JPWO2003041664A1 - Cosmetics with viscous minerals - Google Patents
Cosmetics with viscous minerals Download PDFInfo
- Publication number
- JPWO2003041664A1 JPWO2003041664A1 JP2003543551A JP2003543551A JPWO2003041664A1 JP WO2003041664 A1 JPWO2003041664 A1 JP WO2003041664A1 JP 2003543551 A JP2003543551 A JP 2003543551A JP 2003543551 A JP2003543551 A JP 2003543551A JP WO2003041664 A1 JPWO2003041664 A1 JP WO2003041664A1
- Authority
- JP
- Japan
- Prior art keywords
- group
- component
- cosmetic
- cosmetic according
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002537 cosmetic Substances 0.000 title claims abstract description 106
- 229910052500 inorganic mineral Inorganic materials 0.000 title 1
- 239000011707 mineral Substances 0.000 title 1
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 103
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 125000000962 organic group Chemical group 0.000 claims abstract description 18
- 239000002734 clay mineral Substances 0.000 claims abstract description 17
- 239000003921 oil Substances 0.000 claims description 62
- 239000000843 powder Substances 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 46
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 19
- 229920002050 silicone resin Polymers 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 150000005846 sugar alcohols Polymers 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 230000001166 anti-perspirative effect Effects 0.000 claims description 9
- 239000003213 antiperspirant Substances 0.000 claims description 9
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 9
- 210000004209 hair Anatomy 0.000 claims description 8
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- 239000002131 composite material Substances 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 7
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
- 239000003086 colorant Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 150000002772 monosaccharides Chemical class 0.000 claims description 5
- 150000002482 oligosaccharides Chemical class 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
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- 239000005017 polysaccharide Substances 0.000 claims description 3
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- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
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- 238000004132 cross linking Methods 0.000 claims 1
- 125000000547 substituted alkyl group Chemical group 0.000 claims 1
- -1 3-aminopropyl group Chemical group 0.000 description 135
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- 238000004519 manufacturing process Methods 0.000 description 42
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- 239000002253 acid Substances 0.000 description 28
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- 239000000839 emulsion Substances 0.000 description 24
- 229930195729 fatty acid Natural products 0.000 description 24
- 239000000194 fatty acid Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000007788 liquid Substances 0.000 description 21
- 235000002639 sodium chloride Nutrition 0.000 description 21
- 239000002904 solvent Substances 0.000 description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 19
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 18
- 239000006071 cream Substances 0.000 description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 16
- 238000003756 stirring Methods 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 14
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- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 238000010992 reflux Methods 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 12
- 239000010419 fine particle Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000000049 pigment Substances 0.000 description 12
- 239000004166 Lanolin Substances 0.000 description 11
- 235000019388 lanolin Nutrition 0.000 description 11
- 229940039717 lanolin Drugs 0.000 description 11
- 239000008308 lipophilic cream Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical group C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000006096 absorbing agent Substances 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 description 8
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 8
- 229920000578 graft copolymer Polymers 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 8
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- 239000011347 resin Substances 0.000 description 8
- 238000003892 spreading Methods 0.000 description 8
- 239000001993 wax Substances 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 8
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 7
- 229910000271 hectorite Inorganic materials 0.000 description 7
- 239000010445 mica Substances 0.000 description 7
- 229910052618 mica group Inorganic materials 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
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- 125000003545 alkoxy group Chemical group 0.000 description 6
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- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 description 1
- UUJLHYCIMQOUKC-UHFFFAOYSA-N trimethyl-[oxo(trimethylsilylperoxy)silyl]peroxysilane Chemical compound C[Si](C)(C)OO[Si](=O)OO[Si](C)(C)C UUJLHYCIMQOUKC-UHFFFAOYSA-N 0.000 description 1
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- UJMBCXLDXJUMFB-UHFFFAOYSA-K trisodium;5-oxo-1-(4-sulfonatophenyl)-4-[(4-sulfonatophenyl)diazenyl]-4h-pyrazole-3-carboxylate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-UHFFFAOYSA-K 0.000 description 1
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- 235000005282 vitamin D3 Nutrition 0.000 description 1
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- 229940057977 zinc stearate Drugs 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
- KUPGJMJHAFGISS-UHFFFAOYSA-L zinc;hexadecyl phosphate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCOP([O-])([O-])=O KUPGJMJHAFGISS-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
- A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/26—Aluminium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Dermatology (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Cosmetics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
(A)下記一般式(1)及び/又は一般式(2)で表されるノニオンの親水基を有するシリコーン化合物、並びに(B)粘土鉱物を含有することを特徴とする化粧料が開示されている。但し、R1、R2、R5及びR6は有機基であり、a及びb,cは、それぞれ1.0≦a≦2.5、0.001≦b,c≦1.5である。Disclosed is a cosmetic comprising (A) a silicone compound having a nonionic hydrophilic group represented by the following general formula (1) and / or general formula (2), and (B) a clay mineral. Yes. However, R1, R2, R5 and R6 are organic groups, and a, b and c are 1.0 ≦ a ≦ 2.5, 0.001 ≦ b and c ≦ 1.5, respectively.
Description
技術分野
本発明は、少なくとも、ノニオンの親水基を有する特定のオルガノポリシロキサン及び粘土鉱物を含有する、軽いのび広がりを有し、油っぽさがなく、しっとりとしてみずみずしい上、さっぱりとした使用感を有する化粧料に関し、特に化粧持ちの向上した、温度や経時による変化のない安定性に極めて優れた化粧料に関するものである。
背景技術
乳化化粧料は、一般に水中油型乳化化粧料と油中水型乳化化粧料とに大別される。このうち特に油中水型乳化化粧料は、肌への親和性が良く、肌表面を油膜で被覆して水分の蒸散を防ぎ、肌を乾燥から保護したり、肌にトリートメント効果を付与するなどの性質があることから基礎化粧料として広く用いられている。また、撥水性に優れ、化粧くずれが少なく化粧持ちに優れるなどの理由から、メーキャップ化粧料などのような化粧料や医薬品の基材としても広く用いられている。
このような油中水型化粧料においては、さっぱりとしてべたつきが少なく撥水性の良いものを得るために、シリコーン油が油剤としてよく用いられる。また、このような乳化化粧料を調製する際には、経時安定性の良好なものを得るために、通常、乳化剤としてはシリコーン油との相溶性が良いポリオキシアルキレン変性オルガノポリシロキサン系界面活性剤が汎用されている。
しかしながら、シリコーン油が多量に含まれる乳化化粧料にこの界面活性剤を単に配合するだけでは、経時的に十分な安定性を有する物を得ることが難しかった。そこで、広い温度範囲での経時安定性を確保するために、ワックスやゲル化剤を配合することによって最終的に粘度の高い乳化化粧料に調整されている。しかしながら、このようにするとさっぱり感が減り、べたつきが感じられるようになるので使用感が重くなるという欠点があった。
そこで本発明者等は、使用感を重くするワックスやゲル化剤を使うことなく、使用性が良好であると共に広い温度範囲での経時安定性が良好な化粧料について鋭意検討した結果、ノニオンの親水基を有する特定のオルガノポリシロキサンと粘土鉱物を化粧料に配合することにより、軽いのび広がりを有し、油っぽさがなく、しっとりとしてみずみずしい上さっぱりとした使用感を有すると共に化粧持ちの向上した、温度や経時による変化のない極めて安定性に優れた化粧料が得られる事を見出し、本発明を完成した。
従って、本発明の目的は、使用感に優れると共に化粧持ちの良好な、安定性に優れた化粧料を提供する事にある。
発明の開示
本発明は、少なくとも(A)一般式R1 aR2 bSiO(4−a−b)/2及び/又はR1 aR5 bR6 cSiO(4−a−b−c)/2で表されるノニオンの親水基を有するオルガノポリシロキサン、並びに(B)粘土鉱物を含有することを特徴とする化粧料である。但し、式中のR1は炭素数1〜30のアルキル基、アリール基、アラルキル基、アミノ置換アルキル基、カルボキシル置換アルキル基(一部ハロゲンに置換されていてもよい)、あるいは下記一般式(3)
で表される有機基から選択される同種または異種の有機基、R2は下記一般式(4)、(5)、(6)、(7)及び(8)から選ばれる同種又は異種の有機基である。
Qはエーテル結合及び/又はエステル結合を含有しても良い炭素数3〜20の二価炭化水素基を表す。R3は炭素数4〜30の一価炭化水素基、ハロゲン置換炭化水素基、又はR4−(CO)−で表される有機基、R4は炭素数1〜30の一価炭化水素基及びハロゲン置換炭化水素基である。Xは単糖、オリゴ糖ないしは多糖から誘導される糖残基を表す。a及びbはそれぞれ1.0≦a≦2.5、0.001≦b≦1.5であり、d、e、fはそれぞれ0≦d≦15、0≦e≦50、0≦f≦50の整数、g及びhはそれぞれ、1≦g≦20、1≦h≦20の整数である。
但し、式中のR1は(1)式のものと同じ有機基、R5は(1)式における一般式(4)〜(8)及び下記一般式(9)から選ばれる同種又は異種の有機基、
Qは前記したものと同じであり、R6は下記一般式(10)で表されるオルガノシロキサン残基である。
R7は炭素数1〜30のアルキル基、アリール基、アラルキル基、フッ素置換アルキル基、a、b及びcは、それぞれ1.0≦a≦2.5、0.001≦b≦1.5、0.001≦c≦1.5、kは1≦k≦5の整数であり、mは0≦m≦500の整数である。
発明を実施するための最良の形態
以下、本発明について詳細に説明する。
本発明の化粧料に配合される(A)成分であるノニオンの親水基を有するオルガノポリシロキサンは、下記一般式(1)及び/又は一般式(2)で表されるものである。
但し、式中のR1は炭素数1〜30のアルキル基、アリール基、アラルキル基、アミノ置換アルキル基、カルボキシル置換アルキル基(一部ハロゲンに置換されていてもよい)、あるいは下記一般式(3)
で表される有機基から選択される同種または異種の有機基である。
R1の具体例としてはメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等のアルキル基、シクロペンチル基、シクロヘキシル基等のシクロアルキル基、フェニル基、トリル基等のアリール基、ベンジル基、フェネチル基等のアラルキル基などを挙げることができる。さらに3−アミノプロピル基、3−[(2−アミノエチル)アミノ]プロピル基などのアミノ置換アルキル基、3−カルボキシプロピル基等のカルボキシ置換アルキル基などがあげられる。また、トリフロロプロピル基やノナフロロオクチル基などのように一部の水素がハロゲンに置換された物も挙げられる。
R1の一部は、一般式−CdH2d−O−(C2H4O)e(C3H6O)fR3で表されるアルコール残基及びアルケニルエーテル付加物残基であっても良い。ここでR3は炭素数4〜30の一価炭化水素基、ハロゲン置換炭化水素基、又はR4−(CO)−で表される有機基であって、R4は炭素数1〜30の一価炭化水素基又はハロゲン置換炭化水素基である。d、e、fはそれぞれ0≦d≦15、0≦e≦50、0≦f≦50の整数である。具体的には、
d=0の時:−O−(C2H4O)e(C3H6O)fR3
かつe=0,f=0であれば炭素数4〜30のアルコキシ基、例えばブトキシ基などの低級アルコキシ基からセチルアルコール、オレイルアルコール、ステアリルアルコールなどのオレイロキシ基、ステアロキシ基などの高級アルコキシ基、あるいは酢酸、乳酸、酪酸、オレイン酸、ステアリン酸、ベヘニル酸などの脂肪
酸残基があげられる。
e,f>1であれば高級アルコールのアルキレンオキサイド付加物(末端は水酸基)のアルコール残基となる。
dが1以上で、e=0、f=0の場合には、特にdが3、5あるいは11であることが好ましい。この場合はアリルエーテル、ペンテニルエーテル、ウンデセニルエーテル残基であり、R3の置換基によって、例えばアリルステアリルエーテル残基、ペンテニルベヘニルエーテル残基もしくはウンデセニルオレイルエーテル残基などがあげられる。eもしくはfが0でない場合は、ポリオキシアルキレンを介してアルコキシ基やエステル基が存在する事となる。
ここで、e及びfが何であれ、dが0の時は耐加水分解性に劣る場合があり、またdが15以上であると油臭が強いため、dは3〜5であることが好ましい。
特に、本発明においてはR1全体の50%以上がメチル基であることが好ましく、70%以上であることがさらに好ましい。R1の100%がメチル基であっても良い。
次に、R2は下記一般式(4)、(5)、(6)、(7)及び(8)から選ばれる同種、又は異種の有機基である。
Qはエーテル結合及びエステル結合を含有しても良い炭素数3〜20の二価炭化水素基であり、たとえば−(CH2)2−、−(CH2)3−、−CH2CH(CH3)CH2−、−(CH2)4−、−(CH2)5−、−(CH2)6−、−(CH2)7−、−(CH2)8−、−(CH2)2−CH(CH2CH2CH3)−、−CH2−CH(CH2CH3)−、−(CH2)3−O−(CH2)2−、−(CH2)3−O−(CH2)2−O−(CH2)2−、−(CH2)3−O−CH2CH(CH3)−、−CH2−CH(CH3)−COO(CH2)2−等を例示することができる。
上記化合物(5)〜(7)はポリグリセリンであり、式中のgおよびhは1〜20の整数である。また、水酸基の一部がアルコキシ基あるいはエステル基で置換されていても良い。
次に、Xは単糖、オリゴ糖又は多糖から誘導される糖残基であり、例えばグリコシル基、マンノシル基、ガラクトシル基、リボシル基、アラビノシル基、キシロシル基、フルクトシル基などの単糖基;マルトシル基、セロビオシル基、ラクトシル基、マルトトリオシル基などのオリゴ糖基;セルロース、澱粉などの多糖基が例示される。これらの内、好ましい基としては、単糖基及びオリゴ糖基が挙げられる。
一般式(2)におけるR5は、上記R2における一般式(4)〜(8)及び下記一般式(9)で表される残基の中から選ばれる同種、又は異種の有機基である。
Qは前記したものと同じであり、エーテル結合及びエステル結合を含有していても良い炭素数3〜20の二価炭化水素基である。
一般式(2)におけるR6は下記一般式(10)で表されるオルガノシロキサン残基である。
ここで、式中のkは1〜5の整数であって、特にビニルシロキシ基とSiH基との反応から合成する場合、kは2である。R7は炭素数1〜30のアルキル基、アリール基、アラルキル基、フッ素置換アルキル基、mは0〜500の整数であり、好ましくは1〜50である。mが500より大きいと主鎖との反応性が悪くなるなどの問題が起こる事がある。
R7の具体例としてはメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等のアルキル基、シクロペンチル基、シクロヘキシル基等のシクロアルキル基、フェニル基、トリル基等のアリール基、ベンジル基、フェネチル基等のアラルキル基などを挙げることができる。さらにトリフロロプロピル基やノナフロロオクチル基などのように一部の水素がフッ素で置換された基も挙げられる。
上記の一般式(10)で表されるオルガノシロキサン残基は、ビニルシロキシ基とSiH基の反応によって調製することが出来る。この場合に使用する片末端にビニルシロキシ基を有するオルガノポリシロキサンは、公知の方法により合成可能である。即ちジビニルテトラメチルジシロキサンとヘキサメチルジシロキサンおよびオクタメチルシクロテトラシロキサンとの平衡化反応によって片末端ビニルシロキサンを合成することが可能である。さらに5配位ケイ素錯体触媒やアニオン重合触媒によるヘキサメチルシクロトリシロキサンの開環重合法によって、片末端封鎖率を向上させたシリコーン化合物を合成することもできる。
本発明で用いる一般式(1)のシリコーン化合物は、オルガノハイドロジェンポリシロキサンと、たとえば下記(ii)で表されるアリルエーテル化合物、場合によっては更に、ヘキセンなどのアルキレン化合物や(i)で表されるアリルエーテル化合物を白金触媒又はロジウム触媒の存在下に付加反応させることにより容易に合成することができる。
(但し、式中のR4、e及びfはそれぞれ前記R2の場合のものと同じである。)
本発明で用いる一般式(2)のシリコーン化合物は、オルガノハイドロジェンポリシロキサンと、たとえば上記(ii)で表されるアリルエーテル化合物、下記(iii)で表されるビニルシリコーン化合物、場合によっては更に、ヘキセンなどのアルキレン化合物や上記(i)で表されるアリルエーテル化合物を、白金触媒又はロジウム触媒の存在下に付加反応させることにより容易に合成することができる。
(但し、式中のR7、mはそれぞれ前記(10)式のものと同じである。)
ここで、オルガノハイドロジェンポリシロキサンとしては、直鎖状、環状のいずれでもよいが、付加反応を円滑に進めるためには主として直鎖状であることが好ましい。
オルガノハイドロジェンポリシロキサンと上記一般式(ii)で表される多価アルコール化合物、上記一般式(iii)で表されるシリコーン化合物、並びにアルキレン化合物及び/又は上記一般式(i)で表される有機化合物との合計の混合割合は、SiH基と末端不飽和基のモル比で0.5〜2.0、好ましくは0.8〜1.2である。
上記付加反応は、白金触媒又はロジウム触媒の存在下で行うことが望ましく、具体的には塩化白金酸、アルコール変性塩化白金酸、塩化白金酸−ビニルシロキサン錯体等の触媒が好適に使用される。
なお、触媒の使用量は触媒量とすることができるが、白金又はロジウム量で50ppm以下であることが好ましく特に20ppm以下であることが好ましい。上記付加反応は、必要に応じて有機溶剤中で行ってもよい。有機溶剤としては、例えばメタノール、エタノール、2−プロパノール、ブタノール等の脂肪族アルコール、トルエン、キシレン等の芳香族炭化水素、n−ペンタン、n−ヘキサン、シクロヘキサン等の脂肪族または脂環式炭化水素、ジクロロメタン、クロロホルム、四塩化炭素等のハロゲン化炭化水素等が挙げられる。付加反応条件は特に限定されるものではないが、還流下で1〜10時間反応させることが好ましい。
一般式(1)及び(2)におけるaは1.0〜2.5、好ましくは1.2〜2.3である。aが1.0より小さいと油剤との相溶性に劣り、安定な乳化物を得難い。aが2.5より大きいと親水性に乏しくなるため、やはり安定な乳化物を得難い。bは0.001〜1.5、好ましくは0.05〜1.0である。bが0.001より小さいと、親水性に乏しくなるため安定な乳化物を得難い。bが1.5より大きいと親水性が高くなり過ぎるため、安定な乳化物を得難い。cは0.001〜1.5、好ましくは0.05〜1.0である。cが0.001より小さいと、シリコーン油との相溶性に劣り、安定な乳化物を得難い。cが1.5より大きいと親水性に乏しくなるため、やはり安定な乳化物を得難い。
上記式(1)及び/又は(2)で表される(A)成分のノニオンの親水基を有するオルガノポリシロキサンの重量平均分子量は特に限定されるものではないが、500〜200,000、特に1000〜100,000であることが好ましい。また、その配合量は、化粧料全体の0.05〜30重量%の範囲であることが必要であり、特に、化粧料全体の0.1〜15重量%であることが好ましい。
本発明の化粧料には、(A)成分のノニオンの親水基を有するオルガノポリシロキサンと共に、(B)成分として粘土鉱物が用いられる。ここで、用いられる粘土鉱物は有機変性粘土鉱物であることが好ましい。これは、一般に下記一般式(X,Y)2−3(Si,Al)4O10(OH)2Z1/3/nH2O
(但し、XはAl、Fe(III)、Mn(II)、Cr(III)、YはMg、Fe(II)、Ni、Zn、Cr(III)の何れかを表し、ZはK、Na、Caの何れかを表す。)
で表される水膨潤性粘土鉱物を、第四級アンモニウム塩型カチオン界面活性剤で処理して得られるものである。
具体的には、例えば、モンモリロナイト、バイデライド、ノントロライト、サポナイト、及びヘクトライトなどの天然又は合成(この場合、式中の(OH)基がフッ素で置換されたもの)のモンモリロナイト群(市販品ではビーガム、クニピア、スメクトン、ラポナイト等がある)及びナトリウムシリシックマイカやナトリウムテニオライト又はリチウムテニオライトの名で知られる合成雲母(市販品ではダイモナイト等がある)等の粘土鉱物を、第四級アンモニウム塩型カチオン界面活性剤で処理して得られる。
水膨潤性粘土鉱物を有機変性するために用いる第四級アンモニウム塩型カチオン界面活性剤は、下記一般式で表されるものである。
式中のR7は炭素数10〜22のアルキル基又はベンジル基、R8はメチル基又は炭素数10〜22のアルキル基、R9及びR10は炭素数1〜3のアルキル基又はヒドロキシアルキル基、Xはハロゲン原子又はメチルサルフェート残基を表す。このような第四級アンモニウム塩型カチオン界面活性剤の具体例としては、例えば、ドデシルトリメチルアンモニウムクロリド、ミリスチルトリメチルアンモニウムクロリド、セチルトリメチルアンモニウムクロリド、ステアリルトリメチルアンモニウムクロリド、アラキルトリメチルアンモニウムクロリド、ベヘニルトリメチルアンモニウムクロリド;ミリスチルジメチルエチルアンモニウムクロリド、セチルジメチルエチルアンモニウムクロリド、ステアリルジメチルエチルアンモニウムクロリド、アラキルジメチルエチルアンモニウムクロリド、ベヘニルジメチルエチルアンモニウムクロリド;セチルジエチルメチルアンモニウムクロリド、ステアリルジエチルメチルアンモニウムクロリド、アラキルジエチルメチルアンモニウムクロリド、ベヘニルジエチルメチルアンモニウムクロリド、ベンジルジメチルミリスチルアンモニウムクロリド、ベンジルジメチルセチルアンモニウムクロリド、ベンジルジメチルステアリルアンモニウムクロリド、ベンジルジメチルアラキルアンモニウムクロリド、ベンジルジメチルベヘニルアンモニウムクロリド;ベンジルメチルエチルミリスチルアンモニウムクロリド、ベンジルメチルエチルセチルアンモニウムクロリド、ベンジルメチルエチルステアリルアンモニウムクロリド、ベンジルメチルエチルアラキルアンモニウムクロリド、ベンジルメチルエチルベヘニルアンモニウムクロリド;ジステアリルジメチルアンモニウムクロリド、ジベヘニルジヒドロキシエチルアンモニウムクロリド、及び相当するブロミド等、さらにジパルミチルプロピルエチルアンモニウムメチルサルフェート等が挙げらる。これらの界面活性剤は2種以上混合して使用することも出来る。
有機変性粘土鉱物の代表的なものとしては、ジメチルアルキルアンモニウムヘクトライト、ベンジルジメチルステアリルアンモニウムヘクトライト、塩化ジステアリルジメチルアンモニウム処理ケイ酸アルミニウムマグネシウムなどが挙げられる。これらの市販品としては、ベントン27(ベンジルジメチルステアリルアンモニウムクロライド処理ヘクトライト:ナショナルレッド社製)、ベントン38(ジステアリルジメチルアンモニウムクロライド処理ヘクトライト:ナショナルレッド社製)、S−BenW(豊順社製)等がある。
これら(B)成分としての粘土鉱物の配合量は、化粧料全体の0.05〜30重量%の範囲であることが必要であり、特に、化粧料全体の0.1〜15重量%となるように配合することが好ましい。
本発明の化粧料には、その目的に応じ、(C)成分として1種又は2種以上の油剤を配合することができる。この場合、通常の化粧料に使用されるものであれば、固体、半固体、液体、いずれの油剤も使用することができる。例えば、天然動植物油脂類及び半合成油脂としては、アボガド油、アマニ油、アーモンド油、イボタロウ、エノ油、オリーブ油、カカオ脂、カポックロウ、カヤ油、カルナウバロウ、肝油、キャンデリラロウ、牛脂、牛脚脂、牛骨脂、硬化牛脂、キョウニン油、鯨ロウ、硬化油、小麦胚芽油、ゴマ油、コメ胚芽油、コメヌカ油、サトウキビロウ、サザンカ油、サフラワー油、シアバター、シナギリ油、シナモン油、ジョジョバロウ、セラックロウ、タートル油、大豆油、茶実油、ツバキ油、月見草油、トウモロコシ油、豚脂、ナタネ油、日本キリ油、ヌカロウ、胚芽油、馬脂、パーシック油、パーム油、パーム核油、ヒマシ油、硬化ヒマシ油、ヒマシ油脂肪酸メチルエステル、ヒマワリ油、ブドウ油、ベイベリーロウ、ホホバ油、マカデミアナッツ油、ミツロウ、ミンク油、綿実油、綿ロウ、モクロウ、モクロウ核油、モンタンロウ、ヤシ油、硬化ヤシ油、トリヤシ油脂肪酸グリセライド、羊脂、落花生油、ラノリン、液状ラノリン、還元ラノリン、ラノリンアルコール、硬質ラノリン、酢酸ラノリン、ラノリン脂肪酸イソプロピル、POEラノリンアルコールエーテル、POEラノリンアルコールアセテート、ラノリン脂肪酸ポリエチレングリコール、POE水素添加ラノリンアルコールエーテル、卵黄油等が挙げられる。但し、POEはポリオキシエチレンを意味する。
炭化水素油としては、オゾケライト、スクワラン、スクワレン、セレシン、パラフィン、パラフィンワックス、ポリエチレンワックス、ポリエチレン・ポリプロピレンワックス、流動パラフィン、プリスタン、ポリイソブチレン、マイクロクリスタリンワックス、ワセリン等;高級脂肪酸としては、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘン酸、ウンデシレン酸、オレイン酸、リノール酸、リノレン酸、アラキドン酸、エイコサペンタエン酸(EPA)、ドコサヘキサエン酸(DHA)、イソステアリン酸、12−ヒドロキシステアリン酸等が挙げられる。
高級アルコール油としては、ラウリルアルコール、ミリスチルアルコール、パルミチルアルコール、ステアリルアルコール、ベヘニルアルコール、ヘキサデシルアルコール、オレイルアルコール、イソステアリルアルコール、ヘキシルドデカノール、オクチルドデカノール、セトステアリルアルコール、2−デシルテトラデシノール、コレステロール、フィトステロール、POEコレステロールエーテル、モノステアリルグリセリンエーテル(バチルアルコール)、モノオレイルグリセリルエーテル(セラキルアルコール)等が挙げられる。
エステル油としては、アジピン酸ジイソブチル、アジピン酸2−ヘキシルデシル、アジピン酸ジ−2−ヘプチルウンデシル、イソノナン酸イソノニル、モノイソステアリン酸N−アルキルグリコール、イソステアリン酸イソセチル、トリイソステアリン酸トリメチロールプロパン、ジ−2−エチルヘキサン酸エチレングリコール、2−エチルヘキサン酸セチル、トリ−2−エチルヘキサン酸トリメチロールプロパン、テトラ−2−エチルヘキサン酸ペンタエリスリトール、オクタン酸セチル、オクチルドデシルガムエステル、オレイン酸オレイル、オレイン酸オクチルドデシル、オレイン酸デシル、ジカプリン酸ネオペンチルグリコール、クエン酸トリエチル、コハク酸2−エチルヘキシル、酢酸アミル、酢酸エチル、酢酸ブチル、ステアリン酸イソセチル、ステアリン酸ブチル、セバシン酸ジイソプロピル、セバシン酸ジ−2−エチルヘキシル、乳酸セチル、乳酸ミリスチル、パルミチン酸イソプロピル、パルミチン酸2−エチルヘキシル、パルミチン酸2−ヘキシルデシル、パルミチン酸2−ヘプチルウンデシル、12−ヒドロキシステアリル酸コレステリル、ジペンタエリスリトール脂肪酸エステル、ミリスチン酸イソプロピル、ミリスチン酸オクチルドデシル、ミリスチン酸2−ヘキシルデシル、ミリスチン酸ミリスチル、ジメチルオクタン酸ヘキシルデシル、ラウリン酸エチル、ラウリン酸ヘキシル、N−ラウロイル−L−グルタミン酸−2−オクチルドデシルエステル、リンゴ酸ジイソステアリル等;グリセライド油としては、アセトグリセリル、トリイソオクタン酸グリセリル、トリイソステアリン酸グリセリル、トリイソパルミチン酸グリセリル、モノステアリン酸グリセリル、ジ−2−ヘプチルウンデカン酸グリセリル、トリミリスチン酸グリセリル、ミリスチン酸イソステアリン酸ジグリセリル等が挙げられる。
シリコーン油としては、ジメチルポリシロキサン、メチルフェニルポリシロキサン、メチルハイドロジェンポリシロキサン、ジメチルシロキサン・メチルフェニルシロキサン共重合体等の低粘度から高粘度の直鎖状又は分岐状のオルガノポリシロキサン;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、テトラメチルテトラハイドロジェンシクロテトラシロキサン、テトラメチルテトラフェニルシクロテトラシロキサン等の環状シロキサン;高重合度のガム状ジメチルポリシロキサン、ガム状のジメチルシロキサン・メチルフェニルシロキサン共重合体等のシリコーンゴム、及びシリコーンゴムの環状シロキサン溶液;トリメチルシロキシケイ酸、トリメチルシロキシケイ酸の環状シロキサン溶液、ステアロキシシリコーン等の高級アルコキシ変性シリコーン;高級脂肪酸変性シリコーン、アルキル変性シリコーン、アミノ変性シリコーン、フッ素変性シリコーン、シリコーン樹脂及びシリコーンレジンの溶解物等が挙げられる。フッ素系油剤としては、パーフルオロポリエーテル、パーフルオロデカリン、パーフルオロオクタン等が挙げられる。
これら(C)成分としての油剤の配合量は、剤系によっても異なるが、化粧料全体の1〜98重量%の範囲であることが好ましい。
本発明の化粧料には、その目的に応じ、(D)成分として水を配合することも出来る。その配合量は、剤系によっても異なるが、化粧料全体の1〜98重量%の範囲であることが好ましい。
本発明の化粧料には、その目的に応じ、(E)成分として分子構造中にアルコール性水酸基を有する化合物を1種又は2種以上用いることもできる。
本発明において添加することのできるアルコール性水酸基を有する化合物の具体例としては、エタノール、イソプロパノール等の低級アルコール、ソルビトール、マルトース等の糖アルコール等があり、コレステロール、シトステロール、フィトステロール、ラノステロール等のステロール、ブチレングリコール、プロピレングリコール、ジブチレングリコール等の多価アルコール等がある。配合量は、化粧料全体の0.1〜98重量%の範囲であることが好ましい。
本発明の化粧料には、その目的に応じ、(F)成分として水溶性高分子や水膨潤性高分子を1種又は2種以上用いることもできる。このような高分子としては、例えば、アラビアゴム、トラガカント、ガラクタン、キャロブガム、グアーガム、カラヤガム、カラギーナン、ペクチン、寒天、クインスシード(マルメロ)、デンプン(コメ、トウモロコシ、バレイショ、コムギ)、アルゲコロイド、トラントガム、ローカストビーンガム等の植物系高分子;キサンタンガム、デキストラン、サクシノグルカン、プルラン等の微生物系高分子;コラーゲン、カゼイン、アルブミン、ゼラチン等の動物系高分子;カルボキシメチルデンプン、メチルヒドロキシプロピルデンプン等のデンプン系高分子;メチルセルロース、エチルセルロース、メチルヒドロキシプロピルセルロース、カルボキシメチルセルロース、ヒドロキシメチルセルロース、ヒドロキシプロピルセルロース、ニトロセルロース、セルロース硫酸ナトリウム、カルボキシメチルセルロースナトリウム、結晶セルロース、セルロース粉末等のセルロース系高分子;アルギン酸ナトリウム、アルギン酸プロピレングリコールエステル等のアルギン酸系高分子;ポリビニルメチルエーテル、カルボキシビニルポリマー等のビニル系高分子;ポリオキシエチレン系高分子;ポリオキシエチレンポリオキシプロピレン共重合体系高分子;ポリアクリル酸ナトリウム、ポリエチルアクリレート、ポリアクリルアミド等のアクリル系高分子;ポリエチレンイミン、カチオンポリマーなど他の合成水溶性高分子;ベントナイト、ケイ酸アルミニウムマグネシウム、モンモリロナイト、バイデライト、ノントロナイト、サポナイト、ヘクトライト、無水ケイ酸等の無機系水溶性高分子などがある。また、これらの水溶性高分子には、ポリビニルアルコールやポリビニルピロリドン等の皮膜形成剤も含まれる。配合量は、化粧料全体の0.01〜25重量%の範囲であることが好ましい。
本発明の化粧料には、その目的に応じ、(A)成分であるノニオンの親水基を有するシリコーン化合物以外の界面活性剤を、(G)成分として一種又は二種以上用いることもできる。このような界面活性剤としては、アニオン性、カチオン性、非イオン性及び両性の界面活性剤があるが、これらは特に制限されるものではなく、通常の化粧料に使用されるものであれば、いずれのものも使用することができる。
上記のアニオン性界面活性剤としては、ステアリン酸ナトリウムやパルミチン酸トリエタノールアミン等の脂肪酸セッケン、アルキルエーテルカルボン酸及びその塩、アミノ酸と脂肪酸の縮合物塩、アルカンスルホン酸塩、アルケンスルホン酸塩、脂肪酸エステルのスルホン酸塩、脂肪酸アミドのスルホン酸塩、ホルマリン縮合系スルホン酸塩、アルキル硫酸エステル塩、第二級高級アルコール硫酸エステル塩、アルキル及びアリルエーテル硫酸エステル塩、脂肪酸エステルの硫酸エステル塩、脂肪酸アルキロールアミドの硫酸エステル塩、ロート油等の硫酸エステル塩、アルキルリン酸塩、エーテルリン酸塩、アルキルアリルエーテルリン酸塩、アミドリン酸塩、N−アシルアミノ酸系活性剤等;カチオン性界面活性剤としては、アルキルアミン塩、ポリアミン及びアミノアルコール脂肪酸誘導体等のアミン塩、アルキル四級アンモニウム塩、芳香族四級アンモニウム塩、ピリジウム塩、イミダゾリウム塩等が挙げられる。
非イオン性界面活性剤としては、ソルビタン脂肪酸エステル、グリセリン脂肪酸エステル、ポリグリセリン脂肪酸エステル、プロピレングリコール脂肪酸エステル、ポリエチレングリコール脂肪酸エステル、ショ糖脂肪酸エステル、ポリオキシエチレンアルキルエーテル、ポリオキシプロピレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンソルビトール脂肪酸エステル、ポリオキシエチレングリセリン脂肪酸エステル、ポリオキシエチレンプロピレングリコール脂肪酸エステル、ポリオキシエチレンヒマシ油、ポリオキシエチレン硬化ヒマシ油、ポリオキシエチレンフィトスタノールエーテル、ポリオキシエチレンフィトステロールエーテル、ポリオキシエチレンコレスタノールエーテル、ポリオキシエチレンコレステリルエーテル、直鎖或いは分岐状のポリオキシアルキレン変性オルガノポリシロキサン、直鎖状又は分岐状のポリオキシアルキレン・アルキル共変性オルガノポリシロキサン、アルカノールアミド、糖エーテル、糖アミド等が挙げられ、両性界面活性剤としては、ベタイン、アミノカルボン酸塩、イミダゾリン誘導体、アミドアミン型のもの等が挙げられる。これら(G)成分の配合量は、化粧料全体の0.1〜20重量%であることが好ましく、特に0.2〜10重量%の範囲が好ましい。
本発明の化粧料には、その目的に応じて少なくとも1種の架橋型オルガノポリシロキサンを(H)成分として用いることもできる。
この架橋型オルガノポリシロキサンは、0.65mm2/秒〜100.0mm2/秒(25℃)の低粘度シリコーンを、自重以上の量含んで膨潤するものであることが好ましい。また、この架橋型オルガノポリシロキサンの架橋剤は、分子中に二つ以上のビニル性反応部位を持ち、かつ、ケイ素原子に直接結合した水素原子との間で反応することにより、架橋構造を形成するものであることが好ましい。更に、この架橋型オルガノポリシロキサンは、ポリオキシアルキレン部分、アルキル部分、アルケニル部分、アリール部分、及びフルオロアルキル部分からなる群から選択される少なくとも1種の部分を分子中に含有していても良い。これらは特に限定される物ではないが、市販品としては、シリコーン油でゲル状にしたKSG−15、KSG−16、KSG−18、KSG−21(信越化学工業(株)製)等がある。
また、上記架橋型オルガノポリシロキサンとしては、前記0.65mm2/秒〜100.0mm2/秒(25℃)の低粘度シリコーン以外の油剤を自重以上の量含んで膨潤するものも使用される。この架橋型オルガノポリシロキサンの架橋剤は、分子中に二つ以上のビニル性反応部位を持ち、かつ、ケイ素原子に直接結合した水素原子との間で反応することにより、架橋構造を形成するものであることが好ましい。更に、この架橋型オルガノポリシロキサンは、ポリオキシアルキレン部分、アルキル部分、アルケニル部分、アリール部分、及びフルオロアルキル部分からなる群から選択される少なくとも1種の部分を分子中に含有していても良い。これらは特に限定される物ではないが、市販品としては、炭化水素油やトリグリセライド油でゲル状にしたKSG−31、KSG−32、KSG−33、KSG−34、KSG−41、KSG−42、KSG−43、KSG−44(信越化学工業(株)製)等が挙げられる。
架橋型オルガノポリシロキサンを用いる場合の配合量は、化粧料の総量に対して0.01〜40重量%であることが好ましく、特に0.1〜30重量%であることが好ましい。
本発明の化粧料には、その目的に応じて少なくとも1種のシリコーン樹脂を(I)成分として用いることもできる。
このシリコーン樹脂はアクリル/シリコーングラフト又はブロック共重合体のアクリルシリコーン樹脂であることが好ましい。また、ピロリドン部分、長鎖アルキル部分、ポリオキシアルキレン部分及びフルオロアルキル部分、カルボン酸などのアニオン部分の中から選択される少なくとも1種の部分を分子中に含有するアクリルシリコーン樹脂を使用することもできる。
更にこのシリコーン樹脂は構成成分としてMQ、MDQ、MT、MDT、MDTQ等と表されるシリコーン網状化合物であることが好ましい。このM、D、T、Qは、それぞれ、R3SiO0.5単位、R2SiO単位、RSiO1.5単位、SiO2単位を示すものであり、シリコーン業界では一般に使用されるものである。シリコーン網状樹脂は一般にMQレジンあるいはMT、MDTレジンとして知られており、MDQ、MDTQと示される部分を有することもあり、オクタメチルシクロテトラシロキサンなどの溶解物として市販されているものである。また、ピロリドン部分、長鎖アルキル部分、ポリオキシアルキレン部分及びフルオロアルキル部分、アミノ部分の中から選択される少なくとも1種の部分を分子中に含有していても良い。
アクリルシリコーン樹脂やシリコーン網状化合物等のシリコーン樹脂を用いる場合の配合量は、化粧料の総量に対して0.01〜20重量%であることが好ましく、特に0.1〜10重量%であることが好ましい。
本発明の化粧料には、その目的に応じて、粉体及び/又は着色剤を(J)成分として1種又は2種以上用いることもできる。これらは、通常の化粧料に使用されるものであればその形状(球状、針状、板状等)や粒子径(煙霧状、微粒子、顔料級等)、粒子構造(多孔質、無孔質等)を問わず、いずれのものも使用することができる。例えば無機粉体、有機粉体、界面活性剤金属塩粉体、有色顔料、パール顔料、金属粉末顔料、天然色素等があげられる。
具体例を挙げると、無機粉体としては、酸化チタン、酸化ジルコニウム、酸化亜鉛、酸化セリウム、酸化マグネシウム、硫酸バリウム、硫酸カルシウム、硫酸マグネシウム、炭酸カルシウム、炭酸マグネシウム、タルク、マイカ、カオリン、セリサイト、白雲母、合成雲母、金雲母、紅雲母、黒雲母、リチア雲母、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、ケイ酸カルシウム、ケイ酸バリウム、ケイ酸ストロンチウム、タングステン酸金属塩、ヒドロキシアパタイト、バーミキュライト、ハイジライト、ベントナイト、モンモリロナイト、ヘクトライト、ゼオライト、セラミックスパウダー、第二リン酸カルシウム、アルミナ、水酸化アルミニウム、窒化ホウ素、窒化ボロン、シリカ等が挙げられる。
有機粉体としては、ポリアミドパウダー、ポリエステルパウダー、ポリエチレンパウダー、ポリプロピレンパウダー、ポリスチレンパウダー、ポリウレタンパウダー、ベンゾグアナミンパウダー、ポリメチルベンゾグアナミンパウダー、テトラフルオロエチレンパウダー、ポリメチルメタクリレートパウダー、セルロースパウダー、シルクパウダー、12ナイロンや6ナイロン等のナイロンパウダー、ジメチルシリコーンを架橋した構造を持つ架橋型シリコーン微粉末、ポリメチルシルセスキオキサンの微粉末;スチレン・アクリル酸共重合体、ジビニルベンゼン・スチレン共重合体、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、ポリカーボネイト樹脂等の樹脂粉末;微結晶繊維粉体、デンプン粉末、ラウロイルリジン粉末等が挙げられる。
界面活性剤金属塩粉体(金属石鹸)としては、ステアリン酸亜鉛、ステアリン酸アルミニウム、ステアリン酸カルシウム、ステアリン酸マグネシウム、ミリスチン酸亜鉛、ミリスチン酸マグネシウム、セチルリン酸亜鉛、セチルリン酸カルシウム、セチルリン酸亜鉛ナトリウム等の紛体が挙げられ、有色顔料の具体例としては、酸化鉄、水酸化鉄、チタン酸鉄等の無機赤色系顔料、γ−酸化鉄等の無機褐色系顔料、黄酸化鉄、黄土等の無機黄色系顔料、黒酸化鉄、カーボンブラック等の無機黒色系顔料、マンガンバイオレット、コバルトバイオレット等の無機紫色系顔料、水酸化クロム、酸化クロム、酸化コバルト、チタン酸コバルト等の無機緑色系顔料、紺青、群青等の無機青色系顔料、タール系色素をレーキ化したもの、天然色素をレーキ化したもの、及びこれらの粉体を複合化した合成樹脂粉体等が挙げられる。
パール顔料としては、酸化チタン被覆雲母、酸化チタン被覆マイカ、オキシ塩化ビスマス、酸化チタン被覆オキシ塩化ビスマス、酸化チタン被覆タルク、魚鱗箔、酸化チタン被覆着色雲母等;金属粉末顔料としては、アルミニウムパウダー、カッパーパウダー、ステンレスパウダー等;タール色素としては、赤色3号、赤色104号、赤色106号、赤色201号、赤色202号、赤色204号、赤色205号、赤色220号、赤色226号、赤色227号、赤色228号、赤色230号、赤色401号、赤色505号、黄色4号、黄色5号、黄色202号、黄色203号、黄色204号、黄色401号、青色1号、青色2号、青色201号、青色404号、緑色3号、緑色201号、緑色204号、緑色205号、橙色201号、橙色203号、橙色204号、橙色206号、橙色207号等;天然色素としては、カルミン酸、ラッカイン酸、カルサミン、ブラジリン、クロシン等から選ばれる粉体等が挙げられる。
また、微粒子酸化チタン、微粒子鉄含有酸化チタン、微粒子酸化亜鉛、微粒子酸化セリウム及びそれらの複合体等の紫外線を吸収散乱する粉体も挙げられる。
それぞれの具体例は前述したとおりであるが、これらの粉体は本発明の効果を妨げない範囲で、粉体を複合化したものや、一般油剤、シリコーン油、フッ素化合物、界面活性剤等で処理したものも使用することができ、必要に応じて一種、又は二種以上用いることができる。また、配合量は、化粧料全体の0.1〜50重量%の範囲であることが好ましい。
更に本発明の化粧料には、本発明の効果を妨げない範囲で、通常の化粧料に使用される成分、例えば、(B)成分である粘土鉱物以外の油溶性ゲル化剤、樹脂、制汗剤、紫外線吸収剤、紫外線吸収散乱剤、保湿剤、防腐剤、抗菌剤、香料、塩類、酸化防止剤、pH調整剤、キレート剤、清涼剤、抗炎症剤、美肌用成分(美白剤、細胞賦活剤、肌荒れ改善剤、血行促進剤、皮膚収斂剤、抗脂漏剤等)、ビタミン類、アミノ酸類、核酸、ホルモン、包接化合物、毛髪用固形化剤等を添加することができる。
上記油溶性ゲル化剤としては、アルミニウムステアレート、マグネシウムステアレート、ジンクミリステート等の金属セッケン、N−ラウロイル−L−グルタミン酸、α,γ−ジ−n−ブチルアミン等のアミノ酸誘導体、デキストリンパルミチン酸エステル、デキストリンステアリン酸エステル、デキストリン2−エチルヘキサン酸パルミチン酸エステル等のデキストリン脂肪酸エステル、ショ糖パルミチン酸エステル、ショ糖ステアリン酸エステル等のショ糖脂肪酸エステル、モノベンジリデンソルビトール、ジベンジリデンソルビトール等のソルビトールのベンジリデン誘導体から選ばれるゲル化剤が挙げられる。
制汗剤としては、アルミニウムクロロハイドレート、塩化アルミニウム、アルミニウムセスキクロロハイドレート、ジルコニルヒドロキシクロライド、アルミニウムジルコニウムヒドロキシクロライド、アルミニウムジルコニウムグリシン錯体等から選ばれる制汗剤が挙げられる。
紫外線吸収剤としては、パラアミノ安息香酸等の安息香酸系紫外線吸収剤、アントラニル酸メチル等のアントラニル酸系紫外線吸収剤、サリチル酸メチル等のサリチル酸系紫外線吸収剤、パラメトキシケイ皮酸オクチル等のケイ皮酸系紫外線吸収剤、2,4−ジヒドロキシベンゾフェノン等のベンゾフェノン系紫外線吸収剤、ウロカニン酸エチル等のウロカニン酸系紫外線吸収剤、4−t−ブチル−4’−メトキシ−ジベンゾイルメタン等のジベンゾイルメタン系紫外線吸収剤等が挙げられ、紫外線吸収散乱剤としては、微粒子酸化チタン、微粒子鉄含有酸化チタン、微粒子酸化亜鉛、微粒子酸化セリウム及びそれらの複合体等、紫外線を吸収散乱する粉体が挙げられる。
保湿剤としては、グリセリン、ソルビトール、プロピレングリコール、ジプロピレングリコール、1,3−ブチレングリコール、グルコース、キシリトール、マルチトール、ポリエチレングリコール、ヒアルロン酸、コンドロイチン硫酸、ピロリドンカルボン酸塩、ポリオキシエチレンメチルグルコシド、ポリオキシプロピレンメチルグルコシド等がある。
塩としては、無機塩、有機酸塩、アミン塩及び/又はアミノ酸塩、その他の塩がある。たとえば、塩酸、硫酸、炭酸、硝酸等の無機物のナトリウム塩、カリウム塩、マグネシウム塩、カルシウム塩、アルミニウム塩、ジルコニウム塩、亜鉛塩から選ばれる無機塩、酢酸、デヒドロ酢酸、クエン酸、りんご酸、コハク酸、アスコルビン酸、ステアリン酸等の有機酸類の塩、トリエタノールアミン等のアミン類の塩、グルタミン酸等のアミノ酸類の塩、その他、ヒアルロン酸、コンドロイチン硫酸等の塩、アルミニウムジルコニウムグリシン錯体等があり、さらに化粧品処方中で使用される酸−アルカリ中和塩からも選ぶことができる。
防菌防腐剤としては、パラオキシ安息香酸アルキルエステル、安息香酸、安息香酸ナトリウム、ソルビン酸、ソルビン酸カリウム、フェノキシエタノール等、抗菌剤としては、安息香酸、サリチル酸、石炭酸、ソルビン酸、パラオキシ安息香酸アルキルエステル、パラクロルメタクレゾール、ヘキサクロロフェン、塩化ベンザルコニウム、クロルヘキシジン、トリクロロカルバニリド、感光素、フェノキシエタノール等がある。
酸化防止剤としては、トコフェロール、ブチルヒドロキシアニソール、ジブチルヒドロキシトルエン、フィチン酸等、pH調整剤としては、乳酸、クエン酸、グリコール酸、コハク酸、酒石酸、dl−リンゴ酸、炭酸カリウム、炭酸水素ナトリウム、炭酸水素アンモニウム等;キレート剤としては、アラニン、エデト酸ナトリウム塩、ポリリン酸ナトリウム、メタリン酸ナトリウム、リン酸等、清涼剤としては、L−メントール、カンフル等、抗炎症剤としては、アラントイン、グリチルリチン酸及びその塩、グリチルレチン酸及びグリチルレチン酸ステアリル、トラネキサム酸、アズレン等が挙げられる。
美肌用成分としては、胎盤抽出液、アルブチン、グルタチオン、ユキノシタ抽出物等の美白剤、ロイヤルゼリー、感光素、コレステロール誘導体、幼牛血液抽出液等の細胞賦活剤、肌荒れ改善剤、ノニル酸ワレニルアミド、ニコチン酸ベンジルエステル、ニコチン酸β−ブトキシエチルエステル、カプサイシン、ジンゲロン、カンタリスチンキ、イクタモール、カフェイン、タンニン酸、α−ボルネオール、ニコチン酸トコフェロール、イノシトールヘキサニコチネート、シクランデレート、シンナリジン、トラゾリン、アセチルコリン、ベラパミル、セファランチン、γ−オリザノール等の血行促進剤、酸化亜鉛、タンニン酸等の皮膚収斂剤、イオウ、チアントロール等の抗脂漏剤等が挙げられる。
ビタミン類としては、ビタミンA油、レチノール、酢酸レチノール、パルミチン酸レチノール等のビタミンA類;リボフラビン、酪酸リボフラビン、フラビンアデニンヌクレオチド等のビタミンB2類、ピリドキシン塩酸塩、ピリドキシンジオクタノエート、ピリドキシントリパルミテート等のビタミンB6類、ビタミンB12及びその誘導体、ビタミンB15及びその誘導体等のビタミンB類;L−アスコルビン酸、L−アスコルビン酸ジパルミチン酸エステル、L−アスコルビン酸−2−硫酸ナトリウム、L−アスコルビン酸リン酸ジエステルジカリウム等のビタミンC類;エルゴカルシフェロール、コレカルシフェロール等のビタミンD類;α−トコフェロール、β−トコフェロール、γ−トコフェロール、酢酸dl−α−トコフェロール、ニコチン酸dl−α−トコフェロール、コハク酸dl−α−トコフェロール等のビタミンE類;ビタミンH;ビタミンP;ニコチン酸、ニコチン酸ベンジル、ニコチン酸アミド等のニコチン酸類;パントテン酸カルシウム、D−パントテニルアルコール、パントテニルエチルエーテル、アセチルパントテニルエチルエーテル等のパントテン酸類;ビオチン等がある。
アミノ酸類としては、グリシン、バリン、ロイシン、イソロイシン、セリン、トレオニン、フェニルアラニン、アルギニン、リジン、アスパラギン酸、グルタミン酸、シスチン、システイン、メチオニン、トリプトファン等;核酸としては、デオキシリボ核酸等;ホルモンとしては、エストラジオール、エテニルエストラジオール等が挙げられる。
毛髪固定用高分子化合物としては、両性、アニオン性、カチオン性、非イオン性の各高分子化合物が挙げられる。具体例としては、ポリビニルピロリドン、ビニルピロリドン/酢酸ビニル共重合体等の、ポリビニルピロリドン系高分子化合物;メチルビニルエーテル/無水マレイン酸アルキルハーフエステル共重合体等の酸性ビニルエーテル系高分子化合物;酢酸ビニル/クロトン酸共重合体等の酸性ポリ酢酸ビニル系高分子;(メタ)アクリル酸/アルキル(メタ)アクリレート共重合体、(メタ)アクリル酸/アルキル(メタ)アクリレート/アルキルアクリルアミド共重合体等の酸性アクリル系高分子化合物;N−メタクリロイルエチル−N、N−ジメチルアンモニウム・α−N−メチルカルボキシベタイン/アルキル(メタ)アクリレート共重合体、ヒドロキシプロピル(メタ)アクリレート/ブチルアミノエチルメタクリレート/アクリル酸オクチルアミド共重合体等の両性アクリル系高分子化合物が挙げられる。また、セルロースまたはその誘導体、ケラチンおよびコラーゲンまたはその誘導体等の天然高分子化合物も好適に用いることができる。
本発明における化粧料としては、化粧水、乳液、クリーム、クレンジング、パック、オイルリキッド、マッサージ料、洗浄剤、脱臭剤、ハンドクリーム、リップクリーム等のスキンケア化粧料;メークアップ下地、リキッドファンデーション、油性ファンデーション、頬紅、アイシャドウ、マスカラ、アイライナー、アイブロウ、口紅等のメークアップ化粧料;シャンプー、リンス、トリートメント、セット剤等の毛髪化粧料;制汗剤化粧料、日焼け止め乳液や日焼け止めクリームなどの紫外線防御化粧料等が挙げられる。
またこれらの化粧料の形状としては、液状、乳液状、クリーム状、固形状、ペースト状、ゲル状、粉末状、プレス状、多層状、ムース状、スプレー状、スティック状等、種々の形態を選択することができる。
また、これらの化粧料は、低粘度のものから高粘度のものにいたるまで、温度や経時による変化のない良好な安定性を有する化粧料を得ることができるが、特に本発明においては、粘度が8000mm2/秒(25℃)以下の化粧料の場合でも、温度や経時による変化のない良好な安定性を有する化粧料を得ることができる。また、油中水型乳化化粧料の場合には、低粘度化粧料の安定性を得ることは一般的に非常に難しいが、本発明においては、特定のノニオンの親水基を有するオルガノポリシロキサンと粘土鉱物を含有するので、粘度が8000mm2/秒(25℃)以下の低粘度油中水型乳化化粧料であっても、温度や経時による変化のない非常に良好な安定性を確保することが出来る。
実施例.
以下に、本発明に関して実施例を挙げて説明するが、本発明は、これらによって何ら限定されるものではない。なお、下記一般式においてMe3SiO1/2をM、Me2SiO基をD、Me2HSiO1/2基をMH、MeHSiO基をDHと表記し、MおよびD中のメチル基を置換基Rによって変性した単位をMRおよびDRと表記する。尚,特に断らない限り,以下に記載する「%」は「重量%」を意味する。
製造例1.
反応器に、エチレングリコールモノアリルエーテル{2−(アリルオキシ)エタノール}120gおよび塩化白金酸0.5%のイソプロピルアルコール(IPA)溶液0.05gを仕込み、ペンタメチルジシロキサン148gを50℃で1時間かけて滴下した。滴下直後から発熱が観測され、滴下終了後の内温は110℃であった。
次いで減圧蒸留を行い、100−110℃の留分をとり、平均組成式MMR*1で表されるシロキサン化合物1を得た。このシロキサン化合物1は、無色透明な液状であった。但し、R*1は−C3H6OCH2CH2OHである。
製造例2.
反応器に、平均組成式(M2D11DH 7)のメチルハイドロジェンポリシロキサン170g、ジグリセリンモノアリルエーテル230gおよびイソプロピルアルコール(IPA)200gおよび塩化白金酸0.5%のIPA溶液0.1gを仕込み、溶剤の還流下に反応を行わせた。反応物を減圧下で加熱して溶剤を溜去する事により、平均組成式M2D11DR*2 7で表されるシロキサン化合物2を得た。但し、R*2は−C3H6OCH2CH(OH)CH2OCH2CH(OH)CH2OHである。
このシロキサン化合物2は淡黄色透明な液状であり、粘度は86.0Pa・秒(25℃)、比重は1.1186(25℃)、屈折率は1.4586(25℃)であった。
製造例3.
反応器に、平均組成式(M2D60DH 3)のメチルハイドロジェンポリシロキサン480g、下記(化1)で表されるアリルエーテル誘導体140g、イソプロピルアルコール(IPA)140gおよび塩化白金酸0.5%のIPA溶液0.3gを仕込み、溶剤の還流下に8時間反応を行わせた。
冷却後、反応液をオートクレーブに移した後ラネーニッケル40gを添加し、水素を導入して120℃で3時間反応を行わせた。反応中、水素圧を0.5MPaに保持した。
触媒を濾過した反応混合物を再度反応器に仕込み、0.1NのHCl水溶液28gを添加して、70℃で3時間加水分解を行わせ、アセトンを留出させた。
5%の重曹水5gを添加して中和したのち減圧留去(〜110℃/400Pa)を行い、濾過することによって平均組成式M2D60DR*3 3で表されるシロキサン化合物3を得た。但し、R*3は−C3H6OCH{CH2OCH2CH(OH)CH2OH}2である。
このシロキサン化合物3は淡黄色透明な液状であり、粘度は12.0Pa・秒(25℃)、屈折率は1.417(25℃)であった。
製造例4.
反応器に、平均組成式(M2D40DH 8)のメチルハイドロジェンポリシロキサン360g、前記(化1)で表されるアリルエーテル誘導体130g、1−ヘキサデセン120g、イソプロピルアルコール(IPA)180gおよび塩化白金酸0.5%のIPA溶液0.3gを仕込み、溶剤の還流下に8時間反応させた。冷却後、反応液をオートクレーブに移し、ラネーニッケル40gを添加して水素を導入し、120℃で3時間反応を行わせた。反応中、水素圧を0.5MPaに保持した。
触媒を濾過した反応混合物を再度反応器に仕込み、0.1NのHCl水溶液を26g添加して、70℃で3時間加水分解を行い、アセトンを留出させた。
5%の重曹水4.5gを添加して中和したのち、減圧留去(〜110℃/400Pa)を行い、濾過することによって平均組成式M2D40DR*3 3D1−ヘキサデセン 5で表されるシロキサン化合物4を得た。
このシロキサン化合物4は淡黄色透明な液状であり、粘度は11.0Pa・秒(25℃)、屈折率は1.413(25℃)であった。
製造例5.
反応器に、平均組成式(M2DDH 3)のメチルハイドロジェンポリシロキサン化合物50g、アリルグルコシド300g、及びエチルアルコール400重量部を仕込み、塩化白金酸3%のIPA溶液0.2gを加えて80℃で5時間反応させた。反応液をオートクレーブに移した後ラネーニッケルを50g添加し、水素を導入して100℃で3時間反応を行わせた。反応中、水素圧を1MPaに保持した。触媒を濾過した後、減圧留去(〜110℃/400Pa)することによって粘稠なシロキサン化合物5を300g得た。収率は85%であった。
製造例6.
反応器に、平均組成式(M2DH 2)のメチルハイドロジェンポリシロキサン282gを仕込み、ペンタメチルビニルジシロキサン174gと塩化白金酸0.5%のトルエン溶液0.1gの混合物を滴下し、室温下で撹拌して分岐状ポリシロキサンを得た。別の反応器にジグリセリンモノアリルエーテル210g、イソプロピルアルコール(IPA)210gおよび塩化白金酸0.5%のIPA溶液0.1gを仕込み、先に合成した分岐状ポリシロキサンを溶剤の還流下に滴下して添加した。反応物を減圧下で加熱し、溶剤を溜去する事によって平均組成式M2DR*2DR*4で表されるシロキサン化合物6を得た。
R*4は
である。
このシロキサン化合物6は淡黄色透明な液状であり、粘度は420mm2/秒(25℃)、比重は0.982(25℃)、屈折率は1.4363(25℃)であった。
製造例7.
反応器に、平均組成式(M2DH 2)のメチルハイドロジェンポリシロキサン280g、不飽和度3.48meq/gのポリグリセリンアリルエーテル290g、イソプロピルアルコール(IPA)300gおよび塩化白金酸0.5%のIPA溶液0.3gを仕込み、溶剤の還流下に8時間反応を行わせた。さらに、ペンタメチルビニルジシロキサン174gを溶剤の還流下に滴下して反応を完結させた。
冷却後、減圧留去(〜110℃/400Pa)を行い、濾過することによって平均組成式M2DR*4DR*5で表されるシロキサン化合物7を得た。但し、R*5は−C3H6OCH5CH(CH5OH)O−(CH5CH(OH)CH5OH)mである。
このシロキサン化合物は淡黄色透明な液状であり、粘度は1200mm2/秒(25℃)、屈折率は1.4367(25℃)であった。
製造例8.
反応器に、平均組成式(M2DH 8)のメチルハイドロジェンポリシロキサン320gを仕込み、ペンタメチルビニルジシロキサン270gと塩化白金酸0.5%のトルエン溶液0.1gの混合物を滴下して室温下で撹拌し、分岐状ポリシロキサンを得た。別の反応器に前記(化1)で表されるアリルエーテル誘導体110g、イソプロピルアルコール(IPA)110gおよび塩化白金酸0.5%のIPA溶液0.3gを仕込み、先に合成した分岐状ポリシロキサンを溶剤の還流下に滴下して添加した。更に0.1NのHCl水溶液22gを添加し、70℃で3時間加水分解させ、アセトンを留出させた。5%の重曹水4.0gを添加して中和したのち、反応物を減圧下で加熱して溶剤を溜去し、平均組成式MDR*4 3DR*3 5で表されるシロキサン化合物8を得た。
このシロキサン化合物8は無色透明な液状であり、粘度は174Pa・秒(25℃)、屈折率は1.4687(25℃)であった。
製造例9.
反応器に、平均組成式(M2D40DH 8)で表されるオルガノハイドロジェンシロキサン110gを仕込み、下記平均組成式で表されるオルガノポリシロキサン60gと塩化白金酸0.5%のトルエン溶液0.2部との混合物を滴下し、80℃で3時間反応させた。
次いで、オレイルポリオキシプロピレン−3−アリルエーテル{日本乳化剤(株)製RG−1252(商品名)}48gを添加し、3時間加熱還流することによって反応を完結させた。さらに、前記(化1)で表されるアリルエーテル誘導体30gとIPA100gを加え、80℃で3時間反応させた。
溶剤を減圧下で加熱して溜去し、平均組成式M2D40DR*6 2DR*3 3DR*7 3で表されるシロキサン化合物9を得た。このシロキサン化合物9は、淡褐色透明な液状であり、粘度は320mm2/秒(25℃)、比重は0.980(25℃)、屈折率は1.4275(25℃)であった。但し、
R*6は
R*7は−C3H6O(C3H6O)3C18H35である。
製造例10.
反応器に、平均組成式(M2DH 8)のメチルハイドロジェンポリシロキサン32gを仕込み、ペンタメチルビニルジシロキサン17.5gと塩化白金酸0.5%のトルエン溶液0.1gの混合物を滴下し、室温下で撹拌して分岐状ポリシロキサンを得た。別の反応器にアリルグルセライド(α−体及びβ−体の混合物であり約10%の2量体を含有する)の60%IPA溶液150g、イソプロピルアルコール(IPA)150gおよび塩化白金酸0.5%のIPA溶液0.1gを仕込み、先に合成した分岐状ポリシロキサンを溶剤の還流下に滴下して添加した。反応物を減圧下で加熱して溶剤を溜去する事により、無色粉末状の、平均組成式M2DR*4 2DR*8 6で表されるシロキサン化合物10を得た。但し、R*8は下記(化2)で表されるものである。
製造例11.
反応器に、平均組成式(M2D10DH 5)のメチルハイドロジェンポリシロキサン300gを仕込み、下記平均組成式で表されるオルガノポリシロキサン440gと塩化白金酸0.5%のトルエン溶液0.1gの混合物を滴下し、室温下で撹拌して分岐状ポリシロキサンを得た。
別の反応器に、アリルグリセライド(α−体及びβ−体の混合物であり約10%の2量体を含有する)の60%IPA溶液370g、イソプロピルアルコール(IPA)370gおよび塩化白金酸0.5%のIPA溶液0.1gを仕込み、先に合成した分岐状ポリシロキサンを溶剤の還流下に滴下して添加した。反応物を減圧下で加熱して溶剤を溜去する事により、淡黄色透明な非水溶性のガム状物である、平均組成式M2D10DR*6 2DR*8 3で表されるシロキサン化合物11を得た。
製造例12.
反応器に、平均組成式(M2D42DH 5)のメチルハイドロジェンポリシロキサン350gを仕込み、下記平均組成式で表されるビニルオルガノポリシロキサン160gと塩化白金酸0.5%のトルエン溶液0.2gの混合物を滴下し、室温下で撹拌して分岐状ポリシロキサンを得た。
別の反応器に、前記(化1)で表されるアリルエーテル誘導体140g、イソプロピルアルコール(IPA)200gおよび塩化白金酸0.5%のIPA溶液0.3gを仕込み、先に合成した分岐状ポリシロキサンを溶剤の還流下に滴下して添加した。次いで0.1NのHCl水溶液を28g添加し、70℃で3時間加水分解し、アセトンを留出させた。
反応物を減圧下で加熱して溶剤を溜去する事により、平均組成式M2D42DR*6 2DR*3 3で表されるオルガノポリシロキサン12を得た。
この生成物は無色透明な液状であり、粘度は1100mm2/秒(25℃)、比重は0.990(25℃)、屈折率は1.4150(25℃)であった。
製造例13.
反応器に、平均組成式(DH 4)のメチルハイドロジェンシクロポリシロキサン120gを仕込み、ペンタメチルビニルジシロキサン180gと塩化白金酸0.5%のトルエン溶液0.1gの混合物を滴下し、室温下で撹拌して分岐状ポリシロキサンを得た。別の反応器に、グリセリンモノアリルエーテル140g、イソプロピルアルコール(IPA)140gおよび塩化白金酸0.5%のIPA溶液0.1gを仕込み、先に合成した分岐状ポリシロキサンを溶剤の還流下に滴下して添加した。反応物を減圧下で加熱して溶剤を溜去する事により、平均組成式DR*4 2DR*9 2で表されるシロキサン化合物13を得た。
但し、R*9は−C3H6OCH2CH(OH)CH2OHである。
このシロキサン化合物13は無色透明な液状であり、粘度は1650mm2/秒(25℃)、比重は1.027(25℃)、屈折率は1.4494(25℃)であった。
実施例1〜6及び比較例1〜4:W/O乳化物
表1に示す組成の油系材料に水系材料を添加することにより、W/O乳化物を調製した。
各乳化物の25℃における粘度、室温及び50℃での安定性テスト、塗布時ののび広がりの良さ、べたつきのなさ、並びに後肌のさっぱり感について使用テストを行ない、以下の基準で評価してその平均点で判定した。その結果は表2に示した通りである。
(評価方法)
(安定性)
◎:安定、△:分離気味、×:分離
(使用感)
[評価基準]
5点:非常に良好
4点:良好
3点:普通
2点:やや不良
1点:不良
[判定]
◎:平均点4.5以上
○:平均点3.5以上4.5未満
△:平均点2.5以上3.5未満
×:平均点2.5未満
表2の結果から明らかなように、本発明の実施例1〜6の乳化物は、粘度が8000mm2/秒(25℃)以下であるにもかかわらず、室温及び50℃での安定性が非常に優れている事が分かる。また、実施例1〜6の乳化物は、比較例1〜4の乳化物に比べて、塗布時ののび広がりが良いだけでなく、べたつきもなく、後肌もさらっとして使用感の良い乳化物であった。
実施例7:油中多価アルコール乳化化粧料
(注1)架橋型ジメチルポリシロキサン:KSG15(信越化学工業(株)社製)
(製造方法)
A:成分1〜5、及び7を均一に混合した。
B:成分6を8に溶解し、A)に加えて均一に乳化した。
このようにして得られた油中多価アルコール乳化化粧料は、のび広がりが軽くてべたつきや油っぽさがなく、後肌のしっとりしたものであった。また安定性の良い油中多価アルコール乳化化粧料であることが確認された。
実施例8:固型状油中多価アルコール乳化ファンデーション
(注1)架橋型ジメチルポリシロキサン:KSG15(信越化学工業(株)社製)
(製造方法)
A:成分1〜7、9及び10を80℃に加熱し、均一に混合した。
B:成分8をAに添加し、均一に分散した。
C:あらかじめ80℃に加熱した成分11をB)に加えて乳化した。
このようにして得られた固型状油中多価アルコール乳化ファンデーションは、のび広がりが軽くてべたつきや油っぽさがなく、後肌のしっとりしたものであった。また安定性の良い固型状油中多価アルコール乳化ファンデーションであることが確認された。
実施例9:乳液
(製造方法)
A)成分1〜5を混合した。
B)成分6〜9を混合した後、上記A)を加えて乳化した。
このようにして得られた乳液は、べたつきがなく、のび広がりも軽い上密着感に優れ、おさまりも良く、つやのある仕上がりが得られるものであった。また安定性の良い乳液であることが確認された。
実施例10:油中水型クリーム
(注1)ポリエーテル変性分岐状シリコーン:KF−6028(信越化学工業(株)社製)
(製造方法)
A)成分1〜6を混合した。
B)成分7〜10を混合し、上記A)に加えて攪拌乳化した。
このようにして得られた油中水型クリームは、油っぽさやべたつきがなく、のび広がりも軽くさっぱりとしたものである上密着感に優れ、おさまりも良く、つやのある仕上がりが得られるものであった。また安定性にも非常に優れた油中水型クリームであることが確認された。
実施例11:油中水型クリーム
(注1)架橋型ポリエーテル変性シリコーン:KSG−21(信越化学工業(株)社製)
(製造方法)
A)成分1〜4を混合した。
B)成分5〜10を混合溶解し、上記A)に加えて攪拌乳化した。
このようにして得られた油中水型クリームは、油っぽさやべたつきがなく、のび広がりも軽く、みずみずしいさっぱりとした使用性を持つ上密着感に優れ、おさまりも良いものであった。またマット感のある仕上がりが得られる安定性に優れた油中水型クリームであることが確認された。
実施例12:油中水型メイクアップ下地
(注1)架橋型ポリエーテル変性シリコーン:KSG−21(信越化学工業(株)社製)
(注2)架橋型ジメチルポリシロキサン:KSG−15(信越化学工業(株)社製)
(注3)酸化チタン/シクロペンタシロキサン分散物:SPD−T1S(信越化学工業(株)社製)
(注4)メチルセルロース:メトローズ65−SH4000(信越化学工業(株)社製)
(製造方法)
A)成分1〜8を混合した。
B)成分9〜13、及び15を混合溶解した。
C)上記B)をA)に加えて攪拌乳化し、成分14を添加した。
このようにして得られた油中水型メイクアップ下地は、油っぽさやべたつきがなく、のび広がりも軽く、みずみずしいさっぱりとした使用性を持つ上密着感に優れ、おさまりも良いものであった。またマット感のある仕上がりが得られ、さらに紫外線カット効果のある化粧持ちの良い安定性にも優れた油中水型メイクアップ下地であることが確認された。
実施例13:水中油型クリーム
(注1)架橋型ジメチルポリシロキサン:KSG−16(信越化学工業(株)社製)
(製造方法)
A)成分1〜5を混合した。
B)成分6〜9、及び11を混合溶解した。
C)上記A)を上記B)に加えて攪拌乳化し、成分10を添加した。
このようにして得られた水中油型クリームは、のび広がりの軽い、さっぱりとした使用性を持つ、安定性にも優れた水中油型クリームであることが確認された。
実施例14:油中水型クリーム
(注1)疎水化処理微粒子酸化チタン:平均粒径0.05μmの微粒子酸化チタンを10重量%になるように水に分散させ、次いでSiO2換算で酸化チタンに対して2重量%に相当する量の10重量%ケイ酸ナトリウム溶液(SiO2/Na2Oモル比=0.5)を加えて十分攪拌した後、Al2O3換算で酸化チタンに対して7.5重量%に相当する量の10重量%硫酸アルミニウム溶液を徐々に添加し、酸化チタンの表面にケイ酸の水和物及びアルミナの水和物を沈着させた。反応終了後、ろ過・洗浄・乾燥した後、ジェットミルで粉砕した。これをアクリル−シリコーン系グラフト共重合体(注2)4重量%を加えたイソプロピルアルコール100gに添加し、十分攪拌した後溶媒を留去し、120℃で焼成処理を行った。
(注2)アクリル−シリコーン系グラフト共重合体:KP−541(信越化学工業(株)社製)
(製造方法)
A:成分1〜6を混合し、成分7を添加して均一にした。
B:成分8〜10、及び12を混合溶解した。
C:攪拌下、AにBを徐添して乳化し、成分11を添加してクリームを得た。
このようにして得られた油中水型クリームは、キメが細かく、のび広がりが軽くてべたつきや油っぽさがない上しっとりとしてみずみずしく、さっぱりとした使用感を与えるものであった。また化粧持ちも非常に良く、温度変化や経時による変化がなく安定性に非常に優れていることが確認された。
実施例15:油中水型クリーム
(注1)アルキル変性架橋型ポリエーテル変性シリコーン:KSG−31(信越化学工業(株)社製)
(注2)アルキル・ポリエーテル共変性シリコーン:KF−6026(信越化学工業(株)社製)
(注3)ハイブリッドシリコーン複合粉体:KSP−100(信越化学工業(株)社製)
(注4)アクリル−シリコーン系グラフト共重合体:KP−541(信越化学工業(株)社製)
(製造方法)
A:成分1〜8、及び13を混合した。
B:成分9〜12、及び14を混合溶解し、Aに加えて攪拌乳化した。
このようにして得られた油中水型クリームは、キメが細かく、のび広がりが軽くてべたつきや油っぽさがない上しっとりとしてみずみずしく、さっぱりとした使用感を与えるものであった。また化粧持ちも非常に良く、温度変化や経時による変化がなく安定性に優れていることが確認された。
実施例16:油中水型クリーム
(注1)無水ケイ酸処理酸化亜鉛:酸化亜鉛を50%内包した粒子径0.01〜10μmのシリカ:サンスフェアSZ−5(旭硝子社製)
(注2)オウゴンエキス:50% 1,3−ブチレングリコール水で抽出したもの
(注3)ゲンチアナエキス:20% エタノール水で抽出したもの
(製造方法)
A:成分8〜11、及び17を均一に混合分散した。
B:成分1〜7を混合し、Aを加えた。
C:成分12〜16及び18を混合した後、Bを加えて乳化した。
このようにして得られた油中水型クリームは、キメが細かく、べたつきがなく、のび広がりも軽い上密着感に優れ、おさまりも良く、つやのある仕上がりで化粧持ちも非常に優れていた。また、温度変化や経時によって変化することがなく、安定性にも優れていることが確認された。
実施例17:アイライナー
(注1)有機シリコーン樹脂:KF−7312J(信越化学工業(株)社製)
(製造方法)
A:成分1〜4を混合し、成分5を加えて均一に混合分散した。
B:成分6〜9を混合した。
C:BをAに徐添して乳化し、アイライナーを得た。
以上のようにして得られたアイライナーは、のびが軽くて描きやすく、清涼感があってさっぱりとし、更にべたつきがない使用感であった。また、温度変化や経時による変化もなく、使用性も安定性も非常に優れており、耐水性、耐汗性に優れることはもとより、化粧持ちも非常に良いことが確認された。
実施例18:アイシャドウ
(製造方法)
A:成分1〜5及び12を混合し、成分6〜8を添加して均一に分散した。
B:成分9〜11及び13を均一に溶解した。
C:攪拌下、AにBを徐添して乳化し、アイシャドウを得た。
このようにして得られたアイシャドウは、のび広がりが軽い上油っぽさや粉っぽさがなく、みずみずしく、さっぱりとした使用感を与えるものであった。また耐水性や撥水性、耐汗性が良好で持ちも良く、化粧崩れしにくい上、温度変化や経時による変化がなく安定性にも優れていることが確認された。
実施例19:ファンデーション
(製造方法)
A:成分1〜4、及び15を混合し、成分5〜10を添加して均一にした。
B:成分11〜14、及び16を均一に混合した(水系のpHは9.0)。
C:攪拌下、AにBを徐添して乳化し、ファンデーションを得た。
このようにして得られたファンデーションは、キメが細かい上、のび広がりが軽くてべたつきや油っぽさがなく、しっとりとしてみずみずしく、さっぱりとした使用感を与えるものであった。また化粧持ちも良く、温度変化や経時による変化がない上安定性にも優れていることが確認された。
実施例20:液状乳化ファンデーション
(注1)架橋型ポリエーテル変性シリコーン:KSG21(信越化学工業(株)社製)
(製造方法)
A:成分1〜10を加熱混合し、成分11〜16を添加して均一にした。
B:成分17〜19及び21を加熱溶解した。
C:攪拌下、AにBを徐添して乳化し、冷却した後成分20を添加して液状乳化ファンデーションを得た。
このようにして得られた液状乳化ファンデーションは、粘度が低くキメが細かく、のび広がりが軽くてべたつきや油っぽさがない上しっとりとしてみずみずしく、さっぱりとした使用感を与えるものであった。また化粧持ちも良く、温度変化や経時による変化がない上安定性にも優れていることが確認された。
実施例21:液状ファンデーション
(注1)フッ素変性シリコーン:FL−50(信越化学工業(株)社製)
(注2)フッ素アルキル・ポリエーテル共変性シリコーン:FPD−4694(信越化学工業(株)社製)
(注3)球状ポリメチルシルセスキオキサン粉体:KMP590(信越化学工業(株)社製)
(注4)アクリル−シリコーン系グラフト共重合体:KP−541(信越化学工業(株)社製)
(製造方法)
A:成分9〜15を均一に混合した。
B:成分1〜8を70℃に加熱混合し、Aを加えて均一に分散混合した。
C:成分16〜19及び21を40℃に加温した後Bに徐添して乳化し、冷却して成分20を加え、液状ファンデーションを得た。
このようにして得られた液状ファンデーションは、べたつきがなく、のび広がりも軽い上さっぱりとした高い清涼感を有し、温度変化や経時による変化がなく、安定性の非常に優れたものであることが確認された。
実施例22:クリームファンデーション
(注1)架橋型ポリエーテル変性シリコーン:KSG−21(信越化学工業(株)社製)
(注2)フッ素変性シリコーン複合粉体:KSP−200(信越化学工業(株)社製)
(注3)アクリル−シリコーン系グラフト共重合体:KP−545(信越化学工業(株)社製)
(製造方法)
A)成分1〜7を混合した。
B)成分10〜12、及び14を混合溶解し、上記A)に加えて攪拌乳化した。
C)成分8〜9を混合し、上記B)に加え、さらに成分13を添加して均一にした。
このようにして得られたクリームファンデーションは、べたつきがなく、のび広がりも軽く、しかも、密着感に優れ、おさまりも良いものであった。また、マット感のある仕上がりが得られる上、安定性に優れたクリームファンデーションであることが確認された。
実施例23:油中水型コンパクトファンデーション
(注1)アルキル・ポリエーテル共変性シリコーン:KF−6026(信越化学工業(株)社製)
(注2)アルキル変性架橋型ポリエーテル変性シリコーン:KSG−33(信越化学工業(株)社製)
(製造方法)
A)成分1〜9を加熱溶解した。
B)成分10〜13及び15を成分14に添加し、均一に混合した。
C)成分17を上記B)に加えて均一に分散した。
D)上記C及び成分16を上記A)に加えて攪拌乳化、充填して製品とした。
このようにして得られた油中水型コンパクトファンデーションは、油剤が多いにもかかわらず油っぽさ、べたつきがなく、のび広がりも軽く、さっぱりとした使用性を持つものであった。また、密着感に優れておさまりも良く、化粧もちにも優れた、安定性の良い油中水型コンパクトファンデーションであることが確認された。
実施例24:ファンデーション
(注1)疎水化処理混合粉体
a.微粒子酸化チタン 8.0
b.微粒子酸化亜鉛 4.0
c.タルク 3.0
d.マイカ 3.0
(製造方法)
A:成分a〜dを混合し、それらの粉体に対して、1重量%となるようにジメチルメチルハイドロジェンポリシロキサンを添加した後、加熱処理した。
B:成分1〜6を混合し、成分7〜10を均一に分散した。
C:成分11〜13及び15を混合した後、Bに加えて乳化した。
D:Cに、成分14を加えてファンデーションを得た。
このようにして得られたファンデーションは、べたつきがなく、のび広がりも軽い上密着感に優れ、おさまりも良く、つやのある仕上がりで化粧持ちも非常に優れているものであった。また、温度変化や経時によって変化することがなく、安定性にも優れていることが確認された。
実施例25:口紅
(注1)長鎖アルキル含有アクリルシリコーン樹脂:KP−561(信越化学工業(株)社製)
(注2)メチルフェニルポリシロキサン:KF−54(信越化学工業(株)社製)
(注3)アクリル−シリコーン系グラフト共重合体:KP−541(信越化学工業(株)社製)
(製造方法)
A:成分1〜8及び9の一部を加熱混合して、溶解した。
B:成分10〜16及び9の残部を均一に混合し、Aに加えて均一にした。
このようにして得られた口紅は、のびが軽くて油っぽさや粉っぽさがない上、さっぱりとした使用感を与えるものであった。また耐水性や撥水性が良好で持ちも良く、安定性にも優れているものであった。
実施例26:ブラッシング剤スプレー
(製造方法)
A:成分1〜7を混合した。
B:Aをエアゾール用缶に詰めた後成分8を充填し、ブラッシング剤を得た。
このようにして得られたブラッシング剤スプレーは、ツヤがあって非常になめらかであり、持続性にも優れていた。又、使用時の粉の分散性に優れ、櫛通りが良くツヤのある非常に良いものであることが確認された。
実施例27:ヘアクリーム
(注1)架橋型ポリエーテル変性シリコーン:KSG−21(信越化学工業(株)社製)
(製造方法)
A:成分1〜4を混合した。
B:成分5〜10及び12を均一に混合溶解した。
C:BをAに加えて乳化後、成分11を加えた。
このようにして得られたヘアクリームは、塗布時の伸び、使用後の髪の柔軟性、なめらかさ、まとまり具合、しっとり感、ツヤにおいて、きわめて優れた効果を示すものであった。また安定性にも優れ、総合的に非常に優れたヘアクリームであることが確認された。
実施例28:コンディショニングムース
(注1)架橋型ジメチルポリシロキサン:KSG−16(信越化学工業(株)社製)
(製造方法)
A:成分1〜4を混合した。
B:成分5〜9及び11を均一に混合溶解した。
C:BをAに加えて乳化し、冷却した後成分10を加えた。
D:Cをエアゾール缶に充填し、成分12を添加してコンディショニングムースを得た。
このようにして得られたコンディショニングムースは、しっとり感、柔軟性及びなめらかさに優れ、油性感のない良好な感触のものであった。また、密着感に優れ、おさまりも良く、マット感のある仕上がりが得られる、安定性に優れたコンディショニングムースであることが確認された。
実施例29:トリートメント
(製造方法)
A:成分1〜10を加熱混合し、成分11を加えて均一に分散した。
B:成分12〜13及び15を加熱混合した。
C:AにBを添加し混合し、冷却した後成分14を添加し、トリートメントを得た。
このようにして得られたトリートメントは、使用時にべたつきや重さがなく、毛髪に優れたツヤを与え、さらさら感、なめらかさ、ボリューム感を付与し、櫛通りの良いものであった。また使用性も持続性も優れた、安定性の良いものであることが確認された。
実施例30:油中水型タイプ制汗剤
(注1)架橋型ポリエーテル変性シリコーン:KSG−21(信越化学工業(株)社製)
(注2)フェニル変性ハイブリッドシリコーン複合粉体:KSP−300(信越化学工業(株)社製)
(製造方法)
A:成分1〜5を混合した。
B:成分6〜10、及び12を混合した。
C:BをAに加えて混合乳化し、成分11を添加した。
このようにして得られた油中水型タイプの制汗剤は、のびが軽く、清涼感があってさっぱりとし、べたつきや油感のないものであった。また温度や経時による変化もなく、使用性も安定性も非常に優れている油中水型タイプの制汗剤であった。
実施例31:ロールオンタイプ制汗剤
(注1)架橋型ポリエーテル変性シリコーン:KSG−21(信越化学工業(株)社製)
(注2)架橋型ジメチルポリシロキサン:KSG−15(信越化学工業(株)社製)
(製造方法)
A:成分1〜6を混合した。
B:Aに成分7〜9を加え、均一に分散した。
このようにして得られたロールオンタイプの制汗剤はのびが軽く、清涼感があってさっぱりとして、べたつきや油感のないものであった。また温度や経時による変化もなく、使用性も安定性も非常に優れているものであった。
実施例32:日焼け止め乳液
(注1)トリメチルシロキシケイ酸:X−21−5250(信越化学工業(株)社製)
(製造方法)
A:成分1〜7を加熱混合し、成分8を均一分散した。
B:成分9〜11及び13を加熱混合した。
C:攪拌下でAにBを徐添して乳化し、冷却した後成分12を添加し、日焼け止め乳液を得た。
このようにして得られた日焼け止め乳液は、キメが細かく、のび広がりが軽く、べたつきがない上しっとりとしてみずみずしく、化粧持ちも良いため、紫外線防止効果も持続するものであった。また、温度変化や経時による変化がなく非常に安定性にも優れていることが確認された。
実施例33:サンカットクリーム
(注1)アクリル−シリコーン系グラフト共重合体;KP−545(信越化学工業(株)社製)
(注2)架橋型ポリエーテル変性シリコーン;KSG−21(信越化学工業(株)社製)
(注3)アルキル・ポリエーテル共変性シリコーン;KF−6026(信越化学工業(株)社製)
(製造方法)
A:成分1の一部に成分2を加えて均一にし、成分9を添加してビーズミルにて分散した。
B:成分1の残部及び3〜8を混合し、均一に混合した。
C:成分10〜12及び14を混合して溶解した。
D:BにCを加えて乳化し、A及び成分13を添加してサンカットクリームを得た。
このようにして得られたサンカットクリームは、べたつきがなく、のび広がりも軽い上密着感に優れ、おさまりも良く、つやのある仕上がりで化粧持ちも非常に優れていた。また温度変化や経時に対しても非常に安定であることが確認された。
実施例34:UVカット油中水型乳液
(注1)架橋型ポリエーテル変性シリコーン:KSG−21(信越化学工業(株)社製)
(注2)酸化チタン/シクロペンタシロキサン分散物:SPD−T1S(信越化学工業(株)社製)
(注3)酸化亜鉛/シクロペンタシロキサン分散物:SPD−Z1S(信越化学工業(株)社製)
(製造方法)
A)成分1〜5を混合した。
B)成分8〜10、12を混合溶解し、上記A)に加えて攪拌乳化した。
C)成分6、7、11を上記B)に加えて均一にした。
このようにして得られた油中水型タイプのUVカット乳液は、のびが軽くさっぱりとして、べたつきや油感がなく、透明感があり化粧持ちが良好であった。また温度や経時による変化もなく、使用性も安定性も非常に優れているUVカット乳液であった。
実施例35:UVカット水中油型クリーム
(注1)架橋型メチルフェニルポリシロキサン:KSG−18(信越化学工業(株)社製)
(注2)酸化チタン/シクロペンタシロキサン分散物:SPD−T1S(信越化学工業(株)社製)
(注3)アクリル酸アミド系混合物:セピゲル 305(セピック社製)
(注4)メチルセルロース:メトローズSM−4000(信越化学工業(株)社製)
(製造方法)
A)成分7〜8及び10、12を混合した。
B)成分1〜3及び5〜6を混合し、上記A)に加えて攪拌乳化した。
C)さらに成分4を上記B)に加えた。
D)上記C)に成分9、11を加えて均一にした。
このようにして得られた水中油型タイプのUVカットクリームは、のびが軽くさっぱりとして、べたつきや油感がなく、透明感があり化粧持ちが良好であった。また温度や経時による変化もなく、使用性も安定性も非常に優れているUVカットクリームであった。
以上の実施例は、本発明の化粧料が、軽いのび広がりを有し、油っぽさがなく、しっとりとしてみずみずしい上、さっぱりとした使用感を有するなど、使用感に優れていること、及び化粧持ちも良く、温度や経時による変化のない非常に優れた安定性を有していることを実証するものである。
産業上の利用可能性
本発明の化粧料は、低粘度のものから高粘度のものに至るまで、温度や経時による変化がなく極めて安定性に優れているので、使用感に優れるだけでなく化粧持ちも良好であり、実用的である。 Technical field
The present invention contains at least a specific organopolysiloxane having a nonionic hydrophilic group and a clay mineral, has a light spreading, is non-greasy, moist and fresh, and has a refreshing feeling of use. The present invention relates to a cosmetic, particularly a cosmetic that has improved cosmetic durability and is extremely excellent in stability without change with temperature and time.
Background art
Emulsified cosmetics are generally roughly classified into oil-in-water emulsified cosmetics and water-in-oil emulsified cosmetics. Of these, water-in-oil emulsified cosmetics have a good affinity for the skin, and the skin surface is covered with an oil film to prevent moisture transpiration, protect the skin from drying, and impart a treatment effect to the skin. Because of its nature, it is widely used as a basic cosmetic. In addition, it is widely used as a base material for cosmetics such as makeup cosmetics and pharmaceuticals because of its excellent water repellency, low makeup loss and excellent makeup.
In such a water-in-oil cosmetic, silicone oil is often used as an oil agent in order to obtain a refreshing and less sticky and water-repellent product. Also, when preparing such an emulsified cosmetic, in order to obtain a product with good stability over time, the polyoxyalkylene-modified organopolysiloxane-based surface active agent usually has good compatibility with silicone oil as an emulsifier Agents are widely used.
However, it is difficult to obtain a product having sufficient stability over time by simply blending this surfactant into an emulsified cosmetic containing a large amount of silicone oil. Therefore, in order to ensure stability over time in a wide temperature range, the emulsion is finally adjusted to a highly emulsified cosmetic by blending a wax or a gelling agent. However, this reduces the refreshing feeling and makes it feel sticky, so that the feeling of use becomes heavy.
Therefore, the present inventors have conducted intensive studies on cosmetics that have good usability and good stability over time in a wide temperature range without using waxes or gelling agents that increase the feeling of use. By blending specific organopolysiloxanes with hydrophilic groups and clay minerals into cosmetics, they have a light spread, no oiliness, a moist and fresh refreshing feeling and a long-lasting cosmetic The present inventors have found that an improved cosmetic with excellent stability and no change with temperature and time can be obtained, and the present invention has been completed.
Accordingly, an object of the present invention is to provide a cosmetic material that has excellent usability, has a long makeup, and has excellent stability.
Disclosure of the invention
The present invention provides at least (A) the general formula R1 aR2 bSiO(4-ab) / 2And / or R1 aR5 bR6 cSiO(4-abc) / 2A cosmetic comprising an organopolysiloxane having a nonionic hydrophilic group represented by formula (B) and a clay mineral (B). However, R in the formula1Is an alkyl group having 1 to 30 carbon atoms, aryl group, aralkyl group, amino-substituted alkyl group, carboxyl-substituted alkyl group (which may be partially substituted with halogen), or the following general formula (3)
The same or different organic groups selected from organic groups represented by R,2Is the same or different organic group selected from the following general formulas (4), (5), (6), (7) and (8).
Q represents a C 3-20 divalent hydrocarbon group which may contain an ether bond and / or an ester bond. R3Is a monovalent hydrocarbon group having 4 to 30 carbon atoms, a halogen-substituted hydrocarbon group, or R4An organic group represented by-(CO)-, R4Is a monovalent hydrocarbon group having 1 to 30 carbon atoms and a halogen-substituted hydrocarbon group. X represents a sugar residue derived from a monosaccharide, oligosaccharide or polysaccharide. a and b are 1.0 ≦ a ≦ 2.5 and 0.001 ≦ b ≦ 1.5, respectively, d, e and f are 0 ≦ d ≦ 15, 0 ≦ e ≦ 50 and 0 ≦ f ≦, respectively. The integers 50 and g and h are integers 1 ≦ g ≦ 20 and 1 ≦ h ≦ 20, respectively.
However, R in the formula1Is the same organic group as in formula (1), R5Are the same or different organic groups selected from the general formulas (4) to (8) in the formula (1) and the following general formula (9):
Q is the same as described above and R6Is an organosiloxane residue represented by the following general formula (10).
R7Is an alkyl group having 1 to 30 carbon atoms, an aryl group, an aralkyl group, a fluorine-substituted alkyl group, a, b and c are 1.0 ≦ a ≦ 2.5, 0.001 ≦ b ≦ 1.5, 0, respectively. .001 ≦ c ≦ 1.5, k is an integer of 1 ≦ k ≦ 5, and m is an integer of 0 ≦ m ≦ 500.
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
The organopolysiloxane having a nonionic hydrophilic group as the component (A) to be blended in the cosmetic of the present invention is represented by the following general formula (1) and / or general formula (2).
However, R in the formula1Is an alkyl group having 1 to 30 carbon atoms, aryl group, aralkyl group, amino-substituted alkyl group, carboxyl-substituted alkyl group (which may be partially substituted with halogen), or the following general formula (3)
These are the same or different organic groups selected from the organic groups represented by formula (1).
R1Specific examples of the alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, Examples thereof include aryl groups such as phenyl group and tolyl group, and aralkyl groups such as benzyl group and phenethyl group. Further examples include amino-substituted alkyl groups such as 3-aminopropyl group and 3-[(2-aminoethyl) amino] propyl group, and carboxy-substituted alkyl groups such as 3-carboxypropyl group. Moreover, the thing by which some hydrogen was substituted by the halogen like a trifluoropropyl group, a nonafluoro octyl group, etc. is mentioned.
R1Is part of the general formula -CdH2d-O- (C2H4O)e(C3H6O)fR3An alcohol residue and an alkenyl ether adduct residue represented by Where R3Is a monovalent hydrocarbon group having 4 to 30 carbon atoms, a halogen-substituted hydrocarbon group, or R4An organic group represented by-(CO)-,4Is a C1-C30 monovalent hydrocarbon group or halogen-substituted hydrocarbon group. d, e, and f are integers of 0 ≦ d ≦ 15, 0 ≦ e ≦ 50, and 0 ≦ f ≦ 50, respectively. In particular,
When d = 0: -O- (C2H4O)e(C3H6O)fR3
And if e = 0, f = 0, an alkoxy group having 4 to 30 carbon atoms, for example, a lower alkoxy group such as butoxy group to an oleyloxy group such as cetyl alcohol, oleyl alcohol, stearyl alcohol, higher alkoxy group such as stearoxy group, Or fats such as acetic acid, lactic acid, butyric acid, oleic acid, stearic acid, behenylic acid
Examples include acid residues.
If e, f> 1, it becomes an alcohol residue of an alkylene oxide adduct of higher alcohol (terminal is a hydroxyl group).
When d is 1 or more and e = 0 and f = 0, it is particularly preferable that d is 3, 5 or 11. In this case, it is an allyl ether, pentenyl ether, or undecenyl ether residue, and R3Examples of the substituent include, for example, an allyl stearyl ether residue, a pentenyl behenyl ether residue, or an undecenyl oleyl ether residue. When e or f is not 0, an alkoxy group or an ester group is present via polyoxyalkylene.
Here, whatever e and f are, d may be inferior in hydrolysis resistance when d is 0, and d is preferably 3 to 5 because oil odor is strong when d is 15 or more. .
In particular, in the present invention, R150% or more of the total is preferably a methyl group, more preferably 70% or more. R1100% of may be a methyl group.
Next, R2Is the same or different organic group selected from the following general formulas (4), (5), (6), (7) and (8).
Q is a C3-C20 divalent hydrocarbon group which may contain an ether bond and an ester bond. For example,-(CH2)2-,-(CH2)3-, -CH2CH (CH3) CH2-,-(CH2)4-,-(CH2)5-,-(CH2)6-,-(CH2)7-,-(CH2)8-,-(CH2)2-CH (CH2CH2CH3)-, -CH2-CH (CH2CH3)-,-(CH2)3-O- (CH2)2-,-(CH2)3-O- (CH2)2-O- (CH2)2-,-(CH2)3-O-CH2CH (CH3)-, -CH2-CH (CH3) -COO (CH2)2-Etc. can be illustrated.
The compounds (5) to (7) are polyglycerin, and g and h in the formula are integers of 1 to 20. Further, a part of the hydroxyl group may be substituted with an alkoxy group or an ester group.
Next, X is a sugar residue derived from a monosaccharide, oligosaccharide or polysaccharide, for example, a monosaccharide group such as glycosyl group, mannosyl group, galactosyl group, ribosyl group, arabinosyl group, xylosyl group, fructosyl group; Examples include oligosaccharide groups such as groups, cellobiosyl groups, lactosyl groups, maltotriosyl groups; polysaccharide groups such as cellulose and starch. Among these, preferable groups include monosaccharide groups and oligosaccharide groups.
R in the general formula (2)5R2These are the same or different organic groups selected from the residues represented by the general formulas (4) to (8) and the following general formula (9).
Q is the same as described above, and is a C 3-20 divalent hydrocarbon group which may contain an ether bond and an ester bond.
R in the general formula (2)6Is an organosiloxane residue represented by the following general formula (10).
Here, k in the formula is an integer of 1 to 5, and k is 2 particularly when synthesized from the reaction of a vinylsiloxy group and a SiH group. R7Is an alkyl group having 1 to 30 carbon atoms, an aryl group, an aralkyl group, a fluorine-substituted alkyl group, and m is an integer of 0 to 500, preferably 1 to 50. When m is larger than 500, problems such as poor reactivity with the main chain may occur.
R7Specific examples of the alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, Examples thereof include aryl groups such as phenyl group and tolyl group, and aralkyl groups such as benzyl group and phenethyl group. Further, a group in which a part of hydrogen is substituted with fluorine, such as a trifluoropropyl group or a nonafluorooctyl group, can be mentioned.
The organosiloxane residue represented by the general formula (10) can be prepared by the reaction of a vinylsiloxy group and a SiH group. The organopolysiloxane having a vinylsiloxy group at one end used in this case can be synthesized by a known method. That is, it is possible to synthesize one-end vinylsiloxane by an equilibration reaction of divinyltetramethyldisiloxane with hexamethyldisiloxane and octamethylcyclotetrasiloxane. Furthermore, a silicone compound with an improved one-end blocking ratio can be synthesized by a ring-opening polymerization method of hexamethylcyclotrisiloxane using a pentacoordinate silicon complex catalyst or an anionic polymerization catalyst.
The silicone compound of the general formula (1) used in the present invention is an organohydrogenpolysiloxane, an allyl ether compound represented by (ii) below, for example, an alkylene compound such as hexene, or a compound represented by (i). The allyl ether compound can be easily synthesized by addition reaction in the presence of a platinum catalyst or a rhodium catalyst.
(However, R in the formula4, E and f are R2The same as in the case of. )
The silicone compound of the general formula (2) used in the present invention includes an organohydrogenpolysiloxane, an allyl ether compound represented by the above (ii), a vinyl silicone compound represented by the following (iii), and in some cases And an alkylene compound such as hexene and the allyl ether compound represented by the above (i) can be easily synthesized by addition reaction in the presence of a platinum catalyst or a rhodium catalyst.
(However, R in the formula7, M are the same as those in the formula (10). )
Here, the organohydrogenpolysiloxane may be either linear or cyclic, but is preferably mainly linear to facilitate the addition reaction.
An organohydrogenpolysiloxane and a polyhydric alcohol compound represented by the above general formula (ii), a silicone compound represented by the above general formula (iii), and an alkylene compound and / or the above general formula (i) The total mixing ratio with the organic compound is 0.5 to 2.0, preferably 0.8 to 1.2, in terms of the molar ratio of SiH groups to terminal unsaturated groups.
The addition reaction is desirably performed in the presence of a platinum catalyst or a rhodium catalyst. Specifically, a catalyst such as chloroplatinic acid, alcohol-modified chloroplatinic acid, or chloroplatinic acid-vinylsiloxane complex is preferably used.
In addition, although the usage-amount of a catalyst can be made into a catalytic amount, it is preferable that it is 50 ppm or less by platinum or rhodium amount, and it is especially preferable that it is 20 ppm or less. You may perform the said addition reaction in an organic solvent as needed. Examples of the organic solvent include aliphatic alcohols such as methanol, ethanol, 2-propanol and butanol, aromatic hydrocarbons such as toluene and xylene, aliphatic or alicyclic hydrocarbons such as n-pentane, n-hexane and cyclohexane. , Halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride and the like. Although the addition reaction conditions are not particularly limited, the reaction is preferably performed for 1 to 10 hours under reflux.
A in general formula (1) and (2) is 1.0-2.5, Preferably it is 1.2-2.3. When a is less than 1.0, the compatibility with the oil agent is poor and it is difficult to obtain a stable emulsion. If a is larger than 2.5, the hydrophilicity becomes poor, and it is still difficult to obtain a stable emulsion. b is 0.001 to 1.5, preferably 0.05 to 1.0. When b is smaller than 0.001, it is difficult to obtain a stable emulsion because of poor hydrophilicity. If b is larger than 1.5, the hydrophilicity becomes too high, so that it is difficult to obtain a stable emulsion. c is 0.001 to 1.5, preferably 0.05 to 1.0. When c is smaller than 0.001, the compatibility with silicone oil is poor and it is difficult to obtain a stable emulsion. If c is larger than 1.5, the hydrophilicity is poor, and it is difficult to obtain a stable emulsion.
The weight average molecular weight of the organopolysiloxane having a nonionic hydrophilic group of the component (A) represented by the above formula (1) and / or (2) is not particularly limited, but is 500 to 200,000, particularly It is preferable that it is 1000-100,000. Moreover, the compounding quantity needs to be the range of 0.05-30 weight% of the whole cosmetics, and it is preferable that it is 0.1-15 weight% of the whole cosmetics especially.
In the cosmetic of the present invention, a clay mineral is used as the component (B) together with the organopolysiloxane having a nonionic hydrophilic group as the component (A). Here, the clay mineral used is preferably an organically modified clay mineral. This is generally the following general formula (X, Y)2-3(Si, Al)4O10(OH)2Z1/3/ NH2O
(However, X represents Al, Fe (III), Mn (II), Cr (III), Y represents Mg, Fe (II), Ni, Zn, Cr (III), Z represents K, Na Or any one of Ca.)
Is obtained by treating a water-swellable clay mineral represented by the formula with a quaternary ammonium salt type cationic surfactant.
Specifically, for example, montmorillonite group (commercially available product) of natural or synthetic (in this case, the (OH) group in the formula is substituted with fluorine) such as montmorillonite, bideride, nontrolite, saponite, and hectorite. , And quaternary clay minerals such as sodium silicic mica and synthetic mica known as sodium teniolite or lithium teniolite (there is daimonite in the commercial product). It is obtained by treating with an ammonium salt type cationic surfactant.
The quaternary ammonium salt type cationic surfactant used for organically modifying the water-swellable clay mineral is represented by the following general formula.
R in the formula7Is a C10-22 alkyl group or benzyl group, R8Is a methyl group or an alkyl group having 10 to 22 carbon atoms, R9And R10Represents an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and X represents a halogen atom or a methyl sulfate residue. Specific examples of such quaternary ammonium salt type cationic surfactants include, for example, dodecyltrimethylammonium chloride, myristyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, aralkyltrimethylammonium chloride, behenyltrimethylammonium. Chloride: myristyldimethylethylammonium chloride, cetyldimethylethylammonium chloride, stearyldimethylethylammonium chloride, aralkyldimethylethylammonium chloride, behenyldimethylethylammonium chloride; cetyldiethylmethylammonium chloride, stearyldiethylmethylammonium chloride, aralkyldiethylmethylammonium chloride Black , Behenyl diethylmethylammonium chloride, benzyldimethylmyristylammonium chloride, benzyldimethylcetylammonium chloride, benzyldimethylstearylammonium chloride, benzyldimethylaralkylammonium chloride, benzyldimethylbehenylammonium chloride; benzylmethylethylmyristylammonium chloride, benzylmethylethylcetyl Ammonium chloride, benzylmethyl ethyl stearyl ammonium chloride, benzyl methyl ethyl aralkyl ammonium chloride, benzyl methyl ethyl behenyl ammonium chloride; distearyl dimethyl ammonium chloride, dibehenyl dihydroxyethyl ammonium chloride, and the corresponding bromide, etc., and dipalmiti Propyl ethyl ammonium methylsulfate and the like Ageraru. These surfactants can be used in a mixture of two or more.
Typical examples of the organically modified clay mineral include dimethylalkylammonium hectorite, benzyldimethylstearylammonium hectorite, distearyldimethylammonium chloride-treated aluminum magnesium silicate, and the like. These commercial products include Benton 27 (benzyldimethylstearyl ammonium chloride-treated hectorite: National Red), Benton 38 (distearyldimethylammonium chloride-treated hectorite: National Red), S-BenW (Toyoshunsha) Etc.).
The blending amount of the clay mineral as the component (B) needs to be in the range of 0.05 to 30% by weight of the entire cosmetic, and particularly 0.1 to 15% by weight of the entire cosmetic. It is preferable to blend as described above.
In the cosmetic of the present invention, one or more oil agents can be blended as the component (C) according to the purpose. In this case, any solid, semi-solid, or liquid oil can be used as long as it is used for ordinary cosmetics. For example, natural animal and vegetable oils and semi-synthetic fats and oils include avocado oil, linseed oil, almond oil, ibotarou, eno oil, olive oil, cacao fat, kapok wax, kaya oil, carnauba wax, liver oil, candelilla wax, beef tallow, beef leg fat , Beef bone fat, hydrogenated beef tallow, kyounin oil, whale wax, hydrogenated oil, wheat germ oil, sesame oil, rice germ oil, rice bran oil, sugarcane wax, sasanqua oil, safflower oil, shea butter, cinnamon oil, cinnamon oil, jojo Barrow, shellac wax, turtle oil, soybean oil, tea seed oil, camellia oil, evening primrose oil, corn oil, lard, rapeseed oil, Japanese kiri oil, nukarou, germ oil, horse fat, persic oil, palm oil, palm kernel oil , Castor oil, hydrogenated castor oil, castor oil fatty acid methyl ester, sunflower oil, grape oil, bayberry wax, jojoba oil, macadamia Ritz oil, beeswax, mink oil, cottonseed oil, cotton wax, owl, owl kernel oil, montan wax, coconut oil, hardened coconut oil, tricoconut oil fatty acid glyceride, sheep oil, peanut oil, lanolin, liquid lanolin, reduced lanolin, lanolin alcohol , Hard lanolin, lanolin acetate, lanolin fatty acid isopropyl, POE lanolin alcohol ether, POE lanolin alcohol acetate, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, egg yolk oil and the like. However, POE means polyoxyethylene.
Hydrocarbon oils include ozokerite, squalane, squalene, ceresin, paraffin, paraffin wax, polyethylene wax, polyethylene / polypropylene wax, liquid paraffin, pristane, polyisobutylene, microcrystalline wax, petrolatum, etc .; higher fatty acids include lauric acid, Myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostearic acid, 12-hydroxystearic acid, etc. Can be mentioned.
Higher alcohol oils include lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyl decanol, octyldodecanol, cetostearyl alcohol, 2-decyltetradecinol , Cholesterol, phytosterol, POE cholesterol ether, monostearyl glycerin ether (batyl alcohol), monooleyl glyceryl ether (ceracyl alcohol) and the like.
The ester oils include diisobutyl adipate, 2-hexyldecyl adipate, di-2-heptylundecyl adipate, isononyl isononanoate, N-alkyl glycol monoisostearate, isocetyl isostearate, trimethylolpropane triisostearate, di 2-ethylhexanoic acid ethylene glycol, 2-ethylhexanoic acid cetyl, tri-2-ethylhexanoic acid trimethylolpropane, tetra-2-ethylhexanoic acid pentaerythritol, octyl octoate, octyldodecyl gum ester, oleyl oleate, Octyldodecyl oleate, decyl oleate, neopentyl glycol dicaprate, triethyl citrate, 2-ethylhexyl succinate, amyl acetate, ethyl acetate, butyl acetate, stearyl Isocetyl acid, butyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate, myristyl lactate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl palmitate, 2-heptyl undecyl palmitate, Cholesteryl 12-hydroxystearyl, dipentaerythritol fatty acid ester, isopropyl myristate, octyldodecyl myristate, 2-hexyldecyl myristate, myristyl myristate, hexyldecyl dimethyloctanoate, ethyl laurate, hexyl laurate, N-lauroyl -L-glutamic acid-2-octyldodecyl ester, diisostearyl malate, etc .; As glyceride oil, acetoglyceryl, triisooctanoic acid Riseriru, glyceryl triisostearate, triisopalmitate, glyceryl monostearate, di-2-heptyl undecanoic acid, glyceryl trimyristate, diglyceryl, and the like myristyl isostearate.
Examples of silicone oils include low- to high-viscosity linear or branched organopolysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and dimethylsiloxane / methylphenylsiloxane copolymer; Cyclic siloxanes such as cyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetramethyltetrahydrogencyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane; high degree of polymerization of gum-like dimethylpolysiloxane, gum-like Silicone rubber such as dimethylsiloxane / methylphenylsiloxane copolymer and cyclic siloxane solution of silicone rubber; trimethylsiloxysilicic acid, trimethylsiloxysilica Cyclic siloxane solutions, higher alkoxy modified silicones such as stearoxy silicone; higher fatty acid-modified silicones, alkyl-modified silicones, amino-modified silicones, fluorine-modified silicone, dissolution products of silicone resin and silicone resin and the like. Examples of the fluorinated oil include perfluoropolyether, perfluorodecalin, and perfluorooctane.
The blending amount of the oil agent as the component (C) varies depending on the agent system, but is preferably in the range of 1 to 98% by weight of the entire cosmetic.
In the cosmetic of the present invention, water can be blended as the component (D) according to the purpose. The blending amount varies depending on the agent system, but is preferably in the range of 1 to 98% by weight of the entire cosmetic.
In the cosmetic of the present invention, one or more compounds having an alcoholic hydroxyl group in the molecular structure can be used as the component (E) depending on the purpose.
Specific examples of the compound having an alcoholic hydroxyl group that can be added in the present invention include lower alcohols such as ethanol and isopropanol, sugar alcohols such as sorbitol and maltose, and sterols such as cholesterol, sitosterol, phytosterol, and lanosterol. Examples include polyhydric alcohols such as butylene glycol, propylene glycol, and dibutylene glycol. The blending amount is preferably in the range of 0.1 to 98% by weight of the entire cosmetic.
In the cosmetic of the present invention, one or more water-soluble polymers and water-swellable polymers can be used as the component (F) according to the purpose. Examples of such a polymer include gum arabic, tragacanth, galactan, carob gum, guar gum, caraya gum, carrageenan, pectin, agar, quince seed (malmello), starch (rice, corn, potato, wheat), algae colloid, tant gum Plant polymers such as locust bean gum; microbial polymers such as xanthan gum, dextran, succinoglucan, pullulan; animal polymers such as collagen, casein, albumin, gelatin; carboxymethyl starch, methylhydroxypropyl starch, etc. Starch-based polymers of: methylcellulose, ethylcellulose, methylhydroxypropylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, Cellulosic polymers such as rocellulose, sodium cellulose sulfate, sodium carboxymethylcellulose, crystalline cellulose, cellulose powder; alginic acid polymers such as sodium alginate and propylene glycol alginate; vinyl polymers such as polyvinyl methyl ether and carboxyvinyl polymer Polyoxyethylene polymer; polyoxyethylene polyoxypropylene copolymer polymer; acrylic polymer such as sodium polyacrylate, polyethyl acrylate, polyacrylamide; other synthetic water-soluble high polymers such as polyethyleneimine and cationic polymer Molecule: Inorganic water such as bentonite, magnesium aluminum silicate, montmorillonite, beidellite, nontronite, saponite, hectorite, silicic anhydride There is such as sex polymer. These water-soluble polymers also include film forming agents such as polyvinyl alcohol and polyvinyl pyrrolidone. The blending amount is preferably in the range of 0.01 to 25% by weight of the entire cosmetic.
In the cosmetic of the present invention, one or more surfactants other than the silicone compound having a nonionic hydrophilic group as component (A) can be used as component (G) according to the purpose. Examples of such surfactants include anionic, cationic, nonionic and amphoteric surfactants, but these are not particularly limited as long as they are used in normal cosmetics. Any of these can be used.
Examples of the anionic surfactant include fatty acid soaps such as sodium stearate and triethanolamine palmitate, alkyl ether carboxylic acids and salts thereof, condensates of amino acids and fatty acids, alkane sulfonates, alkene sulfonates, Sulfonates of fatty acid esters, sulfonates of fatty acid amides, formalin condensation sulfonates, alkyl sulfates, secondary higher alcohol sulfates, alkyl and allyl ether sulfates, sulfate esters of fatty acid esters, Fatty acid alkylolamide sulfate ester salt, funnel sulfate sulfate salt, alkyl phosphate, ether phosphate, alkyl allyl ether phosphate, amide phosphate, N-acyl amino acid type activator, etc .; cationic interface Activators include alkyl Min salts, amine salts of polyamine and amino alcohol fatty acid derivatives, alkyl quaternary ammonium salts, aromatic quaternary ammonium salts, pyridinium salts and imidazolium salts.
Nonionic surfactants include sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, poly Oxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene Hydrogenated castor oil, polyoxyethylene phytostanol ether, polyoxyethylene N-phytosterol ether, polyoxyethylene cholestanol ether, polyoxyethylene cholesteryl ether, linear or branched polyoxyalkylene-modified organopolysiloxane, linear or branched polyoxyalkylene / alkyl co-modified organopolysiloxane, alkanol Examples thereof include amides, sugar ethers, sugar amides, and examples of amphoteric surfactants include betaines, aminocarboxylates, imidazoline derivatives, and amidoamine types. The blending amount of these components (G) is preferably 0.1 to 20% by weight of the entire cosmetic, and particularly preferably in the range of 0.2 to 10% by weight.
In the cosmetic of the present invention, at least one cross-linked organopolysiloxane can be used as the component (H) depending on the purpose.
This cross-linked organopolysiloxane is 0.65 mm2/ Second 100.0mm2It is preferable that the low-viscosity silicone of / sec (25 ° C.) swells with an amount more than its own weight. In addition, the crosslinking agent of this crosslinkable organopolysiloxane forms a crosslinked structure by reacting with hydrogen atoms that have two or more vinylic reactive sites in the molecule and are directly bonded to silicon atoms. It is preferable that Further, the crosslinked organopolysiloxane may contain at least one part selected from the group consisting of a polyoxyalkylene part, an alkyl part, an alkenyl part, an aryl part, and a fluoroalkyl part in the molecule. . Although these are not particularly limited, commercially available products include KSG-15, KSG-16, KSG-18, KSG-21 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like gelled with silicone oil. .
The cross-linked organopolysiloxane is 0.65 mm.2/ Second 100.0mm2Those that swell with oils other than low-viscosity silicones / second (25 ° C.) in an amount more than their own weight are used. This crosslinkable organopolysiloxane crosslinker has two or more vinyl reactive sites in the molecule and forms a crosslink structure by reacting with hydrogen atoms directly bonded to silicon atoms. It is preferable that Further, the crosslinked organopolysiloxane may contain at least one part selected from the group consisting of a polyoxyalkylene part, an alkyl part, an alkenyl part, an aryl part, and a fluoroalkyl part in the molecule. . These are not particularly limited, but as commercial products, KSG-31, KSG-32, KSG-33, KSG-34, KSG-41, KSG-42 gelled with hydrocarbon oil or triglyceride oil. , KSG-43, KSG-44 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.
When the cross-linked organopolysiloxane is used, the blending amount is preferably 0.01 to 40% by weight, particularly preferably 0.1 to 30% by weight, based on the total amount of the cosmetic.
In the cosmetic of the present invention, at least one silicone resin can be used as the component (I) depending on the purpose.
The silicone resin is preferably an acrylic / silicone graft or block copolymer acrylic silicone resin. It is also possible to use an acrylic silicone resin containing in the molecule at least one part selected from pyrrolidone moieties, long-chain alkyl moieties, polyoxyalkylene moieties and fluoroalkyl moieties, and anionic moieties such as carboxylic acids. it can.
Further, the silicone resin is preferably a silicone network compound represented as MQ, MDQ, MT, MDT, MDTQ, or the like as a constituent component. M, D, T, and Q are respectively R3SiO0.5Unit, R2SiO unit, RSiO1.5Unit, SiO2Indicates a unit and is commonly used in the silicone industry. The silicone network resin is generally known as MQ resin, MT, or MDT resin, and may have a portion indicated as MDQ or MDTQ, and is commercially available as a dissolved product such as octamethylcyclotetrasiloxane. Further, the molecule may contain at least one part selected from a pyrrolidone part, a long-chain alkyl part, a polyoxyalkylene part, a fluoroalkyl part, and an amino part.
In the case of using a silicone resin such as an acrylic silicone resin or a silicone network compound, the blending amount is preferably 0.01 to 20% by weight, particularly 0.1 to 10% by weight, based on the total amount of the cosmetic. Is preferred.
In the cosmetic of the present invention, one or more kinds of powder and / or colorant can be used as the component (J) according to the purpose. If these are used in normal cosmetics, their shape (spherical, needle-like, plate-like, etc.), particle size (smoke-like, fine particles, pigment grade, etc.), particle structure (porous, nonporous) Any of them can be used. Examples thereof include inorganic powders, organic powders, surfactant metal salt powders, colored pigments, pearl pigments, metal powder pigments, natural dyes and the like.
Specific examples of the inorganic powder include titanium oxide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, and sericite. , Muscovite, synthetic mica, phlogopite, saucite, biotite, lithia mica, silicic acid, anhydrous silicic acid, aluminum silicate, magnesium silicate, magnesium aluminum silicate, calcium silicate, barium silicate, strontium silicate , Metal tungstate, hydroxyapatite, vermiculite, hydrite, bentonite, montmorillonite, hectorite, zeolite, ceramic powder, dicalcium phosphate, alumina, aluminum hydroxide, boron nitride, boron nitride, silica Etc. The.
Organic powders include polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane powder, benzoguanamine powder, polymethylbenzoguanamine powder, tetrafluoroethylene powder, polymethyl methacrylate powder, cellulose powder, silk powder, 12 nylon Nylon powder such as nylon 6 and nylon, crosslinked silicone fine powder having a structure in which dimethyl silicone is crosslinked, fine powder of polymethylsilsesquioxane; styrene / acrylic acid copolymer, divinylbenzene / styrene copolymer, vinyl resin Resin powder such as urea resin, phenol resin, fluorine resin, silicon resin, acrylic resin, melamine resin, epoxy resin, polycarbonate resin; Crystal fiber powder, starch powder, lauroyl lysine powder.
Surfactant metal salt powder (metal soap) includes zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, magnesium myristate, zinc cetyl phosphate, calcium cetyl phosphate, sodium cetyl phosphate, etc. Specific examples of colored pigments include inorganic red pigments such as iron oxide, iron hydroxide, and iron titanate, inorganic brown pigments such as γ-iron oxide, and inorganic yellow pigments such as yellow iron oxide and loess. Pigments, inorganic black pigments such as black iron oxide and carbon black, inorganic purple pigments such as manganese violet and cobalt violet, inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide and cobalt titanate, bitumen, Inorganic blue pigments such as ultramarine blue, tar pigments raked, natural pigments Those ized, and synthetic resin powder or the like composite of these powder and the like.
Examples of the pearl pigment include titanium oxide coated mica, titanium oxide coated mica, bismuth oxychloride, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, fish scale foil, titanium oxide coated colored mica, and the like. Copper powder, stainless steel powder, etc .; As tar pigments, Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 227 No., Red No. 228, Red No. 230, Red No. 401, Red No. 505, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Yellow No. 204, Yellow No. 401, Blue No. 1, Blue No. 2, Blue 201, Blue 404, Green 3, Green 201, Green 204, Green 205, Orange 201, Orange 20 No. orange No. 204, No. 206 orange 207 Orange No. and the like; examples of the natural pigment, carminic acid, laccaic acid, carthamin, brazilin, powders and the like selected and crocin.
Further, powders that absorb and scatter ultraviolet rays, such as fine particle titanium oxide, fine particle iron-containing titanium oxide, fine particle zinc oxide, fine particle cerium oxide, and a composite thereof, may also be mentioned.
Each specific example is as described above, and these powders are those in which powders are combined, general oils, silicone oils, fluorine compounds, surfactants, etc., as long as the effects of the present invention are not hindered. What was processed can also be used and can be used 1 type or 2 types or more as needed. Moreover, it is preferable that a compounding quantity is the range of 0.1 to 50 weight% of the whole cosmetics.
Furthermore, the cosmetics of the present invention include components used in ordinary cosmetics, for example, oil-soluble gelling agents other than clay minerals (B), resins, Sweat agent, UV absorber, UV absorption / scattering agent, moisturizer, antiseptic, antibacterial agent, fragrance, salt, antioxidant, pH adjuster, chelating agent, cooling agent, anti-inflammatory agent, skin cleansing agent (whitening agent, Cell activators, rough skin improving agents, blood circulation promoters, skin astringents, antiseborrheic agents, etc.), vitamins, amino acids, nucleic acids, hormones, clathrate compounds, hair solidifying agents and the like can be added.
Examples of the oil-soluble gelling agent include metal soaps such as aluminum stearate, magnesium stearate, zinc myristate, amino acid derivatives such as N-lauroyl-L-glutamic acid, α, γ-di-n-butylamine, and dextrin palmitic acid. Dextrin fatty acid ester such as ester, dextrin stearic acid ester, dextrin 2-ethylhexanoic acid palmitic acid ester, sucrose fatty acid ester such as sucrose palmitic acid ester, sucrose stearic acid ester, sorbitol such as monobenzylidene sorbitol, dibenzylidene sorbitol And a gelling agent selected from the following benzylidene derivatives.
Examples of the antiperspirant include an antiperspirant selected from aluminum chlorohydrate, aluminum chloride, aluminum sesquichlorohydrate, zirconyl hydroxychloride, aluminum zirconium hydroxychloride, aluminum zirconium glycine complex, and the like.
Examples of UV absorbers include benzoic acid UV absorbers such as paraaminobenzoic acid, anthranilic UV absorbers such as methyl anthranilate, salicylic acid UV absorbers such as methyl salicylate, and cinnamon such as octyl paramethoxycinnamate. Acid UV absorbers, benzophenone UV absorbers such as 2,4-dihydroxybenzophenone, urocanic acid UV absorbers such as ethyl urocanate, dibenzoyl such as 4-t-butyl-4'-methoxy-dibenzoylmethane Methane-based ultraviolet absorbers and the like, and examples of the ultraviolet absorption and scattering agent include powders that absorb and scatter ultraviolet rays, such as fine particle titanium oxide, fine particle iron-containing titanium oxide, fine particle zinc oxide, fine particle cerium oxide, and composites thereof. It is done.
As humectants, glycerin, sorbitol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, glucose, xylitol, maltitol, polyethylene glycol, hyaluronic acid, chondroitin sulfate, pyrrolidone carboxylate, polyoxyethylene methyl glucoside, Examples include polyoxypropylene methyl glucoside.
Examples of the salt include inorganic salts, organic acid salts, amine salts and / or amino acid salts, and other salts. For example, inorganic salts such as hydrochloric acid, sulfuric acid, carbonic acid, nitric acid, inorganic salts selected from sodium, potassium, magnesium, calcium, aluminum, zirconium, zinc, acetic acid, dehydroacetic acid, citric acid, malic acid, Salts of organic acids such as succinic acid, ascorbic acid and stearic acid, salts of amines such as triethanolamine, salts of amino acids such as glutamic acid, other salts such as hyaluronic acid and chondroitin sulfate, aluminum zirconium glycine complex, etc. Yes, it can also be chosen from acid-alkali neutralized salts used in cosmetic formulations.
Antibacterial and antiseptics include paraoxybenzoic acid alkyl esters, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, etc., and antibacterial agents include benzoic acid, salicylic acid, carboxylic acid, sorbic acid, paraoxybenzoic acid alkyl ester , Parachlorometacresol, hexachlorophene, benzalkonium chloride, chlorhexidine, trichlorocarbanilide, photosensitizer, phenoxyethanol and the like.
Antioxidants include tocopherol, butylhydroxyanisole, dibutylhydroxytoluene, phytic acid, etc. pH adjusters include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, dl-malic acid, potassium carbonate, sodium bicarbonate Alanine, sodium edetate, sodium polyphosphate, sodium metaphosphate, phosphoric acid, etc. as a chelating agent, L-menthol, camphor, etc. as an anti-inflammatory agent, allantoin, Examples include glycyrrhizic acid and salts thereof, glycyrrhetinic acid and stearyl glycyrrhetinate, tranexamic acid, and azulene.
As skin beautifying ingredients, placenta extract, whitening agents such as arbutin, glutathione, and yukinoshita extract, royal jelly, photosensitizer, cholesterol derivatives, cell activators such as calf blood extract, rough skin improver, nonyl acid wallenylamide, Nicotinic acid benzyl ester, nicotinic acid β-butoxyethyl ester, capsaicin, gingerone, cantalis tincture, ictamol, caffeine, tannic acid, α-borneol, tocopherol nicotinate, inositol hexanicotinate, cyclandrate, cinnarizine, trazoline, Examples thereof include blood circulation promoters such as acetylcholine, verapamil, cephalanthin and γ-oryzanol, skin astringents such as zinc oxide and tannic acid, and antiseborrheic agents such as sulfur and thianthol.
Vitamins such as vitamin A oil, retinol, retinol acetate, retinol palmitate, etc .; vitamin B2 such as riboflavin, riboflavin butyrate, flavin adenine nucleotide, pyridoxine hydrochloride, pyridoxine dioctanoate, pyridoxine tripalmi Vitamin B6 such as tate, vitamin B12 and derivatives thereof, vitamin B such as vitamin B15 and derivatives thereof; L-ascorbic acid, L-ascorbic acid dipalmitate, L-ascorbic acid-2-sodium sulfate, L- Vitamin Cs such as ascorbic acid phosphate diester dipotassium; Vitamin Ds such as ergocalciferol and cholecalciferol; α-tocopherol, β-tocopherol, γ-tocopherol, dl-α-tocopherol acetate Vitamin E; nicotinic acid dl-α-tocopherol, succinic acid dl-α-tocopherol; vitamin H; vitamin P; nicotinic acids such as nicotinic acid, benzyl nicotinate, and nicotinamide; calcium pantothenate, D-pant Pantothenic acids such as tenenyl alcohol, pantothenyl ethyl ether, acetyl pantothenyl ethyl ether; biotin and the like.
As amino acids, glycine, valine, leucine, isoleucine, serine, threonine, phenylalanine, arginine, lysine, aspartic acid, glutamic acid, cystine, cysteine, methionine, tryptophan, etc .; as nucleic acids, deoxyribonucleic acid, etc .; as hormones, estradiol , Etenyl estradiol and the like.
Examples of the polymer compound for fixing hair include amphoteric, anionic, cationic and nonionic polymer compounds. Specific examples include polyvinyl pyrrolidone polymer compounds such as polyvinyl pyrrolidone and vinyl pyrrolidone / vinyl acetate copolymers; acidic vinyl ether polymer compounds such as methyl vinyl ether / maleic anhydride alkyl half ester copolymers; vinyl acetate / Acidic polyvinyl acetate polymer such as crotonic acid copolymer; acidity such as (meth) acrylic acid / alkyl (meth) acrylate copolymer, (meth) acrylic acid / alkyl (meth) acrylate / alkylacrylamide copolymer Acrylic polymer compound; N-methacryloylethyl-N, N-dimethylammonium / α-N-methylcarboxybetaine / alkyl (meth) acrylate copolymer, hydroxypropyl (meth) acrylate / butylaminoethyl methacrylate / acrylic acid o Amphoteric acrylic polymer compounds such as Chiruamido copolymer. Moreover, natural polymer compounds such as cellulose or derivatives thereof, keratin and collagen or derivatives thereof can also be suitably used.
The cosmetics in the present invention include skin lotions, emulsions, creams, cleansings, packs, oil liquids, massage agents, cleaning agents, deodorants, hand creams, lip balms, and other skin care cosmetics; makeup bases, liquid foundations, oiliness Makeup cosmetics such as foundation, blusher, eye shadow, mascara, eyeliner, eyebrow, lipstick, etc .; hair cosmetics such as shampoo, rinse, treatment, set agent; antiperspirant cosmetics, sunscreen emulsion, sunscreen cream, etc. UV protection cosmetics and the like.
In addition, these cosmetics have various shapes such as liquid, emulsion, cream, solid, paste, gel, powder, press, multilayer, mousse, spray, stick, etc. You can choose.
Further, these cosmetics can obtain cosmetics having good stability without change with temperature and time from low viscosity to high viscosity, but in the present invention, in particular, the viscosity 8000mm2/ S (25 ° C.) or less, it is possible to obtain a cosmetic having good stability that does not change with temperature and time. In the case of a water-in-oil emulsified cosmetic, it is generally very difficult to obtain the stability of a low-viscosity cosmetic. In the present invention, an organopolysiloxane having a specific nonionic hydrophilic group and Containing clay mineral, viscosity is 8000mm2Even in a low-viscosity water-in-oil emulsified cosmetic with a viscosity of not more than / sec (25 ° C.), it is possible to ensure very good stability with no change with temperature and time.
Example.
Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto. In the following general formula, Me3SiO1/2M, Me2SiO group is D, Me2HSiO1/2The group is MH, The MeHSiO group is DHA unit in which a methyl group in M and D is modified with a substituent R is represented by MRAnd DRIs written. Unless otherwise specified, “%” described below means “% by weight”.
Production Example 1
A reactor was charged with 120 g of ethylene glycol monoallyl ether {2- (allyloxy) ethanol} and 0.05 g of isopropyl alcohol (IPA) solution of 0.5% chloroplatinic acid, and 148 g of pentamethyldisiloxane was added at 50 ° C. for 1 hour. It was dripped over. Heat generation was observed immediately after the dropping, and the internal temperature after the dropping was 110 ° C.
Next, vacuum distillation was performed, and a fraction of 100-110 ° C. was taken, and the average composition formula MMR * 1The siloxane compound 1 represented by these was obtained. This siloxane compound 1 was a colorless and transparent liquid. However,R * 1Is -C3H6OCH2CH2OH.
Production Example 2
The average composition formula (M2D11DH 7), 170 g of methyl hydrogen polysiloxane, 230 g of diglycerin monoallyl ether, 200 g of isopropyl alcohol (IPA) and 0.1 g of an IPA solution containing 0.5% of chloroplatinic acid were allowed to react under reflux of the solvent. By heating the reaction under reduced pressure and distilling off the solvent, the average composition formula M2D11DR * 2 7The siloxane compound 2 represented by these was obtained. However,R * 2Is -C3H6OCH2CH (OH) CH2OCH2CH (OH) CH2OH.
This siloxane compound 2 was a pale yellow transparent liquid having a viscosity of 86.0 Pa · sec (25 ° C.), a specific gravity of 1.1186 (25 ° C.) and a refractive index of 1.4586 (25 ° C.).
Production Example 3
The average composition formula (M2D60DH 3) Methylhydrogenpolysiloxane 480 g, allyl ether derivative 140 g represented by the following (Chemical Formula 1), isopropyl alcohol (IPA) 140 g and chloroplatinic acid 0.5% IPA solution 0.3 g were charged under reflux of the solvent. For 8 hours.
After cooling, the reaction solution was transferred to an autoclave, 40 g of Raney nickel was added, hydrogen was introduced, and the reaction was carried out at 120 ° C. for 3 hours. During the reaction, the hydrogen pressure was maintained at 0.5 MPa.
The reaction mixture obtained by filtering the catalyst was charged into the reactor again, 28 g of 0.1N HCl aqueous solution was added, and hydrolysis was performed at 70 ° C. for 3 hours to distill acetone.
After neutralizing by adding 5 g of 5% sodium bicarbonate water, vacuum distillation (˜110 ° C./400 Pa) is performed, and filtration is performed to obtain an average composition formula M2D60DR * 3 3The siloxane compound 3 represented by these was obtained. However,R * 3Is -C3H6OCH {CH2OCH2CH (OH) CH2OH}2It is.
This siloxane compound 3 was a pale yellow transparent liquid having a viscosity of 12.0 Pa · sec (25 ° C.) and a refractive index of 1.417 (25 ° C.).
Production Example 4
The average composition formula (M2D40DH 8) 360 g of methyl hydrogen polysiloxane, 130 g of the allyl ether derivative represented by the above (Chemical Formula 1), 120 g of 1-hexadecene, 180 g of isopropyl alcohol (IPA) and 0.3 g of an IPA solution containing 0.5% chloroplatinic acid. The mixture was reacted for 8 hours under reflux of the solvent. After cooling, the reaction liquid was transferred to an autoclave, Raney nickel 40 g was added, hydrogen was introduced, and the reaction was carried out at 120 ° C. for 3 hours. During the reaction, the hydrogen pressure was maintained at 0.5 MPa.
The reaction mixture obtained by filtering the catalyst was charged again into the reactor, and 26 g of 0.1N HCl aqueous solution was added thereto, followed by hydrolysis at 70 ° C. for 3 hours to distill acetone.
After neutralizing by adding 4.5 g of 5% sodium bicarbonate water, vacuum distillation (˜110 ° C./400 Pa) is performed, and the average composition formula M is filtered by filtration.2D40DR * 3 3D1-Hexadecene 5The siloxane compound 4 represented by this was obtained.
This siloxane compound 4 was a light yellow transparent liquid, having a viscosity of 11.0 Pa · sec (25 ° C.) and a refractive index of 1.413 (25 ° C.).
Production Example 5
The average composition formula (M2DDH 3), 50 g of methyl hydrogen polysiloxane compound, 300 g of allyl glucoside, and 400 parts by weight of ethyl alcohol were added, 0.2 g of an IPA solution containing 3% of chloroplatinic acid was added, and the mixture was reacted at 80 ° C. for 5 hours. After the reaction solution was transferred to an autoclave, 50 g of Raney nickel was added, hydrogen was introduced, and the reaction was carried out at 100 ° C. for 3 hours. During the reaction, the hydrogen pressure was maintained at 1 MPa. After filtering the catalyst, 300 g of viscous siloxane compound 5 was obtained by distilling off under reduced pressure (˜110 ° C./400 Pa). The yield was 85%.
Production Example 6
The average composition formula (M2DH 2) Of methyl hydrogen polysiloxane was added dropwise, and a mixture of 174 g of pentamethylvinyldisiloxane and 0.1 g of a toluene solution of 0.5% chloroplatinic acid was added dropwise and stirred at room temperature to obtain a branched polysiloxane. . In another reactor, 210 g of diglyceryl monoallyl ether, 210 g of isopropyl alcohol (IPA) and 0.1 g of an IPA solution of 0.5% chloroplatinic acid were added, and the previously synthesized branched polysiloxane was added dropwise under reflux of the solvent. And added. The average composition formula M is obtained by heating the reaction under reduced pressure and distilling off the solvent.2DR * 2DR * 4The siloxane compound 6 represented by this was obtained.
R * 4Is
It is.
This siloxane compound 6 is a light yellow transparent liquid with a viscosity of 420 mm.2/ Sec (25 ° C.), the specific gravity was 0.982 (25 ° C.), and the refractive index was 1.4363 (25 ° C.).
Production Example 7
The average composition formula (M2DH 2), 280 g of methylhydrogenpolysiloxane, 290 g of polyglyceryl allyl ether with an unsaturation of 3.48 meq / g, 300 g of isopropyl alcohol (IPA) and 0.3 g of an IPA solution containing 0.5% chloroplatinic acid, and refluxing the solvent The reaction was allowed to run for 8 hours below. Further, 174 g of pentamethylvinyldisiloxane was added dropwise under reflux of the solvent to complete the reaction.
After cooling, vacuum distillation (˜110 ° C./400 Pa) is performed and the average composition formula M is filtered.2DR * 4DR * 5The siloxane compound 7 represented by this was obtained. However, R* 5Is -C3H6OCH5CH (CH5OH) O- (CH5CH (OH) CH5OH)mIt is.
This siloxane compound is a light yellow transparent liquid with a viscosity of 1200 mm.2/ Sec (25 ° C.), the refractive index was 1.4367 (25 ° C.).
Production Example 8
The average composition formula (M2DH 8) Was added dropwise, and a mixture of 270 g pentamethylvinyldisiloxane and 0.1 g toluene solution of 0.5% chloroplatinic acid was added dropwise and stirred at room temperature to obtain a branched polysiloxane. . In another reactor, 110 g of the allyl ether derivative represented by the above (Chemical Formula 1), 110 g of isopropyl alcohol (IPA) and 0.3 g of an IPA solution containing 0.5% chloroplatinic acid were prepared, and the branched polysiloxane synthesized earlier. Was added dropwise under reflux of the solvent. Further, 22 g of 0.1N HCl aqueous solution was added and hydrolyzed at 70 ° C. for 3 hours to distill acetone. After neutralization by adding 4.0 g of 5% aqueous sodium bicarbonate, the reaction was heated under reduced pressure to distill off the solvent, and the average composition formula MDR * 4 3DR * 3 5The siloxane compound 8 represented by this was obtained.
This siloxane compound 8 was a colorless and transparent liquid, and had a viscosity of 174 Pa · sec (25 ° C.) and a refractive index of 1.4687 (25 ° C.).
Production Example 9
The average composition formula (M2D40DH 8), 110 g of an organohydrogensiloxane represented by the following average composition formula is added dropwise, and a mixture of 60 parts of an organopolysiloxane represented by the following average composition formula and 0.2 part of a 0.5% chloroplatinic acid toluene solution is added dropwise at 80 ° C. The reaction was performed for 3 hours.
Next, 48 g of oleyl polyoxypropylene-3-allyl ether {RG-1252 (trade name) manufactured by Nippon Emulsifier Co., Ltd.} was added, and the reaction was completed by heating to reflux for 3 hours. Furthermore, 30 g of the allyl ether derivative represented by the above (Chemical Formula 1) and 100 g of IPA were added and reacted at 80 ° C. for 3 hours.
The solvent is distilled off by heating under reduced pressure.2D40DR * 6 2DR * 3 3DR * 7 3The siloxane compound 9 represented by this was obtained. This siloxane compound 9 is a light brown transparent liquid with a viscosity of 320 mm.2/ Sec (25 ° C.), the specific gravity was 0.980 (25 ° C.), and the refractive index was 1.4275 (25 ° C.). However,
R * 6Is
R * 7Is -C3H6O (C3H6O)3C18H35It is.
Production Example 10
The average composition formula (M2DH 8) Of methylhydrogenpolysiloxane was added dropwise, and a mixture of 17.5 g of pentamethylvinyldisiloxane and 0.1 g of a 0.5% chloroplatinic acid toluene solution was added dropwise and stirred at room temperature to form a branched polysiloxane. Obtained. In a separate reactor, 150 g of a 60% IPA solution of allyl glyceride (a mixture of α-form and β-form containing about 10% dimer), 150 g of isopropyl alcohol (IPA) and 0% chloroplatinic acid A 0.1% 5% IPA solution was charged, and the previously synthesized branched polysiloxane was added dropwise under reflux of the solvent. By heating the reaction product under reduced pressure and distilling off the solvent, a colorless powdery average composition formula M2DR * 4 2DR * 8 6The siloxane compound 10 represented by these was obtained. However,R * 8Is represented by the following (Chemical Formula 2).
Production Example 11
The average composition formula (M2D10DH 5), And a mixture of 440 g of an organopolysiloxane represented by the following average composition formula and 0.1 g of a toluene solution of 0.5% chloroplatinic acid is added dropwise and stirred at room temperature to branch: A polysiloxane was obtained.
In another reactor, 370 g of a 60% IPA solution of allyl glyceride (a mixture of α-form and β-form containing about 10% dimer), 370 g of isopropyl alcohol (IPA) and 0. 0.1 g of a 5% IPA solution was charged, and the previously synthesized branched polysiloxane was added dropwise under reflux of the solvent. An average composition formula M, which is a light yellow transparent water-insoluble gum, by heating the reaction under reduced pressure to distill off the solvent.2D10DR * 6 2DR * 8 3The siloxane compound 11 represented by these was obtained.
Production Example 12.
The average composition formula (M2D42DH 5) Is added dropwise, and a mixture of 160 g vinylorganopolysiloxane represented by the following average composition formula and 0.2 g toluene solution of 0.5% chloroplatinic acid is added dropwise and stirred at room temperature. A branched polysiloxane was obtained.
In another reactor, 140 g of the allyl ether derivative represented by the above (Chemical Formula 1), 200 g of isopropyl alcohol (IPA), and 0.3 g of an IPA solution containing 0.5% chloroplatinic acid were charged. Siloxane was added dropwise under reflux of the solvent. Subsequently, 28 g of 0.1N HCl aqueous solution was added and hydrolyzed at 70 ° C. for 3 hours to distill acetone.
By heating the reaction under reduced pressure and distilling off the solvent, the average composition formula M2D42DR * 6 2DR * 3 3The organopolysiloxane 12 represented by this was obtained.
This product is a colorless and transparent liquid with a viscosity of 1100 mm.2/ Sec (25 ° C.), the specific gravity was 0.990 (25 ° C.), and the refractive index was 1.4150 (25 ° C.).
Production Example 13
In the reactor, the average composition formula (DH 4), 120 g of methyl hydrogen cyclopolysiloxane is added, a mixture of 180 g of pentamethylvinyldisiloxane and 0.1 g of a toluene solution of 0.5% chloroplatinic acid is added dropwise, and stirred at room temperature to obtain a branched polysiloxane. It was. In a separate reactor, 140 g of glycerol monoallyl ether, 140 g of isopropyl alcohol (IPA) and 0.1 g of an IPA solution of 0.5% chloroplatinic acid were added, and the previously synthesized branched polysiloxane was added dropwise under reflux of the solvent. And added. The average composition formula D is obtained by heating the reaction under reduced pressure to distill off the solvent.R * 4 2DR * 9 2The siloxane compound 13 represented by these was obtained.
However,R * 9Is -C3H6OCH2CH (OH) CH2OH.
This siloxane compound 13 is a colorless and transparent liquid with a viscosity of 1650 mm.2/ Sec (25 ° C.), the specific gravity was 1.027 (25 ° C.), and the refractive index was 1.4494 (25 ° C.).
Examples 1-6 and Comparative Examples 1-4: W / O emulsion
A W / O emulsion was prepared by adding a water-based material to the oil-based material having the composition shown in Table 1.
Conduct a use test on the viscosity at 25 ° C of each emulsion, stability test at room temperature and 50 ° C, good spreading at the time of application, no stickiness, and a refreshing feeling on the back skin. The average score was determined. The results are as shown in Table 2.
(Evaluation methods)
(Stability)
A: Stable, Δ: Separation, x: Separation
(Feeling of use)
[Evaluation criteria]
5 points: Very good
4 points: Good
3 points: normal
2 points: Somewhat bad
1 point: Defect
[Judgment]
A: Average score of 4.5 or more
○: Average point 3.5 or more and less than 4.5
Δ: Average score 2.5 or more and less than 3.5
×: Average point less than 2.5
As is clear from the results in Table 2, the emulsions of Examples 1 to 6 of the present invention have a viscosity of 8000 mm.2It can be seen that the stability at room temperature and 50 ° C. is extremely excellent, even though it is less than / sec (25 ° C.). In addition, the emulsions of Examples 1 to 6 have not only good spreading and spreading at the time of application, but also non-stickiness and good feeling after use as compared with the emulsions of Comparative Examples 1 to 4. Met.
Example 7: Polyhydric alcohol emulsified cosmetic in oil
(Note 1) Cross-linked dimethylpolysiloxane: KSG15 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Production method)
A: Components 1 to 5 and 7 were mixed uniformly.
B: Component 6 was dissolved in 8 and added to A) to uniformly emulsify.
The polyhydric alcohol emulsified cosmetic in oil thus obtained had a light spread and no stickiness or oiliness, and was moist on the back skin. Moreover, it was confirmed that it is a polyhydric alcohol emulsified cosmetic in oil with good stability.
Example 8: Polyhydric alcohol emulsification foundation in solid oil
(Note 1) Cross-linked dimethylpolysiloxane: KSG15 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Production method)
A: Components 1 to 7, 9 and 10 were heated to 80 ° C. and mixed uniformly.
B: Component 8 was added to A and dispersed uniformly.
C: Component 11 previously heated to 80 ° C. was added to B) and emulsified.
The polyhydric alcohol emulsified foundation in solid oil thus obtained had a light spread and no stickiness or oiliness, and was moist on the back skin. Moreover, it was confirmed that it is a polyhydric alcohol emulsified foundation in solid oil with good stability.
Example 9: Latex
(Production method)
A) Components 1 to 5 were mixed.
B) After mixing components 6 to 9, the above A) was added and emulsified.
The emulsion thus obtained had no stickiness, light spread, light adhesion, good fit, and a glossy finish. It was also confirmed that the emulsion was stable.
Example 10: Water-in-oil cream
(Note 1) Polyether-modified branched silicone: KF-6028 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Production method)
A) Components 1 to 6 were mixed.
B) Components 7 to 10 were mixed and added to A) and emulsified with stirring.
The water-in-oil cream thus obtained has no oiliness and stickiness, spreads lightly and refreshingly, has an excellent feeling of adhesion, has a good fit, and has a glossy finish. there were. Moreover, it was confirmed that it was a water-in-oil type cream with excellent stability.
Example 11: Water-in-oil cream
(Note 1) Crosslinked polyether-modified silicone: KSG-21 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Production method)
A) Components 1 to 4 were mixed.
B) Components 5 to 10 were mixed and dissolved, and added to A) and emulsified with stirring.
The water-in-oil cream thus obtained had no oiliness and stickiness, light spread, light freshness and excellent usability, and good fit. It was also confirmed that the water-in-oil cream had excellent stability and a matte finish.
Example 12: Water-in-oil makeup base
(Note 1) Crosslinked polyether-modified silicone: KSG-21 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 2) Cross-linked dimethylpolysiloxane: KSG-15 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 3) Titanium oxide / cyclopentasiloxane dispersion: SPD-T1S (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 4) Methylcellulose: Metrolose 65-SH4000 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Production method)
A) Components 1 to 8 were mixed.
B) Components 9 to 13 and 15 were mixed and dissolved.
C) The above B) was added to A) and emulsified with stirring, and Component 14 was added.
The water-in-oil makeup base thus obtained had no oiliness and stickiness, light spread, light freshness and excellent usability, and good fit. . In addition, it was confirmed that it was a water-in-oil makeup base with a matte finish and an excellent UV-cutting effect and good cosmetic durability.
Example 13: Oil-in-water cream
(Note 1) Cross-linked dimethylpolysiloxane: KSG-16 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Production method)
A) Components 1 to 5 were mixed.
B) Components 6 to 9 and 11 were mixed and dissolved.
C) The above A) was added to the above B) and emulsified with stirring, and Component 10 was added.
It was confirmed that the oil-in-water cream thus obtained was an oil-in-water cream with a light spread and a refreshing usability and excellent stability.
Example 14: Water-in-oil cream
(Note 1) Hydrophobized fine particle titanium oxide: Fine particle titanium oxide having an average particle diameter of 0.05 μm is dispersed in water so as to be 10% by weight, and then SiO 2210 wt% sodium silicate solution (SiO2 equivalent to 2 wt% with respect to titanium oxide)2/ Na2O molar ratio = 0.5)2O3A 10 wt% aluminum sulfate solution in an amount corresponding to 7.5 wt% in terms of titanium oxide was gradually added to deposit silicic acid hydrate and alumina hydrate on the surface of titanium oxide. . After completion of the reaction, the mixture was filtered, washed and dried, and then pulverized with a jet mill. This was added to 100 g of isopropyl alcohol to which 4% by weight of an acrylic-silicone graft copolymer (Note 2) was added, and after sufficiently stirring, the solvent was distilled off and a baking treatment was performed at 120 ° C.
(Note 2) Acrylic-silicone graft copolymer: KP-541 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Production method)
A: Components 1 to 6 were mixed, and component 7 was added to make uniform.
B: Components 8 to 10 and 12 were mixed and dissolved.
C: Under stirring, B was gradually added to A to emulsify, and component 11 was added to obtain a cream.
The water-in-oil cream thus obtained was fine in texture, lightly spread, light and not sticky or oily, and moist, fresh and refreshing. In addition, it has been confirmed that the makeup lasting is very good and there is no temperature change or change with time, and the stability is excellent.
Example 15: Water-in-oil cream
(Note 1) Alkyl-modified cross-linked polyether-modified silicone: KSG-31 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 2) Alkyl / polyether co-modified silicone: KF-6026 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 3) Hybrid silicone composite powder: KSP-100 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 4) Acrylic-silicone graft copolymer: KP-541 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Production method)
A: Components 1 to 8 and 13 were mixed.
B: Components 9 to 12 and 14 were mixed and dissolved, and added to A and emulsified with stirring.
The water-in-oil cream thus obtained was fine in texture, lightly spread, light and not sticky or oily, and moist, fresh and refreshing. In addition, it was confirmed that the makeup lasting was very good and there was no change in temperature or change with time, and it was excellent in stability.
Example 16: Water-in-oil cream
(Note 1) Silica-treated zinc oxide: Silica with a particle size of 0.01 to 10 μm containing 50% zinc oxide: Sunsphere SZ-5 (Asahi Glass Co., Ltd.)
(Note 2) Ogon extract: extracted with 50% 1,3-butylene glycol water
(Note 3) Gentian extract: Extracted with 20% ethanol water
(Production method)
A: Components 8 to 11 and 17 were uniformly mixed and dispersed.
B: Components 1 to 7 were mixed and A was added.
C: After mixing components 12 to 16 and 18, B was added to emulsify.
The water-in-oil cream thus obtained had a fine texture, no stickiness, light spread, light adhesion, good fit, a glossy finish and a very long lasting makeup. In addition, it was confirmed that it was stable with no change with temperature or with time.
Example 17: Eyeliner
(Note 1) Organic silicone resin: KF-7712J (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Production method)
A: Components 1 to 4 were mixed, and component 5 was added and mixed and dispersed uniformly.
B: Components 6 to 9 were mixed.
C: B was gradually added to A and emulsified to obtain an eyeliner.
The eyeliner obtained as described above was light and easy to draw, had a refreshing and refreshing feeling, and had a feeling of use with no stickiness. In addition, it was confirmed that there was no change in temperature or change over time, and the usability and stability were excellent, and the durability of the makeup was very good as well as excellent water resistance and sweat resistance.
Example 18: Eyeshadow
(Production method)
A: Components 1 to 5 and 12 were mixed, and components 6 to 8 were added and dispersed uniformly.
B: Components 9 to 11 and 13 were uniformly dissolved.
C: While stirring, B was gradually added to A to emulsify to obtain an eye shadow.
The eye shadow thus obtained had a light spread and no oiliness or powderiness, and gave a fresh and refreshing feeling. In addition, it was confirmed that the water resistance, water repellency and sweat resistance were good and good, and the makeup was not easily lost, and it was excellent in stability with no change in temperature or change with time.
Example 19: Foundation
(Production method)
A: Components 1 to 4 and 15 were mixed, and components 5 to 10 were added to make uniform.
B: Components 11 to 14 and 16 were mixed uniformly (pH of aqueous system was 9.0).
C: Under stirring, B was gradually added to A and emulsified to obtain a foundation.
The foundation thus obtained had a fine texture, light spreading, no stickiness or oiliness, moist and fresh, and a refreshing feeling of use. In addition, it was confirmed that the makeup lasts well, there is no change with temperature or with time, and the stability is also excellent.
Example 20: Liquid emulsion foundation
(Note 1) Crosslinked polyether-modified silicone: KSG21 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Production method)
A: Components 1 to 10 were heated and mixed, and components 11 to 16 were added to make uniform.
B: Components 17 to 19 and 21 were dissolved by heating.
C: While stirring, B was gradually added to A to emulsify, and after cooling, component 20 was added to obtain a liquid emulsion foundation.
The liquid emulsified foundation thus obtained had a low viscosity, a fine texture, light spreading, no stickiness or oiliness, and a fresh, moist and fresh feel. In addition, it was confirmed that the makeup lasts well, there is no change with temperature or with time, and the stability is also excellent.
Example 21: Liquid foundation
(Note 1) Fluorine-modified silicone: FL-50 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 2) Fluoroalkyl-polyether co-modified silicone: FPD-4694 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 3) Spherical polymethylsilsesquioxane powder: KMP590 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 4) Acrylic-silicone graft copolymer: KP-541 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Production method)
A: Components 9 to 15 were mixed uniformly.
B: Components 1 to 8 were heated and mixed at 70 ° C., and A was added and dispersed and mixed uniformly.
C: Ingredients 16 to 19 and 21 were heated to 40 ° C. and then gradually added to B to emulsify, cooled and added with ingredient 20 to obtain a liquid foundation.
The liquid foundation obtained in this way has no stickiness, light spreading, and a refreshing and high refreshing feeling. Was confirmed.
Example 22: Cream foundation
(Note 1) Crosslinked polyether-modified silicone: KSG-21 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 2) Fluorine-modified silicone composite powder: KSP-200 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 3) Acrylic-silicone graft copolymer: KP-545 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Production method)
A) Components 1 to 7 were mixed.
B) Components 10 to 12 and 14 were mixed and dissolved, and added to A) and emulsified with stirring.
C) Components 8 to 9 were mixed and added to the above B), and further component 13 was added to make uniform.
The cream foundation thus obtained had no stickiness, light spread, light adhesion, and good fit. It was also confirmed that the cream foundation had a matte finish and had excellent stability.
Example 23: Water-in-oil compact foundation
(Note 1) Alkyl / polyether co-modified silicone: KF-6026 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 2) Alkyl-modified cross-linked polyether-modified silicone: KSG-33 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Production method)
A) Components 1 to 9 were dissolved by heating.
B) Components 10-13 and 15 were added to component 14 and mixed uniformly.
C) Component 17 was added to B) and dispersed uniformly.
D) The above C and component 16 were added to A) above, and emulsified with stirring and filled to obtain a product.
The water-in-oil compact foundation thus obtained had no oiliness, stickiness, light spread, and refreshed usability despite the large amount of oil. Moreover, it was confirmed that it was a water-in-oil compact foundation with excellent adhesion, good fit, good makeup, and good stability.
Example 24: Foundation
(Note 1) Hydrophobized powder mixture
a. Fine particle titanium oxide 8.0
b. Fine zinc oxide 4.0
c. Talc 3.0
d. Mica 3.0
(Production method)
A: Components a to d were mixed, and dimethylmethylhydrogenpolysiloxane was added to the powder so as to be 1% by weight, followed by heat treatment.
B: Components 1 to 6 were mixed and components 7 to 10 were uniformly dispersed.
C: Components 11 to 13 and 15 were mixed and then added to B to emulsify.
D: Component 14 was added to C to obtain a foundation.
The foundation thus obtained had no stickiness, spread and light, had excellent adhesion, had a good fit, had a glossy finish, and had excellent makeup. In addition, it was confirmed that it was stable with no change with temperature or with time.
Example 25: Lipstick
(Note 1) Long chain alkyl-containing acrylic silicone resin: KP-561 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 2) Methylphenylpolysiloxane: KF-54 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 3) Acrylic-silicone graft copolymer: KP-541 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Production method)
A: A part of components 1 to 8 and 9 were mixed by heating and dissolved.
B: The remaining components 10 to 16 and 9 were mixed uniformly and added to A to make it uniform.
The lipstick thus obtained was light and free of oiliness and powderiness, and gave a refreshing feeling. In addition, the water resistance and water repellency were good and good, and the stability was excellent.
Example 26: Brushing agent spray
(Production method)
A: Components 1 to 7 were mixed.
B: After filling A into an aerosol can, the ingredient 8 was filled to obtain a brushing agent.
The brushing agent spray thus obtained was glossy and very smooth and excellent in sustainability. Moreover, it was confirmed that the powder was excellent in dispersibility at the time of use, excellent in combing, and glossy.
Example 27: Hair cream
(Note 1) Crosslinked polyether-modified silicone: KSG-21 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Production method)
A: Components 1 to 4 were mixed.
B: Components 5 to 10 and 12 were mixed and dissolved uniformly.
C: Component B was added to A after emulsification by adding B to A.
The hair cream thus obtained exhibited extremely excellent effects in terms of elongation at the time of application, hair flexibility after use, smoothness, unity, moist feeling, and gloss. Moreover, it was excellent in stability and it was confirmed that it is a very excellent hair cream overall.
Example 28: Conditioning mousse
(Note 1) Cross-linked dimethylpolysiloxane: KSG-16 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Production method)
A: Components 1 to 4 were mixed.
B: Components 5 to 9 and 11 were mixed and dissolved uniformly.
C: B was added to A to emulsify, and after cooling, component 10 was added.
D: C was filled into an aerosol can, and component 12 was added to obtain a conditioning mousse.
The conditioning mousse thus obtained was excellent in moist feeling, flexibility and smoothness, and had a good feel without oiliness. Further, it was confirmed that the mousse was excellent in stability, had a good fit, had a matte finish, and had excellent stability.
Example 29: Treatment
(Production method)
A: Components 1 to 10 were heated and mixed, and component 11 was added and dispersed uniformly.
B: Components 12 to 13 and 15 were heated and mixed.
C: B was added to A, mixed, cooled, and then component 14 was added to obtain a treatment.
The treatment thus obtained had no stickiness or weight when used, gave an excellent gloss to the hair, gave a smooth, smooth, and voluminous feel, and was comb-like. Moreover, it was confirmed that it was excellent in usability and sustainability and had good stability.
Example 30: Water-in-oil type antiperspirant
(Note 1) Crosslinked polyether-modified silicone: KSG-21 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 2) Phenyl-modified hybrid silicone composite powder: KSP-300 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Production method)
A: Components 1 to 5 were mixed.
B: Components 6 to 10 and 12 were mixed.
C: B was added to A and mixed and emulsified, and Component 11 was added.
The water-in-oil type antiperspirant thus obtained was light in weight, refreshing and refreshing, and not sticky or oily. Moreover, it was a water-in-oil type antiperspirant with no change in temperature and time, and very excellent usability and stability.
Example 31: Roll-on type antiperspirant
(Note 1) Crosslinked polyether-modified silicone: KSG-21 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 2) Cross-linked dimethylpolysiloxane: KSG-15 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Production method)
A: Components 1 to 6 were mixed.
B: Components 7 to 9 were added to A and dispersed uniformly.
The roll-on type antiperspirant thus obtained had a light stretch, a refreshing sensation, and a refreshing, non-sticky or oily sensation. Moreover, there was no change with temperature and time, and the usability and stability were very excellent.
Example 32: Sunscreen latex
(Note 1) Trimethylsiloxysilicate: X-21-5250 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Production method)
A: Components 1 to 7 were heated and mixed, and component 8 was uniformly dispersed.
B: Components 9 to 11 and 13 were heated and mixed.
C: B was gradually added to A under stirring to emulsify, and after cooling, component 12 was added to obtain a sunscreen emulsion.
The sunscreen emulsion thus obtained had a fine texture, light spreading, light and non-sticky, moist and fresh, and good makeup, so that the effect of preventing ultraviolet rays was maintained. Further, it was confirmed that there was no change with temperature or change with time, and that the stability was also excellent.
Example 33: Sun cut cream
(Note 1) Acrylic-silicone graft copolymer; KP-545 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 2) Crosslinked polyether-modified silicone; KSG-21 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 3) Alkyl / polyether co-modified silicone; KF-6026 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Production method)
A: Component 2 was added to part of component 1 to make it uniform, and component 9 was added and dispersed with a bead mill.
B: The remainder of component 1 and 3-8 were mixed and mixed uniformly.
C: Components 10 to 12 and 14 were mixed and dissolved.
D: C was added to B to emulsify, and A and component 13 were added to obtain a sun cut cream.
The sun cut cream thus obtained had no stickiness, spreads lightly, had excellent adhesion, had a good fit, had a glossy finish, and had excellent makeup. It was also confirmed that it is very stable against temperature changes and aging.
Example 34: UV cut water-in-oil emulsion
(Note 1) Crosslinked polyether-modified silicone: KSG-21 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 2) Titanium oxide / cyclopentasiloxane dispersion: SPD-T1S (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 3) Zinc oxide / cyclopentasiloxane dispersion: SPD-Z1S (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Production method)
A) Components 1 to 5 were mixed.
B) Components 8 to 10 and 12 were mixed and dissolved, and added to A) and emulsified with stirring.
C) Components 6, 7, and 11 were added to B) to make uniform.
The thus obtained water-in-oil type UV-cut emulsion was light and refreshing, had no stickiness or oily feeling, was transparent, and had good makeup. Moreover, it was a UV-cut emulsion with no change in temperature and time, and very excellent usability and stability.
Example 35: UV cut oil-in-water cream
(Note 1) Cross-linked methylphenyl polysiloxane: KSG-18 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 2) Titanium oxide / cyclopentasiloxane dispersion: SPD-T1S (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 3) Acrylic acid amide-based mixture: Sepigel 305 (manufactured by Sepic)
(Note 4) Methylcellulose: Metroz SM-4000 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Production method)
A) Components 7 to 8 and 10, 12 were mixed.
B) Components 1 to 3 and 5 to 6 were mixed and added to the above A) and emulsified with stirring.
C) Further component 4 was added to B) above.
D) Ingredients 9 and 11 were added to C) to make uniform.
The oil-in-water type UV cut cream thus obtained was light and refreshing, had no stickiness or oily feeling, was transparent, and had good makeup. Further, it was a UV cut cream with no change in temperature and time, and very excellent usability and stability.
In the above examples, the cosmetic of the present invention has a light spread, no oiliness, moist and fresh, and a refreshing feeling of use, etc. It demonstrates that it has good makeup and has very good stability with no change over time or temperature.
Industrial applicability
The cosmetics of the present invention have excellent stability because there is no change with temperature and aging from low viscosity to high viscosity. It is practical.
Claims (31)
但し、式中のR1は炭素数1〜30のアルキル基、アリール基、アラルキル基、アミノ置換アルキル基、カルボキシル置換アルキル基(一部ハロゲンに置換されていてもよい)、あるいは下記一般式(3)
で表される有機基から選択される同種または異種の有機基、R3は下記一般式(4)、(5)、(6)、(7)及び(8)から選ばれる同種又は異種の有機基である。
Qはエーテル結合及び/又はエステル結合を含有しても良い炭素数3〜20の二価炭化水素基を表す。R3は炭素数4〜30の一価炭化水素基、ハロゲン置換炭化水素基、又はR4−(CO)−で表される有機基、R4は炭素数1〜30の一価炭化水素基及びハロゲン置換炭化水素基である。Xは単糖、オリゴ糖ないしは多糖から誘導される糖残基を表す。a及びbはそれぞれ1.0≦a≦2.5、0.001≦b≦1.5であり、d、e、fはそれぞれ0≦d≦15、0≦e≦50、0≦f≦50の整数、g及びhはそれぞれ、1≦g≦20、1≦h≦20の整数である。
但し、式中のR1は(1)式のものと同じ有機基、R5は(1)式における一般式(4)〜(8)及び下記一般式(9)から選ばれる同種又は異種の有機基、
Qは前記(1)式のものと同じであり、R6は下記一般式(10)で表されるオルガノシロキサン残基である。
但し、R7は炭素数1〜30のアルキル基、アリール基、フッ素置換アルキル基、a、b及びcは、それぞれ1.0≦a≦2.5、0.001≦b≦1.5、0.001≦c≦1.5、kは1≦k≦5の整数であり、mは0≦m≦500の整数である。(A) A cosmetic comprising a silicone compound having a nonionic hydrophilic group represented by the following general formula (1) and / or general formula (2), and (B) a clay mineral.
In the formula, R 1 is an alkyl group having 1 to 30 carbon atoms, an aryl group, an aralkyl group, an amino-substituted alkyl group, a carboxyl-substituted alkyl group (which may be partially substituted with halogen), or the following general formula ( 3)
The same or different organic group selected from the organic groups represented by the formula: R 3 is the same or different organic group selected from the following general formulas (4), (5), (6), (7) and (8) It is a group.
Q represents a C3-C20 divalent hydrocarbon group which may contain an ether bond and / or an ester bond. R 3 is a monovalent hydrocarbon group having 4 to 30 carbon atoms, a halogen-substituted hydrocarbon group, or an organic group represented by R 4 — (CO) —, and R 4 is a monovalent hydrocarbon group having 1 to 30 carbon atoms. And a halogen-substituted hydrocarbon group. X represents a sugar residue derived from a monosaccharide, oligosaccharide or polysaccharide. a and b are 1.0 ≦ a ≦ 2.5 and 0.001 ≦ b ≦ 1.5, respectively, d, e, and f are 0 ≦ d ≦ 15, 0 ≦ e ≦ 50, and 0 ≦ f ≦, respectively. The integers 50 and g and h are integers 1 ≦ g ≦ 20 and 1 ≦ h ≦ 20, respectively.
However, R 1 in the formula is the same organic group as in the formula (1), R 5 is the same or different selected from the general formulas (4) to (8) in the formula (1) and the following general formula (9). Organic groups,
Q is the same as that in the formula (1), and R 6 is an organosiloxane residue represented by the following general formula (10).
However, R 7 is an alkyl group having 1 to 30 carbon atoms, an aryl group, a fluorine-substituted alkyl group, and a, b and c are 1.0 ≦ a ≦ 2.5, 0.001 ≦ b ≦ 1.5, respectively. 0.001 ≦ c ≦ 1.5, k is an integer of 1 ≦ k ≦ 5, and m is an integer of 0 ≦ m ≦ 500.
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JP2001349694 | 2001-11-15 | ||
PCT/JP2002/011402 WO2003041664A1 (en) | 2001-11-15 | 2002-10-31 | Cosmetics containing clay mineral |
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GB0220578D0 (en) * | 2001-12-04 | 2002-10-09 | Unilever Plc | Hair treatement composition |
JP4423121B2 (en) * | 2004-06-25 | 2010-03-03 | 株式会社カネボウ化粧品 | Water-in-oil skin cosmetics |
FR2873031A1 (en) * | 2004-07-16 | 2006-01-20 | Oreal | Anhydrous cosmetic composition useful as skin care or make-up composition and lipstick comprises at least one silicone polymer and at least one surfactant, in a physiological medium |
FR2873032A1 (en) * | 2004-07-16 | 2006-01-20 | Oreal | Anhydrous cosmetic composition, useful in e.g. make-up, lip (lipstick) and/or skin care composition, comprises a silicone polymer in a medium |
FR2873033A1 (en) * | 2004-07-16 | 2006-01-20 | Oreal | Anhydrous cosmetic composition, useful in skin care, lip care and make-up composition, comprises liquid fatty phase, gelling agent for the liquid fatty phase, and silicone polymer |
FR2873034B1 (en) * | 2004-07-16 | 2008-04-18 | Oreal | COSMETIC COMPOSITION IMPROVED. |
KR101320677B1 (en) * | 2005-05-02 | 2013-10-18 | 가부시키가이샤 코세 | Makeup cosmetic |
US20070128137A1 (en) * | 2005-12-02 | 2007-06-07 | Naohisa Yoshimi | Water in oil emulsion compositions containing siloxane elastomers |
JP2007230923A (en) * | 2006-03-01 | 2007-09-13 | Kanebo Cosmetics Inc | Water-in-oil emulsified cosmetic |
JP2006213730A (en) * | 2006-04-28 | 2006-08-17 | Shin Etsu Chem Co Ltd | Cosmetic |
JP4927443B2 (en) * | 2006-05-16 | 2012-05-09 | ポーラ化成工業株式会社 | Emulsifier type skin external preparation |
JP5081432B2 (en) * | 2006-07-04 | 2012-11-28 | 株式会社クラレ | Skin external preparation in the form of water-in-oil emulsifier |
JP5635223B2 (en) * | 2006-07-07 | 2014-12-03 | ポーラ化成工業株式会社 | Skin external preparation suitable for esthetic treatment |
EP2492300B1 (en) | 2009-10-23 | 2018-10-03 | Dow Corning Toray Co., Ltd. | Novel organopolysiloxane copolymer |
JP5878760B2 (en) | 2009-10-23 | 2016-03-08 | 東レ・ダウコーニング株式会社 | Oily material thickener or gelling agent |
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JP6313540B2 (en) | 2011-12-27 | 2018-04-18 | 東レ・ダウコーニング株式会社 | Diglycerin derivative-modified silicone, emulsifier for water-in-oil emulsion containing the same, external preparation and cosmetic |
JP6105920B2 (en) | 2011-12-27 | 2017-03-29 | 東レ・ダウコーニング株式会社 | Co-modified organopolysiloxane, emulsifier for water-in-oil emulsion containing the same, external preparation and cosmetic |
US10406092B2 (en) | 2012-12-28 | 2019-09-10 | Dow Silicones Corporation | Method for producing transparent or semi-transparent liquid glycerin-derivative-modified silicone composition |
JP6566476B2 (en) | 2013-06-13 | 2019-08-28 | ダウ・東レ株式会社 | Long-chain hydrocarbon group-containing diglycerin derivative-modified silicone and use thereof |
JP6607861B2 (en) | 2013-10-31 | 2019-11-20 | ダウ シリコーンズ コーポレーション | Cross-linked composition and method for forming the same |
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KR102313564B1 (en) | 2013-10-31 | 2021-10-19 | 다우 실리콘즈 코포레이션 | Cosmetic composition comprising a carboxy-functional elastomers |
EP3429554A1 (en) | 2016-03-14 | 2019-01-23 | Dow Silicones Corporation | Composition and method of preparation |
JP6882148B2 (en) | 2017-11-29 | 2021-06-02 | 信越化学工業株式会社 | Both continuous microemulsion compositions and cosmetics |
KR102098169B1 (en) * | 2019-09-03 | 2020-04-10 | (주)제이엠월드 | A Compact For Hair Treatment |
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