JP2006335691A - Water-in-oil type emulsion composition - Google Patents
Water-in-oil type emulsion composition Download PDFInfo
- Publication number
- JP2006335691A JP2006335691A JP2005162938A JP2005162938A JP2006335691A JP 2006335691 A JP2006335691 A JP 2006335691A JP 2005162938 A JP2005162938 A JP 2005162938A JP 2005162938 A JP2005162938 A JP 2005162938A JP 2006335691 A JP2006335691 A JP 2006335691A
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- hydrogen atom
- carbon atoms
- oil
- emulsion composition
- Prior art date
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- Granted
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- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 239000000839 emulsion Substances 0.000 title abstract description 17
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 34
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims abstract description 18
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 16
- 239000000194 fatty acid Substances 0.000 claims abstract description 16
- 229930195729 fatty acid Natural products 0.000 claims abstract description 16
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 15
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims abstract description 15
- 229920002545 silicone oil Polymers 0.000 claims abstract description 14
- 150000003410 sphingosines Chemical class 0.000 claims abstract description 11
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 10
- 125000001424 substituent group Chemical group 0.000 claims abstract description 10
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 claims abstract description 8
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 63
- -1 acetoxymethyl group Chemical group 0.000 claims description 59
- 125000004432 carbon atom Chemical group C* 0.000 claims description 52
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 50
- 229920006395 saturated elastomer Polymers 0.000 claims description 27
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 24
- 239000003921 oil Substances 0.000 claims description 23
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 125000003545 alkoxy group Chemical group 0.000 claims description 18
- 125000005113 hydroxyalkoxy group Chemical group 0.000 claims description 18
- 125000004122 cyclic group Chemical group 0.000 claims description 16
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 14
- 239000007762 w/o emulsion Substances 0.000 claims description 14
- 125000004043 oxo group Chemical group O=* 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
- 125000003277 amino group Chemical group 0.000 claims description 11
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 claims description 8
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 6
- 125000002252 acyl group Chemical group 0.000 claims description 4
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims description 2
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- YDNKGFDKKRUKPY-JHOUSYSJSA-N C16 ceramide Natural products CCCCCCCCCCCCCCCC(=O)N[C@@H](CO)[C@H](O)C=CCCCCCCCCCCCCC YDNKGFDKKRUKPY-JHOUSYSJSA-N 0.000 description 10
- CRJGESKKUOMBCT-VQTJNVASSA-N N-acetylsphinganine Chemical compound CCCCCCCCCCCCCCC[C@@H](O)[C@H](CO)NC(C)=O CRJGESKKUOMBCT-VQTJNVASSA-N 0.000 description 10
- ZVEQCJWYRWKARO-UHFFFAOYSA-N ceramide Natural products CCCCCCCCCCCCCCC(O)C(=O)NC(CO)C(O)C=CCCC=C(C)CCCCCCCCC ZVEQCJWYRWKARO-UHFFFAOYSA-N 0.000 description 10
- 150000001783 ceramides Chemical class 0.000 description 10
- VVGIYYKRAMHVLU-UHFFFAOYSA-N newbouldiamide Natural products CCCCCCCCCCCCCCCCCCCC(O)C(O)C(O)C(CO)NC(=O)CCCCCCCCCCCCCCCCC VVGIYYKRAMHVLU-UHFFFAOYSA-N 0.000 description 10
- 239000002537 cosmetic Substances 0.000 description 9
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- 239000003795 chemical substances by application Substances 0.000 description 6
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 5
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 5
- 235000020778 linoleic acid Nutrition 0.000 description 5
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 5
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- AERBNCYCJBRYDG-KSZLIROESA-N phytosphingosine Chemical compound CCCCCCCCCCCCCC[C@@H](O)[C@@H](O)[C@@H](N)CO AERBNCYCJBRYDG-KSZLIROESA-N 0.000 description 5
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 5
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- AERBNCYCJBRYDG-UHFFFAOYSA-N D-ribo-phytosphingosine Natural products CCCCCCCCCCCCCCC(O)C(O)C(N)CO AERBNCYCJBRYDG-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 229940033329 phytosphingosine Drugs 0.000 description 4
- 150000004671 saturated fatty acids Chemical class 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- ATGQXSBKTQANOH-UWVGARPKSA-N N-oleoylphytosphingosine Chemical compound CCCCCCCCCCCCCC[C@@H](O)[C@@H](O)[C@H](CO)NC(=O)CCCCCCC\C=C/CCCCCCCC ATGQXSBKTQANOH-UWVGARPKSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 235000012000 cholesterol Nutrition 0.000 description 3
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000002688 persistence Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
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- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 2
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- OSCJHTSDLYVCQC-UHFFFAOYSA-N 2-ethylhexyl 4-[[4-[4-(tert-butylcarbamoyl)anilino]-6-[4-(2-ethylhexoxycarbonyl)anilino]-1,3,5-triazin-2-yl]amino]benzoate Chemical compound C1=CC(C(=O)OCC(CC)CCCC)=CC=C1NC1=NC(NC=2C=CC(=CC=2)C(=O)NC(C)(C)C)=NC(NC=2C=CC(=CC=2)C(=O)OCC(CC)CCCC)=N1 OSCJHTSDLYVCQC-UHFFFAOYSA-N 0.000 description 2
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004166 Lanolin Substances 0.000 description 2
- BBAFBDLICMHBNU-MFZOPHKMSA-N N-(2-hydroxyoctadecanoyl)-4-hydroxysphinganine Chemical compound CCCCCCCCCCCCCCCCC(O)C(=O)N[C@@H](CO)[C@H](O)[C@H](O)CCCCCCCCCCCCCC BBAFBDLICMHBNU-MFZOPHKMSA-N 0.000 description 2
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Abstract
Description
本発明は、安定性に優れ、しかも使用感が良好な油中水型乳化組成物に関する。 The present invention relates to a water-in-oil emulsion composition having excellent stability and good usability.
油中水型乳化組成物は、皮膚への親和性が良く、また皮膚の表面に被膜を形成して水分の蒸散を防ぐことにより、皮膚を乾燥から保護したり、トリートメント効果を付与する等の特徴を有するため、広く化粧料に使用されている。特に、油性成分として粘度の高い油剤や固形の油剤を用いると、皮膚の保護効果を高めることができる反面、べたつきのある使用感を伴うという欠点が生じる。 The water-in-oil emulsion composition has good affinity to the skin, and forms a film on the surface of the skin to prevent the evaporation of moisture, thereby protecting the skin from drying and imparting a treatment effect, etc. Due to its characteristics, it is widely used in cosmetics. In particular, when an oily agent having a high viscosity or a solid oily agent is used as the oil component, the protective effect of the skin can be enhanced, but there is a drawback that it is accompanied by a sticky feeling of use.
一般に、油中水型乳化組成物の特性を具備したまま、さっぱりとした感触を得るためには、水分量を増やしたり、油剤としてシリコーン油を用いたり、さっぱりとした使用感を呈する粉体を用いることなどが行なわれている。しかしながら、特に粘度の高い油剤や固体脂を含む油性成分を乳化する場合、乳化剤として使用できる界面活性剤が限られたり、また界面活性剤を多量に配合する必要が生じ、べたつき感が増えるなどの問題がある。更に、このような油剤は、水分量を増やしたり、シリコーン油を用いる等、さっぱりとした使用感を得るような乳化組成物の調整を困難にしている。 In general, in order to obtain a refreshing feel while maintaining the characteristics of a water-in-oil emulsion composition, the amount of water is increased, silicone oil is used as an oil agent, or a powder that exhibits a refreshing feeling of use. It has been used. However, when emulsifying oily components including highly viscous oils and solid fats in particular, the surfactants that can be used as emulsifiers are limited, and it is necessary to add a large amount of surfactants, resulting in increased stickiness. There's a problem. Furthermore, such an oil agent makes it difficult to adjust the emulsified composition so as to obtain a refreshing feeling of use, such as increasing the amount of water or using silicone oil.
そこで、水の多い系で使用感が良く安定な油中水型乳化組成物を得るために、さまざまな検討が行なわれている。例えば、特許文献１には、スフィンゴシン類縁体を脂肪酸によりカチオン化し、乳化剤として用いる技術が記載されている。
しかしながら、ここで得られる乳化物は、使用感は良好であるものの、温度変化の激しい場合に不安定になることがあり、安定性の面で、十分満足できるものではなかった。
However, although the emulsion obtained here has good usability, it may become unstable when the temperature changes drastically, and is not sufficiently satisfactory in terms of stability.
本発明の目的は、温度変化の激しい場合にも安定性に優れ、しかも使用感が良好な油中水型乳化組成物を提供することにある。 An object of the present invention is to provide a water-in-oil type emulsion composition which is excellent in stability even when the temperature change is severe and has a good feeling in use.
本発明者は、皮膚に本来存在するスフィンゴシン類と特定の脂肪酸で形成された塩を乳化剤として用いるとともに、更に架橋型ポリエーテル変性シリコーンを加えることにより、過酷な温度変化が生じた場合でも経時安定性に優れ、べたつきや肌への違和感が少なく、使用感が良好な油中水型乳化組成物が得られることを見出した。 The present inventor uses a salt formed of sphingosines originally present in the skin and a specific fatty acid as an emulsifier, and is further stable over time even when severe temperature changes occur by adding a cross-linked polyether-modified silicone. It was found that a water-in-oil emulsified composition having excellent properties, less stickiness and uncomfortable feeling on the skin, and good usability was obtained.
本発明は、次の成分（Ａ）〜（Ｅ）：
（Ａ）一般式（１）で表わされるスフィンゴシン類
The present invention includes the following components (A) to (E):
(A) Sphingosines represented by the general formula (1)
（式中、Ｒ1はヒドロキシル基、カルボニル基又はアミノ基が置換していてもよい、炭素数４〜３０の直鎖、分岐鎖又は環状の飽和又は不飽和の炭化水素基を示し；Ｙはメチレン基、メチン基又は酸素原子を示し；Ｘ1、Ｘ2、及びＸ3は各々独立して水素原子、ヒドロキシル基又はアセトキシ基を示し、Ｘ4は水素原子、アセチル基又はグリセリル基を示すか、隣接する酸素原子と一緒になってオキソ基を形成し（但し、Ｙがメチン基のとき、Ｘ1とＸ2のいずれか一方が水素原子であり、他方は存在しない。Ｘ4がオキソ基を形成するとき、Ｘ3は存在しない。）；Ｒ2及びＲ3は各々独立して水素原子、ヒドロキシル基、ヒドロキシメチル基又はアセトキシメチル基を示し；ａ個のＲは各々独立して水素原子又はアミジノ基であるか、ヒドロキシル基、ヒドロキシアルコキシ基、アルコキシ基及びアセトキシ基から選ばれる置換基を有していてもよい総炭素数１〜８の直鎖又は分岐鎖の飽和又は不飽和の炭化水素基を示し；ａは２又は３の数を示し；破線部は不飽和結合であってもよいことを示す）、
（Ｂ）炭素数６〜３０の脂肪酸、
（Ｃ）架橋型ポリエーテル変性シリコーン、
（Ｄ）シリコーン油、
（Ｅ）シリコーン油以外の油性成分
を含有する油中水型乳化組成物を提供するものである。
(In the formula, R 1 represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 4 to 30 carbon atoms, which may be substituted by a hydroxyl group, a carbonyl group or an amino group; A methylene group, a methine group or an oxygen atom; each of X 1 , X 2 and X 3 independently represents a hydrogen atom, a hydroxyl group or an acetoxy group, and X 4 represents a hydrogen atom, an acetyl group or a glyceryl group Together with an adjacent oxygen atom to form an oxo group (provided that when Y is a methine group, one of X 1 and X 2 is a hydrogen atom and the other does not exist. X 4 is an oxo group) X 3 is not present when R.sup.3 is present.); R 2 and R 3 each independently represents a hydrogen atom, a hydroxyl group, a hydroxymethyl group or an acetoxymethyl group; a R each independently represents a hydrogen atom. Or an amidino group or hydro A linear or branched saturated or unsaturated hydrocarbon group having 1 to 8 carbon atoms which may have a substituent selected from a sil group, a hydroxyalkoxy group, an alkoxy group and an acetoxy group; 2 or 3; the broken line indicates an unsaturated bond)
(B) a fatty acid having 6 to 30 carbon atoms,
(C) a cross-linked polyether-modified silicone,
(D) silicone oil,
(E) A water-in-oil emulsion composition containing an oil component other than silicone oil is provided.
本発明の油中水型乳化組成物は、激しい温度変化が生じた場合でも安定性に優れ、使用感も良好である。 The water-in-oil emulsion composition of the present invention is excellent in stability even when a drastic temperature change occurs, and the usability is also good.
本発明で用いる成分（Ａ）のスフィンゴシン類は、前記一般式（１）で表わされるものである。
式中、Ｒ1は、ヒドロキシル基、カルボニル基又はアミノ基が置換していてもよい、炭素数４〜３０、好ましくはヒドロキシル基が置換していてもよい炭素数７〜２２の直鎖、分岐鎖又は環状の飽和又は不飽和の炭化水素基である。特に、炭素数１０〜２０の直鎖又は分岐鎖のアルキル基、Ｙ側末端にヒドロキシル基を持つ炭素数１０〜２０の直鎖又は分岐鎖のアルキル基で、分岐鎖アルキル基の場合は分岐鎖がメチル分岐のもの等が好ましい。具体的には、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、１−ヒドロキシトリデシル基、１−ヒドロキシペンタデシル基、イソヘキサデシル基、イソステアリル基が好ましい。
The sphingosine component (A) used in the present invention is represented by the general formula (1).
In the formula, R 1 is a straight chain or branched chain having 4 to 30 carbon atoms, preferably 7 to 22 carbon atoms which may be substituted by a hydroxyl group, which may be substituted by a hydroxyl group, a carbonyl group or an amino group. It is a chain or cyclic saturated or unsaturated hydrocarbon group. In particular, a linear or branched alkyl group having 10 to 20 carbon atoms, a linear or branched alkyl group having 10 to 20 carbon atoms having a hydroxyl group at the Y-side end, and a branched chain in the case of a branched alkyl group. Are preferably methyl-branched. Specifically, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a 1-hydroxytridecyl group, a 1-hydroxypentadecyl group, an isohexadecyl group, and an isostearyl group are preferable.
Ｙはメチレン基（ＣＨ2）、メチン基（ＣＨ）又は酸素原子のいずれかを示す。
Ｘ1、Ｘ2、及びＸ3は、各々独立して水素原子、ヒドロキシル基又はアセトキシ基を示し、Ｘ4は水素原子、アセチル基、グリセリル基、隣接する酸素原子と一緒になってオキソ基を形成する置換基を示す。特に、Ｘ1、Ｘ2、及びＸ3のうち０〜１個がヒドロキシル基で、残余が水素原子、及びＸ4が水素原子であるものが好ましい。なお、Ｙがメチン基のとき、Ｘ1とＸ2のいずれか一方のみが水素原子であり、他方は存在しない。また、Ｘ4がオキソ基を形成するとき、Ｘ3は存在しない。
Y represents a methylene group (CH 2 ), a methine group (CH), or an oxygen atom.
X 1 , X 2 , and X 3 each independently represent a hydrogen atom, a hydroxyl group, or an acetoxy group, and X 4 represents an oxo group together with a hydrogen atom, an acetyl group, a glyceryl group, or an adjacent oxygen atom. The substituent to be formed is shown. In particular, it is preferable that 0 to 1 of X 1 , X 2 , and X 3 are hydroxyl groups, the remainder is a hydrogen atom, and X 4 is a hydrogen atom. When Y is a methine group, only one of X 1 and X 2 is a hydrogen atom, and the other does not exist. Also, when X 4 forms an oxo group, X 3 does not exist.
Ｒ2及びＲ3は各々独立して水素原子、ヒドロキシル基、ヒドロキシメチル基又はアセトキシメチル基を示し、特にＲ3は水素原子であることが好ましい。 R 2 and R 3 each independently represent a hydrogen atom, a hydroxyl group, a hydroxymethyl group or an acetoxymethyl group, and R 3 is particularly preferably a hydrogen atom.
また、ａは２又は３の数を示し、ａが２のときＲはＲ4及びＲ5を示し、ａが３のときＲはＲ4、Ｒ5及びＲ6を示す。 A represents a number of 2 or 3, R represents R 4 and R 5 when a is 2, and R represents R 4 , R 5 and R 6 when a is 3.
Ｒ4、Ｒ5及びＲ6は、各々独立して水素原子又はアミジノ基であるか、ヒドロキシル基、ヒドロキシアルコキシ基、アルコキシ基及びアセトキシ基から選ばれる置換基を有していてもよい総炭素数１〜８の直鎖又は分岐鎖の飽和又は不飽和の炭化水素基を示す。ここで炭化水素基に置換し得るヒドロキシアルコキシ基としては炭素数１〜７の直鎖又は分岐鎖のヒドロキシアルコキシ基が好ましい。またアルコキシ基としては炭素数１〜７の直鎖又は分岐鎖のアルコキシ基が好ましい。Ｒ4、Ｒ5及びＲ6としては、例えば水素原子；メチル、エチル、プロピル、２−エチルへキシル、イソプロピル等の直鎖又は分岐鎖アルキル基；ビニル、アリル等のアルケニル基；アミジノ基；ヒドロキシメチル、２−ヒドロキシエチル、１，１−ジメチル−２−ヒドロキシエチル、２−ヒドロキシプロピル、２，３−ジヒドロキシプロピル、２−ヒドロキシ−３−メトキシプロピル、２，３，４，５，６−ペンタヒドロキシへキシル、１，１−ビス（ヒドロキシメチル）エチル、２−（２−ヒドロキシエトキシ）エチル、２−メトキシエチル、１−メチル−２−ヒドロキシエチル、３−ヒドロキシプロピル、３−メトキシプロピル、１，１−ビス（ヒドロキシメチル）−２−ヒドロキシエチル等のヒドロキシル基、ヒドロキシアルコキシ基及びアルコキシ基から選ばれる１〜６個が置換した総炭素数１〜８の炭化水素基が挙げられる。 R 4 , R 5 and R 6 are each independently a hydrogen atom or an amidino group, or may have a substituent selected from a hydroxyl group, a hydroxyalkoxy group, an alkoxy group and an acetoxy group. 1 to 8 linear or branched saturated or unsaturated hydrocarbon groups are shown. Here, the hydroxyalkoxy group that can be substituted with a hydrocarbon group is preferably a linear or branched hydroxyalkoxy group having 1 to 7 carbon atoms. Moreover, as an alkoxy group, a C1-C7 linear or branched alkoxy group is preferable. Examples of R 4 , R 5 and R 6 include a hydrogen atom; a linear or branched alkyl group such as methyl, ethyl, propyl, 2-ethylhexyl and isopropyl; an alkenyl group such as vinyl and allyl; an amidino group; Methyl, 2-hydroxyethyl, 1,1-dimethyl-2-hydroxyethyl, 2-hydroxypropyl, 2,3-dihydroxypropyl, 2-hydroxy-3-methoxypropyl, 2,3,4,5,6-penta Hydroxyhexyl, 1,1-bis (hydroxymethyl) ethyl, 2- (2-hydroxyethoxy) ethyl, 2-methoxyethyl, 1-methyl-2-hydroxyethyl, 3-hydroxypropyl, 3-methoxypropyl, 1 , 1-bis (hydroxymethyl) -2-hydroxyethyl and other hydroxyl groups, hydroxyalkoxy groups And a hydrocarbon group having 1 to 8 carbon atoms substituted by 1 to 6 selected from alkoxy groups.
特に水素原子、又はメチル基、２−ヒドロキシエチル、１，１−ジメチル−２−ヒドロキシエチル、１，１−ビス（ヒドロキシメチル）エチル、２−（２−ヒドロキシエトキシ）エチル等のヒドロキシル基及びヒドロキシアルコキシ基から選ばれる１〜３個が置換していてもよいアルキル基が好ましい。 In particular, hydrogen atom or hydroxyl group such as methyl group, 2-hydroxyethyl, 1,1-dimethyl-2-hydroxyethyl, 1,1-bis (hydroxymethyl) ethyl, 2- (2-hydroxyethoxy) ethyl and hydroxy An alkyl group that may be substituted by 1 to 3 groups selected from alkoxy groups is preferred.
一般式（１）で表わされるスフィンゴシン類としては、次の一般式（２）で表わされる天然のスフィンゴシン類又は同構造の合成物、及びその誘導体（以下、天然型スフィンゴシンと記載する。）又は一般式（３）で表わされるスフィンゴシン構造を有する擬似型スフィンゴシン類（以下、擬似型スフィンゴシンと記載する。）が好ましい。
（Ｉ）一般式（２）で表わされる天然型スフィンゴシン。
Examples of the sphingosine represented by the general formula (1) include natural sphingosine represented by the following general formula (2) or a synthetic product having the same structure, and derivatives thereof (hereinafter referred to as natural sphingosine) or general. Pseudo-type sphingosines having a sphingosine structure represented by formula (3) (hereinafter referred to as pseudo-type sphingosine) are preferable.
(I) A natural sphingosine represented by the general formula (2).
（式中、Ｒ7はヒドロキシル基が置換していてもよい炭素数７〜１９の直鎖、分岐鎖又は環状の飽和又は不飽和の炭化水素基を示し；Ｙ1はメチレン基又はメチン基を示し；Ｘ5、Ｘ6及びＸ7は各々独立して水素原子、ヒドロキシル基又はアセトキシ基を示し、Ｘ8は水素原子を示すか、隣接する酸素原子と一緒になってオキソ基を形成し（但し、Ｙ1がメチン基のとき、Ｘ5とＸ6のいずれか一方が水素原子を示し、他方は存在しない。Ｘ8がオキソ基を形成するとき、Ｘ7は存在しない。）；Ｒ8はヒドロキシメチル基又はアセトキシメチル基を示し；ａ個のＲ1は各々独立して水素原子又はアミジノ基であるか、ヒドロキシル基、ヒドロキシアルコキシ基、アルコキシ基及びアセトキシ基から選ばれる置換基を有していてもよい総炭素数１〜４の直鎖又は分岐鎖の飽和又は不飽和炭化水素基を示し；ａは２又は３の数を示し；破線部は不飽和結合があってもよいことを示す） (In the formula, R 7 represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 7 to 19 carbon atoms which may be substituted by a hydroxyl group; Y 1 represents a methylene group or a methine group; X 5 , X 6 and X 7 each independently represent a hydrogen atom, a hydroxyl group or an acetoxy group, and X 8 represents a hydrogen atom or together with an adjacent oxygen atom, forms an oxo group ( However, when Y 1 is a methine group, one of X 5 and X 6 represents a hydrogen atom and the other does not exist.When X 8 forms an oxo group, X 7 does not exist.); R 8 Represents a hydroxymethyl group or an acetoxymethyl group; a R 1 s are each independently a hydrogen atom or an amidino group, or have a substituent selected from a hydroxyl group, a hydroxyalkoxy group, an alkoxy group and an acetoxy group 1 to 1 carbon total Of a linear or branched, saturated or unsaturated hydrocarbon group; a represents a number of 2 or 3; indicates that the broken line may be an unsaturated bond)
ここでＲ7としては、炭素数７〜１９の直鎖、分岐鎖又は環状の飽和又は不飽和の炭化水素基が好ましく、特に炭素数１３〜１５の直鎖の飽和又は不飽和の炭化水素基が好ましい。ａは２が好ましく、Ｒ1は各々独立して水素原子、又は炭素数１〜４の直鎖もしくは分岐のアルキル基が好ましい。 R 7 is preferably a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 7 to 19 carbon atoms, particularly a linear saturated or unsaturated hydrocarbon group having 13 to 15 carbon atoms. Is preferred. a is preferably 2, and each R 1 is independently a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.
一般式（２）で表わされる天然型スフィンゴシンとしては、具体的には、天然のスフィンゴシン、ジヒドロスフィンゴシン、フィトスフィンゴシン、スフィンガジエニン、デヒドロスフィンゴシン、デヒドロフィトスフィンゴシン、及びこれらのＮ−アルキル体（例えばＮ−メチル体）等が挙げられる。
これらのスフィンゴシンは天然型（Ｄ（＋）体）の光学活性体を用いても、非天然型（Ｌ（−）体）の光学活性体を用いても、更に天然型と非天然型の混合物を用いてもよい。上記化合物の相対立体配置は、天然型の立体配置のものでも、それ以外の非天然型の立体配置のものでも良く、また、これらの混合物によるものでもよい。
特に、PHYTOSPHINGOSINE(INCI名；8th Edition)及び次式で表わされるものが好ましい。
Specific examples of the natural sphingosine represented by the general formula (2) include natural sphingosine, dihydrosphingosine, phytosphingosine, sphingadienin, dehydrosphingosine, dehydrophytosphingosine, and N-alkyl derivatives thereof (for example, N-methyl form) and the like.
These sphingosines may be either natural (D (+)) optically active or non-natural (L (-)) optically active, or a mixture of natural and non-natural types. May be used. The relative configuration of the above compound may be a natural configuration, a non-natural configuration other than that, or a mixture thereof.
In particular, PHYTOSPHINGOSINE (INCI name: 8th Edition) and the following formula are preferable.
これらは、天然からの抽出物及び合成物のいずれでもよく、市販のものを用いることができる。
天然型スフィンゴシンの市販のものとしては、例えば、D-Sphingosine(4-Sphingenine) (SIGMA-ALDRICH社)、DS-phytosphingosine (DOOSAN社)、phytosphingosine（コスモファーム社）が挙げられる。
These may be any of natural extracts and synthetic products, and commercially available products can be used.
Examples of commercially available natural sphingosine include D-Sphingosine (4-Sphingenine) (SIGMA-ALDRICH), DS-phytosphingosine (DOOSAN), and phytosphingosine (Cosmo Farm).
（II）一般式（３）で表わされる擬似型スフィンゴシン。 (II) A pseudo-type sphingosine represented by the general formula (3).
（式中、Ｒ9はヒドロキシル基が置換していてもよい炭素数１０〜２２の直鎖、分岐鎖又は環状の飽和又は不飽和の炭化水素基を示し；Ｘ9は水素原子、アセチル基又はグリセリル基を示し；ａ個のＲ2は各々独立して水素原子又はアミジノ基を示すか、ヒドロキシル基、ヒドロキシアルコキシ基、アルコキシ基及びアセトキシ基から選ばれる置換基を有していてもよい総炭素数１〜８の直鎖又は分岐鎖の飽和又は不飽和の炭化水素基を示し、ａは２又は３の数を示す） (In the formula, R 9 represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 10 to 22 carbon atoms which may be substituted with a hydroxyl group; X 9 represents a hydrogen atom, an acetyl group or A glyceryl group; a R 2 each independently represents a hydrogen atom or an amidino group, or a total carbon which may have a substituent selected from a hydroxyl group, a hydroxyalkoxy group, an alkoxy group and an acetoxy group A linear or branched saturated or unsaturated hydrocarbon group having a number of 1 to 8; a represents a number of 2 or 3)
ここでＲ9としては、炭素数１４〜２０のイソ分岐アルキル基が好ましく、特にイソステアリル基が好ましい。イソステアリル基は、動植物油由来の脂肪酸を用いたダイマー酸製造時の副生成物由来のイソステアルアルコールを原料油として得られるイソステアリル基がもっとも好ましい。
また、ａが２のときＲ2はＲ10及びＲ11を示し、ａが３のときＲ2はＲ10、Ｒ11及びＲ12である。
Here, as R 9 , an iso-branched alkyl group having 14 to 20 carbon atoms is preferable, and an isostearyl group is particularly preferable. The isostearyl group is most preferably an isostearyl group obtained by using, as a raw material oil, an isosteal alcohol derived from a by-product during production of a dimer acid using a fatty acid derived from an animal or vegetable oil.
When a is 2, R 2 represents R 10 and R 11 , and when a is 3, R 2 is R 10 , R 11, and R 12 .
Ｒ10、Ｒ11及びＲ12は、例えば水素原子；メチル、エチル、プロピル、２−エチルへキシル、イソプロピル等の直鎖又は分岐鎖のアルキル基；ビニル、アリル等のアルケニル基；アミジノ基；ヒドロキシメチル、２−ヒドロキシエチル、１，１−ジメチル−２−ヒドロキシエチル、２−ヒドロキシプロピル、２，３−ジヒドロキシプロピル、２−ヒドロキシ−３−メトキシプロピル、２，３，４，５，６−ペンタヒドロキシへキシル、１，１−ビス（ヒドロキシメチル）エチル、２−（２−ヒドロキシエトキシ）エチル、２−メトキシエチル、１−メチル−２−ヒドロキシエチル、３−ヒドロキシプロピル、３−メトキシプロピル、１，１−ビス（ヒドロキシメチル）−２−ヒドロキシエチル等のヒドロキシル基、ヒドロキシアルコキシ基及びアルコキシ基から選ばれる置換基を有する総炭素数１〜８のアルキル基が挙げられる。
特に、Ｒ10及びＲ11のいずれか１つが水素原子で、他方が２−ヒドロキシエチル、１，１−ジメチル−２−ヒドロキシエチル、１，１−ビス（ヒドロキシメチル）エチル、２−（２−ヒドロキシエトキシ）エチルである２級アミンが好ましい。
R 10 , R 11 and R 12 are, for example, a hydrogen atom; a linear or branched alkyl group such as methyl, ethyl, propyl, 2-ethylhexyl and isopropyl; an alkenyl group such as vinyl and allyl; an amidino group; Methyl, 2-hydroxyethyl, 1,1-dimethyl-2-hydroxyethyl, 2-hydroxypropyl, 2,3-dihydroxypropyl, 2-hydroxy-3-methoxypropyl, 2,3,4,5,6-penta Hydroxyhexyl, 1,1-bis (hydroxymethyl) ethyl, 2- (2-hydroxyethoxy) ethyl, 2-methoxyethyl, 1-methyl-2-hydroxyethyl, 3-hydroxypropyl, 3-methoxypropyl, 1 , 1-bis (hydroxymethyl) -2-hydroxyethyl and the like hydroxyl groups, hydroxyalkoxy groups and the like And a C1-C8 alkyl group having a substituent selected from an alkoxy group.
In particular, one of R 10 and R 11 is a hydrogen atom and the other is 2-hydroxyethyl, 1,1-dimethyl-2-hydroxyethyl, 1,1-bis (hydroxymethyl) ethyl, 2- (2- Secondary amines which are hydroxyethoxy) ethyl are preferred.
擬似型スフィンゴシンとしては、Ｒ9がイソステアリル基、Ｘ9が水素原子で、Ｒ10が水素原子、Ｒ11が２−ヒドロキシエチル基、１，１−ビス（ヒドロキシメチル）エチル基、１，１−ジメチル−２−ヒドロキシエチル基、又は２−（２−ヒドロキシエトキシ）エチル基等のヒドロキシル基及びヒドロキシアルコキシ基から選ばれる１〜３個が置換したアルキル基であるものが好ましい。
擬似型スフィンゴシンの具体例としては、次の擬似型スフィンゴシン（ｉ）〜（iv）が挙げられる。
As pseudo-type sphingosine, R 9 is an isostearyl group, X 9 is a hydrogen atom, R 10 is a hydrogen atom, R 11 is a 2-hydroxyethyl group, 1,1-bis (hydroxymethyl) ethyl group, 1,1 -It is preferable that 1-3 substituted by hydroxyl groups and hydroxyalkoxy groups such as dimethyl-2-hydroxyethyl group or 2- (2-hydroxyethoxy) ethyl group are substituted alkyl groups.
Specific examples of the pseudo-sphingosine include the following pseudo-sphingosines (i) to (iv).
成分（Ａ）は２種以上を併用してもよい。本発明の組成物中の成分（Ａ）の含有量は、０．００１〜１０質量％、特に０．００５〜３質量％、更に０．０１〜３質量％であるのが好ましい。 Two or more components (A) may be used in combination. The content of the component (A) in the composition of the present invention is preferably 0.001 to 10% by mass, particularly 0.005 to 3% by mass, and more preferably 0.01 to 3% by mass.
本発明で用いる成分（Ｂ）の脂肪酸は、スフィンゴシン類のアミノ基と酸−塩基の中和反応により塩を形成し、スフィンゴシン類がカチオン化され、活性剤的な働きをするようになると考えられる。スフィンゴシン類の塩は、例えば、通常化合物の構造を特定するために用いられる、赤外吸収分光法やプロトン核磁気共鳴分光法等を用いて確認することができる。
また、脂肪酸の鎖長は乳化する油性成分の種類、乳化組成物の粘度により選択される。例えば、比較的粘度が低い乳液状の乳化組成物の場合には鎖長の短いものを、粘度が高くクリーム状の乳化組成物の場合には、鎖長の長いものを用いることにより、安定な乳化状態が得られる。
It is considered that the fatty acid of component (B) used in the present invention forms a salt by the neutralization reaction between the amino group of sphingosines and acid-base, and the sphingosines are cationized to act as activators. . The salt of sphingosines can be confirmed using, for example, infrared absorption spectroscopy or proton nuclear magnetic resonance spectroscopy, which is usually used for specifying the structure of a compound.
The chain length of the fatty acid is selected depending on the type of oil component to be emulsified and the viscosity of the emulsified composition. For example, in the case of an emulsion composition having a relatively low viscosity, an emulsion composition having a short chain length is used. In the case of a creamy emulsion composition having a high viscosity, a composition having a long chain length is used. An emulsified state is obtained.
成分（Ｂ）の脂肪酸は、炭素数６〜３０であることが必要であり、乳化組成物の安定性や使用感の点から、特に炭素数８〜２２の飽和又は不飽和の脂肪酸が好ましい。炭素数６〜３０のものであると、複数の油性成分の混合型であっても、安定な油中水型乳化組成物を得ることができる。具体的には、カプロン酸、カプリル酸、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、エイコサン酸、ドコサン酸等の飽和脂肪酸；オレイン酸、リノール酸、リノレン酸、リシノレン酸、エイコサペンタエン酸、ドコサヘキサエン酸等の不飽和脂肪酸が含まれる。
これらのうち、炭素数１２〜１８の脂肪酸、特にミリスチン酸、パルミチン酸、ステアリン酸、イソステアリン酸、オレイン酸が、良好な使用感の点から好ましい。
The fatty acid of component (B) needs to have 6 to 30 carbon atoms, and saturated or unsaturated fatty acids having 8 to 22 carbon atoms are particularly preferable from the viewpoint of the stability and usability of the emulsion composition. A stable water-in-oil emulsified composition can be obtained even if it is a mixed type of a plurality of oily components having 6 to 30 carbon atoms. Specifically, saturated fatty acids such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, eicosanoic acid, docosanoic acid; oleic acid, linoleic acid, linolenic acid, ricinolenic acid, eicosapentaene Unsaturated fatty acids such as acid and docosahexaenoic acid are included.
Of these, fatty acids having 12 to 18 carbon atoms, in particular myristic acid, palmitic acid, stearic acid, isostearic acid, and oleic acid are preferable from the viewpoint of a good feeling of use.
成分（Ｂ）の脂肪酸は、２種以上を併用してもよい。本発明の組成物中の成分（Ｂ）の含有量は、０．００１〜１０質量％、特に０．００５〜６質量％、更に０．０１〜３質量％であるのが好ましい。
また、成分（Ｂ）は、成分（Ａ）のスフィンゴシン類のアミン基部分をカチオン化するために有効であり、成分（Ａ）１モルに対して０．３モル以上、特に０．３〜５モル、更に０．５〜３モル含有するのが、乳化組成物の安定性向上のために好ましい。
Two or more types of fatty acids as the component (B) may be used in combination. The content of the component (B) in the composition of the present invention is preferably 0.001 to 10% by mass, particularly 0.005 to 6% by mass, and more preferably 0.01 to 3% by mass.
The component (B) is effective for cationizing the amine group part of the sphingosines of the component (A), and is 0.3 mol or more, particularly 0.3 to 5 mol per 1 mol of the component (A). It is preferable to contain 0.5 mol to 3 mol in order to improve the stability of the emulsion composition.
本発明で用いる成分（Ｃ）の架橋型ポリエーテル変性シリコーンとしては、通常化粧料に用いられるものを使用することができる。例えば、次の一般式（４）で表されるものが挙げられる。 As the crosslinked polyether-modified silicone of component (C) used in the present invention, those usually used in cosmetics can be used. For example, what is represented by following General formula (4) is mentioned.
（式中、各Ｒはメチル基又はフェニル基を示し、各Ｒ'は水素原子、炭素数１〜３０のアルキル基又はアシル基を示し、各Ｒ"は炭素数１〜３０のアルキル基若しくはアシル基、又はケイ素原子１〜３０のシロキサン基を示し、ｄは１〜２０の数を示し、ｅ及びｆは０〜２００の数を示し、ｇは０〜３０の数を示し、ｈは１〜１００の数を示し、ｉは１０〜２０００の数を示し、ｊは１〜１０００の数を示し、ｋは１〜１０００の数を示す）
好ましくは、一般式（４）において、ｇは０〜１５、ｈは１〜４０、ｉは1０〜２００、ｊは１〜５０、ｋは１〜５０である。
このような架橋型ポリエーテル変性シリコーンとしては、例えば、ＫＳＧ２１０、ＫＳＧ３１０、ＫＳＧ３２０、ＫＳＧ３３０、ＫＳＧ３４０（以上、信越化学工業社製）等の市販品を使用することができる。
(In the formula, each R represents a methyl group or a phenyl group, each R ′ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an acyl group, and each R ″ represents an alkyl group or acyl having 1 to 30 carbon atoms. A group, or a siloxane group having 1 to 30 silicon atoms, d represents a number of 1 to 20, e and f represent a number of 0 to 200, g represents a number of 0 to 30, and h represents a number of 1 to 20. 100 represents a number, i represents a number from 10 to 2000, j represents a number from 1 to 1000, and k represents a number from 1 to 1000)
Preferably, in General formula (4), g is 0-15, h is 1-40, i is 10-200, j is 1-50, k is 1-50.
As such a crosslinked polyether-modified silicone, for example, commercially available products such as KSG210, KSG310, KSG320, KSG330, KSG340 (and above, manufactured by Shin-Etsu Chemical Co., Ltd.) can be used.
成分（Ｃ）の架橋型ポリエーテル変性シリコーンは、２種以上を併用してもよい。本発明の組成物中の成分（Ｃ）の含有量は、０．０１〜３０質量％、特に０．１〜２０質量％であるのが、乳化安定性、使用感の点で好ましい。
本発明においては、特に、成分（Ｃ）を含有することで、化粧料の残留性が高まり、保湿感等の効果感が高くなる。また、乳化安定性にも効果があり、より過酷な環境下、例えば輸出時の船倉において赤道通過時に６０℃を超えるような場合や、また、北海道などの寒冷地における冬季の倉庫などでの保存でも、十分な乳化安定性を得ることが可能である。
Two or more kinds of the crosslinked polyether-modified silicone of component (C) may be used in combination. The content of the component (C) in the composition of the present invention is preferably 0.01 to 30% by mass, particularly preferably 0.1 to 20% by mass, from the viewpoint of emulsion stability and usability.
In the present invention, in particular, by containing the component (C), the persistence of the cosmetic is increased, and the effect such as a moisturizing feeling is enhanced. It also has an effect on emulsification stability and is stored in a harsher environment, for example, when it exceeds 60 ° C when passing through the equator in a warehouse during export, or in a winter warehouse in a cold region such as Hokkaido. However, sufficient emulsion stability can be obtained.
本発明で用いる成分（Ｄ）のシリコーン油としては、通常化粧料に用いられる固体、半固体又は液状のシリコーン油を使用することができる。シリコーン油は乳化組成物中で連続相を形成するものであり、塗布時の使用感を向上させることができる。 As the silicone oil of component (D) used in the present invention, a solid, semi-solid or liquid silicone oil usually used in cosmetics can be used. Silicone oil forms a continuous phase in the emulsified composition, and can improve the feeling during use.
かかるシリコーン油としては、例えば、ジメチルポリシロキサン、ジメチルシクロポリシロキサン、メチルフェニルポリシロキサン、メチルハイドロジェンポリシロキサン、高級アルコール変性オルガノポリシロキサン等が挙げられ、特にジメチルポリシロキサン、ジメチルシクロポリシロキサンが好ましい。 Examples of such silicone oil include dimethylpolysiloxane, dimethylcyclopolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, higher alcohol-modified organopolysiloxane, etc., and dimethylpolysiloxane and dimethylcyclopolysiloxane are particularly preferable. .
成分（Ｄ）のシリコーン油は、２種以上を併用してもよい。本発明の組成物中の成分（Ｄ）の含有量は、１〜４０質量％、特に５〜２５質量％であるのが、安定性と使用感の点で好ましい。 Two or more silicone oils of component (D) may be used in combination. The content of the component (D) in the composition of the present invention is preferably 1 to 40% by mass, particularly 5 to 25% by mass, from the viewpoint of stability and usability.
また、成分（Ｃ）と成分（Ｄ）の含有比率（質量比）は、（Ｃ）／（Ｄ）＝１／１００〜１／１、特に１／５０〜１／２、更に１／２０〜１／２であるのが、安定性及び使用感の点から好ましい。 The content ratio (mass ratio) of the component (C) and the component (D) is (C) / (D) = 1/100 to 1/1, particularly 1/50 to 1/2, and further 1/20. A value of 1/2 is preferable from the viewpoints of stability and usability.
本発明で用いる成分（Ｅ）の油性成分は、前記（Ｄ）シリコーン油以外のもので、通常化粧料に使用される、２５℃で固体、半固体又は２５℃で液状の、合成及び天然由来の油性成分を含むことができる。油性成分は、乳化組成物中で連続相を形成するものであり、経時的な乳化安定性の点から、非極性の液状油を主成分とするのが好ましい。 The oily component of component (E) used in the present invention is other than the above (D) silicone oil, and is usually used in cosmetics. Solid at 25 ° C, semisolid or liquid at 25 ° C, synthetic and natural origin Of oily components. The oil component forms a continuous phase in the emulsion composition, and it is preferable that non-polar liquid oil is a main component from the viewpoint of emulsion stability over time.
非極性の液状油（２５℃）としては、例えば流動パラフィン、スクワラン等の炭化水素油；フルオロポリエーテル、パーフルオロアルキルエーテルシリコーン等のフッ素油などが挙げられる。非極性油の含有量は、成分（Ｅ）全体の５０質量％以上、特に７０質量％以上であるのが好ましい。 Examples of the nonpolar liquid oil (25 ° C.) include hydrocarbon oils such as liquid paraffin and squalane; fluorine oils such as fluoropolyether and perfluoroalkylether silicone. The content of the nonpolar oil is preferably 50% by mass or more, particularly 70% by mass or more, based on the entire component (E).
非極性油以外の液状の油性成分としては、例えばリンゴ酸ジイソステアリル、乳酸オクチルドデシル、イソノナン酸イソトリデシル、イソステアリン酸イソプロピル、ミリスチン酸オクチルドデシル等の脂肪酸エステル；ジカプリン酸ネオペンチルグリコール等の脂肪酸とアルコールとからなるエステル油；アミノ酸誘導体；ホホバ油等の植物油；液状ラノリン等の動物油等のエステル油などが挙げられる。 Examples of liquid oil components other than non-polar oils include fatty acid esters such as diisostearyl malate, octyldodecyl lactate, isotridecyl isononanoate, isopropyl isostearate, octyldodecyl myristate; fatty acids such as neopentyl glycol dicaprate and alcohol And ester oils such as: amino acid derivatives; vegetable oils such as jojoba oil; and ester oils such as animal oils such as liquid lanolin.
２５℃で固体又は半固体の油性成分としては、例えばホホバワックス等の植物油；ワセリン、ラノリン、セレシン、マイクロクリスタリンワックス、カルナウバロウ、キャンデリラロウ等のワックス；セラミド及びその誘導体、コレステロール及びその誘導体等の細胞間脂質に分類されるものなどが挙げられる。 Examples of oily components that are solid or semi-solid at 25 ° C. include vegetable oils such as jojoba wax; waxes such as petrolatum, lanolin, ceresin, microcrystalline wax, carnauba wax, and candelilla wax; ceramide and derivatives thereof, cholesterol and derivatives thereof, etc. Examples include those classified as intercellular lipids.
本発明においては、特に乳化組成物としての使用感、保湿効果の向上の点から、油性成分として、セラミド及びその誘導体、コレステロール及びその誘導体等の細胞間脂質を含むことが好ましく、特にセラミド及びその誘導体を含むことが好ましい。セラミド及びその誘導体としては、一般式（５）で表わされるセラミド類を含むことが好ましい。 In the present invention, particularly from the viewpoint of improving the feeling of use as an emulsified composition and the moisturizing effect, it is preferable that the oily component contains intercellular lipids such as ceramide and its derivatives, cholesterol and its derivatives, in particular, ceramide and its It is preferable to include a derivative. As ceramide and its derivatives, it is preferable to contain ceramides represented by the general formula (5).
（式中、Ｒ16はヒドロキシル基、カルボニル基若しくはアミノ基が置換していてもよい、炭素数４〜３０の直鎖、分岐鎖若しくは環状の飽和若しくは不飽和の炭化水素基又は水素原子を示し；Ｚはメチレン基、メチン基又は酸素原子を示し；Ｘ9、Ｘ10及びＸ11は各々独立して水素原子、ヒドロキシル基又はアセトキシ基を示し、Ｘ12は水素原子、アセチル基又はグリセリル基を示すか、隣接する酸素原子と一緒になってオキソ基を形成し（但し、Ｚがメチン基のとき、Ｘ9とＸ10のいずれか一方が水素原子であり、他方は存在しない。Ｘ12がオキソ基を形成するとき、Ｘ11は存在しない。）；Ｒ17及びＲ18は各々独立して水素原子、ヒドロキシル基、ヒドロキシメチル基又はアセトキシメチル基を示し；Ｒ19はヒドロキシル基、カルボニル基又はアミノ基が置換していてもよい、主鎖にエーテル結合、エステル結合又はアミド結合を有していてもよい炭素数５〜６０の直鎖、分岐鎖又は環状の飽和又は不飽和の炭化水素基を示し；Ｒ20は水素原子を示すか、ヒドロキシル基、ヒドロキシアルコキシ基、アルコキシ基及びアセトキシ基から選ばれる置換基を有していてもよい、総炭素数１〜３０の直鎖又は分岐鎖の飽和又は不飽和の炭化水素基を示し（但し、Ｒ16が水素原子、Ｚが酸素原子のときＲ20は総炭素数１０〜３０の炭化水素基であり、Ｒ16が炭化水素基のときＲ20は総炭素数１〜８の炭化水素基である）；破線部は不飽和結合であってもよいことを示す） (In the formula, R 16 represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group or hydrogen atom having 4 to 30 carbon atoms, which may be substituted by a hydroxyl group, a carbonyl group or an amino group. Z represents a methylene group, a methine group or an oxygen atom; X 9 , X 10 and X 11 each independently represent a hydrogen atom, a hydroxyl group or an acetoxy group, and X 12 represents a hydrogen atom, an acetyl group or a glyceryl group; or shown, together with the adjacent oxygen atom, forms an oxo group (provided that when Z is a methine group, one of X 9 and X 10 are hydrogen atoms, is .X 12 to the other is not present when forming an oxo group, X 11 is absent);. R 17 and R 18 are each independently hydrogen atom, a hydroxyl group, a hydroxymethyl group or an acetoxymethyl group; R 19 represents a hydroxyl group, a carbonyl Alternatively, an amino group may be substituted, a C5-C60 linear, branched or cyclic saturated or unsaturated hydrocarbon which may have an ether bond, an ester bond or an amide bond in the main chain R 20 represents a hydrogen atom, or may have a substituent selected from a hydroxyl group, a hydroxyalkoxy group, an alkoxy group and an acetoxy group, a straight chain or branched chain having 1 to 30 carbon atoms in total A saturated or unsaturated hydrocarbon group (where R 16 is a hydrogen atom, Z is an oxygen atom, R 20 is a hydrocarbon group having 10 to 30 carbon atoms in total, and R 16 is a hydrocarbon group) R 20 is a hydrocarbon group having 1 to 8 carbon atoms in total; the broken line indicates that it may be an unsaturated bond)
式中、Ｒ16は、ヒドロキシル基、カルボニル基若しくはアミノ基が置換していてもよい、炭素数４〜３０の、好ましくはヒドロキシル基が置換していてもよい炭素数７〜２２の直鎖、分岐鎖若しくは環状の飽和若しくは不飽和の炭化水素基又は水素原子である。
Ｚはメチレン基、メチン基又は酸素原子のいずれかを示す。
In the formula, R 16 is a straight chain having 4 to 30 carbon atoms, preferably 7 to 22 carbon atoms which may be substituted with a hydroxyl group, which may be substituted with a hydroxyl group, a carbonyl group or an amino group, A branched or cyclic saturated or unsaturated hydrocarbon group or a hydrogen atom.
Z represents a methylene group, a methine group or an oxygen atom.
Ｘ9、Ｘ10及びＸ11は、各々独立して水素原子、ヒドロキシル基又はアセトキシ基を示す。特にＸ9、Ｘ10及びＸ11のうち０〜１個がヒドロキシル基で、残余が水素原子であるのが好ましい。Ｚがメチン基のとき、Ｘ9とＸ10のいずれか一方のみが水素原子であり、他方は存在しない。また、Ｘ12は水素原子かグリセリル基であるのが好ましい。
Ｒ17及びＲ18は、水素原子、ヒドロキシル基、ヒドロキシメチル基又はアセトキシメチル基を示し、好ましいＲ17は水素原子又はヒドロキシメチル基であり、好ましいＲ18は水素原子である。
X 9 , X 10 and X 11 each independently represent a hydrogen atom, a hydroxyl group or an acetoxy group. In particular, it is preferable that 0 to 1 of X 9 , X 10 and X 11 are hydroxyl groups and the remainder is a hydrogen atom. When Z is a methine group, only one of X 9 and X 10 is a hydrogen atom, and the other does not exist. X 12 is preferably a hydrogen atom or a glyceryl group.
R 17 and R 18 represent a hydrogen atom, a hydroxyl group, a hydroxymethyl group or an acetoxymethyl group, preferred R 17 is a hydrogen atom or a hydroxymethyl group, and preferred R 18 is a hydrogen atom.
Ｒ19は、ヒドロキシル基、カルボキシ基又はアミノ基が置換していてもよい、
主鎖にエーテル結合、エステル結合又はアミド結合を有していてもよい炭素数５〜６０の直鎖、分岐鎖又は環状の飽和又は不飽和の炭化水素基を示す。好ましくは、ヒドロキシル基又はアミノ基が置換していてもよい炭素数５〜３５の直鎖、分岐鎖又は環状の飽和又は不飽和の炭化水素基、又は該炭化水素基のω位に、ヒドロキシル基が置換してもよい炭素数８〜２２の直鎖、分岐又は環状の飽和又は不飽和の脂肪酸がエステル結合又はアミド結合したものが挙げられる。結合する脂肪酸としては、イソステアリン酸、１２−ヒドロキシステアリン酸又はリノール酸が好ましい。
R 19 may be substituted with a hydroxyl group, a carboxy group or an amino group,
A linear, branched or cyclic saturated or unsaturated hydrocarbon group having 5 to 60 carbon atoms, which may have an ether bond, an ester bond or an amide bond in the main chain. Preferably, the hydroxyl group or amino group may be substituted a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 5 to 35 carbon atoms, or a hydroxyl group at the ω position of the hydrocarbon group In which a linear, branched, or cyclic saturated or unsaturated fatty acid having 8 to 22 carbon atoms, which may be substituted, is an ester bond or an amide bond. As the fatty acid to be bonded, isostearic acid, 12-hydroxystearic acid or linoleic acid is preferable.
Ｒ20は、水素原子を示すか、ヒドロキシル基、ヒドロキシアルコキシ基、アルコキシ基及びアセトキシ基から選ばれる置換基を有していてもよい総炭素数１〜３０の直鎖又は分岐鎖の飽和又は不飽和の炭化水素基である。Ｒ16が水素原子、Ｚが酸素原子のときＲ20は総炭素数１０〜３０の炭化水素基である。また、Ｒ16が炭化水素基のときＲ20は総炭素数１〜８の炭化水素基である。特に、水素原子あるいは、ヒドロキシル基及びヒドロキシアルコキシ基、アルコキシ基から選ばれる１〜３個が置換していてもよい総炭素数１〜８の炭化水素基が好ましい。ここで、ヒドロキシアルコキシ基及びアルコキシ基としては炭素数１〜７のものが好ましい。 R 20 represents a hydrogen atom, or may have a substituent selected from a hydroxyl group, a hydroxyalkoxy group, an alkoxy group, and an acetoxy group. It is a saturated hydrocarbon group. When R 16 is a hydrogen atom and Z is an oxygen atom, R 20 is a hydrocarbon group having 10 to 30 carbon atoms in total. When R 16 is a hydrocarbon group, R 20 is a hydrocarbon group having 1 to 8 carbon atoms in total. In particular, a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms in which 1 to 3 groups selected from a hydroxyl group, a hydroxyalkoxy group and an alkoxy group may be substituted is preferable. Here, as a hydroxy alkoxy group and an alkoxy group, a C1-C7 thing is preferable.
一般式（５）で表わされるセラミド類としては、特に次の一般式（６）又は（７）で表わされるセラミド類であることが好ましい。
（Ｉ）一般式（６）で表わされる天然由来のセラミド類又は同構造の合成物及びその誘導体（以下、天然型セラミドと記載する。）。
The ceramides represented by the general formula (5) are particularly preferably ceramides represented by the following general formula (6) or (7).
(I) Naturally-derived ceramides represented by the general formula (6) or synthetic products having the same structure and derivatives thereof (hereinafter referred to as natural ceramides).
（式中、Ｒ21はヒドロキシル基が置換していてもよい炭素数７〜１９の直鎖、分岐鎖又は環状の飽和又は不飽和の炭化水素基を示し；Ｚ1はメチレン基又はメチン基を示し；Ｘ13、Ｘ14、及びＸ15は各々独立して水素原子、ヒドロキシル基又はアセトキシ基を示し；Ｘ16は水素原子を示すか、隣接する酸素原子と一緒になってオキソ基を形成し（但し、Ｚ1がメチン基のとき、Ｘ13とＸ14のいずれか一方が水素原子であり、他方は存在しない。Ｘ16がオキソ基を形成するとき、Ｘ15は存在しない。）；Ｒ22はヒドロキシメチル基又はアセトキシメチル基を示し；Ｒ23は水素原子を示すか、炭素数１〜４のアルキル基を示し；Ｒ24はヒドロキシル基が置換していてもよい炭素数５〜３０の直鎖、分岐鎖又は環状の飽和又は不飽和の炭化水素基であるか、又は該アルキル基のω末端に、ヒドロキシル基が置換していてもよい炭素数８〜２２の直鎖又は分岐鎖の飽和又は不飽和の脂肪酸がエステル結合したものを示し；破線部は不飽和結合であってもよいことを示す。） (In the formula, R 21 represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 7 to 19 carbon atoms which may be substituted by a hydroxyl group; Z 1 represents a methylene group or a methine group; X 13 , X 14 and X 15 each independently represent a hydrogen atom, a hydroxyl group or an acetoxy group; X 16 represents a hydrogen atom or together with an adjacent oxygen atom, forms an oxo group. (However, when Z 1 is a methine group, one of X 13 and X 14 is a hydrogen atom and the other does not exist. When X 16 forms an oxo group, X 15 does not exist.) R 22 represents a hydroxymethyl group or an acetoxymethyl group; R 23 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R 24 has 5 to 30 carbon atoms which may be substituted by a hydroxyl group Linear, branched or cyclic saturated or unsaturated hydrocarbon groups Or a linear or branched saturated or unsaturated fatty acid having 8 to 22 carbon atoms which may be substituted with a hydroxyl group at the ω-terminal of the alkyl group; Indicates that it may be an unsaturated bond.)
好ましくは、Ｒ21が炭素数７〜１９、更に好ましくは炭素数１３〜１５の直鎖アルキル基；Ｒ24がヒドロキシル基が置換しても良い炭素数９〜２７の直鎖アルキル基又はリノール酸がエステル結合した炭素数９〜２７の直鎖アルキル基である化合物が挙げられる。また、Ｘ16は水素原子を示すか、酸素原子とともにオキソ基を形成するのが好ましい。特に、Ｒ24としては、トリコシル、１−ヒドロキシペンタデシル、１−ヒドロキシトリコシル、ヘプタデシル、１−ヒドロキシウンデシル、ω位にリノール酸がエステル結合したノナコシル基が好ましい。 Preferably, R 21 is a linear alkyl group having 7 to 19 carbon atoms, more preferably 13 to 15 carbon atoms; R 24 is a linear alkyl group having 9 to 27 carbon atoms which may be substituted by a hydroxyl group, or linoleic acid Is a straight-chain alkyl group having 9 to 27 carbon atoms with an ester bond. X 16 preferably represents a hydrogen atom or forms an oxo group together with an oxygen atom. In particular, R 24 is preferably tricosyl, 1-hydroxypentadecyl, 1-hydroxytricosyl, heptadecyl, 1-hydroxyundecyl, or a nonacosyl group in which linoleic acid is ester-bonded to the ω position.
天然型セラミドの具体的な例示として、スフィンゴシン、ジヒドロスフィンゴシン、フィトスフィンゴシン又はスフィンガジエニンがアミド化されたセラミドType１〜７（例えば、J. Lipid Res., 24：759(1983)の図２、及びJ. Lipid. Res.,35：2069(1994)の図４記載のブタ及びヒトのセラミド類）が挙げられる。 Specific examples of natural ceramides include ceramide types 1 to 7 in which sphingosine, dihydrosphingosine, phytosphingosine or sphingadienin is amidated (for example, J. Lipid Res., 24: 759 (1983), FIG. And J. Lipid. Res., 35: 2069 (1994), porcine and human ceramides described in FIG.
更にこれらのＮ−アルキル体（例えばＮ−メチル体）も含まれる。
これらのセラミドは天然型（Ｄ（−）体）の光学活性体を用いても、非天然型（Ｌ（＋）体）の光学活性体を用いても、更に天然型と非天然型の混合物を用いてもよい。上記化合物の相対立体配置は、天然型の立体配置のものでも、それ以外の非天然型の立体配置のものでも良く、また、これらの混合物によるものでもよい。特にCERAMIDE1、CERAMIDE2、CERAMIDE3、CERAMIDE5、CERAMIDE6IIの化合物(以上、INCI、8th Edition)及び次式で表わされるものが好ましい。
Furthermore, these N-alkyl bodies (for example, N-methyl body) are also included.
These ceramides may be either natural (D (−)) optically active or non-natural (L (+)) optically active, or a mixture of natural and nonnatural. May be used. The relative configuration of the above compound may be a natural configuration, a non-natural configuration other than that, or a mixture thereof. In particular, compounds of CERAMIDE1, CERAMIDE2, CERAMIDE3, CERAMIDE5, CERAMIDE6II (above, INCI, 8th Edition) and those represented by the following formula are preferable.
これらは天然からの抽出物及び合成物のいずれでもよく、市販のものを用いることができる。
このような天然型セラミドの市販のものとしては、Ceramide I、Ceramide III、Ceramide IIIＡ、Ceramide IIIＢ、Ceramide IIIＣ、Ceramide VI（以上、コスモファーム社）、Ceramide TIC-001（高砂香料社）、CERAMIDE II（Quest International社）、DS-Ceramide VI、DS-CLA-Phytoceramide、Ｃ6-Phytoceramide、DS-ceramide Y3S（DOOSAN社）、CERAMIDE２(セダーマ社)が挙げられる。
These may be any of natural extracts and synthetic products, and commercially available products can be used.
Such commercially available ceramides include Ceramide I, Ceramide III, Ceramide IIIA, Ceramide IIIB, Ceramide IIIC, Ceramide VI (above, Cosmo Farm), Ceramide TIC-001 (Takasago Inc.), CERAMIDE II (Quest International), DS-Ceramide VI, DS-CLA-Phytoceramide, C6-Phytoceramide, DS-ceramide Y3S (DOOSAN), CERAMIDE2 (Cedera).
（II）一般式（７）で表わされる擬似型セラミド。 (II) A pseudo-ceramide represented by the general formula (7).
（式中、Ｒ25は、ヒドロキシル基が置換していてもよい炭素数１０〜２２の直鎖、分岐鎖若しくは環状の飽和若しくは不飽和の炭化水素基又は水素原子を示し；Ｘ17は水素原子、アセチル基又はグリセリル基を示し；Ｒ26はヒドロキシル基又はアミノ基が置換していてもよい炭素数５〜２２の直鎖、分岐鎖又は環状の飽和又は不飽和の炭化水素基であるか、又は該炭化水素基のω末端に、ヒドロキシル基が置換していてもよい炭素数８〜２２の直鎖又は分岐鎖の飽和又は不飽和の脂肪酸がエステル結合したものを示し；Ｒ27は水素原子を示すか、ヒドロキシル基、ヒドロキシアルコキシ基、アルコキシ基又はアセトキシ基が置換していてもよい総炭素数１〜３０のアルキル基を示す。） (In the formula, R 25 represents a linear, branched or cyclic saturated or unsaturated hydrocarbon group or hydrogen atom having 10 to 22 carbon atoms which may be substituted with a hydroxyl group; X 17 represents a hydrogen atom; Represents an acetyl group or a glyceryl group; R 26 is a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 5 to 22 carbon atoms which may be substituted with a hydroxyl group or an amino group, Or a hydrocarbon group having an ester bond with a linear or branched saturated or unsaturated fatty acid having 8 to 22 carbon atoms which may be substituted with a hydroxyl group at the ω-terminal; R 27 represents a hydrogen atom; Or a hydroxyl group, a hydroxyalkoxy group, an alkoxy group or an acetoxy group which may be substituted is an alkyl group having 1 to 30 carbon atoms in total.
Ｒ26としては、特にノニル、トリデシル、ペンタデシル、ω位にリノール酸がエステル結合したウンデシル基、ω位にリノール酸がエステル結合したペンタデシル基、ω位に１２−ヒドロキシステアリン酸がエステル結合したペンタデシル基、ω位にメチル分岐イソステアリン酸がアミド結合したウンデシル基が好ましい。 R 26 is particularly nonyl, tridecyl, pentadecyl, an undecyl group in which linoleic acid is ester-bonded to the ω position, a pentadecyl group in which linoleic acid is ester-bonded to the ω position, and a pentadecyl group in which 12-hydroxystearic acid is ester-bonded to the ω position. An undecyl group in which methyl branched isostearic acid is amide-bonded at the ω position is preferred.
Ｒ27は、Ｒ25が水素原子の場合は、ヒドロキシル基、ヒドロキシアルコキシ基、アルコキシ基又はアセトキシ基が置換していてもよい総炭素数１０〜３０の、好ましくは総炭素数１２〜２０のアルキル基であり、Ｒ25がヒドロキシル基が置換していてもよい炭素数１０〜２２の直鎖、分岐鎖又は環状の飽和又は不飽和の炭化水素基である場合には、水素原子を示すか、ヒドロキシル基、ヒドロキシアルコキシ基、アルコキシ基又はアセトキシ基が置換していてもよい総炭素数１〜８のアルキル基を示すのものが好ましい。Ｒ27のヒドロキシアルコキシ基又はアルコキシ基としては炭素数１〜７のものが好ましい。 R 27 is an alkyl having a total carbon number of 10 to 30, preferably a total carbon number of 12 to 20, which may be substituted by a hydroxyl group, hydroxyalkoxy group, alkoxy group or acetoxy group when R 25 is a hydrogen atom. When R 25 is a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 10 to 22 carbon atoms which may be substituted with a hydroxyl group, What shows a C1-C8 alkyl group which the hydroxyl group, the hydroxy alkoxy group, an alkoxy group, or an acetoxy group may substitute is preferable. The hydroxyalkoxy or alkoxy group R 27 preferably has 1 to 7 carbon atoms.
一般式（７）としては、Ｒ25がヘキサデシル基、Ｘ17が水素原子、Ｒ26がペンタデシル基、Ｒ27がヒドロキシエチル基のもの；Ｒ25がヘキサデシル基、Ｘ17が水素原子、Ｒ26がノニル基、Ｒ27がヒドロキシエチル基のもの；又はＲ25がヘキサデシル基、Ｘ17がグリセリル基、Ｒ26がトリデシル基、Ｒ27が３−メトキシプロピル基の擬似型セラミド類が好ましく、一般式（７）のＲ25がヘキサデシル基、Ｘ17が水素原子、Ｒ26がペンタデシル基、Ｒ27がヒドロキシエチル基のものが特に好ましい。 In general formula (7), R 25 is a hexadecyl group, X 17 is a hydrogen atom, R 26 is a pentadecyl group, R 27 is a hydroxyethyl group; R 25 is a hexadecyl group, X 17 is a hydrogen atom, and R 26 is Preferred are pseudoceramides having a nonyl group, R 27 is a hydroxyethyl group; or R 25 is a hexadecyl group, X 17 is a glyceryl group, R 26 is a tridecyl group, and R 27 is a 3-methoxypropyl group. It is particularly preferable that R 25 in 7) is a hexadecyl group, X 17 is a hydrogen atom, R 26 is a pentadecyl group, and R 27 is a hydroxyethyl group.
セラミド類は、成分（Ｅ）中に０．０００１〜５０質量％、特に０．００１〜２０質量％、更に０．０１〜１５質量％含有されるのが好ましい。 Ceramides are preferably contained in the component (E) in an amount of 0.0001 to 50% by mass, particularly 0.001 to 20% by mass, and more preferably 0.01 to 15% by mass.
成分（Ｅ）は２種以上を併用しても良く、特に炭化水素油と２５℃で固体、半固体の油性成分を含むことが好ましく、２５℃で固体、半固体の油性成分としてセラミド及びその誘導体、コレステロール及びその誘導体等の細胞間脂質に分類されるものを含むことが好ましい。本発明の組成物中の成分（Ｅ）の含有量は、１〜７０質量％、特に５〜５０質量％、更に１０〜３０質量％であるのが好ましい。 Component (E) may be used in combination of two or more, and preferably contains hydrocarbon oil and a solid / semi-solid oily component at 25 ° C., and ceramide and its solid / semi-solid oily component at 25 ° C. It is preferable to include those classified into intercellular lipids such as derivatives, cholesterol and derivatives thereof. The content of the component (E) in the composition of the present invention is preferably 1 to 70% by mass, particularly 5 to 50% by mass, and more preferably 10 to 30% by mass.
本発明の油中水型乳化組成物に含まれる水の量は、全組成中に１〜８０質量％、特に７〜７０質量％、更に１５〜６０質量％であるのが好ましい。 The amount of water contained in the water-in-oil emulsion composition of the present invention is preferably 1 to 80% by mass, particularly 7 to 70% by mass, and more preferably 15 to 60% by mass in the total composition.
本発明の油中水型乳化組成物には、上記成分以外に、通常の化粧料で使用される成分、例えば１，３−ブチレングリコール、プロピレングリコール、ジプロピレングリコール、グリセリン、ジグリセリン、ソルビトール、マルチトール、ポリエチレングリコール、グリシンベタイン、キシリトール、トレハロース、尿素、アミノ酸等の保湿剤；キサンタンガム、ヒドロキシエチルセルロース、メチルセルロース、ヒドロキシプロピルグアガム等の水溶性増粘剤；脂肪酸デキストリン、脂肪酸イヌリン等の油溶性高分子；アラントイン、酢酸トコフェロール等の薬効剤；セルロースパウダー、ナイロンパウダー、架橋型シリコーン末、架橋型メチルポリシロキサン、多孔質セルロースパウダー、多孔質ナイロンパウダー等の有機粉体；無水シリカ、酸化亜鉛、酸化チタン等の無機粉体；ユーカリエキス等の植物エキス；カミツレエキス等の美白剤；メントール、カンファー等の清涼剤；pH緩衝剤、酸化防止剤、紫外線吸収剤、防腐剤、香料、殺菌剤、色素などを含有させることができる。 In the water-in-oil emulsion composition of the present invention, in addition to the above components, components used in ordinary cosmetics such as 1,3-butylene glycol, propylene glycol, dipropylene glycol, glycerin, diglycerin, sorbitol, Moisturizers such as maltitol, polyethylene glycol, glycine betaine, xylitol, trehalose, urea, amino acids; water-soluble thickeners such as xanthan gum, hydroxyethyl cellulose, methyl cellulose, hydroxypropyl guar gum; oil-soluble polymers such as fatty acid dextrin and fatty acid inulin ; Medicinal agents such as allantoin and tocopherol acetate; organic powder such as cellulose powder, nylon powder, cross-linked silicone powder, cross-linked methylpolysiloxane, porous cellulose powder, porous nylon powder; Inorganic powders such as zinc oxide and titanium oxide; plant extracts such as eucalyptus extract; whitening agents such as chamomile extract; refreshing agents such as menthol and camphor; pH buffering agents, antioxidants, UV absorbers, preservatives, fragrances , Fungicides, pigments and the like can be included.
本発明の油中水型乳化組成物は、成分（Ａ）〜（Ｅ）を加熱溶解した後、水及びその他の成分を添加して乳化することにより製造される。 The water-in-oil emulsion composition of the present invention is produced by heating and dissolving the components (A) to (E), and then adding and emulsifying water and other components.
本発明の油中水型乳化組成物は、化粧品、医薬品等として適用でき、特に化粧料、例えば乳液、クリーム、ファンデーション、ヘアクリーム等として、特に形態がクリーム状の化粧料に使用するのが好ましい。 The water-in-oil emulsified composition of the present invention can be applied as cosmetics, pharmaceuticals, etc., and is particularly preferably used as cosmetics, for example, emulsions, creams, foundations, hair creams, etc., especially in creamy cosmetics. .
実施例１〜６、比較例１〜２
表１に示す組成の油中水型乳化組成物を下記方法により製造した。得られた乳化組成物について、サイクル安定性、安定性、使用感（すべすべ感）及び皮膚残留性を評価した。結果を表１に併せて示す。
Examples 1-6, Comparative Examples 1-2
A water-in-oil emulsion composition having the composition shown in Table 1 was produced by the following method. The obtained emulsion composition was evaluated for cycle stability, stability, feeling of use (smooth feeling) and skin persistence. The results are also shown in Table 1.
（製造方法）
成分（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）及び（Ｅ）を含む油相成分を８０〜９０℃で加熱撹拌して溶解させ、均一に撹拌しながら、水相成分及びその他の成分を添加した。更に撹拌しながら、室温まで冷却して、油中水型乳化組成物を得た。
(Production method)
The oil phase component including components (A), (B), (C), (D) and (E) is dissolved by heating and stirring at 80 to 90 ° C. Ingredients were added. The mixture was further cooled to room temperature with stirring to obtain a water-in-oil emulsion composition.
（評価方法）
（１）サイクル安定性：
各乳化組成物を、−１５℃〜６０℃を２４時間で１サイクルとする保存庫に入れ、６日間静置した後、室温に戻し、以下の基準で評価した。
◎；乳化分離が認められず、外観上の変化もない。
○；乳化分離は認められないが、外観がわずかに変化。
×；乳化の分離を認め、外観が大きく変化した。
(Evaluation methods)
(1) Cycle stability:
Each emulsified composition was put in a storage box having a cycle of -15 ° C to 60 ° C for 24 hours, allowed to stand for 6 days, returned to room temperature, and evaluated according to the following criteria.
A: No emulsification separation was observed, and there was no change in appearance.
○: No emulsification separation was observed, but the appearance slightly changed.
X: Separation of emulsification was observed, and the appearance was greatly changed.
（２）安定性：
各乳化組成物を、５０℃で、それぞれ１週間静置した後、以下の基準により外観を目視にて評価した。
◎；乳化分離が認められず、外観上の変化もない。
○；乳化分離は認められないが、外観がわずかに変化。
×；乳化の分離を認め、外観が大きく変化した。
(2) Stability:
Each emulsion composition was allowed to stand at 50 ° C. for 1 week, and then the appearance was visually evaluated according to the following criteria.
A: No emulsification separation was observed, and there was no change in appearance.
○: No emulsification separation was observed, but the appearance slightly changed.
X: Separation of emulsification was observed, and the appearance was greatly changed.
（３）使用感：
１０名の専門パネラーにより、各サイクル試験品を０．３ｇ顔に塗布したときの「すべすべ感」を官能評価し、次の基準により判定した。
◎：９名以上が良好（良い）と評価した。
○：７〜８名が良好（良い）と評価した。
×：６名以下が良好（良い）と評価した。
(3) Usability:
A “smooth feeling” when each cycle test product was applied to the face by 10 expert panelists was sensory-evaluated and judged according to the following criteria.
A: Nine or more people evaluated it as good (good).
○: Seven to eight people evaluated it as good (good).
X: 6 or less evaluated as good (good).
（４）皮膚残留性：
各乳化組成物０．３ｇを顔に塗布し、６時間後の肌のすべすべ感を官能評価し、次の基準により判定した。
◎：９名以上が良好（良い）と評価した。
○：７〜８名が良好（良い）と評価した。
×：６名以下が良好（良い）と評価した。
(4) Skin persistence:
0.3 g of each emulsified composition was applied to the face, and the smooth feeling of the skin after 6 hours was subjected to sensory evaluation and judged according to the following criteria.
A: Nine or more people evaluated it as good (good).
○: Seven to eight people evaluated it as good (good).
X: 6 or less evaluated as good (good).
Claims (3)
（Ａ）一般式（１）で表わされるスフィンゴシン類
（Ｂ）炭素数６〜３０の脂肪酸、
（Ｃ）架橋型ポリエーテル変性シリコーン、
（Ｄ）シリコーン油、
（Ｅ）シリコーン油以外の油性成分
を含有する油中水型乳化組成物。 The following components (A) to (E):
(A) Sphingosines represented by the general formula (1)
(B) a fatty acid having 6 to 30 carbon atoms,
(C) a cross-linked polyether-modified silicone,
(D) silicone oil,
(E) A water-in-oil emulsion composition containing an oil component other than silicone oil.
で表されるものである請求項１記載の油中水型乳化組成物。 Component (C) is represented by the general formula (4)
The water-in-oil emulsion composition according to claim 1, which is represented by:
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| JP2009517478A (en) * | 2005-12-02 | 2009-04-30 | ザ プロクター アンド ギャンブル カンパニー | Water-in-oil emulsion composition containing siloxane elastomer |
| JP2009262080A (en) * | 2008-04-25 | 2009-11-12 | San Nopco Ltd | Surfactant |
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| JP2009262080A (en) * | 2008-04-25 | 2009-11-12 | San Nopco Ltd | Surfactant |
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| JP4520903B2 (en) | 2010-08-11 |
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