JP2016160191A - Water-in-oil type emulsion cosmetic - Google Patents
Water-in-oil type emulsion cosmetic Download PDFInfo
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- JP2016160191A JP2016160191A JP2015038306A JP2015038306A JP2016160191A JP 2016160191 A JP2016160191 A JP 2016160191A JP 2015038306 A JP2015038306 A JP 2015038306A JP 2015038306 A JP2015038306 A JP 2015038306A JP 2016160191 A JP2016160191 A JP 2016160191A
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Landscapes
- Cosmetics (AREA)
Abstract
Description
本発明は、油中水型乳化化粧料に関する。 The present invention relates to a water-in-oil emulsified cosmetic.
カルボシロキサンデンドリマー構造を側鎖に有するビニル系重合体を含有した油中水型乳化化粧料は、皮膜性に優れ、毛穴や小じわを目立たなくさせ、化粧持続性に優れている。
例えば、特許文献1には、カルボシロキサンデンドリマー構造を側鎖に有するビニル系重合体と、特定の不揮発性油剤、疎水化処理粉体を含有する油中水型乳化化粧料が記載され、乳化安定性が良好で、のびが良く、べたつきが少なく、皮膜感などの違和感が少ない使用感で、肌の凹凸を目立たなくする効果に優れ、化粧持続性が良好で、経時での凹凸の目立ちやよれが起こりにくいことが記載されている。
また、特許文献2には、カルボシロキサンデンドリマー構造を側鎖に有するビニル系重合体、極性油、ポリエーテル変性シリコーン、酸化鉄又は酸化鉄被覆粉体を含有する化粧料が記載され、使用感や仕上がりの滑らかさ、化粧持続性に優れ、化粧直しがし易いことが記載されている。
A water-in-oil emulsified cosmetic containing a vinyl polymer having a carbosiloxane dendrimer structure in the side chain has excellent film properties, makes pores and fine lines inconspicuous, and has excellent makeup sustainability.
For example, Patent Document 1 describes a water-in-oil emulsified cosmetic containing a vinyl polymer having a carbosiloxane dendrimer structure in the side chain, a specific non-volatile oil agent, and a hydrophobized powder. It has good properties, good spreading, little stickiness, and a feeling of use that has a little uncomfortable feeling such as a film feeling, is excellent in the effect of making the unevenness of the skin inconspicuous, has a good makeup sustainability, and the unevenness of the unevenness over time It is described that is difficult to occur.
Patent Document 2 describes a cosmetic containing a vinyl polymer having a carbosiloxane dendrimer structure in the side chain, polar oil, polyether-modified silicone, iron oxide or iron oxide-coated powder. It describes that it is excellent in smooth finish and makeup sustainability and easy to remake.
本発明者らは、肌のきめが大きく、粗い肌にファンデーションを塗布した場合、粉体が、皮丘部分で上滑りし、皮溝に溜まり易くなり、ファンデーションがきれいに付かない、きちんと肌をカバーできないという課題があることを見出した。 When the foundation is applied to rough skin with a large skin texture, the present inventors do not easily cover the skin, the powder will slide up in the skin hill part and easily accumulate in the skin groove, the foundation will not adhere cleanly I found that there is a problem.
本発明者らは、カルボシロキサンデンドリマー構造を側鎖に有するビニル系重合体、疎水化処理した粉体とともに、特定のエステル油を特定の割合で組み合わせて用いることにより、上記課題を解決した油中水型乳化化粧料が得られることを見出した。 The inventors of the present invention have solved the above problems by using a specific ester oil in combination with a specific ratio in combination with a vinyl polymer having a carbosiloxane dendrimer structure in the side chain and a hydrophobized powder. It has been found that a water-type emulsified cosmetic can be obtained.
本発明は、次の成分(A)、(B)及び(C):
(A)カルボシロキサンデンドリマー構造を側鎖に有するビニル系重合体 0.1〜20質量%、
(B)疎水化処理した粉体、
(C)25℃で液状のペンタエリスリトール脂肪酸エステル及びジペンタエリスリトール脂肪酸エステルから選ばれるエステル油 0.01〜30質量%
を含有し、成分(A)と成分(C)の質量割合(A)/(C)が、0.02〜80である油中水型乳化化粧料に関する。
The present invention includes the following components (A), (B) and (C):
(A) 0.1-20% by mass of a vinyl polymer having a carbosiloxane dendrimer structure in the side chain,
(B) Hydrophobized powder,
(C) Ester oil selected from liquid pentaerythritol fatty acid ester and dipentaerythritol fatty acid ester at 25 ° C. 0.01 to 30% by mass
It is related with the water-in-oil type emulsified cosmetics whose mass ratio (A) / (C) of a component (A) and a component (C) is 0.02-80.
本発明の油中水型乳化化粧料は、塗布後の肌への密着性が高く、高密度に付着して、塗りムラ(抜け)がなく、肌の皮丘に均一に付着するので、優れたカバー力、仕上がりを得ることができる。また、化粧皮膜の追随性に優れ、さらに、塗布後に肌のかさつきが目立たない。 The water-in-oil emulsified cosmetic of the present invention has excellent adhesion to the skin after application, adheres at a high density, has no coating unevenness (omission), and adheres evenly to the skin dermis. Cover power and finish. Moreover, the followability of the cosmetic film is excellent, and further, the skin roughness is not noticeable after application.
本発明で用いる成分(A)のカルボシロキサンデンドリマー構造を側鎖に有するビニル系重合体において、カルボシロキサンデンドリマー構造としては、次式(1)で表される基が好ましい。 In the vinyl polymer having a carbosiloxane dendrimer structure as a component (A) in the side chain used in the present invention, the carbosiloxane dendrimer structure is preferably a group represented by the following formula (1).
式中、Zは2価の有機基であり、pは0又は1であり、R1は炭素原子数1〜10のアルキル基又はアリール基である。尚、複数のR1は、同じであっても、異なっても良い。
X1はi=1とした場合の次式で示されるシリルアルキル基である。
In the formula, Z is a divalent organic group, p is 0 or 1, and R 1 is an alkyl group having 1 to 10 carbon atoms or an aryl group. A plurality of R 1 may be the same or different.
X 1 is a silylalkyl group represented by the following formula when i = 1.
式中、R1は前記と同じであり、R2は炭素原子数2〜10のアルキレン基であり、R3は炭素原子数1〜10のアルキル基である。尚、複数のR1は、同じであっても、異なっても良い。
Xi+1は水素原子、炭素原子数1〜10のアルキル基、アリール基及び上記シリルアルキル基からなる群から選択される基である。iは該シリルアルキル基の階層を示している1〜10の整数であり、aiは0〜3の整数である。
In the formula, R 1 is the same as described above, R 2 is an alkylene group having 2 to 10 carbon atoms, and R 3 is an alkyl group having 1 to 10 carbon atoms. A plurality of R 1 may be the same or different.
X i + 1 is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, and the silylalkyl group. i is an integer of 1 to 10 indicating the hierarchy of the silylalkyl group, and a i is an integer of 0 to 3.
式(1)中、Zは2価の有機基であり、アルキレン基、アリーレン基、アラルキレン基、エステル含有2価有機基、エーテル含有2価有機基、ケトン含有2価有機基、アミド基含有2価有機基が例示される。これらの中でも、次式で示される有機基が好ましい。 In formula (1), Z is a divalent organic group, alkylene group, arylene group, aralkylene group, ester-containing divalent organic group, ether-containing divalent organic group, ketone-containing divalent organic group, amide group-containing 2 A valent organic group is exemplified. Among these, an organic group represented by the following formula is preferable.
式中、R9は炭素原子数1〜10のアルキレン基であり、メチレン基、エチレン基、プロピレン基、ブチレン基が例示される。これらの中でもエチレン基、プロピレン基が好ましい。R10は炭素原子数1〜10のアルキル基であり、メチル基、エチル基、プロピル基、ブチル基が例示される。これらの中でもメチル基が好ましい。R11は炭素原子数1〜10のアルキレン基であり、メチレン基、エチレン基、プロピレン基、ブチレン基等のアルキレン基が例示される。これらの中でもエチレン基が好ましい。dは0〜4の整数であり、eは0又は1である。 In the formula, R 9 is an alkylene group having 1 to 10 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, and a butylene group. Among these, an ethylene group and a propylene group are preferable. R 10 is an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. Among these, a methyl group is preferable. R 11 is an alkylene group having 1 to 10 carbon atoms, and examples thereof include alkylene groups such as a methylene group, an ethylene group, a propylene group, and a butylene group. Among these, an ethylene group is preferable. d is an integer of 0 to 4, and e is 0 or 1.
また、式(1)中、R1は炭素原子数1〜10のアルキル基又はアリール基であり、アルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、イソプロピル基、イソブチル基、シクロペンチル基、シクロヘキシル基が例示され、アリール基としては、フェニル基、ナフチル基が例示される。これらの中でもメチル基、フェニル基が好ましく、メチル基が特に好ましい。
X1はi=1とした場合の次式で示されるシリルアルキル基である。
In the formula (1), R 1 is an alkyl group or aryl group having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, and isobutyl. Group, cyclopentyl group, and cyclohexyl group are exemplified, and as aryl group, phenyl group and naphthyl group are exemplified. Among these, a methyl group and a phenyl group are preferable, and a methyl group is particularly preferable.
X 1 is a silylalkyl group represented by the following formula when i = 1.
式中、R1は前記と同じである。R2は炭素原子数2〜10のアルキレン基であり、エチレン基、プロピレン基、ブチレン基、ヘキシレン基などの直鎖状アルキレン基;メチルメチレン基、メチルエチレン基、1−メチルペンチレン基、1,4−ジメチルブチレン基等の分岐状アルキレン基が例示される。これらの中でも、エチレン基、メチルエチレン基、ヘキシレン基、1−メチルペンチレン基、1,4−ジメチルブチレン基が好ましい。R3は炭素原子数1〜10のアルキル基であり、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基が例示される。Xi+1は水素原子、炭素原子数1〜10のアルキル基、アリール基および上記シリルアルキル基からなる群から選択される基である。aiは0〜3の整数である。iは1〜10の整数であり、これは該シリルアルキル基の階層数、即ち、該シリルアルキル基の繰り返し数を示している。 In the formula, R 1 is the same as described above. R 2 is an alkylene group having 2 to 10 carbon atoms, and a linear alkylene group such as an ethylene group, a propylene group, a butylene group, or a hexylene group; a methylmethylene group, a methylethylene group, a 1-methylpentylene group, 1 And a branched alkylene group such as 1,4-dimethylbutylene group. Among these, an ethylene group, a methylethylene group, a hexylene group, a 1-methylpentylene group, and a 1,4-dimethylbutylene group are preferable. R 3 is an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and an isopropyl group. X i + 1 is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, and the silylalkyl group. a i is an integer of 0-3. i is an integer of 1 to 10, which indicates the number of layers of the silylalkyl group, that is, the number of repetitions of the silylalkyl group.
成分(A)のビニル系重合体としては、(A1)、(A2)以外のビニル系単量体 0〜99.9質量部と、(A2)一般式(2): As the vinyl polymer of component (A), 0-99.9 parts by mass of vinyl monomers other than (A1) and (A2), and (A2) general formula (2):
(式中、Yはラジカル重合可能な有機基であり、R1及びX1は前記と同じである。)
で表されるラジカル重合可能な有機基を有するカルボシロキサンデンドリマー 100〜0.1質量部とを(共)重合させてなるカルボシロキサンデンドリマー構造を含有するビニル系重合体が好ましい。
(In the formula, Y is an organic group capable of radical polymerization, and R 1 and X 1 are the same as described above.)
A vinyl polymer containing a carbosiloxane dendrimer structure obtained by (co) polymerizing 100 to 0.1 parts by mass of a carbosiloxane dendrimer having an organic group capable of radical polymerization represented by
上記式中、Yはラジカル重合可能な有機基であり、R1は炭素原子数1〜10のアルキル基もしくはアリール基である。アルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、イソプロピル基、イソブチル基、シクロペンチル基、シクロヘキシル基が例示される。アリール基としては、フェニル基、ナフチル基が例示される。これらの中でもメチル基,フェニル基が好ましく、メチル基が特に好ましい。 In the above formula, Y is an organic group capable of radical polymerization, and R 1 is an alkyl or aryl group having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the aryl group include a phenyl group and a naphthyl group. Among these, a methyl group and a phenyl group are preferable, and a methyl group is particularly preferable.
このビニル系重合体において、(A1)成分のビニル系単量体は、ラジカル重合性のビニル基を有するものであれば良く、その種類等については特に限定されない。かかるビニル系単量体としては、例えば、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n−プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n−ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸tert−ブチル、(メタ)アクリル酸n−ヘキシル、(メタ)アクリル酸シクロヘキシル等の低級アルキル(メタ)アクリレート;(メタ)アクリル酸2−エチルヘキシル、(メタ)アクリル酸オクチル、(メタ)アクリル酸ラウリル、(メタ)アクリル酸ステアリル等の高級アルキル(メタ)アクリレート;酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、カプロン酸ビニル、2−エチルヘキサン酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル等の脂肪酸ビニルエステル;スチレン、ビニルトルエン、ベンジル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート等の芳香族含有単量体;(メタ)アクリルアミド、N−メチロール(メタ)アクリルアミド、N−メトキシメチル(メタ)アクリルアミド、イソブトキシメトキシ(メタ)アクリルアミド、N,N−ジメチル(メタ)アクリルアミド、ビニルピロリドン、N−ビニルアセトアミド等のアミド基含有ビニル型単量体;(メタ)アクリル酸ヒドロキシエチル、(メタ)アクリル酸ヒドロキシプロピル、グリセリル(メタ)アクリレート、ヒドロキシエチルアクリルアミド等の水酸基含有ビニル型単量体;(メタ)アクリル酸、イタコン酸、クロトン酸、フマル酸、マレイン酸等のカルボン酸含有ビニル型単量体及びそれらの塩;テトラヒドロフルフリル(メタ)アクリレート、ブトキシエチル(メタ)アクリレート、エトキシジエチレングリコール(メタ)アクリレート、ポリエチレングリコール(メタ)アクリレート、ポリプロピレングリコールモノ(メタ)アクリレート、ヒドロキシブチルビニルエーテル、セチルビニルエーテル、2ーエチルヘキシルビニルエーテル等のエーテル結合含有ビニル型単量体;(メタ)アクリル酸グリシジル、(メタ)アリルグリシジルエーテル、メタクリロイルオキシエチルイソシアネート、(メタ)アクリロキシプロピルトリメトキシシラン等の反応性基含有モノマー;片末端に(メタ)アクリル基を含有したポリジメチルシロキサン、片末端にスチリル基を含有するポリジメチルシロキサンなどのマクロモノマー類;ブタジエン;塩化ビニル;塩化ビニリデン;(メタ)アクリロニトリル;フマル酸ジブチル;無水マレイン酸;スチレンスルホン酸、アクリルアミド−2−メチルプロパンスルホン酸のようなスルホン酸基を有するラジカル重合性不飽和単量体、およびそれらのアルカリ金属塩、アンモニウム塩、有機アミン塩;2−ヒドロキシ−3−メタクリルオキシプロピルトリメチルアンモニウムクロライドのような(メタ)アクリル酸から誘導される4級アンモニウム塩;メタクリル酸ジエチルアミノエチルのような3級アミノ基を有するアルコールのメタクリル酸エステル、ビニルピリジンおよびそれらの4級アンモニウム塩などが例示される。 In this vinyl polymer, the vinyl monomer as the component (A1) is not particularly limited as long as it has a radical polymerizable vinyl group. Examples of such vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Lower alkyl (meth) acrylates such as isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate; 2-ethylhexyl (meth) acrylate, ( Higher alkyl (meth) acrylates such as octyl acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl 2-ethylhexanoate, laurin Fatty acid vinyl esters such as vinyl acid vinyl and vinyl stearate; Aromatic monomers such as len, vinyltoluene, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate; (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, isobutoxy Amide group-containing vinyl monomers such as methoxy (meth) acrylamide, N, N-dimethyl (meth) acrylamide, vinylpyrrolidone, N-vinylacetamide; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, Hydroxyl-containing vinyl monomers such as glyceryl (meth) acrylate and hydroxyethylacrylamide; (meth) acrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid and other carboxylic acid-containing vinyl monomers and their salts ; Tetrahydroflu Ether linkages such as ril (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, hydroxybutyl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether Containing vinyl-type monomer; Reactive group-containing monomer such as (meth) acrylic acid glycidyl, (meth) allyl glycidyl ether, methacryloyloxyethyl isocyanate, (meth) acryloxypropyltrimethoxysilane; (meth) acrylic at one end Macromonomers such as polydimethylsiloxane containing a group, polydimethylsiloxane containing a styryl group at one end; butadiene; vinyl chloride; salt (Meth) acrylonitrile; dibutyl fumarate; maleic anhydride; radical polymerizable unsaturated monomers having sulfonic acid groups such as styrenesulfonic acid, acrylamide-2-methylpropanesulfonic acid, and alkali metals thereof Salts, ammonium salts, organic amine salts; quaternary ammonium salts derived from (meth) acrylic acid such as 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride; tertiary amino groups such as diethylaminoethyl methacrylate Examples thereof include methacrylic acid esters of alcohol, vinyl pyridine and quaternary ammonium salts thereof.
また、多官能ビニル系単量体も使用可能であり、例えば、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、1,4−ブタンジオールジ(メタ)アクリレート、1,6−ヘキサンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、トリメチロールプロパントリオキシエチル(メタ)アクリレート、トリス(2−ヒドロキシエチル)イソシアヌレートジ(メタ)アクリレート、トリス(2−ヒドロキシエチル)イソシアヌレートトリ(メタ)アクリレート、スチリル基封鎖ポリジメチルシロキサンなどの不飽和基含有シリコ−ン化合物等が例示される。 Polyfunctional vinyl monomers can also be used. For example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate , Polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meta ) Acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, styryl-blocked polydimethylsiloxane, etc. Saturated group containing silicone - emission compounds and the like.
成分(A2)のカルボシロキサンデンドリマーは、一般式(2)で表されるラジカル重合可能な有機基を有するものであれば良く、その種類等については特に限定されない。一般式(2)中、Yはラジカル重合可能な有機基であり、ラジカル反応可能な有機基であればよいが、具体的には、下記一般式で表される(メタ)アクリロキシ基含有有機基、(メタ)アクリルアミド基含有有機基、スチリル基含有有機基、炭素原子数2〜10のアルケニル基等が挙げられる。 The component (A2) carbosiloxane dendrimer is not particularly limited as long as it has an organic group capable of radical polymerization represented by the general formula (2). In general formula (2), Y is an organic group capable of radical polymerization, and any organic group capable of radical reaction may be used. Specifically, a (meth) acryloxy group-containing organic group represented by the following general formula , (Meth) acrylamide group-containing organic groups, styryl group-containing organic groups, alkenyl groups having 2 to 10 carbon atoms, and the like.
(式中、R4及びR6は水素原子又はメチル基であり、R5及びR8は炭素原子数1〜10のアルキレン基であり、R7は炭素原子数1〜10のアルキル基である。bは0〜4の整数であり、cは0または1である。) Wherein R 4 and R 6 are a hydrogen atom or a methyl group, R 5 and R 8 are alkylene groups having 1 to 10 carbon atoms, and R 7 is an alkyl group having 1 to 10 carbon atoms. B is an integer from 0 to 4 and c is 0 or 1.)
このようなラジカル重合可能な有機基としては、例えば、2−アクリロイルオキシエチル基、3−アクリロイルオキシプロピル基、2−メタクリロイルオキシエチル基、3−メタクリロイルオキシプロピル基、4−ビニルフェニル基、3−ビニルフェニル基、4−(2−プロペニル)フェニル基、3−(2−プロペニル)フェニル基、2−(4−ビニルフェニル)エチル基、2−(3−ビニルフェニル)エチル基、ビニル基、アリル基、メタリル基、5−ヘキセニル基が挙げられる。 Examples of such radically polymerizable organic groups include 2-acryloyloxyethyl group, 3-acryloyloxypropyl group, 2-methacryloyloxyethyl group, 3-methacryloyloxypropyl group, 4-vinylphenyl group, 3-vinylphenyl group, Vinylphenyl group, 4- (2-propenyl) phenyl group, 3- (2-propenyl) phenyl group, 2- (4-vinylphenyl) ethyl group, 2- (3-vinylphenyl) ethyl group, vinyl group, allyl Group, methallyl group, and 5-hexenyl group.
一般式(2)において、i=1、すなわちシリルアルキル基の階層数が1である場合、(A2)成分のカルボシロキサンデンドリマーは、一般式: In the general formula (2), when i = 1, that is, the number of silylalkyl groups is 1, the carbosiloxane dendrimer of the component (A2) has the general formula:
(式中、Y,R1,R2およびR3は前記と同じであり、R12は水素原子または前記R1と同じである。a1は前記aiと同じであるが、1分子中のa1の平均合計数は0〜7である。)で表される。
このようなラジカル重合可能な有機基を含有するカルボキシデンドリマー(A2)としては、下記平均組成式で示されるカルボシロキサンデンドリマーが例示される。
(Wherein, Y, R 1, R 2 and R 3 are as defined above, but .a 1 R 12 is the same as the hydrogen atom or the R 1 is the same as the a i, in one molecule The average total number of a 1 is 0 to 7.)
Examples of such carboxydendrimers (A2) containing radically polymerizable organic groups include carbosiloxane dendrimers represented by the following average composition formula.
このようなカルボシロキサンデンドリマーは、例えば、特開平11―1530号公報、特開2000−63225号公報等に記載された製造方法に従って製造することができる。 Such carbosiloxane dendrimers can be produced, for example, according to the production methods described in JP-A Nos. 11-1530 and 2000-63225.
本発明で用いられるデンドリマー構造を含有するビニル系重合体において、上記(A1)成分と(A2)成分の質量割合は、(A1):(A2)=0:100〜99.9:0.1が好ましく、5:95〜90:10がより好ましく、更に10:90〜80:20となる範囲であるのが好ましい。 In the vinyl polymer containing a dendrimer structure used in the present invention, the mass ratio of the component (A1) to the component (A2) is (A1) :( A2) = 0: 100 to 99.9: 0.1. Is preferably 5:95 to 90:10, more preferably 10:90 to 80:20.
本発明で用いられる成分(A)のカルボシロキサンデンドリマー構造を有するビニル系重合体の数平均分子量は、化粧品原料としての配合のしやすさから、好ましくは、3,000〜2,000,000であり、さらに好ましくは、5,000〜800,000である。また、その性状は、25℃で液状、ガム状、ペースト状、固体状などのいずれでも良いが、得られる化粧皮膜の持続性の観点から、固体状のものが好ましい。また、配合性の観点からは、溶媒によって希釈された溶液や分散液であることが好ましい。なかでも、化粧料中への分散性、作業性の点から、液状油によって希釈された分散液として用いるのが好ましく、シリコーン油、炭化水素油を用いるのが好ましく、ジメチルポリシロキサン、デカメチルシクロペンタシロキサン、イソドデカンを用いるのがより好ましい。 The number average molecular weight of the vinyl polymer having a carbosiloxane dendrimer structure as the component (A) used in the present invention is preferably 3,000 to 2,000,000 from the ease of blending as a cosmetic raw material. More preferably, it is 5,000 to 800,000. Further, the property may be any of liquid, gum, paste, solid, etc. at 25 ° C., but from the viewpoint of the durability of the resulting cosmetic film, a solid one is preferred. Further, from the viewpoint of compoundability, a solution or dispersion diluted with a solvent is preferable. Among these, from the viewpoint of dispersibility in cosmetics and workability, it is preferably used as a dispersion diluted with liquid oil, preferably silicone oil or hydrocarbon oil, dimethylpolysiloxane, decamethylcyclohexane. It is more preferable to use pentasiloxane or isododecane.
カルボシロキサンデンドリマー構造を側鎖に有するビニル系重合体としては、シリコーンデンドリマー・アクリル共重合体が好ましく、FA4001CM(デカメチルシクロペンタシロキサン溶液)、FA4002ID(イソドデカン溶液)(以上、東レ・ダウコーニング社製)等の市販品を用いることができる。 As the vinyl polymer having a carbosiloxane dendrimer structure in the side chain, a silicone dendrimer / acrylic copolymer is preferable, FA4001CM (decamethylcyclopentasiloxane solution), FA4002ID (isododecane solution) (above, manufactured by Toray Dow Corning) ) Etc. can be used.
成分(A)は、1種又は2種以上を用いることができ、含有量は、のびが良く、皮膜形成性・密着性に優れる点から、全組成中に0.1質量%以上であり、0.2質量%以上が好ましく、0.3質量%以上がより好ましく、20質量%以下であり、15質量%以下が好ましく、10質量%以下がより好ましい。また、成分(A)の含有量は、全組成中に0.1〜20質量%であり、0.2〜15質量%が好ましく、0.3〜10質量%がより好ましい。 Component (A) can be used singly or in combination of two or more, and the content is 0.1% by mass or more in the total composition from the viewpoint of good spread and excellent film-forming properties and adhesion, 0.2 mass% or more is preferable, 0.3 mass% or more is more preferable, it is 20 mass% or less, 15 mass% or less is preferable, and 10 mass% or less is more preferable. Moreover, content of a component (A) is 0.1-20 mass% in the whole composition, 0.2-15 mass% is preferable, and 0.3-10 mass% is more preferable.
本発明で用いる成分(B)の粉体は、疎水化処理したものである。
処理される粉体としては、通常の化粧料に用いられるものであれば良く、形状は、球状、板状、針状等の形状;煙霧状(数nm〜数十nm)、微粒子(数十nm〜数百nm)、顔料級(数百nm〜数μm)等の粒子径;多孔質、無孔質等の粒子構造など、限定されるものではない。
The powder of component (B) used in the present invention is hydrophobized.
The powder to be treated may be any powder used in ordinary cosmetics, and the shape is spherical, plate-like, needle-like, etc .; fumes (several nm to several tens of nm), fine particles (several tens of nm) nm to several hundred nm), particle size such as pigment grade (several hundred nm to several μm), etc .; particle structure such as porous and nonporous is not limited.
処理される粉体としては、通常の化粧料に用いられる体質顔料、着色顔料であれば特に制限されず、例えば、ケイ酸、無水ケイ酸、ケイ酸アルミニウム、ケイ酸マグネシウム、ケイ酸アルミニウムマグネシウム、セリサイト、合成セリサイト、タルク、カオリン、クレー、ベントナイト、マイカ、合成マイカ、オキシ塩化ビスマス、酸化ジルコニウム、酸化マグネシウム、酸化チタン、酸化亜鉛、酸化アルミニウム、硫酸カルシウム、硫酸バリウム、硫酸マグネシウム、炭酸カルシウム、炭酸マグネシウム、ベンガラ、黄酸化鉄、黒酸化鉄、群青、酸化クロム、水酸化クロム、カラミン、カーボンブラック等の無機粉体;これらの複合体等である雲母チタン、酸化鉄コーティング雲母、酸化鉄コーティング雲母チタン、微粒子酸化チタン被覆雲母チタン、微粒子酸化亜鉛被覆雲母チタン、ベンガラ被覆雲母チタン、硫酸バリウム被覆雲母チタン、酸化チタン含有ガラスフレーク、酸化亜鉛含有二酸化珪素等の複合無機粉体;ポリアミド、ナイロン、ポリエステル、ポリプロピレン、ポリスチレン、ポリウレタン、ビニル樹脂、尿素樹脂、フェノール樹脂、フッ素樹脂、ケイ素樹脂、アクリル樹脂、メラミン樹脂、エポキシ樹脂、ポリカーボネート樹脂、ジビニルベンゼン・スチレン共重合体、シルクパウダー、セルロース、長鎖アルキルリン酸金属塩、N−モノ長鎖アルキルアシル塩基性アミノ酸等の有機粉体、これらの複合体等の有機粉体;さらに、上記無機粉体と有機粉体との複合粉体などが挙げられる。 The powder to be treated is not particularly limited as long as it is an extender pigment or a color pigment used in ordinary cosmetics, for example, silicic acid, anhydrous silicic acid, aluminum silicate, magnesium silicate, magnesium aluminum silicate, Sericite, synthetic sericite, talc, kaolin, clay, bentonite, mica, synthetic mica, bismuth oxychloride, zirconium oxide, magnesium oxide, titanium oxide, zinc oxide, aluminum oxide, calcium sulfate, barium sulfate, magnesium sulfate, calcium carbonate , Magnesium carbonate, bengara, yellow iron oxide, black iron oxide, ultramarine, chromium oxide, chromium hydroxide, calamine, carbon black, etc .; mica titanium, iron oxide coating mica, iron oxide, etc. Coating mica titanium, fine particle titanium oxide coating Composite inorganic powders such as mother titanium, fine particle zinc oxide-coated mica titanium, bengara-coated mica titanium, barium sulfate-coated mica titanium, titanium oxide-containing glass flakes, zinc oxide-containing silicon dioxide; polyamide, nylon, polyester, polypropylene, polystyrene, polyurethane , Vinyl resin, urea resin, phenol resin, fluororesin, silicon resin, acrylic resin, melamine resin, epoxy resin, polycarbonate resin, divinylbenzene / styrene copolymer, silk powder, cellulose, long chain metal alkyl phosphate, N -Organic powders such as mono long-chain alkyl acyl basic amino acids, organic powders such as composites thereof; and composite powders of the above inorganic powders and organic powders.
粉体を疎水化処理するには、公知の疎水化処理剤及び公知の疎水化処理方法を用いれば良く、例えば、フッ素化合物、シリコーン系化合物、金属石鹸、油剤等の表面処理剤を用い、乾式処理、湿式処理等を行えばよい。表面処理剤の具体例としては、パーフルオロアルキルリン酸エステル、パーフルオロアルキルアルコキシシラン等のフッ素系化合物;メチルハイドロジェンポリシロキサン、環状シリコーン、片末端又は両末端トリアルコキシ基変性オルガノポリシロキサン等のシリコーン系化合物;ステアリン酸アルミニウム、ステアリン酸亜鉛等の金属石鹸、ラウロイルリジン等のアミノ酸系化合物が挙げられる。
なかでも、フッ素化合物処理及びシリコーン処理が好ましく、フッ素化合物処理とシリコーン処理を併用しても良く、シリコーン処理単独がより好ましい。
In order to hydrophobize the powder, a known hydrophobizing agent and a known hydrophobizing method may be used. For example, a surface treatment agent such as a fluorine compound, a silicone compound, a metal soap, or an oil agent may be used. What is necessary is just to perform a process, a wet process, etc. Specific examples of the surface treatment agent include fluorine compounds such as perfluoroalkyl phosphate esters and perfluoroalkylalkoxysilanes; methylhydrogenpolysiloxanes, cyclic silicones, one- or both-end trialkoxy group-modified organopolysiloxanes, etc. Silicone compounds; metal soaps such as aluminum stearate and zinc stearate, and amino acid compounds such as lauroyllysine.
Of these, fluorine compound treatment and silicone treatment are preferred, fluorine compound treatment and silicone treatment may be used in combination, and silicone treatment alone is more preferred.
フッ素化合物としては、下記式で示されるトリデカフルオロオクチルトリエトキシシランが好ましい。
F3C−(CF2)5−(CH2)2−Si−(OCH2CH3)3
粉体を表面処理するフッ素化合物のうちでも、トリデカフルオロオクチルトリエトキシシランで表面処理した粉体を用いることにより、安定性に優れ、肌なじみが良く、つっぱり感やムラづきを抑制し、しっとりした使用感を得ることができる。トリデカフルオロオクチルトリエトキシシランとしては、大東化成工業社より販売されているFHSが好適である。
As the fluorine compound, tridecafluorooctyltriethoxysilane represented by the following formula is preferable.
F 3 C— (CF 2 ) 5 — (CH 2 ) 2 —Si— (OCH 2 CH 3 ) 3
Among the fluorine compounds that surface-treat powder, by using the powder surface-treated with tridecafluorooctyltriethoxysilane, it has excellent stability, good skin fit, moisturizing feeling and unevenness, and moist Can be used. As the tridecafluorooctyltriethoxysilane, FHS sold by Daito Kasei Kogyo Co., Ltd. is suitable.
処理量は粉体によって異なるが、成分(B)の疎水化処理した粉体100質量%に対して、0.05質量%以上が好ましく、0.1質量%以上がより好ましく、50質量%以下が好ましく、20質量%以下がより好ましい。これらの観点を総合すると、処理量は、成分(B)の疎水化処理した粉体100質量%に対して、0.05〜50質量%であるのが好ましく、0.1〜20質量%がより好ましい。この処理量であれば、撥水性及び撥油性が十分に発現し、感触も良好であるので好ましい。 Although the amount of treatment varies depending on the powder, it is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and 50% by mass or less with respect to 100% by mass of the hydrophobized powder of component (B). Is preferable, and 20 mass% or less is more preferable. When these viewpoints are put together, the treatment amount is preferably 0.05 to 50% by mass, and 0.1 to 20% by mass with respect to 100% by mass of the hydrophobized powder of component (B). More preferred. If it is this processing amount, since water repellency and oil repellency will fully express and a touch is also favorable, it is preferable.
成分(B)は、1種又は2種以上を用いることができ、仕上がりと安定性の点から、含有量は、全組成中に0.1質量%以上が好ましく、1質量%以上がより好ましく、8質量%以上がさらに好ましく、40質量%以下が好ましく、30質量%以下がより好ましく、22質量%以下がさらに好ましい。また、成分(B)の含有量は、全組成中に0.1〜40質量%が好ましく、1〜30質量%がより好ましく、8〜22質量%がさらに好ましい。 Component (B) can be used singly or in combination of two or more. From the viewpoint of finish and stability, the content is preferably 0.1% by mass or more, more preferably 1% by mass or more in the total composition. 8 mass% or more is more preferable, 40 mass% or less is preferable, 30 mass% or less is more preferable, and 22 mass% or less is more preferable. Moreover, 0.1-40 mass% is preferable in the whole composition, as for content of a component (B), 1-30 mass% is more preferable, and 8-22 mass% is further more preferable.
本発明において、成分(A)及び(B)の質量割合(A)/(B)は、化粧持ちと使用感の点から、0.005以上が好ましく、0.01以上がより好ましく、0.02以上がさらに好ましく、5以下が好ましく、3以下がより好ましく、1以下がさらに好ましい。また、成分(A)及び(B)の質量割合(A)/(B)は、0.005〜5が好ましく、0.01〜3がより好ましく、0.02〜1がさらに好ましい。 In the present invention, the mass ratio (A) / (B) of the components (A) and (B) is preferably 0.005 or more, more preferably 0.01 or more, from the viewpoint of long-lasting makeup and feeling of use. 02 or more is more preferable, 5 or less is preferable, 3 or less is more preferable, and 1 or less is more preferable. Moreover, 0.005-5 are preferable, as for mass ratio (A) / (B) of a component (A) and (B), 0.01-3 are more preferable, and 0.02-1 are more preferable.
成分(C)のエステル油は、25℃で液状のペンタエリスリトール脂肪酸エステル及びジペンタエリスリトール脂肪酸エステルから選ばれるものである。
液状とは、流動性を有するもので、25℃で液体、ペースト状のものである。なかでも、25℃で液体のものが好ましい。
The component (C) ester oil is selected from pentaerythritol fatty acid esters and dipentaerythritol fatty acid esters which are liquid at 25 ° C.
The liquid state has fluidity and is a liquid or paste at 25 ° C. Among these, a liquid at 25 ° C. is preferable.
ペンタエリスリトール脂肪酸エステル及びジペンタエリスリトール脂肪酸エステルを構成する脂肪酸としては、飽和脂肪酸又は不飽和脂肪酸のいずれでも良く、直鎖脂肪酸又は分岐鎖脂肪酸のいずれでも良いが、肌への密着性や化合物の酸価安定性等の観点から、飽和脂肪酸を用いるのが好ましい。また、これらの脂肪酸は、ヒドロキシ基を有していても良い。このような脂肪酸としては、例えば、カプロン酸、カプリル酸、2−エチルヘキサン酸、イソノナン酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、イソステアリン酸、ヒドロキシステアリン酸、アラキジン酸、ベヘン酸、リグノセリン酸、セロチン酸、モンタン酸、メリシン酸等が挙げられる。また、上記飽和脂肪酸の中でも、炭素数16〜28の飽和脂肪酸が好ましい。このような脂肪酸としては、例えば、パルミチン酸、ステアリン酸、イソステアリン酸、ヒドロキシステアリン酸、アラキジン酸、ベヘン酸、リグノセリン酸、セロチン酸、モンタン酸等が挙げられる。また、炭素数16〜22の飽和脂肪酸がより好ましく、例えば、パルミチン酸、ステアリン酸、イソステアリン酸、ヒドロキシステアリン酸、アラキジン酸、ベヘン酸等が挙げられる。
具体的には、トリポリヒドロキシステアリン酸ジペンタエリスリチル、ペンタイソステアリン酸ジペンタエリスリチル、テトライソステアリン酸ジペンタエリスリチル、(ベヘン酸/ポリヒドロキシステアリン酸)ペンタエリスリチル等が挙げられる。
The fatty acid constituting the pentaerythritol fatty acid ester and dipentaerythritol fatty acid ester may be either a saturated fatty acid or an unsaturated fatty acid, and may be either a straight chain fatty acid or a branched chain fatty acid. From the viewpoint of valence stability and the like, it is preferable to use a saturated fatty acid. Moreover, these fatty acids may have a hydroxy group. Examples of such fatty acids include caproic acid, caprylic acid, 2-ethylhexanoic acid, isononanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, arachidic acid, and behen. Examples include acids, lignoceric acid, serotic acid, montanic acid, and melissic acid. Of the saturated fatty acids, saturated fatty acids having 16 to 28 carbon atoms are preferred. Examples of such fatty acids include palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, and montanic acid. Further, a saturated fatty acid having 16 to 22 carbon atoms is more preferable, and examples thereof include palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, arachidic acid, and behenic acid.
Specific examples include dipentaerythrityl tripolyhydroxystearate, dipentaerythrityl pentaisostearate, dipentaerythrityl tetraisostearate, (behenic acid / polyhydroxystearic acid) pentaerythrityl, and the like.
成分(C)は、塗布後の肌への密着性が高く、高密度に付着して、肌の皮丘に均一に付着する点から、水酸基を有するものが好ましく、例えば、ヒドロキシステアリン酸を有するものが挙げられる。
具体的には、トリポリヒドロキシステアリン酸ジペンタエリスリチル、(ベヘン酸/ポリヒドロキシステアリン酸)ペンタエリスリチル等が挙げられる。
成分(C)としては、塗布後の肌への密着性が高く、高密度に付着して、肌の皮丘に均一に付着し、皮膜の追随性に優れ、さらに、塗布後に肌のかさつきを抑制する点から、ジペンタエリスリトール脂肪酸エステルが好ましく、具体的には、トリポリヒドロキシステアリン酸ジペンタエリスリチルが好ましい。
Ingredient (C) has high adhesion to the skin after application, adheres to the skin at a high density, and preferably has a hydroxyl group, for example, has hydroxystearic acid. Things.
Specific examples include dipentaerythrityl tripolyhydroxystearate, (behenic acid / polyhydroxystearic acid) pentaerythrityl, and the like.
Ingredient (C) has high adhesion to the skin after application, adheres to the skin at a high density, adheres uniformly to the skin dermis, has excellent followability of the film, and further increases skin roughness after application. From the viewpoint of suppression, dipentaerythritol fatty acid ester is preferable, and specifically, dipentaerythritol tripolyhydroxystearate is preferable.
トリポリヒドロキシステアリン酸ジペンタエリスリチルとしては、サラコスWO−6(日清オイリオ社製)、ペンタイソステアリン酸ジペンタエリスリチルとしては、サラコスDP−518N(日清オイリオ社製)等の市販品を用いることができる。
また、テトライソステアリン酸ジペンタエリスリチル、(ベヘン酸/ポリヒドロキシステアリン酸)ペンタエリスリチルは、公知の方法に従って製造することができ、例えば、後記製造例に記載された方法で製造することができる。
Commercially available products such as Saracos WO-6 (manufactured by Nisshin Oillio Co., Ltd.) can be used as dipentaerythrityl tripolyhydroxystearate, and Saracos DP-518N (manufactured by Nisshin Oilio Co., Ltd.) can be used as dipentaerythritol pentaisostearate.
Further, dipentaerythrityl tetraisostearate and (behenic acid / polyhydroxystearic acid) pentaerythrityl can be produced according to a known method, and can be produced, for example, by the method described in Production Examples below.
成分(C)は、1種又は2種以上を用いることができ、塗布後の肌への密着性が高く、高密度に付着して、肌の皮丘に均一に付着する点から、含有量は、全組成中に0.01質量%以上であり、0.05質量%以上が好ましく、0.1質量%以上がより好ましく、0.4質量%以上がさらに好ましく、30質量%以下であり、20質量%以下が好ましく、15質量%以下がより好ましく、10質量%以下がさらに好ましい。また、成分(C)の含有量は、全組成中に0.01〜30質量%であり、0.05〜20質量%が好ましく、0.1〜15質量%がより好ましく、0.4〜10質量%がさらに好ましい。 Component (C) can be used singly or in combination of two or more, and it has high adhesion to the skin after application, adheres densely, and adheres uniformly to the skin dermis. Is 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.4% by mass or more, and 30% by mass or less. 20 mass% or less is preferable, 15 mass% or less is more preferable, and 10 mass% or less is further more preferable. Moreover, content of a component (C) is 0.01-30 mass% in the whole composition, 0.05-20 mass% is preferable, 0.1-15 mass% is more preferable, 0.4- 10 mass% is more preferable.
本発明において、成分(A)及び(C)の質量割合(A)/(C)は、塗布後の肌への密着性が高く、高密度に付着して、塗りムラ(抜け)がなく、肌の皮丘に均一に付着するので、優れたカバー力、仕上がりを得ることができる。また、化粧皮膜の追随性に優れ、さらに、塗布後に肌のかさつきを抑制する点から、0.02以上であり、0.03以上が好ましく、0.05以上がより好ましく、0.1以上がよりさらに好ましく、80以下であり、60以下が好ましく、40以下がより好ましく、20以下がさらに好ましい。また、成分(A)及び(C)の質量割合(A)/(C)は、0.02〜80であり、0.03〜60が好ましく、0.05〜40がより好ましく、0.1〜20がよりさらに好ましい。 In the present invention, the mass ratio (A) / (C) of the components (A) and (C) has high adhesion to the skin after application, adheres at a high density, and has no coating unevenness (missing). Since it adheres evenly to the skin hills, it provides excellent covering power and finish. Moreover, it is 0.02 or more, 0.03 or more is preferable, 0.05 or more is more preferable, and 0.1 or more is preferable from the point which is excellent in the followability of a makeup | decoration film, and also suppresses the roughness of the skin after application | coating. More preferably, it is 80 or less, 60 or less is preferable, 40 or less is more preferable, and 20 or less is further more preferable. Moreover, mass ratio (A) / (C) of component (A) and (C) is 0.02-80, 0.03-60 are preferable, 0.05-40 are more preferable, 0.1 ~ 20 is even more preferred.
本発明の油中水型乳化化粧料は、さらに、成分(D)として、成分(C)を除く、25℃で液状のエステル油を含有することができる。ここで、液状とは流動性を有するもので、ペースト状のものも含まれる。
成分(D)として、成分(C)を除くエステル油としては、モノエステル、ジエステルが好ましく、具体的には、例えば、イソノナン酸イソトリデシル、リンゴ酸ジイソステアリル、ミリスチン酸イソステアリル、ジカプリン酸ネオペンチルグリコール、ジイソステアリン酸ジグリセリル、モノイソステアリン酸モノミリスチン酸グリセリル、パラメトキシケイ皮酸2−エチルヘキシル、酢酸トコフェロール、モノイソステアリン酸ジグリセリル等が挙げられる。
これらのうち、モノエステルがより好ましく、イソノナン酸イソトリデシル、ミリスチン酸イソステアリル、モノイソステアリン酸モノミリスチン酸グリセリル、パラメトキシケイ皮酸2−エチルヘキシル、酢酸トコフェロールがさらに好ましく、パラメトキシケイ皮酸2−エチルヘキシルがよりさらに好ましい。
The water-in-oil emulsified cosmetic of the present invention can further contain an ester oil that is liquid at 25 ° C., excluding the component (C), as the component (D). Here, the liquid state has fluidity, and includes pastes.
As the component (D), the ester oil excluding the component (C) is preferably a monoester or a diester. Specifically, for example, isotridecyl isononanoate, diisostearyl malate, isostearyl myristate, neopentyl dicaprate Examples thereof include glycol, diglyceryl diisostearate, glyceryl monoisostearate, 2-ethylhexyl paramethoxycinnamate, tocopherol acetate, and diglyceryl monoisostearate.
Of these, monoesters are more preferable, isotridecyl isononanoate, isostearyl myristate, glyceryl monoisostearate, 2-ethylhexyl paramethoxycinnamate, tocopherol acetate, and 2-ethylhexyl paramethoxycinnamate. Is even more preferable.
成分(D)として、成分(C)を除くエステル油は、1種又は2種以上を組み合わせて用いることができ、塗布後にしっとり感を付与する点から、含有量は、全組成中に0.1質量%以上が好ましく、0.5質量%以上がより好ましく、1質量%以上がさらに好ましく、20質量%以下が好ましく、10質量%以下がより好ましく、5質量%以下がさらに好ましい。また、成分(C)以外のエステル油の含有量は、全組成中に0.1〜20質量%が好ましく、0.5〜10質量%がより好ましく、1〜5質量%がさらに好ましい。 As the component (D), the ester oil excluding the component (C) can be used singly or in combination of two or more, and the content is 0. 1 mass% or more is preferable, 0.5 mass% or more is more preferable, 1 mass% or more is further more preferable, 20 mass% or less is preferable, 10 mass% or less is more preferable, and 5 mass% or less is further more preferable. Moreover, 0.1-20 mass% is preferable in the whole composition, and, as for content of ester oil other than a component (C), 0.5-10 mass% is more preferable, and 1-5 mass% is further more preferable.
また、本発明において、成分(C)及び(D)の質量割合(C)/(D)は、塗布後の肌への密着性が高く、高密度に付着して、塗りムラ(抜け)がなく、肌の皮丘に均一に付着するので、優れたカバー力、仕上がりを得ることができ、塗布後に肌のかさつきを抑制する点から、0.02以上が好ましく、0.06以上がより好ましく、0.1以上がさらに好ましく、0.2以上がよりさらに好ましく、25以下が好ましく、9以下がより好ましく、4以下がさらに好ましく、2.5以下がよりさらに好ましい。成分(C)及び成分(D)の質量割合(C)/(D)質量割合は、0.02〜25が好ましく、0.06〜9がより好ましく、0.1〜4がさらに好ましく、0.2〜2.5がよりさらに好ましい。 Moreover, in this invention, the mass ratio (C) / (D) of component (C) and (D) has high adhesiveness to the skin after application | coating, it adheres with high density, and coating unevenness (missing) is carried out. Since it adheres uniformly to the skin dermis, it is possible to obtain excellent covering power and finish, and 0.02 or more is preferable, and 0.06 or more is more preferable from the viewpoint of suppressing skin roughness after application. 0.1 or more is more preferable, 0.2 or more is more preferable, 25 or less is preferable, 9 or less is more preferable, 4 or less is further preferable, and 2.5 or less is more preferable. 0.02-25 are preferable, as for the mass ratio (C) / (D) mass ratio of a component (C) and a component (D), 0.06-9 are more preferable, 0.1-4 are more preferable, 0 2 to 2.5 is even more preferable.
本発明の油中水型乳化化粧料は、さらに、(E)揮発性油を含有することができる。
かかる揮発性油としては、揮発性炭化水素油、揮発性シリコーン油が好ましい。揮発性とは、35〜87℃の引火点を有するものである。
成分(E)のうち、揮発性炭化水素油としては、例えば、n−デカン、n−ウンデカン、n−ドデカン等のパラフィン系炭化水素油;イソデカン、イソドデカン等のイソパラフィン系炭化水素油;シクロデカン、シクロドデカン等の環状パラフィン炭化水素油が挙げられる。これらのうち、イソパラフィン系炭化水素油が好ましく、イソドデカンがより好ましい。
The water-in-oil emulsified cosmetic of the present invention can further contain (E) a volatile oil.
As such a volatile oil, a volatile hydrocarbon oil and a volatile silicone oil are preferable. Volatile has a flash point of 35-87 ° C.
Among the components (E), examples of the volatile hydrocarbon oil include paraffinic hydrocarbon oils such as n-decane, n-undecane and n-dodecane; isoparaffinic hydrocarbon oils such as isodecane and isododecane; cyclodecane, cyclo Examples thereof include cyclic paraffin hydrocarbon oils such as dodecane. Of these, isoparaffinic hydrocarbon oil is preferable, and isododecane is more preferable.
また、揮発性シリコーン油としては、例えば、ジメチルポリシロキサン(1.5cs)、ジメチルポリシロキサン(2cs)等の直鎖状ジメチルポリシロキサン;トリス(トリメチルシリル)メチルシラン、テトラキス(トリメチルシリル)シラン等の分岐状シロキサン;オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン、ドデカメチルシクロヘキサシロキサン等の環状ジメチルシロキサンなどが挙げられる。
成分(E)としては、塗布後の使用感や塗布後の化粧膜が肌にきれいに密着する点から、揮発性シリコーン油が好ましい。
Examples of the volatile silicone oil include linear dimethylpolysiloxanes such as dimethylpolysiloxane (1.5 cs) and dimethylpolysiloxane (2cs); branched forms such as tris (trimethylsilyl) methylsilane and tetrakis (trimethylsilyl) silane. Siloxane; and cyclic dimethylsiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane and the like.
As the component (E), a volatile silicone oil is preferable from the viewpoint that the feeling after use and the decorative film after application are in close contact with the skin.
成分(E)は、1種又は2種以上を用いることができ、塗布後の使用感の点から、含有量は、全組成中に1質量%以上が好ましく、5質量%以上がより好ましく、20質量%以上がさらに好ましく、50質量%以下が好ましく、40質量%以下がより好ましく、35質量%以下がさらに好ましい。また、成分(E)の含有量は、全組成中に1〜50質量%が好ましく、5〜40質量%がより好ましく、20〜35質量%がさらに好ましい。 Component (E) can be used singly or in combination of two or more. From the viewpoint of the feeling after application, the content is preferably 1% by mass or more, more preferably 5% by mass or more in the total composition, 20 mass% or more is more preferable, 50 mass% or less is preferable, 40 mass% or less is more preferable, and 35 mass% or less is further more preferable. Moreover, 1-50 mass% is preferable in the whole composition, as for content of a component (E), 5-40 mass% is more preferable, and 20-35 mass% is further more preferable.
本発明において、水の含有量は、全組成中に5質量%以上が好ましく、10質量%以上がより好ましく、15質量%以上がさらに好ましく、70質量%以下が好ましく、50質量%以下がより好ましく、40質量%以下がさらに好ましい。 In the present invention, the content of water is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, more preferably 70% by mass or less, and more preferably 50% by mass or less in the total composition. Preferably, 40 mass% or less is more preferable.
本発明の油中水型乳化化粧料は、前記成分以外に、通常化粧料に用いられる成分、例えば、前記以外の油性成分、界面活性剤、顔料、水溶性高分子、酸化防止剤、香料、色素、防腐剤、増粘剤、pH調整剤、血行促進剤、冷感剤、制汗剤、殺菌剤、皮膚賦活剤、保湿剤、清涼剤等を含有することができる。 In addition to the above components, the water-in-oil emulsified cosmetics of the present invention are usually used in cosmetics, for example, other oily components, surfactants, pigments, water-soluble polymers, antioxidants, perfumes, A coloring agent, preservative, thickener, pH adjuster, blood circulation promoter, cooling agent, antiperspirant, bactericidal agent, skin activator, moisturizer, refreshing agent and the like can be contained.
本発明の油中水型乳化化粧料は、通常の方法に従って製造することができ、液状、乳液液、ペースト状、クリーム状、ジェル状等の剤型にすることができ、乳液状、クリーム状が好ましい。
また、本発明の油中水型乳化化粧料は、化粧下地、ファンデーション、コンシーラー;ほお紅、アイシャドウ、マスカラ、アイライナー、アイブロウ、オーバーコート剤、口紅等のメイクアップ化粧料;日やけ止め乳液、日焼け止めクリーム等の紫外線防御化粧料などとして適用することができる。なかでも、化粧下地、リキッドファンデーション、コンシーラーがより好ましい。
本発明の油中水型乳化化粧料は、単品のみの使用においても、リキッドファンデーションやパウダーファンデーション・白粉等の粉体化粧料の重ね付けにおいても使用することができる。
上述した実施形態に関し、本発明は、更に以下の組成物を開示する。
The water-in-oil emulsified cosmetic of the present invention can be produced according to a usual method, and can be made into a liquid, emulsion, paste, cream, gel, etc., emulsion, cream Is preferred.
Further, the water-in-oil emulsified cosmetic of the present invention comprises a makeup base, foundation, concealer; makeup cosmetics such as blusher, eyeshadow, mascara, eyeliner, eyebrow, overcoat agent, lipstick; sunscreen emulsion, It can be applied as UV protection cosmetics such as sunscreen cream. Among these, a makeup base, a liquid foundation, and a concealer are more preferable.
The water-in-oil emulsified cosmetic of the present invention can be used in the case of using only a single product, or in the case of overlaying powder cosmetics such as liquid foundation, powder foundation, and white powder.
This invention discloses the following compositions further regarding embodiment mentioned above.
<1>次の成分(A)、(B)及び(C):
(A)カルボシロキサンデンドリマー構造を側鎖に有するビニル系重合体 0.1〜20質量%、
(B)疎水化処理した粉体、
(C)25℃で液状のペンタエリスリトール脂肪酸エステル及びジペンタエリスリトール脂肪酸エステルから選ばれるエステル油 0.01〜30質量%
を含有し、成分(A)と成分(C)の質量割合(A)/(C)が、0.02〜80である油中水型乳化化粧料。
<1> The following components (A), (B) and (C):
(A) 0.1-20% by mass of a vinyl polymer having a carbosiloxane dendrimer structure in the side chain,
(B) Hydrophobized powder,
(C) Ester oil selected from liquid pentaerythritol fatty acid ester and dipentaerythritol fatty acid ester at 25 ° C. 0.01 to 30% by mass
A water-in-oil emulsified cosmetic comprising a component (A) and a component (C) having a mass ratio (A) / (C) of 0.02 to 80.
<2>成分(A)において、カルボシロキサンデンドリマー構造が、次式(1) <2> In the component (A), the carbosiloxane dendrimer structure has the following formula (1)
{式中、Zは2価の有機基であり、pは0又は1であり、R1は炭素原子数1〜10のアルキル基又はアリール基である。X1はi=1とした場合の次式で示されるシリルアルキル基である。 {In the formula, Z is a divalent organic group, p is 0 or 1, and R 1 is an alkyl group or an aryl group having 1 to 10 carbon atoms. X 1 is a silylalkyl group represented by the following formula when i = 1.
(式中、R1は前記と同じであり、R2は炭素原子数2〜10のアルキレン基であり、R3は炭素原子数1〜10のアルキル基であり、Xi+1は水素原子、炭素原子数1〜10のアルキル基、アリール基及び上記シリルアルキル基からなる群から選択される基である。iは該シリルアルキル基の階層を示している1〜10の整数であり、aiは0〜3の整数である。)}
で表される基である前記<1>記載の油中水型乳化化粧料。
<3>成分(A)のビニル系重合体が、(A1)ビニル系単量体 0〜99.9質量部と、(A2)一般式:
(In the formula, R 1 is the same as above, R 2 is an alkylene group having 2 to 10 carbon atoms, R 3 is an alkyl group having 1 to 10 carbon atoms, and X i + 1 is a hydrogen atom. , A group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group, and the above silylalkyl group, i is an integer of 1 to 10 indicating the hierarchy of the silylalkyl group, a i is an integer from 0 to 3.)}
The water-in-oil emulsified cosmetic according to <1>, which is a group represented by the formula:
<3> Component (A) vinyl polymer is (A1) 0-99.9 parts by mass of vinyl monomer and (A2) general formula:
{式中、Yはラジカル重合可能な有機基であり、R1は炭素原子数1〜10のアルキル基又はアリール基であり、X1はi=1とした場合の次式で示されるシリルアルキル基である。 {Wherein Y is a radically polymerizable organic group, R 1 is an alkyl group or aryl group having 1 to 10 carbon atoms, and X 1 is a silylalkyl represented by the following formula when i = 1. It is a group.
(式中、R1は前記と同じであり、R2は炭素原子数2〜10のアルキレン基であり、R3は炭素原子数1〜10のアルキル基であり、Xi+1は水素原子、炭素原子数1〜10のアルキル基、アリール基及び上記シリルアルキル基からなる群から選択される基である。iは該シリルアルキル基の階層を示している1〜10の整数であり、aiは0〜3の整数である。)}
で表されるラジカル重合可能な有機基を有するカルボシロキサンデンドリマー 100〜0.1質量部とを重合させてなるものである前記<1>又は<2>記載の油中水型乳化化粧料。
<4>(A2)中のラジカル重合可能な有機基Yが、一般式
(In the formula, R 1 is the same as above, R 2 is an alkylene group having 2 to 10 carbon atoms, R 3 is an alkyl group having 1 to 10 carbon atoms, and X i + 1 is a hydrogen atom. , A group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group, and the above silylalkyl group, i is an integer of 1 to 10 indicating the hierarchy of the silylalkyl group, a i is an integer from 0 to 3.)}
The water-in-oil emulsified cosmetic according to <1> or <2>, wherein 100 to 0.1 parts by mass of a carbosiloxane dendrimer having an organic group capable of radical polymerization represented by formula (1) is polymerized.
<4> The organic group Y capable of radical polymerization in (A2) has the general formula
(式中、R4は水素原子又はメチル基であり、R5は炭素原子数1〜10のアルキレン基である。)
で表されるアクリル基又はメタクリル基含有有機基、一般式:
(In the formula, R 4 is a hydrogen atom or a methyl group, and R 5 is an alkylene group having 1 to 10 carbon atoms.)
An acrylic group or methacryl group-containing organic group represented by the general formula:
(式中、R6は水素原子又はメチル基であり、R7は炭素原子数1〜10のアルキル基であり、R8は炭素原子数1〜10のアルキレン基であり、bは0〜4の整数であり、cは0又は1である。)
で表されるスチリル基含有有機基及び炭素原子数2〜10のアルケニル基からなる群から選択される基である前記<3>記載の油中水型乳化化粧料。
Wherein R 6 is a hydrogen atom or a methyl group, R 7 is an alkyl group having 1 to 10 carbon atoms, R 8 is an alkylene group having 1 to 10 carbon atoms, and b is 0 to 4 And c is 0 or 1.)
The water-in-oil emulsified cosmetic according to <3>, which is a group selected from the group consisting of a styryl group-containing organic group and an alkenyl group having 2 to 10 carbon atoms.
<5>成分(A)のカルボシロキサンデンドリマー構造を側鎖に有するビニル系重合体が、好ましくは、シリコーンデンドリマー・アクリル共重合体である前記<1>〜<4>のいずれか1記載の油中水型乳化化粧料。
<6>成分(A)の含有量が、好ましくは、全組成中に0.2質量%以上であって、0.3質量%以上がより好ましく、15質量%以下が好ましく、10質量%以下がより好ましい前記<1>〜<5>のいずれか1記載の油中水型乳化化粧料。
<5> The oil according to any one of <1> to <4>, wherein the vinyl polymer having a carbosiloxane dendrimer structure as a component (A) in the side chain is preferably a silicone dendrimer / acrylic copolymer. Water-in-water emulsified cosmetic.
The content of the <6> component (A) is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, preferably 15% by mass or less, and preferably 10% by mass or less in the total composition. The water-in-oil emulsified cosmetic according to any one of <1> to <5>, wherein is more preferable.
<7>成分(B)において、疎水化処理が、好ましくは、フッ素化合物処理、シリコーン処理であって、フッ素化合物処理とシリコーン処理を併用しても良く、シリコーン処理単独がより好ましい前記<1>〜<6>のいずれか1記載の油中水型乳化化粧料。
<8>成分(B)において、疎水化処理が、好ましくは、トリデカフルオロオクチルトリエトキシシラン処理である前記<1>〜<6>のいずれか1記載の油中水型乳化化粧料。
<9>成分(B)において、疎水化処理の処理量が、成分(B)の疎水化処理した粉体100質量%に対して、好ましくは、0.05質量%以上であって、0.1質量%以上がより好ましく、50質量%以下が好ましく、20質量%以下がより好ましい前記<1>〜<8>のいずれか1記載の油中水型乳化化粧料。
<10>成分(B)の含有量が、好ましくは、全組成中に0.1質量%以上であって、1質量%以上がより好ましく、8質量%以上がさらに好ましく、40質量%以下が好ましく、30質量%以下がより好ましく、22質量%以下がさらに好ましい前記<1>〜<9>のいずれか1記載の油中水型乳化化粧料。
<7> In the component (B), the hydrophobizing treatment is preferably a fluorine compound treatment or a silicone treatment, and the fluorine compound treatment and the silicone treatment may be used in combination, and the silicone treatment alone is more preferred <1> The water-in-oil emulsified cosmetic according to any one of to <6>.
<8> The water-in-oil emulsion cosmetic according to any one of <1> to <6>, wherein in the component (B), the hydrophobization treatment is preferably tridecafluorooctyltriethoxysilane treatment.
<9> In component (B), the amount of hydrophobization treatment is preferably 0.05% by mass or more with respect to 100% by mass of the hydrophobized powder of component (B), and 1 mass% or more is more preferable, 50 mass% or less is preferable, and 20 mass% or less is more preferable, The water-in-oil type emulsion cosmetic in any one of said <1>-<8>.
The content of <10> component (B) is preferably 0.1% by mass or more in the total composition, more preferably 1% by mass or more, further preferably 8% by mass or more, and 40% by mass or less. The water-in-oil emulsified cosmetic according to any one of <1> to <9>, preferably 30% by mass or less, and more preferably 22% by mass or less.
<11>成分(A)及び(B)の質量割合(A)/(B)が、好ましくは、0.005以上であって、0.01以上がより好ましく、0.02以上がさらに好ましく、5以下が好ましく、3以下がより好ましく、1以下がさらに好ましい前記<1>〜<10>のいずれか1記載の油中水型乳化化粧料。
<12>成分(C)のエステル油が、好ましくは、トリポリヒドロキシステアリン酸ジペンタエリスリチル、ペンタイソステアリン酸ジペンタエリスリチル、テトライソステアリン酸ジペンタエリスリチル、(ベヘン酸/ポリヒドロキシステアリン酸)ペンタエリスリチルであって、トリポリヒドロキシステアリン酸ジペンタエリスリチル、(ベヘン酸/ポリヒドロキシステアリン酸)ペンタエリスリチルがより好ましく、トリポリヒドロキシステアリン酸ジペンタエリスリチルがさらに好ましい前記<1>〜<11>のいずれか1記載の油中水型乳化化粧料。
<13>成分(C)のエステル油が、好ましくは、水酸基を有するものであって、トリポリヒドロキシステアリン酸ジペンタエリスリチル、(ベヘン酸/ポリヒドロキシステアリン酸)ペンタエリスリチルがより好ましい前記<1>〜<12>のいずれか1記載の油中水型乳化化粧料。
<14>成分(C)のエステル油が、好ましくは、ジペンタエリスリトール脂肪酸エステルであって、トリポリヒドロキシステアリン酸ジペンタエリスリチルがより好ましい前記<1>〜<13>のいずれか1記載の油中水型乳化化粧料。
<11> The mass ratio (A) / (B) of the components (A) and (B) is preferably 0.005 or more, more preferably 0.01 or more, still more preferably 0.02 or more, 5 or less is preferable, 3 or less is more preferable, and 1 or less is more preferable. The water-in-oil emulsified cosmetic according to any one of the above items <1> to <10>.
<12> The ester oil of component (C) is preferably dipentaerythrityl tripolyhydroxystearate, dipentaerythrityl pentaisostearate, dipentaerythrityl tetraisostearate, (behenic acid / polyhydroxystearic acid) pentaerythrityl, and tripolyhydroxystearin The water-in-oil emulsion cosmetic according to any one of <1> to <11>, wherein dipentaerythrityl acid and (behenic acid / polyhydroxystearic acid) pentaerythrityl are more preferred, and dipentaerythrityl tripolyhydroxystearate is more preferred.
<13> The ester oil of component (C) preferably has a hydroxyl group, and dipentaerythrityl tripolyhydroxystearate and (behenic acid / polyhydroxystearic acid) pentaerythrityl are more preferred <1> to <12> The water-in-oil emulsified cosmetic according to any one of 12>.
<14> The oil-in-oil type according to any one of <1> to <13>, wherein the ester oil of component (C) is preferably a dipentaerythritol fatty acid ester, and more preferably dipentaerythritol tripolyhydroxystearate. Emulsified cosmetic.
<15>成分(C)の含有量が、好ましくは、全組成中に0.05質量%以上であって、0.1質量%以上がより好ましく、0.4質量%以上がさらに好ましく、20質量%以下が好ましく、15質量%以下がより好ましく、10質量%以下がさらに好ましい前記<1>〜<14>のいずれか1記載の油中水型乳化化粧料。
<16>成分(A)及び(C)の質量割合(A)/(C)が、好ましくは、0.03以上であって、0.05以上がより好ましく、0.1以上がよりさらに好ましく、60以下が好ましく、40以下がより好ましく、20以下がさらに好ましい前記<1>〜<15>のいずれか1記載の油中水型乳化化粧料。
The content of <15> component (C) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.4% by mass or more, in the total composition, 20 The water-in-oil emulsified cosmetic according to any one of <1> to <14>, which is preferably at most mass%, more preferably at most 15 mass%, further preferably at most 10 mass%.
<16> The mass ratio (A) / (C) of the components (A) and (C) is preferably 0.03 or more, more preferably 0.05 or more, and even more preferably 0.1 or more. 60 or less is more preferable, 40 or less is more preferable, and 20 or less is more preferable, The water-in-oil emulsified cosmetic according to any one of the above <1> to <15>.
<17>更に、成分(D)として、成分(C)を除く、25℃で液状のエステル油を含有することができ、好ましくは、モノエステル、ジエステルを含有し、モノエステルがより好ましく、イソノナン酸イソトリデシル、ミリスチン酸イソステアリル、モノイソステアリン酸モノミリスチン酸グリセリル、パラメトキシケイ皮酸2−エチルヘキシル、酢酸トコフェロールがさらに好ましく、パラメトキシケイ皮酸2−エチルヘキシルがよりさらに好ましい前記<1>〜<16>のいずれか1記載の油中水型乳化化粧料。
<18>成分(D)として、成分(C)を除くエステル油の含有量が、好ましくは、全組成中に0.1質量%以上であって、0.5質量%以上がより好ましく、1質量%以上がさらに好ましく、20質量%以下が好ましく、10質量%以下がより好ましく、5質量%以下がさらに好ましい前記<17>記載の油中水型乳化化粧料。
<19>成分(C)及び成分(D)の質量割合(C)/(D)が、好ましくは、0.02以上であって、0.06以上がより好ましく、0.1以上がさらに好ましく、0.2以上がよりさらに好ましく、25以下が好ましく、9以下がより好ましく、4以下がさらに好ましく、2.5以下がよりさらに好ましい前記<17>又は<18>記載の油中水型乳化化粧料。
<20>さらに、(E)揮発性油を含有することができ、好ましくは、揮発性シリコーン油を含有する前記<1>〜<19>のいずれか1記載の油中水型乳化化粧料。
<21>成分(E)の含有量が、好ましくは、全組成中に1質量%以上であって、5質量%以上がより好ましく、20質量%以上がさらに好ましく、50質量%以下が好ましく、40質量%以下がより好ましく、35質量%以下がさらに好ましい前記<20>記載の油中水型乳化化粧料。
<22>水の含有量が、好ましくは、全組成中に5質量%以上であって、10質量%以上がより好ましく、15質量%以上がさらに好ましく、70質量%以下が好ましく、50質量%以下がより好ましく、40質量%以下がさらに好ましい前記<1>〜<21>のいずれか1記載の油中水型乳化化粧料。
<17> Furthermore, as component (D), an ester oil that is liquid at 25 ° C., excluding component (C), can be contained, preferably monoesters and diesters are contained, monoesters are more preferred, and isononane <1> to <16, wherein isotridecyl acid, isostearyl myristate, glyceryl monoisostearate, 2-ethylhexyl paramethoxycinnamate, and tocopherol acetate are more preferable, and 2-ethylhexyl paramethoxycinnamate is more preferable. > The water-in-oil emulsified cosmetic according to any one of the above.
<18> As the component (D), the content of the ester oil excluding the component (C) is preferably 0.1% by mass or more and more preferably 0.5% by mass or more in the total composition. The water-in-oil emulsified cosmetic according to the above <17>, more preferably at least 20% by mass, more preferably at most 20% by mass, even more preferably at most 10% by mass.
<19> The mass ratio (C) / (D) of the component (C) and the component (D) is preferably 0.02 or more, more preferably 0.06 or more, and further preferably 0.1 or more. 0.2 or more is more preferable, 25 or less is preferable, 9 or less is more preferable, 4 or less is more preferable, and 2.5 or less is more preferable, and the water-in-oil emulsification according to the above <17> or <18> Cosmetics.
<20> The water-in-oil emulsified cosmetic according to any one of <1> to <19>, further comprising (E) a volatile oil, preferably containing a volatile silicone oil.
The content of <21> component (E) is preferably 1% by mass or more in the total composition, more preferably 5% by mass or more, further preferably 20% by mass or more, and preferably 50% by mass or less, The water-in-oil emulsified cosmetic according to <20>, wherein 40% by mass or less is more preferable, and 35% by mass or less is more preferable.
The content of <22> water is preferably 5% by mass or more in the total composition, more preferably 10% by mass or more, further preferably 15% by mass or more, preferably 70% by mass or less, and 50% by mass. The water-in-oil emulsified cosmetic according to any one of <1> to <21>, wherein the following is more preferable, and 40% by mass or less is more preferable.
製造例1((ベヘン酸/ポリヒドロキシステアリン酸)ペンタエリスリチルの製造)
(1)撹拌機、温度計、窒素ガス吹込管及び水分分離器を備えた1Lの四つ口フラスコに、12−ヒドロキシステアリン酸(小倉合成工業社製、商品名「12−ヒドロ酸HP」、純度:99質量%)540gを仕込み、触媒として全体仕込み量の0.1%の塩化スズ、及び還流溶剤として全体仕込み量の5%のキシロールを加え、窒素気流下、生成した水を除去しながら200℃の温度で、15時間反応を行い、12−ヒドロキシステアリン酸重合物を得た。得られた重合物の酸価を測定したところ、酸価は19.4mgKOH/gであり、酸価より算出した平均重合度は10.2であることから、得られた生成物は12−ヒドロキシステアリン酸10量体であった。
Production Example 1 (Production of (behenic acid / polyhydroxystearic acid) pentaerythrityl)
(1) In a 1 L four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas blowing tube and a water separator, 12-hydroxystearic acid (trade name “12-hydroacid HP” manufactured by Kokura Gosei Kogyo Co., Ltd., Purity: 99% by mass) 540 g, 0.1% tin chloride of the total charge as a catalyst, and 5% xylol of the total charge as a reflux solvent, while removing the generated water in a nitrogen stream Reaction was performed at a temperature of 200 ° C. for 15 hours to obtain a 12-hydroxystearic acid polymer. When the acid value of the obtained polymer was measured, the acid value was 19.4 mgKOH / g, and the average degree of polymerization calculated from the acid value was 10.2. Therefore, the obtained product was 12-hydroxy. It was a 10-mer stearic acid.
(2)次いで、撹拌機、温度計、窒素ガス吹込管及び水分分離器を備えた1Lの四つ口フラスコに、上述のようにして得られた12−ヒドロキシステアリン酸重合物(酸価:19.4mgKOH/g、10量体)514g、ベヘン酸(ユニケマ社製、商品名「PRIFRAC2989」)82g及びペンタエリスリトール(李長栄化学工業社製、商品名「ペンタエリスリトール」)16gを加え、窒素気流下、生成した水を除去しながら210℃の温度で、生成物の酸価が1.4mgKOH/g以下になるまで反応を行った。
反応終了後、触媒を濾別し、次に活性白土を用いて脱色後、常法にて脱臭を行い、常温でペースト状のエステル化反応生成物(テトラ(ポリ12−ヒドロキシステアリン酸/ベヘン酸)ペンタエリスリチル)246gを得た。
得られたエステル化反応生成物の酸価は1.6mgKOH/gであり、水酸基価は21mgKOH/gであった。また、得られたエステル化反応生成物の脂肪酸残基における7量体以上の12−ヒドロキシステアリン酸重合物のモル比(%)は43%であり、ベヘン酸のモル比(%)は57%であり、
(2) Next, in a 1 L four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas blowing tube and a water separator, the 12-hydroxystearic acid polymer (acid value: 19) obtained as described above was used. .4 mg KOH / g, 10-mer) 514 g, behenic acid (manufactured by Unikema, trade name “PRIFRAC 2989”) 82 g and pentaerythritol (Li Changei Chemical Co., trade name “Pentaerythritol”) 16 g are added under nitrogen flow. The reaction was performed at a temperature of 210 ° C. while removing the generated water until the acid value of the product was 1.4 mgKOH / g or less.
After completion of the reaction, the catalyst is filtered off, then decolorized using activated clay, deodorized by a conventional method, and a paste-form esterification reaction product (tetra (poly-12-hydroxystearic acid / behenic acid) at room temperature. ) Pentaerythrityl) 246 g was obtained.
The acid value of the obtained esterification reaction product was 1.6 mgKOH / g, and the hydroxyl value was 21 mgKOH / g. The molar ratio (%) of the 12-hydroxystearic acid polymer of 7-mer or more in the fatty acid residue of the obtained esterification reaction product is 43%, and the molar ratio (%) of behenic acid is 57%. And
製造例2(テトライソステアリン酸ジペンタエリスリチルの製造)
攪拌機、温度計、窒素ガス吹込管及び水分離管を備えた3Lの4つロフラスコに、ジペンタエリスリトール〔商品名:ジ・ペンタリット、広栄化学工業社製〕58.4g(0.23モル)と2−(1,3,3−トリメチル)ブチル−5,7,7−トリメチルオクタン酸〔商品名:イソステアリン酸、日産化学工業社製〕293.9g(1.03モル)を仕込んだ(原料仕込み質量比=10:50.3)。その後、ジブチルチンオキサイド(触媒)を全仕込み量の0.05質量%、キシレン(還流溶剤)を全仕込み量の5質量%加え、攪拌しながら200〜250℃で約21時間反応を行った。反応終了後、還流溶剤であるキシレンを減圧留去した。キシレンを除去した反応物を、活性白土により吸着処理し、次いで60℃程度まで冷却後ろ過し、常法にて脱臭・蒸留処理を行うことで、テトライソステアリン酸ジペンタエリスリチルを245g得た。
テトライソステアリン酸ジペンタエリスリチルの酸価は0.2、水酸基価は81、凝固点−16℃であり、−30℃でも曇らなかった。また、25℃における粘度は、35万mPa・sであり、25℃で液状であった。粘度は、ブルックフィールド型粘度計(BH型)を用い、25℃にてローターNo.6を用い、2rpmにて測定した。
Production Example 2 (Production of dipentaerythrityl tetraisostearate)
In a 3 L four-necked flask equipped with a stirrer, thermometer, nitrogen gas blowing tube and water separation tube, dipentaerythritol [trade name: dipentarit, manufactured by Guangei Chemical Industry Co., Ltd.] 58.4 g (0.23 mol) 2- (1,3,3-trimethyl) butyl-5,7,7-trimethyloctanoic acid [trade name: isostearic acid, manufactured by Nissan Chemical Industries, Ltd.] 293.9 g (1.03 mol) was charged (raw material charge) Mass ratio = 10: 50.3). Thereafter, 0.05% by mass of dibutyltin oxide (catalyst) and 5% by mass of xylene (refluxing solvent) were added to the total charged amount, and the reaction was performed at 200 to 250 ° C. for about 21 hours while stirring. After completion of the reaction, xylene as a refluxing solvent was distilled off under reduced pressure. The reaction product from which xylene was removed was adsorbed with activated clay, then cooled to about 60 ° C., filtered, and deodorized and distilled by a conventional method to obtain 245 g of dipentaerythrityl tetraisostearate.
Dipentaerythrityl tetraisostearate had an acid value of 0.2, a hydroxyl value of 81, a freezing point of -16 ° C, and was not cloudy even at -30 ° C. The viscosity at 25 ° C. was 350,000 mPa · s, and it was liquid at 25 ° C. The viscosity was measured using a Brookfield viscometer (BH type) at 25 ° C. with rotor No. 6 and measured at 2 rpm.
実施例1〜8及び比較例1〜3
表1に示す組成の油中水型乳化化粧料を製造し、塗布後の肌への密着性、塗布後の肌への追随性、塗布後の肌のかさつきの目立たなさ、塗布後の肌の皮丘への付着性、塗布後の肌のカバー力及びファンデーションの塗布状態を評価した。結果を表1に併せて示す。
Examples 1-8 and Comparative Examples 1-3
Manufactures water-in-oil emulsified cosmetics having the composition shown in Table 1, adhesion to the skin after application, followability to the skin after application, inconspicuous skin roughness after application, The adhesion to the skin, the covering power of the skin after application, and the application state of the foundation were evaluated. The results are also shown in Table 1.
(製法)
粉体相成分を混合粉砕し、別途混合した油相成分に添加してディスパー(2000rpm)で10分間分散した。その後、水相成分を添加し、ディスパー(800rpm)で10分間撹拌することにより、油中水型乳化化粧料を得た。
(Manufacturing method)
The powder phase component was mixed and ground, added to the separately mixed oil phase component, and dispersed with a disper (2000 rpm) for 10 minutes. Then, the water phase component was added and stirred for 10 minutes with a disper (800 rpm) to obtain a water-in-oil emulsified cosmetic.
(評価方法I)
専門評価者10人が、各油中水型乳化化粧料を肌に塗布した後の肌への密着性、塗布後の肌への追随性、塗布後の肌のかさつきの目立たなさ、塗布後の肌の皮丘への付着性及び塗布後の肌のカバー力を、以下の基準で官能評価した。なお、表中の評価結果は、専門評価者10人の合計点で示した。
(Evaluation Method I)
10 expert evaluators applied to each skin after applying each water-in-oil emulsified cosmetic, adhesion to the skin after application, inconspicuous skin roughness after application, The adhesion to the skin dermis and the covering power of the skin after application were sensory evaluated according to the following criteria. In addition, the evaluation result in a table | surface was shown by the total score of 10 expert evaluators.
(1)塗布後の肌への密着性:
5;肌にすべて密着している。
4;肌にほぼ密着している。
3;肌に一部が密着していない。
2;肌にあまり密着していない。
1;肌に密着していない。
(1) Adhesion to the skin after application:
5: All in close contact with the skin.
4; Almost in close contact with the skin.
3; A part of the skin is not in close contact.
2; not very close to the skin.
1; not in close contact with the skin.
(2)塗布後の肌への追随性:
5;顔を動かしでも、塗布後の化粧膜が肌にしっかり追随している。
4;顔を動かしでも、塗布後の化粧膜のほぼ肌に追随している。
3;顔を動かすと、塗布後の化粧膜がやや筋状になり、肌に追随しない。
2;顔を動かすと、塗布後の化粧膜が一部分で割れ、肌に追随しない。
1;顔を動かすと、塗布後の化粧膜がはっきり割れ、肌に追随しない。
(2) Followability to skin after application:
5; Even if the face is moved, the applied cosmetic film follows the skin firmly.
4: Even when the face is moved, the skin of the decorative film after application is almost following the skin.
3; When the face is moved, the decorative film after application becomes slightly streaky and does not follow the skin.
2; When the face is moved, the decorative film after application is partially broken and does not follow the skin.
1: When the face is moved, the decorative film after application is clearly broken and does not follow the skin.
(3)塗布後の肌のかさつきの目立たなさ:
5;かさつきを感じない。
4;かさつきをわずかに感じる。
3;かさつきがやや感じられる。
2;かさつきを感じる。
1;かさつきをかなり感じる。
(3) Skin roughness after application is not noticeable:
5; I don't feel the bulk.
4; I feel a little bit thick.
3; Somewhat rough feeling is felt.
2; feels thick.
1; I feel a lot of bulkiness.
(4)塗布後の肌の皮丘への付着性:
5;化粧料が肌のきめの皮丘部分にすべて付着している。
4;化粧料が肌のきめの皮丘部分にほぼ付着している。
3;化粧料が肌のきめの皮丘部分に一部が付着していない。
2;化粧料が肌のきめの皮丘部分にあまり付着していない。
1;化粧料が肌のきめの皮丘部分に付着していない。
(4) Adhesion of skin to skin after application:
5: All the cosmetics are attached to the skin of the skin.
4; Cosmetics are almost adhered to the skin hill part of the skin.
3; A part of the cosmetic does not adhere to the skin hill part of the skin.
2; Cosmetics do not adhere much to the skin hill part of the skin.
1; Cosmetics are not adhering to the skin hill part of the skin.
(5)塗布後の肌のカバー力:
5;肌の色ムラのカバー力がある。
4;肌の色ムラのカバー力がほぼある。
3;肌の色ムラのカバー力がややある。
2;肌の色ムラのカバー力があまりない。
1;肌の色ムラのカバー力がない。
(5) Skin covering power after application:
5: There is a covering power for uneven skin color.
4: There is almost a covering power for uneven skin color.
3; There is a slight covering power of uneven skin color.
2: There is not much covering power for uneven skin color.
1: There is no covering power for uneven skin color.
(評価方法II)
(6)ファンデーションの塗布状態:
専門評価者10人が、各油中水型乳化化粧料を黒色の人工皮革に20mg/60cm2となるように25μmコーターで均一に引き延ばした後、常温で1時間乾燥した。この化粧膜の塗布状態を、160倍のマイクロスコープ(ハイロックス社製、マイクロスコープ)を用い、以下の基準で官能評価した。なお、表中の評価結果は、専門評価者10人の合計点で示した。
5;ファンデーションの抜けがなく、高密度に付着している。
4;ファンデーションの抜けが少々あるが、密に付着している。
3;ファンデーションの抜けが少々あり、あまり密に付着していない。
2;ファンデーションの抜けが小さく、複数あり、密に付着していない。
1;ファンデーションの抜けが大きく、複数あり、密に付着していない。
(Evaluation Method II)
(6) Foundation application state:
Ten professional evaluators uniformly spread each water-in-oil emulsified cosmetic on black artificial leather to 20 mg / 60 cm 2 with a 25 μm coater, and then dried at room temperature for 1 hour. The application state of this decorative film was subjected to sensory evaluation based on the following criteria using a 160 times microscope (manufactured by Hilox Co., Ltd.). In addition, the evaluation result in a table | surface was shown by the total score of 10 expert evaluators.
5: The foundation does not come off and adheres at a high density.
4; The foundation is missing a little, but it adheres densely.
3; There are few missing foundations, and they do not adhere very closely.
2; Foundation missing is small, there are multiple, and it is not closely attached.
1: The missing foundation is large, there are multiple, and it is not closely attached.
実施例9(油中水型下地ファンデーション)
実施例1〜7と同様にして、以下に示す組成の油中水型下地ファンデーションを製造した。
得られた油中水型下地ファンデーションは、塗布後の肌への密着性が高く、高密度に付着して、頬での塗りムラ(抜け)がなく、肌の皮丘に均一に付着するので、優れたカバー力、仕上がりを得ることができる。また、化粧皮膜の追随性に優れ、さらに、塗布後に肌のかさつきが目立たないものであった。
Example 9 (water-in-oil base foundation)
In the same manner as in Examples 1 to 7, water-in-oil base foundations having the following composition were produced.
The resulting water-in-oil foundation foundation has high adhesion to the skin after application, adheres to the skin at a high density, does not cause uneven coating on the cheeks, and adheres uniformly to the skin dermis. Excellent covering power and finish can be obtained. Moreover, the followability of the cosmetic film was excellent, and the skin was not noticeable after application.
(成分)
(A)シリコーンデンドリマー・アクリル共重合体
(30%デカメチルシクロペンタシロキサン溶液(東レ・ダウコーニング社製、FA4001CM)) 10.0(質量%)
(B)トリデカフルオロオクチルトリエトキシシラン処理酸化チタン 9.4
(B)トリデカフルオロオクチルトリエトキシシラン処理ベンガラ*3
0.4
(B)トリデカフルオロオクチルトリエトキシシラン処理黄酸化鉄*3
1.6
(B)トリデカフルオロオクチルトリエトキシシラン処理黒酸化鉄*3
0.2
(B)トリデカフルオロオクチルトリエトキシシラン処理タルク*3 2.0
(B)メチルハイドロジェンポリシロキサン2質量%処理微粒子酸化亜鉛
(テイカ社製、MZ−500、比表面積25m2/g) 3.0
(C)トリポリヒドロキシステアリン酸ジペンタエリスリチル
(日清オイリオ社製、サラコスWO−6) 2.0
(D)パラメトキシケイ皮酸2−エチルヘキシル 3.0
(E)デカメチルシクロペンタシロキサン 8.9
(E)ジメチルポリシロキサン
(信越化学工業社製、KF−96L−2cs) 15.0
ジメチルポリシロキサン・ポリオキシアルキレン共重合体
(東レ・ダウコーニング社製、シリコーンSH3775M) 3.0
エタノール 7.5
硫酸マグネシウム 1.0
精製水 バランス
合計 100.0
*3:トリデカフルオロオクチルトリエトキシシラン5質量%処理したもの
(component)
(A) Silicone dendrimer / acrylic copolymer (30% decamethylcyclopentasiloxane solution (manufactured by Dow Corning Toray, FA4001CM)) 10.0 (mass%)
(B) Tridecafluorooctyltriethoxysilane-treated titanium oxide 9.4
(B) Tridecafluorooctyltriethoxysilane-treated Bengala * 3
0.4
(B) Tridecafluorooctyltriethoxysilane treated yellow iron oxide * 3
1.6
(B) Tridecafluorooctyltriethoxysilane-treated black iron oxide * 3
0.2
(B) Tridecafluorooctyltriethoxysilane-treated talc * 3 2.0
(B) Methyl hydrogen polysiloxane 2 mass% treated fine particle zinc oxide (manufactured by Teika, MZ-500, specific surface area 25 m 2 / g) 3.0
(C) Dipentaerythrityl tripolyhydroxystearate (Nisshin Oilio Co., Ltd., Saracos WO-6) 2.0
(D) 2-Ethylhexyl paramethoxycinnamate 3.0
(E) Decamethylcyclopentasiloxane 8.9
(E) Dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., KF-96L-2cs) 15.0
Dimethylpolysiloxane / polyoxyalkylene copolymer (manufactured by Dow Corning Toray, silicone SH3775M) 3.0
Ethanol 7.5
Magnesium sulfate 1.0
Purified water balance
Total 100.0
* 3: Treated with 5% by mass of tridecafluorooctyltriethoxysilane
Claims (8)
(A)カルボシロキサンデンドリマー構造を側鎖に有するビニル系重合体 0.1〜20質量%、
(B)疎水化処理した粉体、
(C)25℃で液状のペンタエリスリトール脂肪酸エステル及びジペンタエリスリトール脂肪酸エステルから選ばれるエステル油 0.01〜30質量%
を含有し、成分(A)と成分(C)の質量割合(A)/(C)が、0.02〜80である油中水型乳化化粧料。 The following components (A), (B) and (C):
(A) 0.1-20% by mass of a vinyl polymer having a carbosiloxane dendrimer structure in the side chain,
(B) Hydrophobized powder,
(C) Ester oil selected from liquid pentaerythritol fatty acid ester and dipentaerythritol fatty acid ester at 25 ° C. 0.01 to 30% by mass
A water-in-oil emulsified cosmetic comprising a component (A) and a component (C) having a mass ratio (A) / (C) of 0.02 to 80.
で表される基である請求項1〜5のいずれか1項記載の油中水型乳化化粧料。 In component (A), the carbosiloxane dendrimer structure has the following formula (1)
The water-in-oil emulsified cosmetic according to any one of claims 1 to 5, wherein
で表されるラジカル重合可能な有機基を有するカルボシロキサンデンドリマー 100〜0.1質量部とを重合させてなるものである請求項1〜6のいずれか1項記載の油中水型乳化化粧料。 Component (A) vinyl polymer comprises (A1) 0-99.9 parts by weight of vinyl monomer and (A2) general formula:
The water-in-oil emulsified cosmetic according to any one of claims 1 to 6, wherein 100 to 0.1 parts by mass of a carbosiloxane dendrimer having an organic group capable of radical polymerization represented by formula (1) is polymerized. .
で表されるアクリル基又はメタクリル基含有有機基、一般式:
で表されるスチリル基含有有機基及び炭素原子数2〜10のアルケニル基からなる群から選択される基である請求項7記載の油中水型乳化化粧料。 The radically polymerizable organic group Y in (A2) has the general formula
An acrylic group or methacryl group-containing organic group represented by the general formula:
The water-in-oil emulsified cosmetic according to claim 7, which is a group selected from the group consisting of a styryl group-containing organic group and an alkenyl group having 2 to 10 carbon atoms.
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JP2018035091A (en) * | 2016-08-31 | 2018-03-08 | 花王株式会社 | Water-in-oil type emulsion cosmetic |
WO2020142388A1 (en) | 2018-12-31 | 2020-07-09 | Dow Silicones Corporation | Composition, method of preparing copolymer, and methods and end uses thereof |
WO2020142474A1 (en) | 2018-12-31 | 2020-07-09 | Dow Silicones Corporation | Acrylate-functional branched organosilicon compound, method of preparing same, and copolymer formed therewith |
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