JP3884720B2 - Hairdresser - Google Patents

Description

この結果、皮膜形成性高分子を配合した整髪剤において、両末端に炭化水素基が結合したオキシエチレン／オキシアルキレン誘導体を配合することにより、ジプロピレングリコール、ジメチルポリシロキサン等の一般的な保湿成分を等量配合した場合と比較して、セット保持力に優れ、べたつかず、なめらかな使用感触を有し、仕上がりの軽さ、しっとり感に優れ、さらにつややかな質感が付与されることが明らかとなった。
【００７２】
つづいて、本発明者らは、前記試験用基本組成１において、配合する皮膜形成性高分子の種類を各種変化させて、前記表１と同様にして官能評価を行った。結果を表２〜４に示す。
・N-メタクロイルN，N-シ゛メチルアンモニウム・α-N-メチルカルホ゛キシヘ゛タイン・メタクリル酸アルキルエステル共重合体（ユカフォーマーSM：三菱化学株式会社製） １２．０質量％
【表２】

【００７３】
・ヒ゛ニルヒ゜ロリト゛ン・N,N-シ゛メチルアミノエチルメタクリル酸共重合体シ゛エチル硫酸塩液（HCホ゜リマー：大阪有機化学株式会社製） １５．０質量％
【表３】

【００７４】
・ヒ゛ニルヒ゜ロリト゛ン・酢酸ヒ゛ニル共重合体(PVP/VA:ISP株式会社製) ５．０質量％
【表４】

上記のように、いずれの皮膜形成性高分子を配合した場合にも、本発明のアルキレンオキシド誘導体を配合することにより、他の保湿成分を配合した場合と比較して、セット保持力に優れ、べたつかず、なめらかな使用感触を有し、仕上がりの軽さ、しっとり感に優れ、さらにつややかな質感を持った整髪剤を得ることができた。
【００７５】
アルキレンオキシド誘導体
以上の結果から、本発明者らは、アルキレンオキシド誘導体の組成に関し、整髪剤としての適性についての検討を進めた。
［Ｒ^１，Ｒ^２の決定］
本発明者らは、アルキレンオキシド誘導体のＲ^１，Ｒ^２と整髪剤としての適性との相関について検討するため、Ｒ^１、Ｒ^２の異なる各種アルキレンオキシド誘導体を配合した整髪剤について、前記基準による官能評価を行った。結果を表５に示す。なお、配合処方としては前記基本組成１（非乳化系水性セットローション）を用い、特に断りの無い限り、いずれの化合物もＥＯ，ＰＯ部は
［（ＥＯ）_１０／（ＰＯ）_１０］
を用いている。
【００７６】
【表５】

表５より明らかなように、Ｒ^１，Ｒ^２の両者の炭素数が１〜４の場合（化合物２，３，４）には、いずれも使用感触、セット保持力、仕上がり感に優れていた。
これに対し、Ｒ^１，Ｒ^２が水素であった場合（化合物１）には、べたつき感が強く、またＲ^１がＣ１２であった場合（化合物６）には、使用感触、仕上がり感がともに好ましくないものとなった。一方、Ｒ^１，Ｒ^２の炭素数の和が７であって、化合物４よりも少ない場合にも、Ｒ^１がＣ６となる（化合物５）としっとり感が劣る傾向にあった。
以上のことから、本発明にかかるアルキレンオキシド誘導体には、Ｒ^１，Ｒ^２ともに炭素数が１〜４の炭化水素基であることが必要である。
【００７７】
なお、実際の製造にあたってはＲ^１，Ｒ^２のすべてが炭化水素基により置換されるとは限らないため、その未置換（Ｈ）の化合物の許容存在割合について検討を行った。結果を表６に示す。なお、未置換の割合は、炭化水素基の数（Ｘ）に対する水素原子の数（Ｙ）の割合Ｙ／Ｘで表わす。なお、下記表６中、１：２＝５：９５は、化合物１と化合物２を５：９５の割合で混合し、所定のＹ／Ｘを調整したことを意味する。
【００７８】
【表６】

前記表６より明らかなように、Ｒ^１，Ｒ^２について未反応のものが存在しても、その量が少なければ（Ｙ／Ｘ＝０．０５４）大きな影響はないが、Ｙ／Ｘが０．２０３になると明らかにべたつき感を生じる。更に本発明者等の詳細な検討の結果、Ｙ／Ｘは０．１５以下であることが必要であることが明らかとなった。
【００７９】
［オキシアルキレン基、オキシエチレン基］
次に本発明者らはアルキレンオキシド誘導体におけるオキシアルキレン基、オキシエチレン基の存在と整髪剤としての適性について検討を行った。結果を次の表７に示す。
【００８０】
【表７】

【００８１】
【化５】

表７において、化合物１１、化５に示す化合物１２においては効果が低いことから明らかなように、本発明においては、使用中、仕上がりの感触の点から、オキシアルキレン基及びオキシエチレン基の両者の存在が不可欠である。また、化合物１２の結果から、本発明の効果は単に親水性、疎水性の調整効果ではないものとも考えられる。本発明者らの更なる詳細な検討によりオキシアルキレン基及びオキシエチレン基の合計に対するオキシエチレン基の好適な割合は２０〜８０質量％であることが明らかとなった。
【００８２】
更に本発明者らは同一アルキレン基数、オキシエチレン基数でブロックポリマー、ランダムポリマーを製造し、その比較を行った。
【表８】

前記表８より明らかなように、ブロックポリマーであってもランダムポリマーであっても本発明の効果を奏することができるが、特にランダムポリマーの場合に優れた使用感を得ることができる。
【００８３】
アルキレンオキシド誘導体の配合量
前記基本組成１において、アルキレンオキシド誘導体の配合量を各種変化させた整髪剤（非乳化系水性セットローション）を調製し、官能評価を行った結果を表９に示す。なお、アルキレンオキシド誘導体としてはCH₃[(EO)₁₄/(PO)₇]CH₃を用いた。
【００８４】
【表９】

表９に示す結果より、本発明の効果は、０．０１質量％程度から認められるが、特に顕著に認められるのは１．０質量％以上である。但し、２０．０質量％を超えると、セット保持力、仕上がり後の軽さが劣る傾向にある。したがって、アルキレンオキシド誘導体の配合量は、好ましくは１．０〜２０．０質量％、更に好ましくは５．０〜１０．０質量％である。
【００８５】
Ｂ）固形油分配合系整髪剤
つづいて本発明者らは、固形油分配合系の整髪剤へのアルキレンオキシド誘導体の適用について検討するため、前記各種アルキレンオキシド誘導体を用い、下記の試験用基本組成２を用いて実際に整髪剤（乳化系ヘアワックス）を調製し、官能評価を行った。
試験用基本組成２ 乳化系ヘアワックス
（１）カルナバロウ ５．０ 質量％
（２）マイクロクリスタリンワックス ８．０
（３）アルキレンオキシド誘導体 ５．０
（４）イオン交換水 残 余
（５）流動パラフィン ８．０
（６）テトラオクタン酸エリスリット ３．０
（７）ステアリン酸 ３．０
（８）プロピレングリコール ５．０
（９）ポリオキシエチレン硬化ヒマシ油 １．０
（１０）トリエタノールアミン ０．２
（製法）
（３）、（４）、（８）を攪拌混合した溶液に、（１）、（２）、（５）〜（７）、（９）までを混合し、加温攪拌を行い均一にした溶液を添加し、攪拌混合溶液を得た。これに（１０）を添加し中和を行なった後にホモミキサーにて乳化処理を行い、オンレーターにて冷却をすることで、乳化系ヘアワックスを得た。
【００８６】
本発明者らは前記基本組成２において、各種アルキレンオキシド誘導体及び各種の保湿成分を各３．０質量％配合した乳化系ヘアワックスについて、前記基準による官能評価を行った。結果を表１０に示す。
【表１０】

表１０に示す結果より、固形油分を配合した整髪剤においても、本発明のアルキレンオキシド誘導体を配合することにより、他の一般的な保湿成分と比較して、セット保持力に優れ、べたつかず、なめらかな使用感触を有し、仕上がりの軽さ、しっとり感に優れ、さらにつややかな質感が付与されることが明らかとなった。
【００８７】
アルキレンオキシド誘導体の配合量
前記基本組成２において、アルキレンオキシド誘導体の配合量を各種変化させた整髪剤（乳化系ヘアワックス）を調製し、官能評価を行った結果を表１１に示す。なお、アルキレンオキシド誘導体としてはCH₃[(EO)₉/(PO)₂]CH₃を用いた。
【００８８】
【表１１】

表１１に示す結果より、油分を配合した系においても、前記表９に示した皮膜剤高分子配合系の場合と同様に、アルキレンオキシド誘導体の配合量は、好ましくは１．０〜２０．０質量％、更に好ましくは５．０〜１０．０質量％であることが明らかとなった。
【００８９】
以下、本発明にかかる整髪剤の好適な配合例について示す。

＜製法及び効果＞
（１）〜（９）を混合撹拌し、均一とする（ヘアスプレー原液）。この原液をエアゾール缶に４５重量部詰め、弁をする。次いで、液化石油ガス５５重量部を充填し、ヘアスプレーを得た。得られたヘアスプレーは、セット保持力が良好で、且つべたつかず、なめらかで、仕上がりの軽さ、しっとり感に優れ、さらにつややかな質感を有するものであった。
【００９０】

＜製法及び効果＞
（９）に（２）〜（５）を添加し、撹拌混合する。次いで、この混合液に、（８）に（１）（６）（７）（１０）を添加し混合撹拌したものを添加し、粘度３５０００ｍＰａ・ｓのヘアジェルを得た。得られたヘアジェルは、セット保持力が良好で、且つべたつかず、なめらかで、仕上がりの軽さ、しっとり感に優れ、さらにつややかな質感を有するものであった。
【００９１】
配合例３ 乳化系ヘアワックス
（１）ポリオキシエチレン(14モル)ポリオキシプロピレン(7モル)ジメチルエーテル ５．０質量％
（２）ビニルピロリドン/酢酸ビニル共重合体 ２．０
（３）イオン交換水 残 余
（４）プロピレングリコール １０．０
（５）流動パラフィン ７．０
（６）テトラオクタン酸エリスリット ２．０
（７）パラフィン ３．０
（８）ステアリン酸 ３．０
（９）セレシン ２．０
（１０）ポリオキシエチレン硬化ヒマシ油 １．０
（１１）トリエタノールアミン ０．２
＜製法及び効果＞
（１）〜（４）を攪拌混合した溶液に、（５）〜（１０）までを混合し、加温攪拌を行い均一にした溶液を添加し、攪拌混合溶液を得た。これに（１１）を添加し中和を行なった後にホモミキサーにて乳化処理を行い、オンレーターにて冷却をすることで、乳化系ヘアワックスを得た。得られた乳化系ヘアワックスは、セット保持力が良好で、且つべたつかず、なめらかで、仕上がりの軽さ、しっとり感に優れ、さらにつややかな質感を有するものであった。
【００９２】
【発明の効果】
本発明によれば、特定構造のアルキレンオキシド誘導体を配合することによって、優れたセット保持力と良好な使用感触、仕上がり感、具体的には手のべたつきがなく、なめらかで、仕上がりが軽く、しっとりとし、さらにツヤやかな質感を併せ持った整髪剤を得ることが出来る。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a hair styling agent, in particular, a set holding power for hair, and improvement in usability and finish feeling.
[0002]
[Prior art]
Conventionally, hair setting agents, styling agents and the like have been widely used as hair styling agents. Most of these hairdressing agents are obtained by dissolving a film-forming polymer or solid oil as a main component for fixing a hairstyle in water, a lower alcohol or a mixed solvent thereof.
[0003]
The film-forming polymer or solid oil has the function of fixing the hairs together to hold the set, but conventionally used ones are sticky in the process from application to the hair to dry finishing. There was no smooth. Also, the finished feel was not supple, and the moist feel, light finish and glossy finish required in recent years were not obtained. In order to eliminate such drawbacks, attempts have been made to improve the stickiness during drying and the finishing feeling after drying by adding cosmetic oils, surfactants, polyhydric alcohols, etc. to polymer compounds and solid oils. It was. However, a hair styling agent having an effect of imparting a set holding power and use feeling that is sufficiently satisfactory, a moist feeling and a light finish, and a glossy texture has not yet been obtained.
[0004]
In recent years, hair treatment agents containing amphoteric polymer compounds and cationic polymers (for example, see Patent Documents 1 and 2), and hair treatment agents containing amphoteric polymer compounds and anionic polymers (for example, Patent Document 3). Have been developed).
However, these hair treatment agents are also not sufficient in terms of the non-stickiness from application to drying, and the finished hair feels irritated, which is not always satisfactory.
[0005]
Furthermore, in recent years, hair styling agents (for example, see Patent Document 4) containing polyoxyethylene dicarboxylic acid ester and a film-forming polymer have been developed, but the moist feeling of finished hair and the effect of giving gloss to hair. It was not always satisfactory.
[0006]
[Patent Document 1]
Japanese Patent Publication No. 2-44446
[Patent Document 2]
Japanese Patent Publication No. 3-14805
[Patent Document 3]
Japanese Patent Publication No. 3-21524
[Patent Document 4]
JP 2001-206824 A
[0007]
[Problems to be solved by the invention]
Further, in recent years, many techniques combining a film-forming polymer or a solid oil and a separately prepared emulsion composition can be seen, but these compositions cause creaming because the emulsion is mixed. It had a problem that it had to be shaken before use.
[0008]
From such a background, the adhesive strength between the hairs is sufficient, the formed film is rich in elasticity, does not get ridiculous, has an excellent set holding power, and does not become sticky in the process from application to dry finishing, The development of a hair styling agent that produces a light and glossy texture with a light finish is desired.
An object of the present invention is to provide a hair styling agent that has both excellent set holding power for hair, good usability and a finished feeling.
[0009]
[Means for Solving the Problems]
As a result of diligent research in view of the above problems, the present inventors have blended an alkylene oxide derivative having a specific structure with a hair-forming agent together with a film-forming polymer or a solid oil component, thereby providing excellent set holding power, The inventors have found that a hair styling agent having good usability, specifically, no stickiness of the hand, light finish, and glossy texture can be obtained, and the present invention has been completed.
[0010]
  That is, the hairdressing agent of the present invention comprises an alkylene oxide derivative represented by the following general formula (I):, One or more skins selected from the following (II)Contains film-forming polymer and / or solid oil with melting point of 40 ° C or higherAnd have set holding powerFeatures.
[Chemical 2]
R ¹ O-[(AO)_m(EO)_n] -R²      (I)
(In the formula, AO is an oxyalkylene group having 3 to 4 carbon atoms, EO is an oxyethylene group, m and n are average addition moles of oxyalkylene groups and oxyethylene groups having 3 to 4 carbon atoms, respectively, 1 ≦ m ≦ 70, 1 ≦ n ≦ 70 The ratio of the oxyethylene group to the total of the oxyalkylene group having 3 to 4 carbon atoms and the oxyethylene group is 20 to 80% by mass. The group and the oxyethylene group may be added in blocks or randomly.¹, R²Are the same or different hydrocarbon groups having 1 to 4 carbon atoms or hydrogen atoms.is there. However, R ¹ , R ² A monoalkyl ether in which any one of them is a hydrogen atom, and R ¹ , R ² Non-alkyl ethers in which both are hydrogen atoms are impurities,R¹And R²The ratio of the number of hydrogen atoms to the number of hydrocarbon groups is 0.15 or lessIn such a range, these monoalkyl ethers and / or non-alkyl ethers may be included.)
(II) Polyvinylpyrrolidone, vinyl acetate / vinyl pyrrolidone copolymer, vinyl pyrrolidone / dimethylaminopropyl methacrylamide copolymer, vinyl pyrrolidone / dimethylaminoethyl methacrylate copolymer, vinyl caprolactam / vinyl pyrrolidone / dimethylaminoethyl methacrylate telomer Telomer of vinyl acetate / monobutylmaleic acid / isobornyl acrylate, telomer of vinylcaprolactam / vinylpyrrolidone / dimethylaminomethacrylamide, vinylpyrrolidone / N, N-dimethylaminoethylmethacrylic acid copolymer diethyl sulfate solution, vinyl Pyrrolidone / methylvinylimidazolinium chloride copolymer, alkyl methacrylate / dimethylaminoethyl methacrylate copolymer, vinyl pyrrolidone / medium Tylvinylimidazole copolymer / vinylcaprolactam copolymer, cetyldimethyl-2-hydroxyethylammonium dihydrophosphate, lauryl / myristyltrimethylammonium sulfate, vinylpyrrolidone / dimethylaminopropylmethacrylamide / t-butyl acrylate phosphate, Methyl vinyl ether / maleic anhydride copolymer monoalkyl ester, methyl vinyl ether / maleic acid ethyl ester copolymer, acrylic resin alkanolamine liquid, ethyl acrylate / acrylic acid amide / acrylic acid copolymer, ethyl acrylate / methacrylic acid Copolymer, vinyl acetate / crotonic acid copolymer, vinyl acetate / crotonic acid neodecanoate vinyl copolymer, hydroxypropyl acrylate / butylaminoethyl methacrylate / acrylic Octyl amide copolymer, octyl acrylamide acrylic resin, N- methacryloyl N, N- dimethyl ammonium-alpha-N-methyl carboxy betaine-alkyl methacrylate copolymer fluids.
[0011]
In the hair styling agent, it is preferable that the alkylene oxide derivative has an oxyalkylene group and an oxyethylene group added randomly. Moreover, in the said hairdressing agent, it is suitable that content of an alkylene oxide derivative is 0.01-20.0 mass% with respect to the hairdressing agent whole quantity.
[0012]
Moreover, in the said hairdressing agent, it is suitable that content of film forming polymer is 0.1-30.0 mass% with respect to the hairdressing agent whole quantity as dry solid content.
[0013]
Moreover, in the said hairdressing agent, it is suitable that content of solid oil whose melting | fusing point is 40 degreeC or more is 0.1-30.0 mass% with respect to the hairdressing agent whole quantity.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, preferred embodiments of the present invention will be described in detail.
In the alkylene oxide derivative represented by the formula (I), which is characteristic in the present invention, AO is an oxyalkylene group having 3 to 4 carbon atoms, specifically, an oxypropylene group, an oxybutylene group, an oxyisobutylene group, an oxy A trimethylene group, an oxytetramethylene group, etc. are mentioned. Preferably, an oxypropylene group and an oxybutylene group are mentioned.
[0015]
m is the average number of added moles of the oxyalkylene group having 3 to 4 carbon atoms, and 1 ≦ m ≦ 70, preferably 2 ≦ m ≦ 20. n is the average number of added moles of oxyethylene groups, and 1 ≦ n ≦ 70, preferably 2 ≦ n ≦ 20. If the oxyalkylene group having 3 to 4 carbon atoms or the oxyethylene group is 0, the moist feeling is lowered, and if it exceeds 70, the sticky feeling is produced, and the smooth feeling is not sufficiently obtained.
Moreover, it is preferable that the ratio of the oxyethylene group with respect to the sum total of a C3-C4 oxyalkylene group and an oxyethylene group is 20-80 mass%. When the proportion of the oxyethylene group is less than 20% by mass, the moist feeling tends to be inferior, and when it exceeds 80% by mass, the smooth feeling tends to be inferior.
[0016]
The order of adding ethylene oxide and alkylene oxide having 3 to 4 carbon atoms is not particularly specified. Further, the oxyethylene group and the oxyalkylene group having 3 to 4 carbon atoms may be added in a block shape or in a random shape. The block shape includes not only a two-stage block but also a three-stage block. Preferably, those added randomly are listed.
R¹And R²May be the same type, or a hydrocarbon group having 1 to 4 carbon atoms and a hydrogen atom may be mixed, or different hydrocarbon groups having 1 to 4 carbon atoms may be mixed. However, R¹And R²Among the hydrocarbon groups, the ratio of hydrocarbon groups and hydrogen atoms is such that the ratio Y / X of the number of hydrogen atoms (Y) to the number of hydrocarbon groups (X) is 0.15 or less, preferably 0.06. It is as follows. When the ratio of Y / X exceeds 0.15, a sticky feeling comes out.
[0017]
Examples of the alkylene oxide derivative used in the present invention include polyoxyethylene (10 mol) polyoxypropylene (10 mol) dimethyl ether, polyoxyethylene (9 mol) polyoxypropylene (2 mol) dimethyl ether, polyoxyethylene (14 Mol) polyoxypropylene (7 mol) dimethyl ether, polyoxyethylene (6 mol) polyoxypropylene (14 mol) dimethyl ether, polyoxyethylene (15 mol) polyoxypropylene (5 mol) dimethyl ether, polyoxyethylene (25 mol) Polyoxypropylene (25 mol) dimethyl ether, polyoxyethylene (9 mol) polyoxybutylene (2 mol) dimethyl ether, polyoxyethylene (14 mol) polyoxybutylene (7 mol) dimethyl Ether, polyoxyethylene (10 mol) polyoxypropylene (10 mol) diethyl ether, polyoxyethylene (10 mol) polyoxypropylene (10 mol) dipropyl ether, polyoxyethylene (10 mol) polyoxypropylene (10 mol) ) Dibutyl ether and the like.
[0018]
The alkylene oxide derivative of the present invention can be produced by a known method. For example, it can be obtained by subjecting a compound having a hydroxyl group to addition polymerization of ethylene oxide and an alkylene oxide having 3 to 4 carbon atoms, and then subjecting an alkyl halide to an ether reaction in the presence of an alkali catalyst.
The blending amount of the alkylene oxide derivative is preferably 0.01 to 20.0% by mass, more preferably 0.5 to 10.0% by mass, based on the total amount of the hairdressing agent. If it is less than 0.01% by mass, the effect of the blending is not exhibited, and if it exceeds 20.0% by mass, the set holding power and the lightness of the finish tend to be inferior.
[0019]
The film-forming polymer used in the present invention has the ability to form a film-like film when a solvent such as alcohol or water in which the polymer is dissolved is volatilized, and is usually used for cosmetics. And the following polymer compounds are mentioned.
Nonionic polymers include, for example, polyvinyl pyrrolidone, vinyl acetate / vinyl pyrrolidone copolymer, vinyl pyrrolidone / dimethylaminopropyl methacrylamide copolymer, vinyl pyrrolidone / dimethylaminoethyl methacrylate copolymer, vinyl caprolactam / vinyl pyrrolidone / dimethyl. Examples thereof include telomers of aminoethyl methacrylate, telomers of vinyl acetate / monobutylmaleic acid / isobornyl acrylate, telomers of vinylcaprolactam / vinylpyrrolidone / dimethylaminomethacrylamide, and the like. Preferably, a vinyl acetate / vinyl pyrrolidone copolymer is used from the viewpoint of hair styling properties and setting power.
[0020]
Examples of cationic polymers include vinyl pyrrolidone / N, N-dimethylaminoethyl methacrylic acid copolymer diethyl sulfate solution, vinyl pyrrolidone / methyl vinyl imidazolinium copolymer, alkyl methacrylate / dimethylaminoethyl methacrylate copolymer Polymer, vinylpyrrolidone / methylvinylimidazole copolymer / vinylcaprolactam copolymer, cetyldimethyl-2-hydroxyethylammonium dihydrophosphate, lauryl / myristyltrimethylammonium sulfate, vinylpyrrolidone / dimethylaminopropylmethacrylamide / t-acrylic And acid butyl phosphate. A vinyl pyrrolidone / N, N-dimethylaminoethyl methacrylic acid copolymer diethyl sulfate solution is preferable from the viewpoint of hair styling and feel.
[0021]
Examples of the anionic polymer include methyl vinyl ether / maleic anhydride copolymer monoalkyl ester, methyl vinyl ether / maleic acid ethyl ester copolymer, acrylic resin alkanolamine solution, ethyl acrylate / acrylic acid amide / acrylic acid copolymer Copolymer, ethyl acrylate / methacrylic acid copolymer, vinyl acetate / crotonic acid copolymer, vinyl acetate / crotonic acid neodecanoic acid vinyl copolymer, hydroxypropyl acrylate / butylaminoethyl methacrylate / octylamide acrylate copolymer Examples thereof include merging and octylacrylamide acrylic resin. Preferably, an ethyl acrylate / methacrylic acid copolymer is used from the viewpoint of hair styling and setting power.
[0022]
Examples of the amphoteric polymer include N-methacryloyl N, N-dimethylammonium / α-N-methylcarboxybetaine / methacrylic acid alkyl ester copolymer solution.
[0023]
In the hairdressing agent of the present invention, the blending amount of the film-forming polymer is 0.1 to 30.0% by mass, preferably 1.0 to 20.0% by mass, based on the total amount of the hairdressing agent as a dry solid content. . If it is less than 0.1% by mass, the effect as a hair styling agent cannot be obtained, and if it exceeds 30.0% by mass, it is undesirably applied to the hair and applied to the hair.
[0024]
The solid oil used in the present invention is a wax having a melting point of 40 ° C. or higher, and those usually used in cosmetics are exemplified, and the following solid oil is exemplified.
Examples of waxes include candelilla wax having a melting point of 68 to 72 ° C, carnauba wax having a melting point of 80 to 86 ° C, wood wax having a melting point of 50 to 53.5 ° C, bead wax having a melting point of 60 to 67 ° C, beeswax, cotton Examples include wax, bayberry wax, ibotarou, montan wax, and sugarcane wax. Examples of the hydrocarbon oil include paraffin, ceresin, microcrystalline wax, 12-hydroxystearic acid, and the like. Among them, preferred are candelilla wax, carnauba wax, bees wax, paraffin, ceresin, and microcrystalline wax.
[0025]
In the hairdressing agent of the present invention, the blending amount of the solid oil is 0.1 to 30.0% by mass, preferably 1.0 to 20.0% by mass, based on the total amount of the hairdressing agent. If it is less than 0.1% by mass, the effect as a hair styling agent cannot be obtained, and if it exceeds 30.0% by mass, it is undesirably applied to the hair and applied to the hair.
[0026]
The film-forming polymer and the solid oil may be used alone or in combination of two or more, respectively, or one or more of the film-forming polymers and one or two of the solid oil. You may use together with a seed or more.
[0027]
The hairdressing agent of the present invention includes other components that are usually used in cosmetics and pharmaceuticals, for example, powder components, liquid fats and oils, solid fats and oils, waxes, hydrocarbon oils, higher fatty acids, and higher alcohols in addition to the above-described essential components. , Ester oil, silicone oil, anionic surfactant, cationic surfactant, amphoteric surfactant, nonionic surfactant, water-soluble polymer, thickener, film agent, UV absorber, sequestering agent, lower Alcohols, polyhydric alcohols, sugars, amino acids, organic amines, polymer emulsions, pH adjusters, skin nutrients, vitamins, antioxidants, antioxidant auxiliaries, fragrances, water, etc. are appropriately blended as necessary. Depending on the dosage form, it can be produced by a conventional method. Specific ingredients that can be blended are listed below, but the hair conditioner of the present invention can be prepared by blending the above essential blending ingredients and any one or more of the following ingredients.
[0028]
Examples of the powder component include inorganic powders (for example, talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, saucite, biotite, permiculite, magnesium carbonate, calcium carbonate, silicic acid. Aluminum, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (baked gypsum), calcium phosphate, fluorine apatite, hydroxyapatite, ceramic powder , Metal soap (eg, zinc myristate, calcium palmitate, aluminum stearate), boron nitride, etc .; organic powder (eg, polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, polystyrene Powder, copolymer resin powder of styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, etc.); inorganic white pigment (eg, titanium dioxide, zinc oxide, etc.); inorganic red pigment (eg, Iron oxide (Bengara), iron titanate, etc .; Inorganic brown pigments (eg, γ-iron oxide, etc.); Inorganic yellow pigments (eg, yellow iron oxide, loess, etc.); Inorganic black pigments (eg, black oxide) Iron, low-order titanium oxide, etc.); inorganic purple pigments (eg, mango violet, cobalt violet, etc.); inorganic green pigments (eg, chromium oxide, chromium hydroxide, cobalt titanate, etc.); inorganic blue pigments (eg, Pearl pigments (eg titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored oxidation) Tan-coated mica, bismuth oxychloride, fish scale foil, etc.); metal powder pigments (eg, aluminum powder, copper powder, etc.); organic pigments such as zirconium, barium or aluminum lake (eg, red 201, red 202, red 204) No., red 205, red 220, red 226, red 228, red 405, orange 203, orange 204, yellow 205, yellow 401, and blue 404, organic pigments such as red 3 , Red 104, Red 106, Red 227, Red 230, Red 401, Red 505, Orange 205, Yellow 4, Yellow 5, Yellow 202, Yellow 203, Green 3 and Blue No. 1 etc.); natural pigments (for example, chlorophyll, β-carotene, etc.) and the like.
[0029]
Examples of liquid oils include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, southern castor oil, castor oil, linseed oil , Safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagiri oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin and the like.
[0030]
Examples of the hydrocarbon oil include liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax, and the like.
[0031]
Examples of the higher fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, toluic acid, isostearic acid, linoleic acid, linolenic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid ( DHA) and the like.
[0032]
Examples of higher alcohols include linear alcohols (eg, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol); branched chain alcohols (eg, monostearyl glycerin ether (batyl alcohol) ), 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyl decanol, isostearyl alcohol, octyldodecanol and the like.
[0033]
Synthetic ester oils include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, myristyl lactate Lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, monoisostearate N-alkyl glycol, neopentyl glycol dicaprate, apple Acid diisostearyl, di-2-heptylundecanoic acid glycerin, tri-2-ethylhexanoic acid trimethylolpropane, triisostearic acid trimethylo Propane, tetra-2-ethylhexanoate pentaerythritol, glycerol tri-2-ethylhexanoate, glycerol trioctanoate, glycerol triisopalmitate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmi Tate, glyceryl trimyristate, glyceride tri-2-heptylundecanoate, castor oil fatty acid methyl ester, oleyl oleate, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2 -Octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate Le, diisopropyl sebacate, 2-ethylhexyl succinate, and triethyl citrate.
[0034]
Examples of the silicone oil include linear polysiloxanes (for example, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.); cyclic polysiloxanes (for example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexyl). And silicone resins that form a three-dimensional network structure, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.) It is done.
[0035]
Examples of anionic surfactants include saturated branched fatty acid salts and fatty acid salts other than unsaturated fatty acid salts blended as essential components, such as linear fatty acid salts (sodium laurate, sodium palmitate, etc.), and higher alkyl sulfates. Ester salts (eg, sodium lauryl sulfate, potassium lauryl sulfate, etc.); alkyl ether sulfate esters (eg, POE-lauryl sulfate triethanolamine, POE-sodium lauryl sulfate); N-acyl sarcosine acids (eg, lauroyl sarcosine sodium) Higher fatty acid amide sulfonates (for example, sodium N-myristoyl-N-methyltaurine, sodium coconut oil fatty acid methyltaurine sodium, sodium laurylmethyltaurine, etc.); phosphate ester salts (POE-sodium oleyl ether, POE) -Stearyl A Sulfosuccinate (eg, sodium di-2-ethylhexyl sulfosuccinate, sodium monolauroyl monoethanolamide polyoxyethylene sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc.); alkylbenzene sulfonate (eg, linear dodecyl) Sodium benzene sulfonate, linear dodecyl benzene sulfonate triethanolamine, linear dodecyl benzene sulfonic acid, etc.); higher fatty acid ester sulfates (eg, hardened coconut oil fatty acid sodium glycerine sulfate); N-acyl glutamate (eg, N -Monosodium lauroyl glutamate, disodium N-stearoyl glutamate, N-myristoyl-L-monosodium glutamate, etc.); sulfated oil (eg, low Oils, etc.); POE-alkyl ether carboxylic acids; POE-alkyl allyl ether carboxylates; α-olefin sulfonates; higher fatty acid ester sulfonates; secondary alcohol sulfates; higher fatty acid alkylolamide sulfates; Examples include sodium lauroyl monoethanolamide succinate; N-palmitoyl aspartate ditriethanolamine; sodium caseinate and the like.
[0036]
Examples of the cationic surfactant include alkyltrimethylammonium salts (eg, stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, etc.); alkylpyridinium salts (eg, cetylpyridinium chloride, etc.); distearyldimethylammonium dialkyldimethylammonium chloride; Poly (N, N'-dimethyl-3,5-methylenepiperidinium chloride); alkyl quaternary ammonium salt; alkyldimethylbenzylammonium salt; alkylisoquinolinium salt; dialkyl morpholinium salt; POE-alkylamine; Examples include alkylamine salts; polyamine fatty acid derivatives; amyl alcohol fatty acid derivatives; benzalkonium chloride; benzethonium chloride and the like.
[0037]
Examples of amphoteric surfactants include imidazoline-based amphoteric surfactants (eg, 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide). Side-1-carboxyethyloxy disodium salt, etc.); betaine surfactants (for example, 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkylbetaine, amide betaine) , Sulfobetaine, etc.).
[0038]
Examples of the lipophilic nonionic surfactant include sorbitan fatty acid esters (for example, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, Sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexylate, diglycerol sorbitan tetra-2-ethylhexylate); glycerin polyglycerin fatty acids (eg mono cottonseed oil fatty acid glycerin, monoerucic acid glycerin, sesquioleate glycerin, monostearin) Glycerin acid, α, α'-oleic acid pyroglutamate glycerin, monostearic acid glycerin malic acid, etc.); propylene glycol fatty acid esters (eg monostearies) Propylene glycolate, etc.); hardened castor oil derivative; glycerin alkyl ether, etc.
[0039]
Examples of hydrophilic nonionic surfactants include POE-sorbitan fatty acid esters (for example, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate). POE sorbite fatty acid esters (eg, POE-sorbite monolaurate, POE-sorbite monooleate, POE-sorbite pentaoleate, POE-sorbite monostearate, etc.); POE-glycerin fatty acid esters (eg, POE- POE-monooleate such as glycerol monostearate, POE-glycerol monoisostearate, POE-glycerol triisostearate); POE-fatty acid esters (eg POE-distearate, POE-monodiolate, ethylene glycol distearate, etc.) POE-alkyl ethers (eg POE- Lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, POE-cholestanol ether, etc.); Pluronic type (eg, Pluronic, etc.); POE / POP-alkyl ether (For example, POE / POP-cetyl ether, POE / POP-2-decyltetradecyl ether, POE / POP-monobutyl ether, POE / POP-hydrogenated lanolin, POE / POP-glycerin ether, etc.); Tetra POE / Tetra POP-ethylenediamine condensates (eg Tetronic, etc.); POE-castor oil hardened castor oil derivatives (eg POE-castor oil, POE-hardened castor oil, POE-hardened castor oil monoisostearate, POE-hardened castor Oil triisostearate, POE-hardened castor oil monopyroglutamic acid monoisostearic acid diester, POE-hardened castor oil maleic acid, etc.) POE-beeswax lanolin derivatives (eg POE-sorbite beeswax); alkanolamides (eg coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide, etc.); POE-propylene glycol fatty acid ester; POE-alkylamine POE-fatty acid amide; sucrose fatty acid ester; alkyl ethoxydimethylamine oxide; trioleyl phosphate and the like.
[0040]
Examples of the humectant include polyethylene glycol, propylene glycol, glycerin, 1,3-butylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate Sodium lactate, bile salt, dl-pyrrolidone carboxylate, short-chain soluble collagen, diglycerin (EO) PO adduct, Izayoi rose extract, yarrow extract, merirot extract and the like.
[0041]
Examples of natural water-soluble polymers include plant-based polymers (for example, gum arabic, gum tragacanth, galactan, guar gum, carob gum, caraya gum, carrageenan, pectin, agar, quince seed (malmello), alge colloid (guckweed extract), starch (Rice, corn, potato, wheat), glycyrrhizic acid); microbial polymers (eg, xanthan gum, dextran, succinoglucan, bullulan, etc.); animal polymers (eg, collagen, casein, albumin, gelatin, etc.), etc. Is mentioned.
[0042]
Semi-synthetic water-soluble polymers include, for example, starch polymers (eg, carboxymethyl starch, methylhydroxypropyl starch, etc.); cellulose polymers (methylcellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate) Hydroxypropylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, crystalline cellulose, cellulose powder and the like); alginic acid polymers (for example, sodium alginate, propylene glycol alginate, etc.) and the like.
[0043]
Examples of UV absorbers include benzoic acid UV absorbers (eg, paraaminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester. N, N-dimethyl PABA ethyl ester, N, N-dimethyl PABA butyl ester, N, N-dimethyl PABA ethyl ester, etc.); anthranilic acid-based UV absorbers (for example, homomenthyl-N-acetyl anthranilate, etc.); Salicylic acid ultraviolet absorbers (for example, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, etc.); cinnamic acid ultraviolet absorbers (for example, octylcinnamate, ethyl- 4-isopropyl cinnamate, meth -2,5-diisopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxy Cinnamate, octyl-p-methoxycinnamate (2-ethylhexyl-p-methoxycinnamate), 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenyl Cinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl-diparamethoxycinnamate, etc.); benzophenone UV absorbers (for example, 2,4-dihydroxybenzophenone, 2 , 2'-Dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfone Acid salt, 4-phenylbenzophenone, 2-ethylhexyl-4′-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone, etc.); 3- ( 4'-methylbenzylidene) -d, l-camphor, 3-benzylidene-d, l-camphor; 2-phenyl-5-methylbenzoxazole; 2,2'-hydroxy-5-methylphenylbenzotriazole; (2'-hydroxy-5'-t-octylphenyl) benzotriazole; 2- (2'-hydroxy-5'-methylphenylbenzotriazole; dibenzalazine; dianisoylmethane; 4-methoxy-4'-t-butyldiben Irumetan; 5- (3,3-dimethyl-2-norbornylidene) -3-pentan-2-one, and the like.
[0044]
Examples of the sequestering agent include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, tetrasodium edetate Sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, trisodium ethylenediaminehydroxyethyl triacetate and the like.
[0045]
Examples of the lower alcohol include ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol and the like.
Examples of the polyhydric alcohol include divalent alcohols (for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, tetramethylene glycol, 2,3-butylene glycol, Pentamethylene glycol, 2-butene-1,4-diol, hexylene glycol, octylene glycol, etc.); trivalent alcohol (eg, glycerin, trimethylolpropane, etc.); tetravalent alcohol (eg, 1,2,6) -Pentaerythritol such as hexanetriol); pentavalent alcohol (for example, xylitol, etc.); hexavalent alcohol (for example, sorbitol, mannitol, etc.); polyhydric alcohol polymer (for example, diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene Glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, tetraglycerin, polyglycerin, etc.); divalent alcohol alkyl ethers (for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene) Glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono 2-methylhexyl ether, ethylene glycol isoamyl ether, ethylene glycol benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, etc.) ; Dihydric alcohol alkyl ester Tellurium (for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether , Propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, etc.); divalent alcohol Ether esters (eg, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diazinate, ethylene glycol disuccinate, diethylene glycol monoethyl ether acetate, diethylene glycol) Monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate, etc .; glycerin monoalkyl ethers (eg, xyl alcohol, ceralkyl alcohol) Sugar alcohol (eg, sorbitol, maltitol, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, amylolytic sugar, maltose, xylitolose, amylolytic sugar reducing alcohol, etc.); Solid; Tetrahydrofurfuryl alcohol; POE-Tetrahydrofurfuryl alcohol; POP-Butyl ether; POP / POE-Butyl ether; Tripolyoxypropylene glycerin ether; POP-Glycerine ether; Examples include ether and polyglycerin.
[0046]
Monosaccharides include, for example, tricarbon sugars (eg, D-glyceryl aldehyde, dihydroxyacetone, etc.); tetracarbon sugars (eg, D-erythrose, D-erythrulose, D-threose, erythritol, etc.); pentose sugars (eg, L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose, etc .; hexose (eg, D-glucose, D-talose, D -Bucicose, D-galactose, D-fructose, L-galactose, L-mannose, D-tagatose, etc.); pentose sugar (eg, aldoheptose, heproose, etc.); octose sugar (eg, octulose, etc.); For example, 2-deoxy-D-ribose, 6-deoxy-L-galactose, 6-deoxy-L-mannose, etc .; amino sugar (eg, D-glucosamine, D-galactosamine, shea Acid, Aminouron acid, muramic acid); uronic acid (e.g., D- glucuronic acid, D- mannuronic acid, L- guluronic acid, D- galacturonic acid, L- iduronic acid) and the like.
[0047]
Examples of the oligosaccharides include sucrose, gnocyanose, umbelliferose, lactose, planteose, isoliquinoses, α, α-trehalose, raffinose, lycnose, stachyose verbus course and the like.
[0048]
Examples of the polysaccharide include cellulose, quince seed, chondroitin sulfate, starch, galactan, dermatan sulfate, glycogen, gum arabic, heparan sulfate, hyaluronic acid, tragacanth gum, keratan sulfate, chondroitin, xanthan gum, mucoitin sulfate, guar gum, dextran, kerato sulfate. , Locust bean gum, succinoglucan, caronic acid and the like.
[0049]
Examples of amino acids include neutral amino acids (eg, threonine, cysteine, etc.); basic amino acids (eg, hydroxylysine, etc.) and the like. Examples of amino acid derivatives include acyl sarcosine sodium (lauroyl sarcosine sodium), acyl glutamate, acyl β-alanine sodium, glutathione, and pyrrolidone carboxylic acid.
[0050]
Examples of the organic amine include monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, and 2-amino-2-methyl-1-propanol. Is mentioned.
[0051]
Examples of the polymer emulsion include an acrylic resin emulsion, a polyethyl acrylate emulsion, an acrylic resin liquid, a polyacryl alkyl ester emulsion, a polyvinyl acetate resin emulsion, and a natural rubber latex.
[0052]
Examples of the pH adjuster include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.
Examples of vitamins include vitamins A, B1, B2, B6, C, E and derivatives thereof, pantothenic acid and derivatives thereof, biotin and the like.
[0053]
Examples of the antioxidant include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters and the like.
Examples of the antioxidant assistant include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, kephalin, hexametaphosphate, phytic acid, ethylenediaminetetraacetic acid, and the like.
[0054]
Other components that can be blended include, for example, preservatives (ethyl paraben, butyl paraben, etc.); anti-inflammatory agents (eg, glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin, etc.); Extract, placenta extract, saxifrage extract, arbutin, etc.); various extracts (eg, buckwheat, auren, shikon, peonies, assembly, birch, sage, loquat, carrot, aloe, mallow), iris, grape, yokuinin, loofah, lily , Saffron, nematode, ginger, hypericum, onionis, garlic, red pepper, chimney, red snapper, seaweed, etc.), activator (for example, royal jelly, photosensitizer, cholesterol derivative, etc.); blood circulation promoter (for example, nonenyl acid wallenylamide, nicotine) Acid Gyl ester, nicotinic acid β-butoxyethyl ester, capsaicin, gingerone, cantalis tincture, ictamol, tannic acid, α-borneol, nicotinic acid tocopherol, inositol hexanicotinate, cyclandrate, cinnarizine, trazoline, acetylcholine, verapamil, cephalanthin , Γ-oryzanol, etc.); antiseborrheic agents (eg, sulfur, thianthol, etc.); anti-inflammatory agents (eg, tranexamic acid, thiotaurine, hypotaurine, etc.) and the like.
[0055]
The dosage form of the hairdressing agent of the present invention may be any of a solubilization system, an emulsification system, a powder dispersion system, an oil-water two-layer system, an oil-water-powder three-layer system, etc. Particularly preferred. Preferable use modes of the hair styling agent of the present invention include aerosol hair spray, pump hair spray, foam aerosol, hair mist, set lotion, hair styling gel, hair liquid, hair wax and the like.
[0056]
【Example】
Examples The present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In addition, all compounding quantities are shown by the mass%.
First, the evaluation method employed in the present invention will be described.
[0057]
[Evaluation methods]
Evaluation (1) Less stickiness after application to drying
Twenty subjects applied 3 g of sample to a hair strand (4 g), shaped the shape with a comb, and sensory-evaluated the stickiness until drying. The evaluation criteria are as follows.
A: Very good (more than 18 subjects answered good)
○: Good (the number of subjects who answered good was 8 or more and less than 18)
Δ: Slightly bad (the number of subjects who answered good was 5 or more and less than 8)
×: Bad (the number of subjects who answered good was less than 5)
[0058]
Evaluation (2) Smoothness from application to drying
Twenty subjects applied 3 g of the sample to hair strands (4 g), adjusted the shape with a comb, and sensory-evaluated the smoothness until drying. The evaluation criteria are the same as (1) above.
[0059]
Evaluation (3) Set holding power
A sample of 0.5 g was uniformly applied to a hair bundle having a length of 15 cm and a weight of 1 g, wound on a rod having a diameter of 2 cm, and left in a high temperature chamber at 45 ° C. for 6 hours to be completely dried. After drying, the rod was removed and the apparent length (L1) of the hair bundle was measured. Next, the hair bundle is suspended in a constant temperature and humidity of 25 ° C. and humidity of 90%, taken out after 30 minutes, the apparent length (L2) of the hair bundle is measured again, and the set holding effect is obtained by the following equation. It was. The closer this value is to 100, the higher the set holding effect.
Set holding force = {(15-L2) / (15-L1)} × 100 (%)
A: Very good (set holding force of 80% or more)
○: Good (set holding power 50% or more, less than 80%)
Δ: Slightly bad (set holding force 30% or more, less than 50%)
X: bad (set holding power less than 30%)
[0060]
Evaluation (4) Lightness of finished hair
The lightness of the finished hair strands dried in (1) was subjected to sensory evaluation by 20 subjects. The evaluation criteria are as follows.
◎: Light (more than 18 subjects answered that it was light)
○: Slightly light (the number of subjects who answered that it was light was 8 or more and less than 18)
Δ: Slightly heavy (the number of subjects who answered that it was light was 5 or more and less than 8)
X: Heavy (the number of subjects who answered that it was light was less than 5)
[0061]
Evaluation (5) Moist feeling of finished hair
The moist feeling of the finished hair strands dried in (1) was sensorially evaluated by 20 subjects. The evaluation criteria are as follows.
◎: Very good (more than 18 subjects answered moist)
○: Good (the number of subjects who answered moist was 8 or more and less than 18)
Δ: Slightly bad (the number of subjects who answered moist was 5 or more and less than 8)
X: Bad (the number of subjects who answered moist was less than 5)
[0062]
Evaluation (6) Finished hair gloss
The glossiness of the hair strands dried in (1) was sensory evaluated by 20 subjects. The evaluation criteria are as follows.
A: Very good (more than 18 subjects answered that they were shiny)
○: Good (the number of subjects who answered that there was gloss is 8 or more and less than 18)
△: Slightly bad (The number of subjects who answered that there was gloss is 5 or more and less than 8)
×: Bad (the number of subjects who answered that there was gloss is less than 5)
[0063]
Next, synthesis examples of alkylene oxide derivatives according to the present invention will be shown. Hereinafter, the oxyethylene group is abbreviated as EO, the oxypropylene group is abbreviated as PO, and the oxybutylene group is abbreviated as BO.
[0064]
Synthesis Example 1 Synthesis of block polymer
Polyoxyethylene (10 mol) Polyoxypropylene (10 mol) Dimethyl ether
[Chemical Formula 3]
CH₃O (EO)₅(PO)₁₀(EO)₅CH₃
[0065]
76 g of propylene glycol and 3.1 g of potassium hydroxide as a catalyst were charged into an autoclave. After the air in the autoclave was replaced with dry nitrogen, the catalyst was completely dissolved at 140 ° C. with stirring. Next, 522 g of propylene oxide was dropped with a dropping device and stirred for 2 hours. Subsequently, 440 g of ethylene oxide was dropped with a dropping device and stirred for 2 hours. Next, 224 g of potassium hydroxide was charged and the inside of the system was replaced with dry nitrogen, and then 188 g of methyl chloride was injected at a temperature of 80 to 130 ° C. and reacted for 5 hours. Thereafter, the reaction composition was taken out from the autoclave, neutralized with hydrochloric acid to pH 6 to 7, and treated at a reduced pressure of -0.095 MPa (50 mmHg) at 100 ° C for 1 hour in order to remove the contained water. Further, filtration was performed to remove the salt produced after the treatment, and the alkylene oxide derivative represented by the chemical formula 3 was obtained.
Samples which were sampled and reacted before reacting with methyl chloride had a hydroxyl value of 110, the hydroxyl value of Compound 1 was 0.3, and the ratio of the number of hydrogen atoms to the number of terminal methyl groups was 0.003, so that the hydrogen atoms were almost completely It has been converted to a methyl group.
[0066]
Synthesis Example 2 Random polymer synthesis example
Polyoxyethylene (10 mol) Polyoxypropylene (10 mol) Dimethyl ether
[Formula 4]
CH₃O [(EO)₁₀/ (PO)₁₀] CH₃
[0067]
In the following examples, EO represents an oxyethylene group, PO represents an oxypropylene group, and [(EO) / (PO)] represents a random bond.
76 g of propylene glycol and 3.1 g of potassium hydroxide as a catalyst were charged into an autoclave. After the air in the autoclave was replaced with dry nitrogen, the catalyst was completely dissolved at 140 ° C. with stirring. Next, a mixture of 440 g of ethylene oxide and 522 g of propylene oxide was dropped with a dropping device and stirred for 2 hours. Next, 224 g of potassium hydroxide was charged and the inside of the system was replaced with dry nitrogen, and then 188 g of methyl chloride was injected at a temperature of 80 to 130 ° C. and reacted for 5 hours. Thereafter, the reaction composition was taken out from the autoclave, neutralized with hydrochloric acid to pH 6 to 7, and treated at a reduced pressure of -0.095 MPa (50 mmHg) at 100 ° C for 1 hour in order to remove the contained water. Further, filtration was performed to remove the salt produced after the treatment, and an alkylene oxide derivative represented by the chemical formula 4 was obtained.
Samples that were sampled and reacted before reacting with methyl chloride had a hydroxyl value of 107, compound 1 had a hydroxyl value of 0.4, and the ratio of the number of hydrogen atoms to the number of terminal methyl groups was 0.004, so that the hydrogen atoms were almost completely It has been converted to a methyl group.
[0068]
A) Hair conditioner with film-forming polymer
In order to examine the application to a hair styling agent blended with a film-forming polymer, the present inventors first prepared various alkylene oxide derivatives according to the above synthesis examples, and used the following basic composition for testing. A hair styling agent (non-emulsifying aqueous set lotion) was actually prepared and evaluated.
[0069]
Basic composition for testing 1 Non-emulsifying aqueous set lotion
(1) Acrylic resin alkanolamine liquid 12.0% by mass
(Plus size L-53P: manufactured by Kyoyo Chemical Co., Ltd.)
(2) Alkylene oxide derivative 5.0
(3) Ion exchange water remaining
(4) Ethanol 30.0
(5) Propylene glycol 5.0
(6) Polyoxyethylene hydrogenated castor oil 1.0
(Manufacturing method)
(1) to (6) were mixed and stirred to obtain a non-emulsifying aqueous set lotion.
[0070]
First, the present inventors performed a sensory evaluation based on the above criteria for a non-emulsifying aqueous set lotion containing 5.0% by mass of various alkylene oxide derivatives or various moisturizing components in the basic composition 1. The results are shown in Table 1.
[0071]
[Table 1]

  As a result, in hair styling agents containing a film-forming polymer, by adding an oxyethylene / oxyalkylene derivative having a hydrocarbon group bonded to both ends, general moisturizing ingredients such as dipropylene glycol and dimethylpolysiloxane It is clear that it has superior set holding power, non-stickiness, smooth use feeling, excellent finish lightness, moist feeling, and a more glossy texture compared to the case of blending an equal amount of became.
[0072]
  Subsequently, the present inventors performed sensory evaluation in the same manner as in Table 1 by changing various types of the film-forming polymer to be blended in the basic composition for testing 1. The results are shown in Tables 2-4.
・ N-methacryloyl N, N-dimethylammonium ・ α-N-methylcarboxybetaine ・ alkyl methacrylate copolymer (Yukaformer SM: manufactured by Mitsubishi Chemical Corporation) 12.0% by mass
[Table 2]

[0073]
-Vinyl pyrrolidone-N, N-dimethylaminoethyl methacrylic acid copolymer diethyl sulfate solution (HC polymer: manufactured by Osaka Organic Chemical Co., Ltd.) 15.0% by mass
[Table 3]

[0074]
-Vinyl pyrrolidone-vinyl acetate copolymer (PVP / VA: made by ISP Co., Ltd.) 5.0 mass%
[Table 4]

  As described above, even when any film-forming polymer is blended, by blending the alkylene oxide derivative of the present invention, compared to the case where other moisturizing ingredients are blended, the set holding power is excellent. The hair styling agent was smooth and non-sticky, had a light finish, was moist, and had a glossy texture.
[0075]
Alkylene oxide derivatives
From the above results, the present inventors proceeded with studies on the suitability as a hair styling agent with respect to the composition of the alkylene oxide derivative.
[R¹, R²Decision]
The inventors have determined that R of alkylene oxide derivatives.¹, R²In order to examine the correlation between the hair and the suitability as a hair styling agent, R¹, R²The hair styling agent blended with various alkylene oxide derivatives having different from each other was subjected to sensory evaluation based on the above criteria. The results are shown in Table 5. The basic composition 1 (non-emulsifying aqueous set lotion) was used as a compounding formulation, and unless otherwise specified, all compounds are EO, PO parts.
[(EO)₁₀/ (PO)₁₀]
Is used.
[0076]
[Table 5]

As is clear from Table 5, R¹, R²When the number of carbon atoms of the two was 1 to 4 (compounds 2, 3, and 4), all were excellent in use feeling, set holding power, and finished feeling.
In contrast, R¹, R²When is a hydrogen (compound 1), the sticky feeling is strong, and R¹When C was C12 (Compound 6), both the feeling of use and the feeling of finish were unfavorable. On the other hand, R¹, R²Even when the sum of the number of carbon atoms is 7 and less than that of the compound 4,¹Tended to be inferior in moist feeling with C6 (Compound 5).
From the above, the alkylene oxide derivative according to the present invention includes R¹, R²Both are hydrocarbon groups having 1 to 4 carbon atoms.
[0077]
In actual production, R¹, R²Since not all of these are substituted with hydrocarbon groups, the allowable abundance ratio of the unsubstituted (H) compound was examined. The results are shown in Table 6. The unsubstituted ratio is represented by the ratio Y / X of the number of hydrogen atoms (Y) to the number of hydrocarbon groups (X). In Table 6 below, 1: 2 = 5: 95 means that Compound 1 and Compound 2 were mixed at a ratio of 5:95 to adjust a predetermined Y / X.
[0078]
[Table 6]

As apparent from Table 6, R¹, R²Even if there is an unreacted substance for Y, if the amount thereof is small (Y / X = 0.054), there is no significant influence, but when Y / X becomes 0.203, a sticky feeling is clearly produced. Furthermore, as a result of detailed studies by the present inventors, it has become clear that Y / X needs to be 0.15 or less.
[0079]
[Oxyalkylene group, oxyethylene group]
Next, the present inventors examined the presence of oxyalkylene groups and oxyethylene groups in alkylene oxide derivatives and their suitability as hairdressing agents. The results are shown in Table 7 below.
[0080]
[Table 7]

[0081]
[Chemical formula 5]

In Table 7, as apparent from the low effect of Compound 11 and Compound 12 shown in Chemical Formula 5, in the present invention, both the oxyalkylene group and the oxyethylene group are used from the viewpoint of finish during use. Existence is essential. Further, from the result of the compound 12, it is considered that the effect of the present invention is not merely a hydrophilicity and hydrophobicity adjustment effect. Further detailed studies by the present inventors have revealed that a suitable ratio of oxyethylene groups to the total of oxyalkylene groups and oxyethylene groups is 20 to 80% by mass.
[0082]
Furthermore, the inventors produced block polymers and random polymers with the same number of alkylene groups and the same number of oxyethylene groups, and compared them.
[Table 8]

As can be seen from Table 8, the effect of the present invention can be obtained with either a block polymer or a random polymer, but an excellent feeling in use can be obtained particularly in the case of a random polymer.
[0083]
Blending amount of alkylene oxide derivative
Table 9 shows the results obtained by preparing hair styling agents (non-emulsifying aqueous set lotions) in which the amount of the alkylene oxide derivative was changed in the basic composition 1 and performing sensory evaluation. As the alkylene oxide derivative, CH_Three[(EO)₁₄/ (PO)₇] CH_ThreeWas used.
[0084]
[Table 9]

From the results shown in Table 9, the effect of the present invention is recognized from about 0.01% by mass, but particularly remarkable is 1.0% by mass or more. However, if it exceeds 20.0 mass%, the set holding power and the lightness after finishing tend to be inferior. Therefore, the blending amount of the alkylene oxide derivative is preferably 1.0 to 20.0% by mass, and more preferably 5.0 to 10.0% by mass.
[0085]
B) Hair conditioner containing solid oil
Subsequently, in order to examine the application of the alkylene oxide derivative to a solid oil-containing hair styling agent, the present inventors actually used the above-mentioned various alkylene oxide derivatives and actually used the hair styling agent ( An emulsified hair wax) was prepared and subjected to sensory evaluation.
Basic composition for testing 2 emulsified hair wax
(1) Carnauba 5.0% by mass
(2) Microcrystalline wax 8.0
(3) Alkylene oxide derivative 5.0
(4) Residual ion exchange water
(5) Liquid paraffin 8.0
(6) Tetraoctanoic acid eryslit 3.0
(7) Stearic acid 3.0
(8) Propylene glycol 5.0
(9) Polyoxyethylene hydrogenated castor oil 1.0
(10) Triethanolamine 0.2
(Manufacturing method)
(1), (2), (5) to (7), (9) are mixed into the solution obtained by stirring and mixing (3), (4), and (8), and the mixture is heated and stirred to make it uniform. The solution was added to obtain a stirred mixed solution. (10) was added thereto, neutralized, and then emulsified with a homomixer and cooled with an on-lator to obtain an emulsified hair wax.
[0086]
  The present inventors performed sensory evaluation on the basis of the above criteria for an emulsified hair wax in which 3.0% by mass of each of the alkylene oxide derivatives and various moisturizing components in the basic composition 2 was blended. The results are shown in Table 10.
[Table 10]

  From the results shown in Table 10, even in the hair styling compounded with a solid oil, by blending the alkylene oxide derivative of the present invention, compared to other general moisturizing ingredients, the set holding power is excellent and non-sticky. It has been found that it has a smooth feel, is light in finish, has a moist feel, and has a smooth texture.
[0087]
Blending amount of alkylene oxide derivative
Table 11 shows the results of preparing hair styling agents (emulsified hair waxes) in which the blending amount of the alkylene oxide derivative was changed in the basic composition 2 and performing sensory evaluation. As the alkylene oxide derivative, CH_Three[(EO)₉/ (PO)₂] CH_ThreeWas used.
[0088]
[Table 11]

From the results shown in Table 11, the amount of the alkylene oxide derivative is preferably 1.0 to 20.0 in the system in which oil is blended, as in the case of the coating agent polymer blending system shown in Table 9 above. It became clear that it was mass%, More preferably, it was 5.0-10.0 mass%.
[0089]
Hereafter, it shows about the suitable compounding example of the hairdressing agent concerning this invention.

<Manufacturing method and effect>
(1) to (9) are mixed and stirred to make uniform (hair spray stock solution). 45 parts by weight of this stock solution is packed in an aerosol can and valved. Next, 55 parts by weight of liquefied petroleum gas was filled to obtain a hair spray. The obtained hair spray had a good set holding power, was not sticky, was smooth, had a light finish, was moist, and had a glossy texture.
[0090]

<Manufacturing method and effect>
(2) to (5) are added to (9) and mixed with stirring. Subsequently, (1) (6) (7) (10) was added to (8) and mixed and stirred into this mixed solution, and a hair gel having a viscosity of 35000 mPa · s was obtained. The obtained hair gel had a good set holding power, was not sticky, was smooth, had a light finish, had a moist feeling, and had a glossy texture.
[0091]
Formulation Example 3 Emulsified hair wax
(1) Polyoxyethylene (14 mol) Polyoxypropylene (7 mol) Dimethyl ether 5.0% by mass
(2) Vinylpyrrolidone / vinyl acetate copolymer 2.0
(3) Ion exchange water remaining
(4) Propylene glycol 10.0
(5) Liquid paraffin 7.0
(6) Tetraoctanoic acid eryslit 2.0
(7) Paraffin 3.0
(8) Stearic acid 3.0
(9) Ceresin 2.0
(10) Polyoxyethylene hydrogenated castor oil 1.0
(11) Triethanolamine 0.2
<Manufacturing method and effect>
A solution obtained by mixing (1) to (4) with stirring and mixing was added to (5) to (10), and a solution that was heated and stirred to be uniform was added to obtain a stirred mixed solution. (11) was added thereto and neutralized, followed by emulsification with a homomixer and cooling with an on-lator to obtain an emulsified hair wax. The obtained emulsified hair wax had good set holding power, was not sticky, was smooth, had a light finish, was moist, and had a glossy texture.
[0092]
【The invention's effect】
According to the present invention, by blending an alkylene oxide derivative having a specific structure, excellent set holding power and good use feeling, finish feeling, specifically, no stickiness of the hand, smooth, light finish, moist In addition, it is possible to obtain a hair styling agent having a more glossy texture.

Claims (5)

And alkylene oxide derivative represented by the following formula (I), containing the one or more skin film forming polymer and / or a melting point above 40 ° C. The solid oil component selected from the following (II) , integer hair agent characterized by having a set retention.

(In the formula, AO is an oxyalkylene group having 3 to 4 carbon atoms, EO is an oxyethylene group, m and n are average addition moles of oxyalkylene groups and oxyethylene groups having 3 to 4 carbon atoms, respectively, 1 ≦ m ≦ 70, 1 ≦ n ≦ 70 The ratio of the oxyethylene group to the total of the oxyalkylene group having 3 to 4 carbon atoms and the oxyethylene group is 20 to 80% by mass. The group and the oxyethylene group may be added in a block form or in a random form, and R ¹ and R ² may be the same or different and each may be a hydrocarbon group having 1 to 4 carbon atoms or a hydrogen atom. there. However, R ^1, both of monoalkyl ethers body and R ^1, R ² is any one of a hydrogen atom R ² is a hydrogen atom non alkyl ethers thereof is an impurity, R ¹ and R The ratio of the number of hydrogen atoms to hydrocarbons radix within 0.15 or less, may contain these monoalkyl ether thereof and / or non-alkyl ether thereof.)
(II) Polyvinylpyrrolidone, vinyl acetate / vinyl pyrrolidone copolymer, vinyl pyrrolidone / dimethylaminopropyl methacrylamide copolymer, vinyl pyrrolidone / dimethylaminoethyl methacrylate copolymer, vinyl caprolactam / vinyl pyrrolidone / dimethylaminoethyl methacrylate telomer Telomer of vinyl acetate / monobutylmaleic acid / isobornyl acrylate, telomer of vinylcaprolactam / vinylpyrrolidone / dimethylaminomethacrylamide, vinylpyrrolidone / N, N-dimethylaminoethylmethacrylic acid copolymer diethyl sulfate solution, vinyl Pyrrolidone / methylvinylimidazolinium chloride copolymer, alkyl methacrylate / dimethylaminoethyl methacrylate copolymer, vinyl pyrrolidone / medium Tylvinylimidazole copolymer / vinylcaprolactam copolymer, cetyldimethyl-2-hydroxyethylammonium dihydrophosphate, lauryl / myristyltrimethylammonium sulfate, vinylpyrrolidone / dimethylaminopropylmethacrylamide / t-butyl acrylate phosphate, Methyl vinyl ether / maleic anhydride copolymer monoalkyl ester, methyl vinyl ether / maleic acid ethyl ester copolymer, acrylic resin alkanolamine liquid, ethyl acrylate / acrylic acid amide / acrylic acid copolymer, ethyl acrylate / methacrylic acid Copolymer, vinyl acetate / crotonic acid copolymer, vinyl acetate / crotonic acid neodecanoate vinyl copolymer, hydroxypropyl acrylate / butylaminoethyl methacrylate / acrylic Octyl amide copolymer, octyl acrylamide acrylic resin, N- methacryloyl N, N- dimethyl ammonium-alpha-N-methyl carboxy betaine-alkyl methacrylate copolymer fluids.   The hair styling agent according to claim 1, wherein the alkylene oxide derivative is a product in which oxyalkylene groups and oxyethylene groups are randomly added.   The hair styling agent according to claim 1 or 2, wherein the content of the alkylene oxide derivative is 0.01 to 20.0 mass% with respect to the total amount of the hair styling agent.   The hair styling agent according to any one of claims 1 to 3, wherein the content of the film-forming polymer is 0.1 to 30.0% by mass with respect to the total amount of the hair styling agent as a dry solid content. Hair styling agent.   The hairdressing agent according to any one of claims 1 to 3, wherein the solid oil content having a melting point of 40 ° C or higher is 0.1 to 30.0 mass% with respect to the total amount of the hairdressing agent. Hairdressing agent.