JP2006028112A - Hair cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prepare a hair cosmetic excellent in hair-straightening effect and straight-retaining force, protecting the hair from heat of straight iron, imparting natural gloss and flexibility to the hair and excellent in spraying characteristics applied to the hair. <P>SOLUTION: This hair cosmetic is obtained by formulating an aerosol stock solution containing a specific silicone having high polymerization degree, a specific poly(oxyethylene-oxypropylene)-alkylene-methylpolysiloxane copolymer and a volatile oil solution and a propellant at (5/95) to (30/70) ratio (mass ratio ) of the aerosol stock solution to the propellant. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a hair cosmetic, and in particular, is a spray that is excellent in the effect of straightening hair and maintaining the straightness, protects the hair from the heat of a straight iron, gives a natural luster and suppleness, and is applied to the hair. The present invention relates to a hair cosmetic having excellent properties.

  In recent years, hairstyles have been diversified, especially in younger teenagers and twentieth generations, who long for straight hair that flutters in the wind, and various hair cosmetics are used for that purpose. Examples of hair cosmetics to be used include hair gels, hair creams, hair foams, hair lotions, etc. Generally, oils such as silicone oils, ester oils, hydrocarbon oils, and polymer compounds having film-forming ability are straight. It is blended as a component that demonstrates the effect. In particular, liquid oils typified by silicone oil are widely used for the purpose of giving hair feel and gloss. For example, by blending high molecular silicone and low boiling point silicone oil, smoothness of hair and set retention Hair non-aqueous aerosol spray composition that imparts a glossy and smooth feel by an aerosol spray composition comprising a powerful hair cosmetic (see Patent Document 1), a high molecular weight dimethylpolysiloxane, a non-aqueous solvent and a propellant ( Patent Document 2) is disclosed. However, although these compositions containing polymer silicone are excellent in gloss and touch, they are poor in the effect of actually straightening the hair. As a result, the hair becomes stiff and the conditioning properties are insufficient. For this reason, there has been a strong demand for a hair cosmetic that is excellent in the effect of straightening hair and maintaining the straightness, and that protects the hair from the heat of a straight iron and gives natural luster and flexibility.

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

  The purpose of the present invention is excellent in the effect of straightening hair and straightness, protecting the hair from the heat of a straight iron, giving a natural luster and suppleness, and spraying properties applied to the hair. The object is to provide an excellent hair cosmetic.

[式中、Ｒ¹はメチル基または一部がフェニル基を表し、Ｒ²はＲ³と同一またはメチル基または水酸基を表し、Ｒ³は式Ｒ⁴Ｚ｛Ｒ⁴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−ＮＲ⁵ ₂、−Ｎ⁺Ｒ⁵ ₃Ａ^-、−ＮＲ⁵（ＣＨ₂ＮＲ⁵ ₂、−ＮＲ⁵（ＣＨ₂）_aＮ⁺Ｒ⁵ ₃Ａ^-および−ＮＲ⁵（ＣＨ₂）_aＮ（Ｒ⁵）Ｃ＝Ｏ（Ｒ⁶）、Ｒ⁵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、Ｒ⁶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、p＋qは５００〜２，５００の整数を表す。]で表される高重合シリコーン、
（Ｂ）一般式２：

（式中、Ｒ⁷はメチル基または一部がフェニル基を表し、ｘは０〜５０の整数、ｙは０〜５０の整数、ｒは５〜３００の整数、ｓは２〜４０の整数を表す。）で表されるブロック共重合型のポリ（オキシエチレン・オキシプロピレン）・アルキレン・メチルポリシロキサン共重合体
（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
を含有するエアゾール原液と噴射剤とを、エアゾール原液／噴射剤＝５／９５〜３０／７０（質量比）の比率で配合することを特徴とする毛髪化粧料である。また、本発明の請求項２は、更に上記成分（Ａ）と成分（Ｂ）が、成分（Ａ）／成分（Ｂ）＝５／１〜１／５（質量比）であることを特徴とする請求項１記載の毛髪化粧料である。 That is, claim 1 of the present invention includes the following components (A) to (C):
(A) General formula 1:

[Wherein 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, R ³ represents a formula R ⁴ Z {R ⁴ represents 3 to 6 carbon atoms And Z represents —NR ⁵ ₂ , —N ⁺ R ⁵ ₃ A ⁻ , —NR ⁵ (CH ₂ 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 an alkyl group having carbon atoms of hydrogen or 1 to 4, carbon atoms R ⁶ is 1 to 4 And A represents a chlorine, iodine or bromine atom, and a represents an integer of 2 to 6), and represents a monovalent group selected from the group consisting of: }, P + q represents an integer of 500 to 2,500. ] Highly polymerized silicone represented by
(B) General formula 2:

(Wherein R ⁷ represents a methyl group or a part thereof represents a phenyl group, x represents an integer of 0 to 50, y represents an integer of 0 to 50, r represents an integer of 5 to 300, and s represents an integer of 2 to 40. Block copolymer type poly (oxyethylene / oxypropylene) / alkylene / methylpolysiloxane copolymer (C) represented by the following formula: Isoparaffinic hydrocarbon having a boiling point in the range of 100 to 260 ° C., silicon number An aerosol stock solution and a propellant containing one or more kinds selected from the group consisting of 2 to 8 volatile silicones and methyltristrimethylsiloxysilane, an aerosol stock solution / propellant = 5/95 to 30/70 (mass ratio) It is a hair cosmetic characterized by being blended at a ratio of Moreover, Claim 2 of the present invention is further characterized in that the component (A) and the component (B) are component (A) / component (B) = 5/1 to 1/5 (mass ratio). The hair cosmetic composition according to claim 1.

  As a result of intensive studies to achieve the above object, the present inventors have found that a specific highly polymerized silicone, a specific poly (oxyethylene / oxypropylene) / alkylene / methylpolysiloxane copolymer, A combination of aerosol solution made of natural oil and propellant in combination at a specific ratio provides excellent hair straightening and straightness, protects the hair from the heat of a straight iron, and has a natural luster and suppleness. The present invention was completed by finding a feature excellent in spray characteristics applied to hair.

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

The highly polymerized silicone which is the component (A) of the present invention is represented by the general formula 1, wherein R ¹ represents a methyl group or part of a phenyl group, R ² represents 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, and Z represents —NR ⁵ ₂ , —N ⁺ R ⁵ ₃ A ⁻ , —NR ⁵ (CH ₂ 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 is hydrogen or 1 to 4 carbons Represents an alkyl group having an atom, R ⁶ represents an alkyl group having 1 to 4 carbon atoms, A represents a chlorine, iodine or bromine atom, and a is an integer of 2 to 6). Represents a monovalent group. }, P + q represents an integer of 500 to 2,500. }, And the molecular weight is about 20,000 to 200,000. When p + q is less than 500, the smoothness of the hair is inferior, and when p + q exceeds 2,500, the silicone gum accumulates in the hair by repeated use, which is not preferable. Specifically, dimethylpolysiloxane, methylphenylpolysiloxane, dimethiconol, terminal hydroxyl group methylphenylpolysiloxane, amino group or ammonium group-modified silicone, etc. with a fluid viscosity that does not reach a soft rubber shape at room temperature, 25 ° C.
In which a viscosity of 10,000 to 3 million mm ² / s is exhibited. These highly polymerized silicones are commercially available. Examples thereof include 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. Examples thereof include SH200C (10,000 cs to 3.5 million cs) manufactured by GE, TSF-451 (6,000 cs to 3 million cs) manufactured by GE Toshiba Silicones, TSF4707, TSF4705, and the like.
In the present invention, one or two or more of these highly polymerized silicones can be appropriately selected and used. The amount of the highly polymerized silicone is preferably 1 to 50% by mass (hereinafter, %, And preferably 5 to 30%. If it is less than 1%, the straight effect is inferior, and if it exceeds 50%, the viscosity of the aerosol stock solution becomes high and unevenly adheres to the hair, which may cause wrinkles and the like.

The poly (oxyethylene / oxypropylene) / alkylene / methylpolysiloxane copolymer which is the component (B) of the present invention is represented by the general formula 2, wherein R ⁷ represents a methyl group or a part thereof represents a phenyl group, m Is an integer from 2 to 5, x is an integer from 0 to 50, y is an integer from 0 to 50, r is an integer from 5 to 300, s is an integer from 2 to 40, and the properties flow from soft rubber at normal temperature. It exhibits a viscosity of 500 to 50 million mm ² / s at 25 ° C. Specific examples include polyoxyethylene / butylene / dimethylpolysiloxane copolymer, polyoxyethylene / polyoxypropylene / butylene / dimethylpolysiloxane copolymer, and poly-silicone-13. These poly (oxyethylene / oxypropylene) / alkylene / methylpolysiloxane copolymers are commercially available. Examples thereof include FZ-2203, FZ-2207, FZ-2222, FZ-2231 manufactured by Nippon Unicar Co., Ltd. Examples thereof include ABN SILWET series such as FZ-2232, FZ-2234, FZ-2233, FZ-2235, FZ-2236, FZ-2237, FZ-2238, and FZ-2239.
In the present invention, one or two or more of these poly (oxyethylene / oxypropylene) / alkylene / methylpolysiloxane copolymers can be appropriately selected and used. Is preferably 1 to 50%, and more preferably 5 to 30%. If it is less than 1%, it will be crumpled and a sufficient effect cannot be obtained, and if it exceeds 50%, it may adhere unevenly to the hair, causing it to become stiff or sticky.

In the present invention, the component (A) and the component (B) are preferably in the range of component (A) / component (B) = 5/1 to 1/5 (mass ratio), more preferably Component (A) / Component (B) = 3/1 to 1/3 (mass ratio). When this range is exceeded, when the mass ratio of the component (A) exceeds 5/1, the hair feels soft and supple, and the mass ratio of the component (A) becomes 1/5 or less. The straight effect may be inferior.

Examples of the volatile oil as component (C) of 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-1.5c manufactured by Shin-Etsu Chemical Co., Ltd.
s, KF-995, Toray Dow Corning Silicone SH244, SH344, SH245, DC345, DC246, SH200C-1cs, SH200C-1.5cs, GE Toshiba Silicones TSF404, TSF405, TSF4045, TSF451-1A, TSF451 -1.5A and the like. 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 two or more of these volatile oils can be appropriately selected and used. The blending amount of these volatile oils is preferably 5 to 90%, more preferably 10 to 80% in the aerosol stock solution. If it is less than 5%, components (A) and (B) cannot be dissolved, the viscosity of the aerosol stock solution is high, and it may not be uniformly applied to the hair, and if it exceeds 90%, the straight durability is poor. There is a case.

  In addition, in the aerosol solution for hair cosmetics of the present invention, in addition to the above essential components, various components generally used in hair cosmetics, for example, water, surfactants, polymer compounds, oils and fats, if necessary. , Powders, silicones, pH adjusters, moisturizers, UV absorbers, UV dispersants, pigments, liquid alcohols, plant extracts, bactericides, antiseptics, antioxidants, chelating agents, drugs, fragrances, etc. It can mix | blend suitably in the range which does not impair the effect of this invention.

In the hair cosmetic composition of the present invention, a propellant is used to spray the aerosol stock solution. As propellants, hydrocarbons such as liquefied petroleum gas (LPG) mainly composed of propane, n-butane, i-butane, etc., ethers such as dimethyl ether, methyl ethyl ether, diethyl ether, carbon dioxide gas, nitrogen gas Compressed gas such as oxygen.
These propellants can be used alone or in admixture of two or more, and the mixing ratio (mass ratio) of the aerosol stock solution and the propellant is aerosol stock solution / propellant = 5 / 95-30 / 70. Is more preferable, and the range of 10/90 to 20/80 is more preferable. When the formulation ratio of the aerosol stock solution is less than 5%, the function of exerting the straight effect is inferior, and when the blending ratio of the aerosol stock solution exceeds 30%, the spray is not uniform and becomes uneven on the hair. The function of the present invention is not exhibited.

  In the present invention, adjustment of the injection amount differs depending on the composition of the aerosol stock solution, the ratio of the mixture with the propellant, the injection port shape of the injection button, etc., but mainly adjusts the valve hole diameter (stem hole diameter, housing hole diameter) and the injection button hole diameter as appropriate. This can be done. However, since it becomes difficult to obtain a uniform spray when the stem hole diameter is increased, it is effective to sufficiently increase the housing hole diameter.

  Moreover, the hair cosmetics of this invention can be manufactured by a conventional method. For example, components (A) to (C) and other additives as necessary are mixed and dispersed or emulsified to adjust the aerosol stock solution and fill the aerosol pressure resistant container with the propellant together with the propellant. To do. In addition, spray forms are spray forms, mist forms, foam forms of general aerosols, and hair cosmetics to be applied before using a straight iron, treatments, shampoos, rinses and other cosmetics for hair Used as In addition to cosmetics, it can be used for spray agents for clothes, hard surface agents such as car wax, animal cosmetics, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, the technical scope of this invention is not limited by these Examples. In addition, the test method regarding the various tests (a straight effect, a straight continuous effect, glossiness, suppleness, stickiness) as described in an Example is shown below.

(1) Sensory test Targeting 20 professional panelists to use the hair cosmetics of the examples and comparative examples, sensory for each item of hair straightness, straightness sustainability, hair gloss, suppleness A test was conducted and evaluation was performed according to the following criteria.

Judgment criteria (1) Straight effect ◎: 15 or more people on the panel judge that the straight state is good ○: 10 to 15 people on the panel judge that the straight state is good △: 5 or more people on the panel and less than 10 people ×: It is judged that 15 or more people on the panel are in a poor straight state. (2) Sustainability of straight ◎: It is judged that 15 or more people on the panel are kept in a straight state. 10 or more and less than 15 people on the panel are judged to be in a straight state. Δ: It is judged that 5 to 10 people on the panel are in a straight state. ×: 15 or more people on the panel are straight. Judgment that the state is not maintained (3) Shiny ◎: It is judged that 15 or more people of the panel have natural gloss ○: It is judged that 10 or more and 15 people of the panel have natural gloss Δ: No. 5 or more and less than 10 in the panel are judged to have a natural luster ×: 15 or more in the panel are judged not to have a natural luster (4) Flexibility ◎: 15 or more in the panel are judged to be pliable ○: It is judged that 10 or more and less than 15 people on the panel are flexible. △: It is judged that 5 or more and less than 10 people on the panel are flexible. ×: It is judged that 15 or more people on the panel are not flexible.

(2) Damage prevention effect test by ironing The hair cosmetics of Examples and Comparative Examples were applied to a commercially available hair bundle (10 g, 20 cm), and using (Hair Iron Venus manufactured by Fuji Package Co., Ltd.) for 1 minute at 150 ° C. The ironing operation was performed. Thereafter, washing and drying were carried out, and these operations were repeated 5 times. Then, the ironed hair was hydrolyzed with hydrochloric acid, amino acid analysis was performed, and the amount of cysteic acid was quantified. In addition, it shows that the damage of hair is progressing, so that cysteic acid content rate is high.

Examples 1-9, Comparative Examples 1-7
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 apparent from Table 1, the hair cosmetic composition of the present invention was clearly superior to any of the tests regarding the straight effect, the straight-lasting effect, the gloss, the suppleness, and the stickiness as compared with the comparative example.

  Hereinafter, other formulation examples of the hair cosmetic composition of the present invention will be given as examples. In addition, as for the hair cosmetics of these examples, the above-mentioned straight effect, straight sustaining effect, gloss, suppleness, and stickiness were examined. there were.

Example 10
<Aerosol stock solution> Compounding amount (%)
(1) Highly polymerized silicone (GE Toshiba Silicones, X21-5613) 25.0
(2) Poly (oxyethylene), butylene,
Methylpolysiloxane copolymer (FZ-2250, manufactured by Nihon Unicar) 25.0
(3) Light liquid isoparaffin (Nippon Yushi Co., Ltd., Pearl Ream 4) 30.0
(4) Decamethylpentacyclosiloxane 19.0
(5) Camellia oil 0.1
(6) Octyl paramethoxycinnamate 0.1
(7) Natural vitamin E 0.3
(8) Fragrance 0.5
<Gas filling> Compounding amount (%)
(9) Aerosol stock solution 10.0
(10) Propellant (liquefied petroleum gas) 90.0

(Manufacturing method) (1) to (8) are uniformly mixed and dissolved to prepare an aerosol stock solution (9), filled into an aerosol can, and after mounting a valve, filled with liquefied petroleum gas of (10) to form a mist. A hair cosmetic to be ejected was prepared.

Example 11
<Aerosol stock solution> Compounding amount (%)
(1) Highly polymerized silicone (GE Toshiba Silicones, X-21-5613) 10.0
(2) Poly (oxyethylene / oxypropylene) /
Butylene / methylpolysiloxane copolymer (Nihon Unicar Co., Ltd., L-45-10cs) 20.0
(3) Light liquid isoparaffin (Nippon Yushi Co., Ltd., Pearl Ream 4) 50.0
(4) Dimethylpolysiloxane (10 cs) 10.0
(5) Jojoba oil 1.0
(6) Olive Squalane 1.0
(7) Octyl paramethoxycinnamate 1.0
(8) Diethyl sebacate 1.0
(9) Isononyl isononanoate 0.5
(10) Oil-soluble Novara extract 0.5
<Gas filling> Compounding amount (%)
(11) Aerosol stock solution 15.0
(12) Liquefied petroleum gas 80.0
(13) Dimethyl ether 5.0

(Production method) (1) to (10) are uniformly mixed and dissolved to prepare an aerosol stock solution (11), which is filled into an aerosol can, and after mounting a valve, is filled with a propellant of (12) and (13). Thus, a hair cosmetic to be ejected in the form of a mist was prepared.

Example 12
<Aerosol stock solution> Compounding amount (%)
(1) Highly polymerized silicone (GE Toshiba Silicone, XF-B8072) 10.0
(2) Poly (oxyethylene), butylene,
Methylpolysiloxane copolymer (FZ-2250, manufactured by Nihon Unicar) 10.0
(3) Light liquid isoparaffin (Nippon Yushi Co., Ltd., Pearl Ream 4) 30.0
(4) Decamethylpentacyclosiloxane 20.0
(5) 95 degree alcohol 29.5
(6) Fragrance 0.5
<Gas filling> Compounding amount (%)
(7) Aerosol stock solution 25.0
(8) Propellant (liquefied petroleum gas) 75.0

(Production method) (1) to (6) are uniformly mixed and dissolved to prepare an aerosol stock solution (7), which is filled in an aerosol resin bottle, and after the valve is mounted, the propellant (8) is filled. A hair cosmetic to be ejected in the form of a mist was prepared.

As described above, the present invention is excellent in the effect of straightening the hair and the straight persistence, protects the hair from the heat of the straight iron, gives natural luster and suppleness, and has excellent spray characteristics applied to the hair. It is obvious to provide a hair cosmetic.

Claims (2)

The following components (A) to (C)
(A) General formula 1:

[Wherein 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, R ³ represents a formula R ⁴ Z {R ⁴ represents 3 to 6 carbon atoms And Z represents —NR ⁵ ₂ , —N ⁺ R ⁵ ₃ A ⁻ , —NR ⁵ (CH ₂ 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 an alkyl group having carbon atoms of hydrogen or 1 to 4, carbon atoms R ⁶ is 1 to 4 And A represents a chlorine, iodine or bromine atom, and a represents an integer of 2 to 6), and represents a monovalent group selected from the group consisting of: }, P + q represents an integer of 500 to 2,500. ] Highly polymerized silicone represented by
(B) General formula 2:

(Wherein R ⁷ represents a methyl group or a part thereof represents a phenyl group, x represents an integer of 0 to 50, y represents an integer of 0 to 50, r represents an integer of 5 to 300, and s represents an integer of 2 to 40. Block copolymer type poly (oxyethylene / oxypropylene) / alkylene / methylpolysiloxane copolymer (C) represented by the following formula: Isoparaffinic hydrocarbon having a boiling point in the range of 100 to 260 ° C., silicon number An aerosol stock solution and a propellant containing one or more kinds selected from the group consisting of 2 to 8 volatile silicones and methyltristrimethylsiloxysilane, an aerosol stock solution / propellant = 5/95 to 30/70 (mass ratio) Hair cosmetics characterized by being formulated at a ratio of The said cosmetics (A) and a component (B) are component (A) / component (B) = 5/1-1/5 (mass ratio), The hair cosmetics of Claim 1 characterized by the above-mentioned.