination of a specific amino-modified or ammonium-modified silicone and a specific hydroxy ether amine. It exhibits a very high effect in moistness, smoothness, softness and the like, and can exhibit excellent feel at all stages from application to rinsing and drying.

<Amino-modified or ammonium-modified silicone>
The amino-modified or ammonium-modified silicone of component (A) used in the hair cosmetic composition of the present invention is represented by the general formula (I).
The average value of the degree of polymerization m + n in the modified silicone (I) is preferably in the range of 4000 to 6000. If it is less than 4000 (low degree of polymerization), the effect is insufficient and stickiness occurs. In addition, the stability of the compound itself is deteriorated. If it exceeds 6000 (the degree of polymerization is high), the finish will be non-uniform and the hair will be stiff. In addition, blending into hair cosmetics becomes difficult.

The average value of n / m is preferably 0.005 to 0.03, particularly preferably 0.005 to 0.01. When the amination rate is low , the adsorptivity to hair is poor and the sustainability of the effect tends to be poor. On the other hand, if it exceeds 0.03 (amination rate is too high), a sticky feeling is imparted to the hair.
The amino-modified or ammonium-modified silicone can be used alone or in combination of two or more. Even when two or more types are used in combination, the average value of m + n and n / m needs to be within the above range.

The amino-modified or ammonium-modified silicone of the present invention can be produced by the same production method as a general amino-modified or ammonium-modified silicone. For example, it can be produced by subjecting γ-aminopropylmethyldiethoxysilane, cyclic dimethylpolysiloxane, and hexamethyldisiloxane to a polycondensation reaction in the presence of an alkali catalyst.
The compounding amount of the amino-modified or ammonium-modified silicone in the present invention is 0.01 to 10% by mass, preferably 0.1 to 5% by mass in the total amount of the hair cosmetic. If it is less than 0.01% by mass, a sufficient effect cannot be obtained.

Since the amino-modified or ammonium-modified silicone of the present invention has a high viscosity, it is preferably dissolved in a low-viscosity liquid oil and blended in the hair cosmetic. Examples of the low-viscosity liquid oil include chain silicone, cyclic silicone, and isoparaffinic hydrocarbon.
Examples of the chain silicone oil include dimethylpolysiloxane (viscosity 0.65 to 200 cSt / 25 ° C.).
Examples of the cyclic silicone oil include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and tetradecamethylcyclohexasiloxane.
Examples of isoparaffinic hydrocarbons include isoparaffinic hydrocarbons having a boiling point in the range of 60 to 260 ° C. under normal pressure, such as Isopar A (registered trademark), C, D, E, G, H, K, L, M, Shellsol 71 (registered trademark) from Shell, Saltol 100 (registered trademark) from Philip or 130, 220, etc. .

As the low-viscosity liquid oil, any one or two or more kinds can be used, and the total blending amount is preferably 1 to 50 times (mass) with respect to amino modification or ammonium modification, It is preferable that it is 1-90 mass%.
The amino-modified or ammonium-modified silicone and the low-viscosity liquid oil may be separately blended in the hair cosmetic and dissolved in the system.

<Hydroxyetheramine>
The hydroxy ether amine (B) used in the present invention is represented by the formula (II).
In formula (II), one or both of R ¹ and R ² is a hydroxy ether group represented by the following general formula (III).
In the formula (III), R is preferably an alkyl group, more preferably an alkyl group having 12 to 22 carbon atoms.
n is preferably 1 to 3, and more preferably 1.

The hydroxy ether amine of the formula (II) can be produced, for example, by the method described in JP-A No. 2004-323495, but other known methods may be used.
Japanese Patent Application Laid-Open No. 2004-323495 describes that hydroxyetheramine is blended in hair cosmetics for the purpose of flexibility, moistness, smoothness, slipperiness, and the like of hair after drying. However, the blending of hydroxy ether amine has a limit in the effect, which is not sufficient, and lacks smoothness and fingering during rinsing.
In the hair cosmetic composition of the present invention, by using a specific amino / ammonium modified silicone and hydroxy ether amine in combination, both act synergistically, and the effect is significantly improved compared to when each is used alone. Is recognized. Japanese Patent Application Laid-Open No. 2004-323495 does not suggest any combined effect of hydroxyetheramine and amino / ammonium modified silicone.

  In the hair cosmetic composition of the present invention, the amount of hydroxyetheramine is preferably 0.01 to 10% by mass, more preferably 1 to 5% by weight. If the blending amount is too small, a sufficient effect cannot be exhibited, and even if blended excessively, the effect is not improved and may adversely affect.

In the present invention, it is preferable to add an inorganic acid and / or an organic acid in order to neutralize the hydroxy ether amine and adjust the pH of the composition.
Examples of the inorganic acid include hydrochloric acid, sulfuric acid, and phosphoric acid, and examples of the organic acid include acetic acid, lactic acid, glycolic acid, citric acid, glutamic acid, malic acid, and succinic acid. , Glutamic acid.
In this invention, 1 type (s) or 2 or more types of inorganic acid / organic acid can be used.

  In the hair cosmetic composition of the present invention, the blending amount of the inorganic acid / organic acid is preferably 0.3 to 5 mol times, more preferably 0.5 to 3 mol times, per mol of hydroxy ether amine. It is preferable that the hair cosmetic is adjusted to pH 2 to 8, more preferably 3 to 6 from the feel of the hair and the stability of the product.

<Reactive silicone block copolymer>
In addition to the above essential components, when the reactive silicone block copolymer represented by the general formula (IV) is further blended, the conditioning effect, particularly the smoothness and moist feeling of the hair after rinsing and drying can be further improved. Can do.
In formula (IV), R ¹ is a monovalent hydrocarbon group containing no aliphatic unsaturation independently of each other. Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a dodecyl group, a phenyl group, and a phenethyl group, and a methyl group, an ethyl group, and a phenyl group are preferable, and a methyl group is particularly preferable.

Specific examples of X groups,

などが挙げられる。
Ｘ基としては、−（ＣＨ_２）_３ＮＨ_２、−（ＣＨ_２）_３ＮＨ（ＣＨ_２）_２ＮＨ_２、−（ＣＨ_２ ）_３Ｎ（ＣＨ_３）_２、−（ＣＨ_２）_３Ｎ（ＣＨ_３）（ＣＨ_２）_２Ｎ（ＣＨ_３）_２等のアミノ基含有基や−（ＣＨ_２）_３Ｎ^＋（ＣＨ_３）_３Ｃｌ⁻等のアンモニウム基含有基であることが効果の点で好ましい。

And the like.
X group includes — (CH ₂ ) ₃ NH ₂ , — (CH ₂ ) ₃ NH (CH ₂ ) ₂ NH ₂ , — (CH ₂ ) ₃ N (CH ₃ ) ₂ , — (CH ₂ ) ₃ N ( _{CH 3) (CH 2) 2} N (CH 3) or an amino group-containing group ₂ such as ^{_{- (CH 2) 3 N +}} (CH 3) 3 Cl - in terms of the effect that the ammonium group-containing group such as preferable.

In formula (IV), Y is a divalent organic group, one bond end of which is bonded to an adjacent silicon atom by carbon-silicon, and the other bond end is bonded to a polyoxyalkylene block by an oxygen atom. .
Examples of the divalent organic group represented by ^{Y, -R 4 -, - R 4} -CO -, - R 4 -NHCO -, - R 4 -NHCONHR 5 -NHCO- or ^-R 4 -OOCNH-R ^5- NHCO- (wherein R ⁴ is a divalent alkylene group such as an ethylene group, propylene group, butylene group, etc., and R ⁵ is a divalent alkylene group such as the group exemplified as R ⁴ or a divalent group. arylene group, _{e.g., -C 6 H 4 -, -} C 6 H 4 -C 6 H 4 -, - C 6 H 4 -CH 2 -C 6 H 4 -, - C 6 H 4 -CH (CH 3) -C ₆ H ₄ - is, etc.).. The group Y is preferably —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ ) CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ —, — (CH ₂ ). _{2 CO -, - (CH 2} ) 3 NHCO -, - (CH 2) 3 NHCONHC 6 H 4 NHCO- or _{- (CH 2) 3 OOCNHC 6} H 4 is NHCO-, especially preferred group Y is a divalent alkylene Groups (—CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ ) CH ₂ —, etc.), with —CH ₂ CH (CH ₃ ) CH ₂ — being most preferred.

  In the formula (IV), n is an integer of 2 to 4, preferably 2 to 3, and more preferably 2. The polyoxyalkylene block may be composed of only one kind of oxyalkylene group or may contain two or more kinds of oxyalkylene groups.

The reactive silicone block copolymer can be produced by using a known method, for example, a method described in JP-A-5-310944. Further, SILSTLE series (Toray Dow Corning) can be used, and (bisisobutyl PEG-14 / amodimethicone) copolymer can be preferably used.
In the present invention, one or more types of reactive silicone block copolymers can be used.

  Although the compounding quantity of a reactive silicone type block copolymer is not restrict | limited in particular, 0.01-10 mass% in hair cosmetics, Furthermore, 0.1-5 mass% is preferable. If the amount is too small, the effect is not sufficiently exhibited. If the amount is too large, an increase in the effect corresponding to the effect cannot be expected, and the touch may be adversely affected.

In addition to the above essential components, other components can be blended in the hair cosmetic of the present invention within a quantitative and qualitative range that does not impair the effects of the present invention.
For example, as a humectant, for example, ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, glycerin, diglycerin, triglycerin, tetraglycerin, 1,3-butylene glycol, 1,4-butylene glycol, xylitol, sorbitol, Monosaccharides such as maltitol, glucose, maltose, sucrose, fructose, maltotriose, threitol, erythritol, starch, degraded sugar reducing alcohol, disaccharides or oligosaccharides and their derivatives, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronin Acid, atelocollagen, cholesteryl-12-hydroxystearate, sodium lactate, dl-pyrrolidone carboxylate, soluble collagen, diglycerin (EO) PO adduct, isoyara rose extract, cornflower Aspergillus extract, Merirot extract, isoprene glycol, sodium polyglutamate, alkylene oxide derivatives {eg POE (14) POP (7) dimethyl ether, POE (10) POP (10) dimethyl ether, POE (6) POP (14) dimethyl ether, POE (25) POP (40) dimethyl ether, POE (25) POP (25) dimethyl ether, POE (7) POP (12) dimethyl ether, POE (22) POP (40) dimethyl ether, POE (35) POP (40) dimethyl ether, POE (45) POP (34) dimethyl ether, POE (50) POP (40) dimethyl ether, POE (55) POP (30) dimethyl ether, POE (30) POP (34) dimethyl ether, P E (25) POP (30) dimethyl ether, POE (27) POP (14) dimethyl ether, POE (55) POP (28) dimethyl ether, POE (36) POP (41) dimethyl ether, POE (7) POP (12) dimethyl ether, POE (17) POP (4) dimethyl ether, POE (14) POB (7) dimethyl ether, POE (10) POP (10) diethyl ether, POE (10) POP (10) dipropyl ether, POE (10) POP (10 ) Dibutyl ether} and the like, and one or more of these are used.
The POE, POP, and POB are abbreviations for polyoxyethylene, polyoxypropylene, and polyoxybutylene, respectively.

  Furthermore, by further incorporating hair repair ingredients such as lecithin, hydrolyzed protein and its derivatives, amino acids such as glutamic acid, arginine, glycine, alanine, serine, proline, leucine and isoleucine, vitamins and ceresin, hair repair -A hair cosmetic that is excellent in protective effect and that lasts for a long time can be obtained.

  Oils such as liquid paraffin, squalane, lanolin derivatives, higher alcohols, various ester oils, avocado oil, palm oil, beef tallow, jojoba oil, polyalkylene glycol polyethers and their carboxylic acid oligoester compounds, terpene hydrocarbon oils, UV absorbers, UV scattering agents, acrylic resins, silicone resins, polyvinylpyrrolidone and other resins, soy protein, gelatin, collagen, silk fibroin, elastin and other protein or protein degradation products, ethyl paraben, butyl paraben and other preservatives Activators such as biotin and pantothenic acid derivatives, γ-oryzanol, sodium dextran sulfate, blood circulation promoters such as vitamin E derivatives and nicotinic acid derivatives, antiseborrheic agents such as sulfur and thianthol, ethanol, isopropanol, tetrachlorodifluoroethane Diluents and the like, thickeners such as carboxyvinyl polymers, drugs, perfumes, coloring material, may be enemy Yichun blended as required a surfactant or the like.

  The dosage form of the present invention is not particularly limited as long as the effects of the present invention are not impaired, and any of solubilization system, emulsification system, powder dispersion system, oil-water two-layer system, oil-water-powder three-layer system, etc. It doesn't matter. What is necessary is just to manufacture in accordance with a conventional method in order to make these dosage forms.

The composition of the hair cosmetic of the present invention can be applied to any cosmetic used for hair, so-called hair cleaning agents such as shampoos, hair rinses, hair conditioners, hair treatments, hair packs, hair sprays, styling agents, etc. And so-called hair treatment agents.
In addition, the form of use may include both those that are applied to the hair and thoroughly rinsed after being applied to the entire hair, and those that are not washed away. The hair cosmetic of the present invention is a type of hair that is used after being applied by rinsing. Particularly suitable for conditioners.
Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples. Unless otherwise specified, the blending amount indicates mass%.

A hair conditioner composition was prepared according to the following test composition (1) and used as a sample.
Test composition (1):
Amino-modified silicone See table Hydroxyetheramine See table Cetyl alcohol 5.0
Glutamic acid 0.6
Ion exchange water to 100
(Preparation method)
A water-soluble component (glutamic acid) is heated and dissolved in ion exchange water to make it uniform. To this is added an oil-soluble component (hydroxyetheramine, cetyl alcohol) mixed with heating, and further amino-modified silicone is added, followed by emulsification and cooling.

The evaluation method is as follows.
Evaluation 1: Smoothness at the time of rinsing After each sample was applied to the hair, the smoothness when the sample was rinsed was subjected to sensory evaluation by 20 professional panelists. Judgment criteria are as follows.
A: More than 17 out of 20 responded that they were smoother than the control.
○: 13 to 16 out of 20 responded that they were smoother than the control.
Δ: 8 to 12 out of 20 responded that they were smoother than the control.
×: 7 or less of 20 responded that they were smoother than the control.

Evaluation 2: Smoothness after drying (no stickiness)
After each sample was applied to the hair, it was rinsed away, and the smoothness of the hair after drying (no stickiness) was subjected to sensory evaluation by 20 professional panelists. Judgment criteria are as follows.
A: More than 17 out of 20 responded that they were smoother than the control.
○: 13 to 16 out of 20 responded that they were smoother than the control.
Δ: 8 to 12 out of 20 responded that they were smoother than the control.
×: 7 or less of 20 responded that they were smoother than the control.

Evaluation 3: Moist feeling after drying
Each sample was applied to the hair, rinsed, and sensory evaluation was performed by 20 professional panelists on the moist feeling of the hair after drying (the absence of roughness). Judgment criteria are as follows.
A: More than 17 out of 20 responded that they were moist than the control.
○: 13 to 16 out of 20 responded that they were moist than the control.
Δ: 8 to 12 out of 20 responded that they were moist than the control.
×: 7 or less of 20 responded that they were moist than the control.

Evaluation 4: Dry feeling after drying Each sample was applied to the hair, rinsed, and the dry feeling of the hair after drying was subjected to sensory evaluation by 20 professional panelists. Judgment criteria are as follows.
A: 17 or more out of 20 responded that there was a feeling of smoother than the control.
○: 13 to 16 out of 20 responded that there was a smoother feeling than the control.
Δ: 8 to 12 out of 20 responded that there was a feeling of smoother than the control.
×: 7 or less of 20 responded that there was a more smooth feeling than the control.

Evaluation 5: Softness after drying (no stiffness)
Each sample was applied to the hair, rinsed, and sensory evaluation was performed by 20 professional panelists on the softness (no firmness) of the hair after drying. Judgment criteria are as follows.
A: 17 or more out of 20 responded that they were softer than the control.
○: 13 to 16 out of 20 responded that they were softer than the control.
Δ: 8 to 12 out of 20 responded that they were softer than the control.
X: 7 or less of 20 responded that it was softer than the control.

Test Example 1 Combination of amino-modified silicone and hydroxyetheramine

Table 1 shows the results of comparative evaluation using Sample 1 (with no hydroxy ether amine) as a control (reference) (the same applies to Tables 2 to 5).
As shown in Table 1, when amino acid-modified silicone alone (sample 1) or hydroxyetheramine alone (sample 2) is used together (sample 3), the smoothness at the time of rinsing is increased. A very high effect was obtained in all of smoothness, smoothness, moistness and softness after drying.
Although hydroxyetheramine is equivalent or less effective than amino-modified silicone, significant improvement in the effect was recognized by using both in combination.
Therefore, it is considered that some synergistic action is acting between the amino-modified silicone and the hydroxy ether amine.

Test Example 2 Amino-modified silicone

From Table 2, when amino-modified silicones having m + n of 4000 to 6000 and n / m of 0.005 to 0.03 (samples 4 to 5) are used, the combined use with hydroxy ether amine is highly effective. Obtained. Further, when a plurality of amino-modified silicones that are outside the above range alone were used together as in Sample 10, a high effect was obtained if the average value was within the above range.
On the other hand, when m + n or n / m is outside the above range (samples 6 to 9), sufficient effects were not obtained even when hydroxyetheramine was used in combination. Moreover, although the amino modified silicone which is in the said range independently is mix | blended like the samples 11-12, sufficient effect was not acquired even when the average value was outside the said range.

Test Example 3 Hydroxyetheramine

As shown in Table 3, when the specific hydroxy ether amine according to the present invention is used (samples 13 to 17), the amino-modified silicone and the conventional amino compound are used in combination with the conventional amino compound (samples 20 to 21). The combined effect of was extremely high.
From the above, it is considered that a synergistic effect is exhibited only between the specific amino-modified silicone and the specific hydroxy ether amine.

Test Example 4 Amino-modified silicone content

As shown in Table 4, if the amount of amino-modified silicone is too small, the effect is not sufficiently exhibited, and if it is too much, the effect tends to decrease.
Therefore, the compounding amount of the amino-modified silicone in the hair cosmetic is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass.

Test Example 5 Hydroxy ether amine content

As shown in Table 5, if the amount of hydroxy ether amine is too small, the effect is not sufficiently exhibited, and if it is too much, the effect tends to decrease.
Therefore, the blending amount of the hydroxy ether amine in the hair cosmetic is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass.

Test Example 6 Reactive silicone block copolymer formulation A hair conditioner was prepared according to the following test composition (2) and used as a sample.
Test composition (2):
Amino-modified silicone 3.0% by mass
Hydroxy ether amine 2.0
Reactive silicone block copolymer See table Setostearyl alcohol 5.0
Glutamic acid 0.6
Ion exchange water to 100

* Copolymer 1: reactive silicone block copolymer ^{_{[R 1 = R 2 = CH}} 3, X = C 3 H 6 NHC 2 H 4 NH 2, Y = CH 2 CH (CH 3) CH 2, n = 2, c = 14, average molecular weight of the copolymer = about 3,100, average molecular weight of the siloxane block = about 2,500, a: b = 100: 0.9]

ａ：ｂ＝１００：３、平均分子量＝約８，０００ * Comparative copolymer a: amino-modified silicone (no polyoxyalkylene block), trade name SM8904C (Toray Dow Corning Co., Ltd.)

a: b = 100: 3, average molecular weight = about 8,000

* Comparative copolymer b: linear block type polyether-modified silicone (no amino modification), trade name FZ-2233 (Nihon Unicar Co., Ltd.)

Table 6 shows the results of comparative evaluation using Sample 36 (without reactive silicone block copolymer) as a control.
As shown in Table 6, when the reactive silicone block copolymer according to the present invention was blended (samples 37 and 40 to 42), the effect was improved as compared with the control, and the smoothness and fingering at the time of rinsing were particularly good. The effect was significantly improved. In addition, the smoothness and moist feeling after drying were improved.
In the case where a silicone copolymer having no polyoxyalkylene group (sample 38) or a silicone copolymer having no reactive functional group such as an amino group (sample 39) is blended, such an improvement effect is obtained. Almost not recognized.
Moreover, if there are too few reactive silicone type block copolymers, sufficient effect will not be acquired, but if too much, an effect will fall. Therefore, the reactive silicone block copolymer is preferably 0.01 to 10% by mass, and more preferably 1 to 5% by mass in the hair cosmetic.

  Examples of the hair cosmetic composition of the present invention are shown below. When any of the hair cosmetics was applied, it was well-familiar with the hair and was excellent in smoothness after rinsing, smoothness after drying, moist feeling, smooth feeling and softness.

Formulation Example 1 Hair Oil (1) Light liquid isoparaffin 85% by mass
(2) Amino-modified polymer silicone 2
(In the general formula (I), R ¹ = methyl, R ² = − (CH ₂ ) ₃ N (CH ₃ ) (CH ₂ ) ₂ N (CH ₃ ) ₂ , m = 4000, n = 20, a = 3 )
(3) Methylphenylpolysiloxane 5
(4) Hydroxy ether amine 1 0.2
(5) Citric acid 0.05
(6) Perfume appropriate amount (production method)
After mixing (1) to (5), (6) is added to make uniform.

Formulation Example 2 Hair Spray
(1) Volatile isoparaffin 16% by mass
(2) Dimethylpolysiloxane 7
(3) Propylene glycol 5
(4) Ethanol appropriate amount (5) Purified water 2
(6) Amino-modified polymer silicone 4
(In the general formula (I), R ¹ = methyl, R ² is — (CH ₂ ) ₃ N (CH ₃ ) ₂ , m = 4000, n = 20, a = 3)
(7) Poly (oxyethylene / oxypropylene) /
Methyl polysiloxane copolymer 4
(8) Hydroxy ether amine 2 0.2
(9) Citric acid 0.05
(10) Perfume appropriate amount
(11) LPG residue (manufacturing method)
(3) to (9) are mixed and the mixture of (1) to (2) is added and emulsified. After adding (10) and making it uniform, the container is filled together with (11).

Formulation Example 5 Hair Cream (1) Liquid Paraffin 5% by mass
(2) Petrolatum 2
(3) Dimethylpolysiloxane 5
(4) Ammonium modified silicone 1
(In the general formula (I), R ¹ = _{^{methyl, R 2 = - (CH 2}} ) 3 N + (CH 3) 2 C 18 H 37 Cl -, m = 5000, n = 25, a = 3)
(5) Cetanol 4
(6) Stearyl alcohol 1
(7) Hydroxy ether amine 5 0.2
(8) Citric acid 0.05
(9) 1,3-butylene glycol 10
(10) Polyoxyethylene / polyoxypropylene dimethyl ether 2
(11) Polyoxypropylene glyceryl ether 2
(12) Polyoxyethylene glyceryl isostearate 2
(13) Lipophilic glyceryl monostearate 2
(14) Polymer JR-400 ^™ (manufactured by Toho Chemical Industry Co., Ltd.) 0.5
(15) Hydrolyzed wheat protein 0.1
(16) paraoxybenzoic acid ester appropriate amount (17) purified water residue (18) perfume appropriate amount (production method)
The oil layers (1) to (7) and the aqueous layers (8) to (17) are dissolved and mixed by heating, and (18) is added to the oil layer to make it uniform, and then the two layers are mixed. Emulsify.

Formulation Example 6 Hair Cream (1) Liquid Paraffin 10% by mass
(2) Vaseline 3
(3) Dimethylpolysiloxane 2
(4) Amino-modified silicone 1
(In general formula (I), R ¹ = methyl, R ² =-(CH ₂ ) ₃ N (CH ₂ ) ₂ , m = 5000, n = 25, a = 3)
(5) Propylene glycol 10
(6) Polyoxypropylene (40) butyl ether 2
(7) Hydroxy ether amine 1 0.2
(8) Citric acid 0.05
(9) Tetra-2-ethylhexanoic acid pentaerythrit 3
(10) Polyoxyethylene hydrogenated castor oil 2
(11) Potassium hydroxide 0.1
(12) Carboxyvinyl polymer 0.3
(13) Hydroxyethyl polyacrylate 0.1
-Acryloyldimethyltaurine sodium copolymer (14) Camellia seed oil 0.01
(15) Purified water residue (16) Perfume appropriate amount (production method)
A mixture of (1) to (8), (14) and (16) is added to the mixture of (9) to (12) and emulsified. (13) is added to make uniform, then neutralized with (15), and further stirred to make uniform.

Formulation Example 7 Hair Cream (1) Methylpolysiloxane 10% by mass
(2) Amino-modified silicone 1
(In general formula (I), R ¹ = methyl, R ² =-(CH ₂ ) ₃ NH ₂ , m = 4000, n = 20, a = 3)
(3) Polyoxyethylene / methylpolysiloxane copolymer 0.1
(4) Poly (oxyethylene / oxyproprene)
Methyl polysiloxane copolymer 0.1
(5) Volatile isoparaffin 2
(6) Crosslinked polyether-modified silicone 2.5
(7) Hydroxy ether amine 3 0.2
(8) Citric acid 0.05
(9) Dextrin ester 1
(10) Polyaspartic acid 0.1
(11) Glycine 0.1
(12) Ethanol 5
(13) Paraben 0.25
(14) Fragrance appropriate amount (15) Dye appropriate amount (16) Water Residue (Production method)
(1) to (9) and (14) (15) are mixed and homogenized, and the mixture of (10) to (13) and (16) is added and emulsified.

Formulation Example 8 Hair Lotion (1) Light isoparaffin 15% by mass
(2) Amino-modified silicone 3
(In general formula (I), R ¹ = methyl, R ² =-(CH ₂ ) ₃ N (CH ₃ ) C ₂ H ₅ , m = 5000, n = 50, a = 3)
(3) Dimethyl silicone 6
(4) 1,3-butylene glycol 2
(5) Polyoxyethylene (60 mol) hydrogenated castor oil ester 2
(6) Titanium oxide sol 10
(7) Ethanol 15
(8) Hydroxy ether amine compound 1 0.2
(9) Citric acid 0.05
(10) Purified water Residue (11) Perfume appropriate amount (production method)
What mixed (1)-(3) and (10), (11) is added to (4)-(9) and emulsified.

Formulation Example 9 Hairist (1) Amino-modified silicone 0.2% by mass
(In general formula (I), R ¹ = hydroxyl group, R ² =-(CH ₂ ) ₃ NH ₂ , m = 4000, n = 120, a = 3)
(2) Dimethylpolysiloxane 1
(3) Ethanol 5
(4) Stearyl alcohol 0.1
(5) Behenyl alcohol 0.2
(6) Glycerin 2
(7) Dipropylene glycol 1
(8) 1,3-butylene glycol 1
(9) Alkyltrimethylammonium chloride (77%) 0.5
(10) Hydroxy ether amine 5 0.2
(11) Citric acid 0.05
(12) Vinylpyrrolidone 2.5
N, N-dimethylaminoethyl methacrylic acid copolymer (13) Arginine 0.1
(14) Lecithin 0.1
(15) Octyl methoxycinnamate 0.1
(16) paraoxybenzoic acid ester appropriate amount (17) purified water residue (18) perfume appropriate amount (production method)
The oil layer mixed with (1) to (4) and the aqueous layer mixed with (5) to (17) are heated and dissolved, and the former is added to the latter and emulsified. (18) is added to make uniform.

Formulation Example 11 Hair Conditioner (1) Isopentyldiol 5.0% by mass
(2) Sorbitol 5.0
(3) Dimethicone (1 million cSt) 1.5
(4) Dimethicone (20 cSt) 2.0
(5) Stearyl alcohol 3.0
(6) Behenyl alcohol 2.0
(7) Hydroxy ether amine 1 0.2
(8) Citric acid 0.05
(9) Cetyl isooctanoate 1.0
(10) Aminopropyl dimethicone (m = 4000, n = 120) 0.2
(11) Arginine 0.01
(12) PEG-90M 0.02
(13) Stearyl dihydroxypropyl dimonium oligosaccharide 0.05
(14) Citric acid 0.07
(15) Appropriate amount of phenoxyethanol (16) Appropriate fragrance Appropriate amount (17) Soy lecithin 0.1
(18) Hydrolyzed wheat protein / hydrolyzed wheat starch 0.02
(19) N-lauroyl glutamic acid
Di (phytosteryl / 2-octyldodecyl) 0.1
(20) Camellia seed oil 0.001
(21) Purified water residue (production method)
A water-soluble component is dissolved by heating to make it uniform. To this, an oil-soluble component mixed and heated and dissolved is added, emulsified, and then cooled.

Formulation Example 12 Hairist (1) Amino-modified silicone 0.2% by mass
(In general formula (I), R ¹ = hydroxyl group, R ² =-(CH ₂ ) ₃ NH ₂ , m = 4000, n = 120, a = 3)
(2) Dimethylpolysiloxane 1
(3) Ethanol 5
(4) Stearyl alcohol 0.1
(5) Behenyl alcohol 0.2
(6) Glycerin 2
(7) Reactive silicone block copolymer (Copolymer 1) 1
(8) 1,3-butylene glycol 1
(9) Alkyltrimethylammonium chloride (77%) 0.5
(10) Hydroxy ether amine 5 0.2
(11) Citric acid 0.05
(12) Vinylpyrrolidone 2.5
N, N-dimethylaminoethyl methacrylic acid copolymer (13) Arginine 0.1
(14) Lecithin 0.1
(15) Octyl methoxycinnamate 0.1
(16) paraoxybenzoic acid ester appropriate amount (17) purified water residue (18) perfume appropriate amount (production method)
The oil layer mixed with (1) to (4) and the aqueous layer mixed with (5) to (17) are heated and dissolved, and the former is added to the latter and emulsified. (18) is added to make uniform.

Formulation Example 14 Hair Conditioner (1) Isopentyldiol 5.0% by mass
(2) Sorbitol 5.0
(3) Dimethicone (1 million cSt) 1.5
(4) Dimethicone (20 cSt) 2.0
(5) Stearyl alcohol 3.0
(6) Behenyl alcohol 2.0
(7) Hydroxy ether amine 1 0.2
(8) Citric acid 0.05
(9) Reactive silicone block copolymer (Copolymer 1) 1.0
(10) Aminopropyl dimethicone (m = 4000, n = 120) 0.2
(11) Arginine 0.01
(12) PEG-90M 0.02
(13) Stearyl dihydroxypropyl dimonium oligosaccharide 0.05
(14) Citric acid 0.07
(15) Appropriate amount of phenoxyethanol (16) Appropriate fragrance Appropriate amount (17) Soy lecithin 0.1
(18) Hydrolyzed wheat protein / hydrolyzed wheat starch 0.02
(19) N-lauroyl glutamic acid
Di (phytosteryl / 2-octyldodecyl) 0.1
(20) Purified water residue (manufacturing method)
A water-soluble component is dissolved by heating to make it uniform. To this, an oil-soluble component mixed and heated and dissolved is added, emulsified, and then cooled.

Claims (4)

A hair cosmetic comprising the following components (A) and (B):
(A) Amino-modified or ammonium-modified silicone represented by the following general formula (I).

[In formula (I), each R ¹ independently represents a methyl group, a phenyl group or a hydroxyl group.
R ² is independently a group represented by the formula —R ⁴ Z, R ⁴ is an alkylene group having 3 to 6 carbon atoms, Z is a nitrogen-containing group, and the following formula:

(R ⁵ is independently a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, R ⁶ is an alkyl group having 1 to 30 carbon atoms, A is a chlorine atom, bromine atom or iodine atom, b is an integer of 2 to 6) It is a group represented by.
a is an integer of 0 to 3, m and n are each a positive integer, the average value of m + n is 4000 to 6000, and the average value of n / m is 0.005 to 0.03. ]
(B) A hydroxy ether amine compound represented by the following general formula (II).

[In the formula (II), R ¹ and R ² are each an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group or a group represented by the following general formula (III), but at least one of R ¹ and R ² / Or both are groups represented by the general formula (III). R ³ is an alkyl group having 1 to ³ carbon atoms or a hydroxyalkyl group.

(In the formula (III), R is a linear or branched alkyl group having 6 to 24 carbon atoms, an alkenyl group or a hydroxyalkyl group, and n is an integer of 1 to 5)]
The hair cosmetic according to claim 1, wherein the amount of each component in the hair cosmetic is in the following range.
(A) 0.01-10.0 mass%.
(B) 0.01-10.0 mass%. The hair cosmetic composition according to claim 1 or 2, further comprising a reactive silicone block copolymer represented by the following general formula (IV).

[In the formula (IV), R ¹ is a monovalent hydrocarbon group containing no aliphatic unsaturation.
X is

It is a reactive functional group shown by either .
R ² represents any group defined by R ¹ or X.
n is an integer of 2-4.
a is an integer of at least 2, b is an integer of at least 1, c is an integer of at least 4, and d is an integer of at least 2.
Y is carbon - Represents a divalent organic group bonded to the polyoxyalkylene block in the adjacent silicon atom by a silicon, and by oxygen ^{atoms, -R 4 -, - R 4} -CO -, - R 4 -NHCO —, —R ⁴ —NHCONHR ⁵ —NHCO— or —R ⁴ —OOCNH—R ⁵ —NHCO— (R ⁴ is a divalent alkylene group selected from an ethylene group, a propylene group and a butylene group, R ⁵ represents the divalent alkylene group exemplified as R ⁴ , or —C ₆ H ₄ —, —C ₆ H ₄ —C ₆ H ₄ —, —C ₆ H ₄ —CH ₂ —C ₆ H ₄ —, —C ₆ H ₄ —CH (CH ₃ ) —C ₆ H ₄ — is a divalent arylene group) .
The average molecular weight of the siloxane block is 250 to 10,000 , the average molecular weight of each polyoxyalkylene block is 200 to 10,000 , and the siloxane block constitutes 25 to 95% by mass of the copolymer . The coalescence has an average molecular weight of at least 1,000. ]
  A hair conditioner composition comprising the hair cosmetic composition according to any one of claims 1 to 3.