JP4473589B2 - Hair cosmetics - Google Patents

Description

  The present invention relates to a hair cosmetic characterized in that it is a non-aqueous system that imparts a natural luster to hair, is non-sticky, provides a smooth feel, an excellent conditioning effect, and is excellent in stability. Is.

  Conventionally, hair gels, hair creams, hair foams, hair lotions and the like have been used as hair cosmetics. These hair cosmetics are generally formulated by solubilizing, dispersing or emulsifying an oil component such as silicone oil, ester oil or hydrocarbon oil, or a polymer compound capable of forming a film. For the purpose of imparting water, liquid oil typified by silicone oil is widely used. For example, by blending high molecular silicone and low boiling point silicone oil, it contains hair cosmetics (see Patent Document 1) having smooth hair and set retention, high molecular weight dimethylpolysiloxane, non-aqueous solvent and propellant. An aerosol spray composition discloses a hair non-aqueous aerosol spray composition (see Patent Document 2) that imparts gloss and a smooth feel. However, the compositions containing these high molecular silicones are excellent in gloss, but have drawbacks in that the hair becomes dry when dried in winter and the conditioning properties such as the smoothness of the hair are insufficient. . Especially in recent years, it has become popular to perform coloring, and hair is caused by chemical agents such as alkali and hydrogen peroxide and heat by using a dryer or iron to make curly hair. Damaged hair is increasing, such as the alteration of proteins on the surface and inside the hair. In these hairs, the above-described conventional compositions have been insufficient to impart a smooth feel, a smooth hair, a natural finish such as calmness. Therefore, there is a strong demand for hair cosmetics that give a natural luster, are not sticky, have a smooth feel, and an excellent conditioning effect.

JP 63-183517 A Japanese Patent Laid-Open No. 4-128213

  The object of the present invention is to provide a hair cosmetic material that gives a natural luster to hair, has no stickiness, has a smooth feel, has an excellent conditioning effect, and has excellent stability. is there.

  As a result of intensive studies to achieve the above object, the present inventors have formulated a specific high molecular silicone, a specific low molecular silicone, a volatile oil agent, and a specific vegetable oil in combination. The present invention has been completed by finding that it is glossy, has no stickiness, has a smooth feel, imparts an excellent conditioning effect, and is excellent in stability.

[式中、Ｒ^１はメチル基または一部がフェニル基を表し、
Ｒ^２はＲ^３と同一またはメチル基または水酸基を表し、
Ｒ^３は式Ｒ^４Ｚ
｛Ｒ^４は３〜６の炭素原子を有する２価のアルキレン基を表し、
Ｚは−ＮＲ^５ _２、−Ｎ^＋Ｒ^５ _３Ａ⁻、−ＮＲ^５（ＣＨ_２）_ａＮ^＋Ｒ^５ _３Ａ⁻および−ＮＲ^５（ＣＨ_２）_ａＮ（Ｒ^５）Ｃ＝Ｏ（Ｒ^６）
〔Ｒ^５は水素または１〜４の炭素原子を有するアルキル基を表し、Ｒ^６は１から４の炭素原子を有するアルキル基を表し、Ａは塩素、ヨウ素または臭素原子を表し、ａは２〜６の整数である〕
からなる群から選ばれる１価の基を表す。｝
で表し、ｍ＋ｎは５００〜２，５００の整数を表す。]
で表される高分子シリコーンを１〜３０質量％、
That is, the invention of claim 1 of the present invention is a hair cosmetic containing the following (A) to (D) and being non-aqueous,
(A) General formula 1:

[Wherein R ¹ represents a methyl group or a part thereof represents a phenyl group;
R ² is the same as R ³ or represents a methyl group or a hydroxyl group,
R ³ represents the formula R ⁴ Z
{R ⁴ represents a divalent alkylene group having 3 to 6 carbon atoms;
Z represents —NR ⁵ ₂ , —N ⁺ R ⁵ ₃ A ⁻ , —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 a chlorine, iodine or bromine atom; It is an integer of 6.]
Represents a monovalent group selected from the group consisting of }
M + n represents an integer of 500 to 2,500. ]
1 to 30% by mass of a polymeric silicone represented by

（Ｒ^７はメチル基または一部がフェニル基を表し、Ｒ^８はメチル基または水酸基を表し、ｐは１０〜１００の整数を表す。）で表される低分子シリコーンを０．５〜５０質量％、（Ｃ）沸点が１００〜２６０℃の範囲にあるイソパラフィン系炭化水素、珪素数が２〜８の揮発性シリコーン、メチルトリストリメチルシロキシシランからなる揮発性油剤より選ばれた一種類以上を３０〜９５質量％、（Ｄ）ヨウ素価が１２０以下の植物油を０．２〜１０質量％、
請求項２の発明は、下記（Ａ）〜（Ｄ）を含有し、非水系であることを特徴とする毛髪化粧料。（Ａ）ジメチルポリシロキサン、メチルフェニルポリシロキサン、ジメチコノール、末端水酸基メチルフェニルポリシロキサン、アミノ基またはアンモニウム基変性シリコーンから選ばれる、２５℃において１万〜５００万ｍｍ^２／ｓの粘度を示すシリコーンを１〜３０質量％、（Ｂ）ジメチルポリシロキサン、メチルフェニルポリシロキサンから選ばれる、２５℃において６〜３００ｍｍ^２／ｓの粘度を示すシリコーンを０．５〜５０質量％、（Ｃ）沸点が１００〜２６０℃の範囲にあるイソパラフィン系炭化水素、珪素数が２〜８の揮発性シリコーン、メチルトリストリメチルシロキシシランからなる群より選ばれた一種類以上を３０〜９５質量％、（ Ｄ ） ヨウ素価が１ ２ ０ 以下の植物油を０．２〜１０質量％、
請求項３の発明は、更に油溶性紫外線吸収剤を含有する請求項１または２いずれかに記載の毛髪化粧料である。
(B) General formula 2:

(R ⁷ represents a methyl group or a part thereof represents a phenyl group, R ⁸ represents a methyl group or a hydroxyl group, and p represents an integer of 10 to 100) %, (C) one or more selected from volatile oils consisting of isoparaffinic hydrocarbons having a boiling point in the range of 100 to 260 ° C., volatile silicones having 2 to 8 silicon numbers, and methyltristrimethylsiloxysilane. -95% by mass, (D) a vegetable oil having an iodine value of 120 or less; 2 to 10% by mass,
Invention of Claim 2 contains the following (A)-(D), and is non-aqueous hair cosmetics characterized by the above-mentioned. (A) A silicone having a viscosity of 10,000 to 5,000,000 mm ² / s at 25 ° C. selected from dimethylpolysiloxane, methylphenylpolysiloxane, dimethiconol, terminal hydroxyl group methylphenylpolysiloxane, amino group or ammonium group-modified silicone 1 to 30 % by mass, (B) 0.5 to 50% by mass of silicone having a viscosity of 6 to 300 mm ² / s selected at 25 ° C. selected from dimethylpolysiloxane and methylphenylpolysiloxane, and (C) a boiling point of 100 30 to 95% by mass of one or more selected from the group consisting of isoparaffinic hydrocarbons in the range of ˜260 ° C., volatile silicones having 2 to 8 silicons, and methyltristrimethylsiloxysilane, (D) iodine value Is a vegetable oil having a 1 or less of 1 2 0 or less. 2 to 10% by mass,
The invention of claim 3 is the hair cosmetic composition according to claim 1 or 2, further comprising an oil-soluble ultraviolet absorber.

  According to the present invention, it is possible to provide a hair cosmetic that imparts a natural luster to hair, is non-sticky, and has a smooth feel and an excellent conditioning effect.

Hereinafter, embodiments of the present invention will be described in detail.

In the polymeric silicone represented by the general formula 1 used in the present invention, R ¹ represents a methyl group or a part thereof represents a phenyl group, R ² represents the same as R ³ or represents a methyl group or a hydroxyl group, and R ³ represents a formula R ⁴ Z ^{{R 4} represents a divalent alkylene group having 3-6 carbon atoms, Z is _{^{-NR 5 2, -N + R 5}} 3 a -, -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, and R ⁶ represents 1 to 4 carbon atoms. represents an alkyl group having atoms, a is chlorine, represents an iodine or bromine atom, a is a monovalent group selected from the group consisting of a is] an integer from 2 to 6. Expressed in}, m + n is of high molecular weight represented an integer of 500 to 2,500, the molecular weight is 20000 to 200000, the properties are liquidity does not lead to a soft rubber-like at room temperature It has a certain viscosity and a viscosity of 10,000 to 5,000,000 mm ² / s at 25 ° C. Specific examples include dimethylpolysiloxane, methylphenylpolysiloxane, dimethiconol, terminal hydroxyl group methylphenylpolysiloxane, amino group or ammonium group modified silicone. These high molecular silicones are commercially available. For example, KF-96H (10,000 cs to 1 million cs), KF-8015, KF-8017, KF-8020, Toray Dow Corning Silicone manufactured by Shin-Etsu Chemical Co., Ltd. SH200C (10,000 cs to 3.5 million cs) manufactured by GE Toshiba Silicone Co., Ltd., TSF-451 (6,000 cs to 1 million cs), TSF4707, TSF4705, etc.

  In the present invention, the blending amount of the polymeric silicone is usually 1 to 30% by mass (hereinafter referred to as%), preferably 5 to 20%, based on the total amount of the hair cosmetic. If it is less than 1%, a sufficient effect may not be obtained, and if it exceeds 30%, it may adhere unevenly to the hair and cause wrinkles or the like, which is not preferable.

In the low molecular silicone represented by the general formula 2 used in the present invention, R ⁷ represents a methyl group or part of a phenyl group, R ⁸ represents a methyl group or a hydroxyl group, and p is an integer of 10 to 100. is of the molecular type, the molecular weight is 5 00～8,00 0, properties in a liquid having fluidity at ordinary temperature and shows a viscosity of 6~300mm ² / s at 25 ° C.. Specific examples include dimethylpolysiloxane and methylphenylpolysiloxane. These low molecular silicones are commercially available. Examples thereof include KF-96A (10 cs to 300 cs), KF-50 (100 cs to 300 cs), KF manufactured by Shin-Etsu Chemical Co., Ltd.
-53, KF-54, KF-56, SH200C (10 cs to 300 cs) manufactured by Toray Dow Corning Silicone, SH-556, TSF-451 (6 cs to 300 cs) manufactured by GE Toshiba Silicone, TSF431, TSF433, TSF437, SF1550, TSF484, etc. are mentioned.

  In the present invention, the blending amount of the low molecular silicone is usually 0.5 to 50%, preferably 1 to 40% based on the total amount of the hair cosmetic. If it is less than 0.5%, the effect such as suppleness may be insufficient, and if it exceeds 50%, the desired natural luster may not be obtained, which is not preferable.

Examples of the volatile oil used in the present invention include isoparaffinic hydrocarbons having a boiling point in the range of 100 to 260 ° C., volatile silicones having 2 to 8 silicon numbers, and methyltristrimethylsiloxysilane. Isoparaffinic hydrocarbon having a boiling point in the range of 100 to 260 ° C. is obtained by refining from light petroleum isoparaffin having 12 to 28 carbon atoms obtained by hydrogenation of a copolymer of isobutene and n-butene, and petroleum. Examples thereof include light liquid paraffin having 6 to 30 carbon atoms, which is a volatile hydrocarbon mixture. For example, NAS-3, NAS-4, NAS-5, manufactured by Nippon Oil & Fats Co., Ltd., Isopar C, D, manufactured by Exxon, E, E, G, H, K, L, M, Shellzol 71 manufactured by Shell, Nippon Petrochemicals Nippon Imesol 300, 400, Saltroll 100 manufactured by Philippe , 130, 22 and the like. Examples of volatile silicones having 2 to 8 silicon atoms include octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, tetradecamethylcyclohexasiloxane, octamethyltrisiloxane, and decamethyltetrasiloxane. For example, KF-96A-1cs, KF-96A-1.5cs, KF-995 manufactured by Shin-Etsu Chemical Co., Ltd., SH244, SH344, SH245, DC345, DC246, SH200C-1cs, SH200C- manufactured by Toray Dow Corning Silicone Co., Ltd. 1.5 cs, TSF404, TSF405, TSF4045, TSF451-1A, TSF451-1.5A, etc. manufactured by GE Toshiba Silicone are included. Methyltristrimethylsiloxysilane is another name, methyltrimethicone, and examples of commercially available products include TMF-1.5 manufactured by Shin-Etsu Chemical Co., Ltd.

  In the present invention, one or more of these volatile oils can be appropriately selected and used. The blending amount of these volatile oils is usually 30 to 95%, preferably 40 to 90%, based on the total amount of the hair cosmetic. If it is less than 30%, strong stickiness may occur on the hair, and if it exceeds 95%, the intended effect may be insufficient, which is not preferable.

  The vegetable oils used in the present invention are vegetable oils classified into non-drying vegetable oils and semi-drying vegetable oils. As fatty acids constituting the main component triglycerides, the content of linoleic acid and linolenic acid is low, and cosmetic raw material standards and general tests. When the test is carried out by the method and iodine value measurement method, the value is 120 or less vegetable oil. In the case of a vegetable oil having an iodine value of more than 120, when blended with a non-aqueous hair cosmetic, storage stability is poor, turbidity and precipitation occur, and it is unfavorable because it deteriorates and precipitates even when exposed to sunlight. Examples of vegetable oils having an iodine value of 120 or less include: sasanqua oil, camellia oil, peanut oil, castor oil, olive oil, wheat germ oil, sesame oil, cottonseed oil, rapeseed oil, corn oil, sunflower oil, high oleic sunflower oil, grape seed Oil, avocado oil, almond oil, rice bran oil, rice oil, soybean oil, persic oil, apricot oil, shea butter, macadamia nut oil, vegetable oil such as medofoam oil, vegetable ester such as jojoba oil, vegetable squalane, etc. Plant hydrocarbons and the like.

  In the present invention, one or more of these vegetable oils can be appropriately selected and used, and the blending amount is usually 0.1 to 10% based on the total amount of the hair cosmetic, Preferably, it is 0.2 to 5%. If it is less than 0.1%, it may not be possible to give a supple feel to the hair, and if it exceeds 10%, stickiness or the like may occur.

  In the present invention, by further containing an oil-soluble ultraviolet absorber, storage stability and hair damage from ultraviolet rays can be prevented. Examples of oil-soluble UV absorbers include octyl paradimethylaminobenzoate, benzoate ester UV absorbers such as ethyl 4- [N, N-di (2-hydroxypropyl) amino] benzoate, octyl salicylate, benzyl salicylate, Salicylic acid UV absorbers such as p-tert-butylphenyl salicylate, cinnamate UV absorbers such as benzyl cinnamate, octyl paramethoxycinnamate and isopropyl paramethoxycinnamate, hydroxymethoxybenzophenone, dihydroxydimethoxybenzophenone And benzophenone-based ultraviolet absorbers such as cinnamate-based ultraviolet absorbers are preferred in view of their effects. Moreover, the compounding quantity of these oil-soluble ultraviolet absorbers is 0.05 to 5% normally, Preferably it is 0.1 to 1%. If it is less than 0.05%, an effect on storage stability may not be observed, and if it exceeds 5%, it may be unfavorable in touch.

The hair cosmetic composition of the present invention is non-aqueous that does not contain water, and blending water causes turbidity and separation or precipitation of various oil agents, which is not preferable. Further, the hair cosmetic composition of the present invention can be used in various forms, for example, blended into a dosage form to be applied to hair such as a liquid form such as hair oil or hair lotion, an aerosol form such as hair spray or glow spray, It can be produced according to a conventional method.

  Further, the hair cosmetic composition of the present invention may be variously used in cosmetics, quasi-drugs, pharmaceuticals and the like as necessary in addition to the above-mentioned components and within the range not impairing the effects of the present invention. Ingredients such as oils, moisturizers, thickeners, dyes, fragrances, bactericides, preservatives, UV absorbers, solvents, anti-inflammatory agents, antiandrogens, hair restorers, antioxidants, refreshing agents, herbal extracts And vitamins can be added as appropriate.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, the technical scope of this invention is not limited by these Examples. In addition, the sensory test (natural glossiness, stickiness, smoothness, and unity) described in the Examples and test methods relating to the stability test are shown below.

(1) Sensory test Targeting 20 specialist panels, the hair cosmetics of the examples and comparative examples were used, and a sensory test was conducted for each of the natural luster, stickiness, smoothness and unity on the hair. Evaluation was performed according to the following criteria.

Judgment Criteria (1) Natural Gloss ◎: It is judged that 15 or more people of the panel are natural glossy ○: It is judged that 10 or more and less than 15 people of the panel are natural glossy △: 5 or more people of the panel 10 or more people Less than 15 panelists judged to have a natural gloss x: More than 15 panelists judged not to be natural glossy (2) Stickiness ◎: More than 15 panelists judged to have no stickiness ○: 10 panelists to less than 15 panelists Judged that there is no stickiness △: Judged that 5 or more and 10 people on the panel were not sticky ×: Judged that 15 or more people on the panel were sticky (3) Smoothness ◎: 15 or more people on the panel were smooth Judgment: Judged that 10 or more and less than 15 people on the panel are smooth Δ: Judged that 5 or more and less than 10 people on the panel were smooth ×: Judged that 15 or more people on the panel were not smooth (4) Summary ◎ : Panel 15: More than 15 people in the panel are judged to be well organized ○: More than 10 people on the panel and less than 15 people are judged to be well organized △: More than 5 people on the panel and less than 10 people are judged to be well organized ×: More than 15 people on the panel Judged to be bad

(2) Stability test 100 mL of each hair cosmetic composition of Examples and Comparative Examples was filled in a bottle container, left in a constant temperature bath at 40 ° C. for 3 months, and the appearance change of the solution was visually evaluated. The evaluation was performed according to the following criteria.
Judgment criteria ○: There is no turbidity or precipitation, and the appearance does not change at all. △: Slightly cloudy or turbid. ×: Turbidity occurs, separation or precipitation occurs.

Examples 1-10, Comparative Examples 1-3
Hair cosmetics having the formulations shown in Table 1 were prepared according to a conventional method, and the above tests were conducted for evaluation. The results are also shown in Table 1.

  As is clear from Table 1, the hair cosmetic composition of the present invention is clearly superior to any of the tests related to sensory tests (natural glossiness, stickiness, smoothness, and unity) and stability tests as compared with the comparative examples. It was.

  Hereinafter, other formulation examples of the hair cosmetic composition of the present invention will be given as examples. For the hair cosmetics of these examples, the above-mentioned sensory tests (natural glossiness, stickiness, smoothness, unity) and stability tests were examined, and all the examples had excellent characteristics. It was good.

Example 6
Compounding amount (%)
(1) High molecular silicone
(GE Toshiba Silicone, XF-B8072) 15.0
(2) Low molecular silicone
(Toray Dow Corning Silicone, SH-556) 2.0
(3) Light liquid isoparaffin
(Nippon Yushi Co., Ltd., Pearl Ream 4) 40.0
(4) Decamethylpentacyclosiloxane 40.0
(5) Almond oil 1.0
(6) Camellia oil 1.0
(7) Octyl paramethoxycinnamate 0.5
(8) Natural vitamin E 0.1
(9) Fragrance 0.4

(Production Method) (1) to (9) were uniformly mixed and dissolved by a conventional method to obtain a transparent liquid hair cosmetic.

Example 7
Compounding amount (%)
(1) High molecular silicone
(GE Toshiba Silicone, X-21-5613) 5.0
(2) Low molecular silicone
(Nippon Unicar FZ-209) 5.0
(3) Light liquid isoparaffin
(Nippon Yushi Co., Ltd., Pearl Ream 4) 85.0
(4) Almond oil 3.0
(5) Olive Squalane 1.0
(6) Octyl paramethoxycinnamate 0.5
(7) Natural vitamin E 0.1
(8) Fragrance 0.4

(Production Method) (1) to (8) were uniformly mixed and dissolved by a conventional method to obtain a transparent liquid hair cosmetic.

Example 8
Compounding amount (%)
(1) High molecular silicone
(GE Toshiba Silicone, X-21-5613) 20.0
(2) Low molecular silicone
(Nihon Unicar Co., Ltd., L-45-10cs) 30.0
(3) Light liquid isoparaffin
(Nippon Yushi Co., Ltd., Pearl Ream 4) 45.0
(4) Olive oil 1.0
(5) Jojoba oil 1.0
(6) Olive Squalane 1.0
(7) Octyl paramethoxycinnamate 0.1
(8) Diethyl sebacate 0.4
(9) Isononyl isononanoate 0.1
(10) Oil-soluble Novara extract 0.5
(11) N-lauroyl-L-glutamic acid
Di (phytosteryl, 2-octyldodecyl) 0.5
(12) Fragrance 0.4

(Production Method) (1) to (12) were uniformly mixed and dissolved by a conventional method to obtain a transparent liquid hair cosmetic.

Example 10 (aerosol hair restorer)
Compounding amount (%)
<Undiluted solution formulation>
(1) High molecular silicone
(GE Toshiba Silicone, XF-B8072) 12.0
(2) Low molecular silicone
(Toray Dow Corning, SH-556) 5.0
(3) Light liquid isoparaffin
(Nippon Yushi Co., Ltd., Pearl Ream 4) 50.0
(4) Decamethylpentacyclosiloxane 28.0
(5) Almond oil 1.0
(6) Octyl paramethoxycinnamate 2.0
(7) Fragrance 1.0
<Filling prescription>
(8) Stock solution 50.0
(9) Liquefied petroleum gas 50.0

(Manufacturing method) Each component of the stock solution formulation was mixed and dissolved to prepare a stock solution, which was filled in a can. After mounting the valve, a liquefied petroleum gas was filled to prepare an aerosol formulation.

  The fragrance | flavor used in said each prescription is the following.

  As described above, the present invention can provide a hair cosmetic that gives the hair a natural luster, has no stickiness, has a smooth feel, and has an excellent conditioning effect. For example, hair oil, hair It can be blended into a dosage form to be applied to hair, such as a liquid form such as lotion, and an aerosol form such as hair spray and glow spray, and can be produced according to a conventional method.

Claims (2)

A hair cosmetic comprising the following (A) to (D) and being non-aqueous (excluding for washing away) .
(A) General formula:

[Wherein R ¹ represents a methyl group or a part thereof represents a phenyl group,
R ² is the same as R ³ or represents a methyl group or a hydroxyl group,
R ³ is the formula R ⁴ Z
{R ⁴ represents a divalent alkylene group having 3 to 6 carbon atoms;
Z represents —NR ⁵ ₂ , —N ⁺ R ⁵ ₃ A ⁻ , —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 a chlorine, iodine or bromine atom; It is an integer of 6.]
Represents a monovalent group selected from the group consisting of }
M + n represents an integer of 500 to 2,500. ]
1 to 30% by mass of a polymeric silicone represented by
(B) General formula:

(R ⁷ represents a methyl group or a part thereof represents a phenyl group, R ⁸ represents a methyl group or a hydroxyl group, and p represents an integer of 10 to 100) %, (C) one or more selected from the group consisting of isoparaffinic hydrocarbons having a boiling point in the range of 100 to 260 ° C., volatile silicones having 2 to 8 silicon, and methyltristrimethylsiloxysilane. mass%,
(D) 0.2-10 mass% of vegetable oil whose iodine number is 120 or less. Furthermore, hair cosmetic composition of claim 1 containing an oil-soluble ultraviolet absorber.