JPWO2020036064A1 - 水中油型乳化化粧料 - Google Patents
水中油型乳化化粧料 Download PDFInfo
- Publication number
- JPWO2020036064A1 JPWO2020036064A1 JP2020537405A JP2020537405A JPWO2020036064A1 JP WO2020036064 A1 JPWO2020036064 A1 JP WO2020036064A1 JP 2020537405 A JP2020537405 A JP 2020537405A JP 2020537405 A JP2020537405 A JP 2020537405A JP WO2020036064 A1 JPWO2020036064 A1 JP WO2020036064A1
- Authority
- JP
- Japan
- Prior art keywords
- oil
- water emulsified
- group
- emulsified cosmetic
- acid
- 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 219
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- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 65
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- 150000004706 metal oxides Chemical class 0.000 claims abstract description 16
- 150000007514 bases Chemical class 0.000 claims abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 62
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- 125000000962 organic group Chemical group 0.000 claims description 51
- 239000010419 fine particle Substances 0.000 claims description 37
- 125000000217 alkyl group Chemical group 0.000 claims description 30
- 125000002947 alkylene group Chemical group 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 22
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- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 7
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- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- 239000000344 soap Substances 0.000 description 6
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 6
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- QPQANCNBWQXGTQ-UHFFFAOYSA-N trihydroxy(trimethylsilylperoxy)silane Chemical compound C[Si](C)(C)OO[Si](O)(O)O QPQANCNBWQXGTQ-UHFFFAOYSA-N 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 4
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- LINXHFKHZLOLEI-UHFFFAOYSA-N trimethyl-[phenyl-bis(trimethylsilyloxy)silyl]oxysilane Chemical compound C[Si](C)(C)O[Si](O[Si](C)(C)C)(O[Si](C)(C)C)C1=CC=CC=C1 LINXHFKHZLOLEI-UHFFFAOYSA-N 0.000 description 1
- SVTUWEUXLNHYPF-UHFFFAOYSA-N trimethyl-[propyl-bis(trimethylsilyloxy)silyl]oxysilane Chemical compound CCC[Si](O[Si](C)(C)C)(O[Si](C)(C)C)O[Si](C)(C)C SVTUWEUXLNHYPF-UHFFFAOYSA-N 0.000 description 1
- 229940118594 trimethylolpropane triisostearate Drugs 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- 229940117972 triolein Drugs 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 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
- UEVAMYPIMMOEFW-UHFFFAOYSA-N trolamine salicylate Chemical compound OCCN(CCO)CCO.OC(=O)C1=CC=CC=C1O UEVAMYPIMMOEFW-UHFFFAOYSA-N 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- 229940105125 zinc myristate Drugs 0.000 description 1
- 229940012185 zinc palmitate Drugs 0.000 description 1
- 229940057977 zinc stearate Drugs 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
- GJAPSKMAVXDBIU-UHFFFAOYSA-L zinc;hexadecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O GJAPSKMAVXDBIU-UHFFFAOYSA-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
- GBFLQPIIIRJQLU-UHFFFAOYSA-L zinc;tetradecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O GBFLQPIIIRJQLU-UHFFFAOYSA-L 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
Description
[1](A)50℃で液状のカルボン酸変性シリコーン、
(B)ビニル系重合体エマルション、
(C)塩基性化合物、及び、
(D)疎水性微粒子金属酸化物からなる無機紫外線防御剤
を含む、水中油型乳化化粧料
により達成され、好適には、
[2]前記の(D)疎水性微粒子金属酸化物からなる無機紫外線防御剤100質量部に対して、
前記の(A)50℃で液状のカルボン酸変性シリコーンが5〜40質量部となる範囲の量であり、
前記の(B)ビニル系重合体エマルションが、当該エマルション中の固形分の含有量が0.5〜10質量部となる範囲の量であり、
前記の成分(A)および成分(B)を含まない場合に比べて化粧料全体のSPF値が向上していることを特徴とする、[1]に記載の水中油型乳化化粧料
により達成される。
[3]前記(A)カルボン酸変性シリコーンが、下記構造式(1):
(式中、
Rcは、一般式:-R1-(OR2)p-(O)w-R3-COOH(R1 は炭素数2〜22の直鎖又は分岐鎖のアルキレン基を表し、R2 は炭素数2〜4の直鎖又は分岐鎖のアルキレン基を表し、R3 は結合手(−)又は炭素数1〜22の直鎖若しくは分岐鎖のアルキレン基を表し、pは0〜200の数を表し、wは0又は1の数を表す)で示されるカルボキシル基含有有機基を表し、
Rは、同一又は異なり、炭素数1〜22のアルキル若しくはアルコキシ基又はフェニル基を表し、
R´は、Rc又はRであり、
a、bは各々0又は正の数であり、a+bは0〜30の範囲の数であり、bが0のとき、R´の少なくとも一方はRcである。)で表される、[1]又は[2]に記載の水中油型乳化化粧料。
[4] 前記(A)カルボン酸変性シリコーンが室温(25℃)で液状である、[1]〜[3]のいずれか1項に記載の水中油型乳化化粧料。
[5]前記(A)カルボン酸変性シリコーンが、下記構造式(2):
(式中、
Rcは、一般式:-R1-(OR2)p-(O)w-R3-COOH(R1 は炭素数2〜22の直鎖又は分岐鎖のアルキレン基を表し、R2 は炭素数2〜4の直鎖又は分岐鎖のアルキレン基を表し、R3 は結合手(−)又は炭素数1〜22の直鎖若しくは分岐鎖のアルキレン基を表し、pは0〜200の数を表し、wは0又は1の数を表す)で示されるカルボキシル基含有有機基を表し、
Rは、同一又は異なり、炭素数1〜22のアルキル若しくはアルコキシ基又はフェニル基を表し、
R´は、Rc又はRであり、
a、bは各々正の数であり、a+bは2〜20の範囲の数であり、a/bは0.3〜3.0の範囲である。)で表される、[1]〜[4]のいずれか1項に記載の水中油型乳化化粧料。
[6] 前記(A)カルボン酸変性シリコーンを化粧料の全質量に対して0.5〜15質量%の範囲で含む、[1]〜[5]のいずれか1項に記載の水中油型乳化化粧料。
[7] 前記の(B)ビニル系重合体エマルションが、アクリル酸エステル単量体またはメタクリル酸エステル単量体を共重合させてなるアクリル系共重合体ポリマーのエマルションである、[1]〜[6]のいずれか1項に記載の水中油型乳化化粧料。
[8] 前記の(B)ビニル系重合体エマルションが、
(b1)アクリル酸/メタクリル酸アルキル共重合体ポリマー、
(b2)アクリル酸/メタクリル酸スチレン共重合体ポリマー、および
(b3)カルボシロキサンデンドロン構造を有するアクリル酸/メタクリル酸共重合体ポリマー
から選ばれる1種類以上のアクリル系共重合体ポリマーのエマルションである、[1]〜[7]のいずれか1項に記載の水中油型乳化化粧料。
[9] 前記の(D)疎水性微粒子金属酸化物からなる無機紫外線防御剤が、平均粒子径が1〜200nmの範囲である、疎水化微粒子酸化チタン又は疎水化微粒子酸化亜鉛である、[1]〜[8]のいずれか1項に記載の水中油型乳化化粧料。
[10] さらに、(E)油剤を含む、[1]〜[9]のいずれか1項に記載の水中油型乳化化粧料。
[11] 前記の(E)油剤が少なくとも1種の紫外線吸収剤を含む、[10]に記載の水中油型乳化化粧料。
[12] さらに、(F)油溶性皮膜形成剤を含む、[1]〜[11]のいずれか1項に記載の水中油型乳化化粧料。
[13] さらに、(G)多価アルコールを含む、[1]〜[12]のいずれか1項に記載の水中油型乳化化粧料。
[14] さらに、(H)水溶性紫外線吸収剤を含む、[1]〜[13]のいずれか1項に記載の水中油型乳化化粧料。
[15] 日焼け止め化粧料である、[1]〜[14]のいずれか1項に記載の水中油型乳化化粧料。
本発明の化粧料は、少なくとも1種の、50℃で液状の(A)カルボン酸変性シリコーンを含む。なお、前記(A)カルボン酸変性シリコーンは50℃及び1気圧下で液状であればよく、例えば、室温(25℃)において固体であってもよい。
特開2002−114849号公報に記載の、以下のいずれかのカルボキシル基含有有機基を有するオルガノポリシロキサン:
(式中、R1〜R24は、同一又は異なって、ヘテロ原子を含む置換基を有していてもよい、炭素数2〜22の直鎖若しくは分岐鎖状のアルキレン基、アルケニレン基又はアリーレン基を示し、Xは−O−又はNH−を示し、Mは水素原子を示す)、
特表2005−524747号公報に記載の以下のカルボキシル基含有有機基を有するオルガノポリシロキサン:
R’は、水素原子、又は1〜30個の炭素原子を有するアルキル基を表し、
Eは、存在しないか、又は1〜5個の炭素原子、好ましくは1〜3個の炭素原子を有し、任意に、1〜30個の炭素原子を有する1個以上のアルキル基によって置換されたアルキレン残基であり;Mは、水素原子である)、
特開2009−263643号公報に記載の、以下の平均組成式で表されるカルボキシル基含有有機基を有するオルガノポリシロキサン:
R2は下記式(2)で表される基であり、cが0の場合にはR2は該オルガノポリシロキサンの少なくとも一の末端に結合されており、
R3は下記式(3)で表される基であり、
(式中、Rcは、前記一般式:-R1-(OR2)p-(O)w-R3-COOHで示されるカルボキシル基含有有機基を表し、Rは、同一又は異なり、炭素数1〜22のアルキル若しくはアルコキシ基又はフェニル基を表し、R´は、Rc又はRであり、a、bは各々0以上の範囲の数であり、a+bは0〜1000の範囲の数である。但し、b=0のとき、R´の少なくとも一方はRcである。)で表されるオルガノポリシロキサンが挙げられる。特に、特開平8-109263号公報に開示されたカルボン酸変性シリコーン、国際公開第2009/22621号等に開示されたカルボン酸変性シリコーンの一部(シロキサンデンドロン構造を有するもの以外)は、前記構造式(1)で表され、且つ、本発明において好適に使用されるカルボン酸変性シリコーンに含まれる。
(式中、
Rcは、一般式:-R1-(OR2)p-(O)w-R3-COOH(R1 は炭素数2〜22の直鎖又は分岐鎖のアルキレン基を表し、R2 は炭素数2〜4の直鎖又は分岐鎖のアルキレン基を表し、R3 は結合手(−)又は炭素数1〜22の直鎖若しくは分岐鎖のアルキレン基を表し、pは0〜200の数を表し、wは0又は1の数を表す)で示されるカルボキシル基含有有機基を表し、
Rは、同一又は異なり、炭素数1〜22のアルキル若しくはアルコキシ基又はフェニル基を表し、
R´は、Rc又はRであり、
a、bは各々正の数であり、a≧2が好ましく、また、b≧2が好ましく、
a+bは2〜20の範囲の数であり、2〜15が好ましく、2〜10がより好ましく、
a/bは0.3〜3.0の範囲であり、0.3〜2.5が好ましく、0.3〜2.0がより好ましく、0.5〜2.0が更により好ましい。)で表されるものがより好ましい。
本発明の化粧料は、アクリル酸/メタクリル酸共重合体ポリマー等のビニル系重合体エマルションを含む。当該ビニル系重合体は、肌上等に化粧膜を形成する皮膜形成成分または水系の増粘剤であり、かつ、前記(A)カルボン酸変性シリコーンとの併用により、疎水性粉体である無機紫外線防御成分に由来する紫外線防御性(特に、SPF値)を向上させる成分である。(B)ビニル系重合体エマルションを単独で使用した場合、化粧料のSPF値をブーストする効果は限定的であり、両者を併用することで化粧料のSPF値をブーストする効果が十分に発揮される。
(b2)アクリル酸/メタクリル酸スチレン共重合体ポリマー、および
(b3)カルボシロキサンデンドロン構造を有するアクリル酸/メタクリル酸共重合体ポリマー
から選ばれる1種類以上のアクリル系共重合体ポリマーのエマルションがあげられる。
本発明の水中油型乳化化粧料は少なくとも1種の(C)塩基性化合物を含む。成分(C)は、前記の(A)カルボン酸変性シリコーンのカルボン酸変性部位をアニオン化することができ、該(A)カルボン酸変性シリコーンの界面活性剤としての機能を向上させる。特に、本発明の水中油型乳化化粧料は、(D)疎水性微粒子金属酸化物からなる無機紫外線防御剤を含むものであるが、前記の成分(A)と成分(C)を併用することで、成分(A)単独に比べて、成分(D)を本発明の水中油型乳化化粧料の水相中に良好に分散することができ、化粧料全体の安定性および皮膜形成性を改善するだけでなく、成分(A)の助剤として、化粧料全体のSPF値をブーストする効果に貢献する。
本発明の水中油型乳化化粧料は、無機紫外線防御剤を含み、当該成分に由来するUV−B波(波長280〜315nm)を遮断する効果が、前記の成分(A)および成分(B)の併用により、さらに向上されていることを特徴とする。紫外線遮蔽効果の指標は前記のSPF値であるが、本発明の水中油型乳化化粧料は、同量の無機紫外線防御剤を含む場合、成分(A)および成分(B)を含まない場合に比べて、化粧料全体としてのSPF値が向上し、紫外線を遮蔽する効果がさらに改善されている。また、成分(D)は疎水性粉体であり、SPF値向上を目的として大量に配合すると、水中油型乳化化粧料の使用感を損なう場合があるが、上記のように本発明の水中油型乳化化粧料においては、化粧料全体としてSPF値をブーストする効果を発言するので、使用感を損なわない程度の成分(D)の使用量で、高いSPF値を達成できるという利点を有する。また、本発明における成分(D)は、水相および油相中に分散可能であるが、上記の(C)塩基性化合物の使用により、水中油型乳化化粧料の水相中に良好に分散した状態となり、化粧料としての使用感、紫外線防御効果および石鹸等による洗浄性がさらに改善される。
本発明の水中油型乳化化粧料は、任意で成分(D)以外の疎水性粉体を含むことができる。これらの粉体は、白色及び着色顔料、体質顔料を含む。白色及び着色顔料は化粧料の着色等に使用され、一方、体質顔料は、化粧料の感触改良等に使用される。また、これらの粉体自体の表面が疎水性でない場合は、その表面に上記の成分(D)同様に疎水化処理が施されているものである。なお、これらの疎水性粉体同士を複合化してもよい。
本発明の化粧料は少なくとも1種の(E)油剤を含む。油剤は、本発明の化粧料中において油相を形成する。
前記(E)油剤は少なくとも1種の紫外線吸収剤を含むことができる。すなわち、本発明の化粧料の油相は紫外線吸収剤を含むことができる。紫外線吸収剤は有機系であることが好ましく、親油性であることがより好ましく、油溶性であることが更により好ましい。上記の成分(D)である無機紫外線防御成分のほかに、(E)油剤である有機系の紫外線吸収剤を含むことにより、化粧料全体としてより高いSPF値を実現できるほか、UV−B波(波長280〜315nm)以外のUV−A波(波長315〜380nm)に対する紫外線防御/遮蔽効果をさらに改善できる実益がある。なお、本発明にかかる水中油型乳化化粧料は(E)油剤である紫外線吸収剤のほかに、後述する(H)水溶性紫外線吸収剤を含むことができ、かつ、好ましい。
パラメトキシケイ皮酸ベンジル、パラメトキシケイ皮酸2−エチルヘキシル、ジパラメトキシケイ皮酸モノ−2−エチルヘキサン酸グリセリル等のケイ皮酸系紫外線吸収剤;
ヒドロキシメトキシベンゾフェノン、ジヒドロキシメトキシベンゾフェノン、ジヒドロキシベンゾフェノン、テトラ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;
パラアミノ安息香酸、パラアミノ安息香酸エチル、パラアミノ安息香酸グリセリル、パラジメチルアミノ安息香酸アミル、パラジメチルアミノ安息香酸オクチル、4−[N,N−ジ(2−ヒドロキシプロピル)アミノ]安息香酸エチル、ジエチルアミノヒドロキシベンゾイル安息香酸ヘキシル等の安息香酸エステル系紫外線吸収剤;
サリチル酸エチレングリコール、サリチル酸フェニル、サリチル酸オクチル、サリチル酸ベンジル、サリチル酸パラ−ターシャリーブチルフェニル、サリチル酸ホモメンチル等のサリチル酸系紫外線吸収剤;
エチルヘキシルトリアゾン(2,4,6−トリス[4−(2−エチルヘキシルオキシカルボニル)アニリノ]1,3,5−トリアジン)、ビスエチルヘキシルオキシフェノールメトキシフェニルトリアジン等のトリアジン系紫外線吸収剤;
4−ターシャリーブチル−4’−メトキシジベンゾイルメタン、アントラニル酸メンチル、2−(2−ヒドロキシ−5−メチルフェニル)ベンゾトリアゾール、ジメトキシベンジリデンジオキソイミダゾリジンプロピオン酸2−エチルヘキシル、オクトクリレン、ジメチコジエチルベンザルマロネート等のその他の紫外線吸収剤
本発明の水中油型乳化化粧料は水を含む。水は、本発明の化粧料中において水相を形成する成分であり、前記の(E)油剤の乳化粒子のほか、成分(A)および成分(C)の存在下において、成分(D)その他の疎水性粉体が水相中に安定して分散した構造を有する。
本発明の水中油型乳化化粧料は少なくとも1種の(F)油溶性皮膜形成剤を含んでもよい。上記の成分(A)〜成分(D)、特に成分(A)であるカルボン酸変性シリコーンと(F)油溶性皮膜形成剤を併用することで、化粧料全体として高い安定性を備え、且つ、優れた耐水性を有する化粧膜を与える水中油型乳化化粧料が提供可能である。
(F1)M単位及びQ単位を含有するシリコーン樹脂、
(F2)シリコーンアクリレート
(F2)T単位を含有するシリコーン樹脂、及び、
(F3)シリコーンレジンガム
からなる群から選択される少なくとも1種がより好ましい。
本発明の水中油型乳化化粧料は少なくとも1種の(G)多価アルコールを含むことができる。
本発明の水中油型乳化化粧料は油相の他、水相についても紫外線吸収剤を含んでよく、化粧量全体のSPF値やPA指標の値をさらに向上させることができる場合がある。具体的には、水相に溶解可能な、少なくとも1種の(H)水溶性紫外線吸収剤を含んでよい。
本発明の水中油型乳化化粧料には、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その他の成分:例えば、親水性粉体、成分(G)以外の保湿剤、成分(B)以外の増粘剤(たとえば、メチルセルロース、グァーガム等の水溶性増粘剤)、ゲル化剤、防腐剤、抗菌剤、香料、塩類、酸化防止剤、成分(C)以外のpH調整剤、キレート剤、清涼剤、抗炎症剤、生理活性成分(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、包接化合物等を添加することができる。その他の成分は特に限定されるものではない。
本発明の水中油型乳化化粧料の製造工程は任意であり、前記各成分を混合して、50℃で液状の(A)カルボン酸変性シリコーン、(B)ビニル系重合体エマルション、(C)塩基性化合物、(D)疎水性微粒子金属酸化物からなる無機紫外線防御剤、(E)油剤、および水を含む水中油型乳化化粧料を調製できる限り、特に限定されない。
本発明の水中油型乳化化粧料は、クリーム状、ゲル状、乳液状、液状のいずれの形態であってもよい、本発明の化粧料は、例えば、乳液、クリーム、美容液等の基礎化粧料、下地化粧料、サンスクリーン剤、ファンデーション、アイシャドー、アイライナー、水おしろい等のメイクアップ化粧料として使用することができ、また毛髪・頭皮用のサンスクリーン剤、一時染毛剤等として使用することもできる。また、後述する日焼け止め化粧料の実施形態は、特に限定されるものではないが、ローション状、リキッド状、ゲル状、ミスト・スプレー状(エアゾール型を含む)、液状、固形状、オイル状、泡状等の形態で用いることができる。
本発明の水中油型乳化化粧料は、上記の感触等の利点を生かしながら、UV−B波(波長280〜315nm)を遮断する効果の程度を表す指標であるSPF値が改善されており、特に、日焼け止め化粧料に適する。本発明の水中油型乳化化粧料である日焼け止め化粧料は、成分(A)〜成分(D)の組み合わせを含まない場合に、成分(D)単独で実現されるSPF値よりも、化粧料全体として高いSPF値を有する。
[合成例1]
撹拌機、還流冷却器、滴下ロート及び温度計を備えたフラスコにウンデシレン酸トリメチルシリル230.67g , 白金− 1 , 3 − ジビニル− 1 , 1 , 3 , 3 − テトラメチルジシロキサン錯体の0.042g を加え、7 0 − 8 0 ℃ の範囲を保つように、下記一般式で表されるS i − H シロキサン129.33g を滴下した。
滴下終了後、2 時間、110 ℃ で熟成した後、水素発生法 によりS i − H 結合の消失を確認した。低沸点分を減圧下、留去した。その後、脱イーオン水90g を加え、還流下4時間熟成し、脱保護を行った。その後再び低沸点分を減圧下除去し、化合物1 を得た。分析の結果、下記化学構造式で示される化合物1であることが確認された。
表1〜3に示す各成分を使用して下記製造方法により実施例1〜12及び比較例1の組成物を製造した。表1中の各成分の配合量は、特記しない限り「質量%」(「重量%」)を表す。
(1)A相の成分を混合する。
(2)B相の成分を混合する。
(3)C相の成分を混合する。
(4)常温にて、B相の成分の混合物にA相の成分の混合物を少量ずつ添加し、エマルションを調製する。
(4)上記エマルジョンにC相の成分を混合する。
(5)上記エマルションにD相の成分を混合して化粧料を調製する。
注1:合成例1のカルボン酸変性シリコーン
注2:ACULYNTM 33A RHEOLOGY MODIFIER(ダウケミカル製)
注3:MTY−02(テイカ製)
注4:SOLTEXTM INO POLYMER(ダウケミカル製)
注5:SunSpheresTM PGL SPF Booster(ダウケミカル製)
注6:DOWSILTM FA−4103 SILICONE ACRYLATE EMULSION(ダウ・東レ株式会社製)
注7:EPITEXTM 66 POLYMER(ダウケミカル製)
20名の女性パネリストの顔面に評価対象(日焼け止め化粧料)を塗布し、塗布時の使用感(みずみずしさ、さっぱり感)について、下記の基準に従って官能評価を行った。
◎:20名中16名以上が、みずみずしい、さっぱりしていると回答
○:20名中11〜15名が、みずみずしい、さっぱりしていると回答
△:20名中6〜10名が、みずみずしい、さっぱりしていると回答
×:20名中5名以下が、みずみずしい、さっぱりしていると回答
HELIOPLATE HD6(HelioScreenLab社製)に評価対象(日焼け止め化粧料)を2mg/cm2となるように均一に塗布し、SPF測定機器UV−1000S(Labsphere社製)を用いてSPF値およびPA値を測定した。表1〜3に記載した値は、試験サンプル3つに対して、それぞれ10箇所測定を行い、最大値および最小値を除いた平均値である。
Claims (15)
- (A)50℃で液状のカルボン酸変性シリコーン、
(B)ビニル系重合体エマルション、
(C)塩基性化合物、及び、
(D)疎水性微粒子金属酸化物からなる無機紫外線防御剤
を含む、水中油型乳化化粧料。 - 前記の(D)疎水性微粒子金属酸化物からなる無機紫外線防御剤100質量部に対して、
前記の(A)50℃で液状のカルボン酸変性シリコーンが5〜40質量部となる範囲の量であり、
前記の(B)ビニル系重合体エマルションが、当該エマルション中の固形分の含有量が0.5〜10質量部となる範囲の量であり、
前記の成分(A)および成分(B)を含まない場合に比べて化粧料全体のSPF値が向上していることを特徴とする、請求項1に記載の水中油型乳化化粧料。 - 前記(A)カルボン酸変性シリコーンが、下記構造式(1):
(式中、
Rcは、一般式:-R1-(OR2)p-(O)w-R3-COOH(R1 は炭素数2〜22の直鎖又は分岐鎖のアルキレン基を表し、R2 は炭素数2〜4の直鎖又は分岐鎖のアルキレン基を表し、R3 は結合手(−)又は炭素数1〜22の直鎖若しくは分岐鎖のアルキレン基を表し、pは0〜200の数を表し、wは0又は1の数を表す)で示されるカルボキシル基含有有機基を表し、
Rは、同一又は異なり、炭素数1〜22のアルキル若しくはアルコキシ基又はフェニル基を表し、
R´は、Rc又はRであり、
a、bは各々0又は正の数であり、a+bは0〜30の範囲の数であり、bが0のとき、R´の少なくとも一方はRcである。)で表される、請求項1又は請求項2に記載の水中油型乳化化粧料。 - 前記(A)カルボン酸変性シリコーンが室温(25℃)で液状である、請求項1〜請求項3のいずれか1項に記載の水中油型乳化化粧料。
- 前記(A)カルボン酸変性シリコーンが、下記構造式(2):
(式中、
Rcは、一般式:-R1-(OR2)p-(O)w-R3-COOH(R1 は炭素数2〜22の直鎖又は分岐鎖のアルキレン基を表し、R2 は炭素数2〜4の直鎖又は分岐鎖のアルキレン基を表し、R3 は結合手(−)又は炭素数1〜22の直鎖若しくは分岐鎖のアルキレン基を表し、pは0〜200の数を表し、wは0又は1の数を表す)で示されるカルボキシル基含有有機基を表し、
Rは、同一又は異なり、炭素数1〜22のアルキル若しくはアルコキシ基又はフェニル基を表し、
R´は、Rc又はRであり、
a、bは各々正の数であり、a+bは2〜20の範囲の数であり、a/bは0.3〜3.0の範囲である。)で表される、請求項1〜請求項4のいずれか1項に記載の水中油型乳化化粧料。 - 前記(A)カルボン酸変性シリコーンを化粧料の全質量に対して0.5〜15質量%の範囲で含む、請求項1〜請求項5のいずれか1項に記載の水中油型乳化化粧料。
- 前記の(B)ビニル系重合体エマルションが、アクリル酸エステル単量体またはメタクリル酸エステル単量体を共重合させてなるアクリル系共重合体ポリマーのエマルションである、請求項1〜請求項6のいずれか1項に記載の水中油型乳化化粧料。
- 前記の(B)ビニル系重合体エマルションが、
(b1)アクリル酸/メタクリル酸アルキル共重合体ポリマー、
(b2)アクリル酸/メタクリル酸スチレン共重合体ポリマー、および
(b3)カルボシロキサンデンドロン構造を有するアクリル酸/メタクリル酸共重合体ポリマー
から選ばれる1種類以上のアクリル系共重合体ポリマーのエマルションである、請求項1〜請求項7のいずれか1項に記載の水中油型乳化化粧料。 - 前記の(D)疎水性微粒子金属酸化物からなる無機紫外線防御剤が、平均粒子径が1〜200nmの範囲である、疎水化微粒子酸化チタン又は疎水化微粒子酸化亜鉛である、請求項1〜請求項8のいずれか1項に記載の水中油型乳化化粧料。
- さらに、(E)油剤を含む、請求項1〜請求項9のいずれか1項に記載の水中油型乳化化粧料。
- 前記の(E)油剤が少なくとも1種の紫外線吸収剤を含む、請求項10に記載の水中油型乳化化粧料。
- さらに、(F)油溶性皮膜形成剤を含む、請求項1〜請求項11のいずれか1項に記載の水中油型乳化化粧料。
- さらに、(G)多価アルコールを含む、請求項1〜請求項12のいずれか1項に記載の水中油型乳化化粧料。
- さらに、(H)水溶性紫外線吸収剤を含む、請求項1〜請求項13のいずれか1項に記載の水中油型乳化化粧料。
- 日焼け止め化粧料である、請求項1〜請求項14のいずれか1項に記載の水中油型乳化化粧料。
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EP3960152A4 (en) * | 2019-04-24 | 2023-06-07 | Dow Toray Co., Ltd. | COSMETIC PREPARATIONS |
JP7448352B2 (ja) * | 2019-12-24 | 2024-03-12 | 株式会社 資生堂 | 水中油型乳化日焼け止め化粧料 |
EP4227347A1 (en) | 2020-10-09 | 2023-08-16 | Dow Toray Co., Ltd. | Carboxylic acid-comodified organopolysiloxane and use therefor |
WO2023201023A1 (en) * | 2022-04-15 | 2023-10-19 | Sri International | Sprayable-skin formulations |
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- 2019-07-31 EP EP19849584.8A patent/EP3838255A4/en active Pending
- 2019-07-31 US US17/267,940 patent/US20210330571A1/en active Pending
- 2019-07-31 CN CN201980060168.2A patent/CN112689500B/zh active Active
- 2019-07-31 JP JP2020537405A patent/JP7348189B2/ja active Active
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US20210330571A1 (en) | 2021-10-28 |
CN112689500B (zh) | 2023-09-12 |
WO2020036064A1 (ja) | 2020-02-20 |
JP7348189B2 (ja) | 2023-09-20 |
EP3838255A4 (en) | 2022-05-11 |
EP3838255A1 (en) | 2021-06-23 |
CN112689500A (zh) | 2021-04-20 |
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