JP6307259B2 - 表面処理粉体、それを含むスラリー組成物、化粧料用原料及び化粧料 - Google Patents
表面処理粉体、それを含むスラリー組成物、化粧料用原料及び化粧料 Download PDFInfo
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- JP6307259B2 JP6307259B2 JP2013256303A JP2013256303A JP6307259B2 JP 6307259 B2 JP6307259 B2 JP 6307259B2 JP 2013256303 A JP2013256303 A JP 2013256303A JP 2013256303 A JP2013256303 A JP 2013256303A JP 6307259 B2 JP6307259 B2 JP 6307259B2
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- 229940011671 vitamin b6 Drugs 0.000 description 1
- 229940021056 vitamin d3 Drugs 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010497 wheat germ oil Substances 0.000 description 1
- 230000029663 wound healing Effects 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- 235000010447 xylitol Nutrition 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
- 229960002675 xylitol Drugs 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229940105125 zinc myristate Drugs 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 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
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 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
- 150000003754 zirconium Chemical class 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- 235000007680 β-tocopherol Nutrition 0.000 description 1
- 239000011590 β-tocopherol Substances 0.000 description 1
- 239000002478 γ-tocopherol Substances 0.000 description 1
- QUEDXNHFTDJVIY-DQCZWYHMSA-N γ-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-DQCZWYHMSA-N 0.000 description 1
Images
Landscapes
- Cosmetics (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
(a)透過電子顕微鏡を用いて測定した平均粒子径が5〜100nmの無機微粒子と、
(b)1種類以上のカルボン酸変性シリコーンと
を含み、前記無機微粒子の表面の一部又は全部が、前記カルボン酸変性シリコーンで処理されている、表面処理粉体によって達成される。
Aは、CqH2qで表される直鎖状又は分岐鎖状のアルキレン基であり、qは0〜20の整数であり、
但し、一般式(1)で表されるオルガノシロキサン誘導体の1分子中に含まれるケイ素原子の平均合計数は2〜100である}
R7及びR8は、それぞれ独立に、炭素数1〜6のアルキル基又はフェニル基であり、
Bは、炭素数2〜20の直鎖状又は分岐鎖状のアルキレン基であり、
iは、Xiで示されるシリルアルキル基の階層を表し、該シリルアルキル基の繰り返し数である階層数がnのとき1〜nの整数であり、階層数nは1〜10の整数であり、
aiは、iが1のときは0〜2の整数であり、iが2以上のときは3未満の整数であり、
Xi+1は、iがn未満のときは該シリルアルキル基であり、i=nのときはメチル基である)であることが好ましい。
(a)透過電子顕微鏡を用いて測定した平均粒子径が5〜100nmの無機微粒子と、
(b)1種類以上のカルボン酸変性シリコーンと
を含むことを特徴とする。
Aは、CqH2qで表される直鎖状又は分岐鎖状のアルキレン基であり、qは0〜20の整数であり、
但し、一般式(1)で表されるオルガノシロキサン誘導体の1分子中に含まれるケイ素原子の平均合計数は2〜100である}。
R7及びR8は、それぞれ独立に、炭素数1〜6のアルキル基又はフェニル基であり、
Bは、炭素数2〜20の直鎖状又は分岐鎖状のアルキレン基であり、
iは、Xiで示されるシリルアルキル基の階層を表し、該シリルアルキル基の繰り返し数である階層数がnのとき1〜nの整数であり、階層数nは1〜10の整数であり、
aiは、iが1のときは0〜2の整数であり、iが2以上のときは3未満の整数であり、
Xi+1は、iがn未満のときは該シリルアルキル基であり、i=nのときはメチル基である)
HSi(−O−SiR2H)fRL 3−f
(式中、Rは炭素原子数1〜6のアルキル基又はフェニル基であり、RLはそれぞれ独立に、置換又は非置換の一価炭化水素基であり、fは1〜3の整数である)で示されるジメチルシロキシ基を有するオルガノシランと、CH=CH2−ACOOSiMe3で表されるビニル末端を有するカルボン酸トリメチルシリル誘導体(式中、Aは一般式(1)で定義した基である)とを、白金系金属触媒の存在下に付加反応させ、下記一般式(1−1)の中間体を得る工程。
RBSi(O−R6)ai(OSiR7R8−Xi+1)3−ai
(式中、RBは炭素数2〜20の直鎖状又は分岐鎖状のアルケニル基であり、R6、R7、R8、Xi+1、及びaiは一般式(1)で定義した基及び数である)で示されるアルケニル基を有するオルガノシランと、工程(1)で得られた一般式(1−1)の中間体とを、白金系触媒の存在下に付加反応させ、下記一般式(1−2)の中間体を得る工程。
Si{−O−SiR2−B−Si(O−R6)ai(OSiR7R8−Xi+1)3−ai}fRL 3−f−(CH2)2−A−COOSiMe3 (1−2)
一般式(1−2)の中間体に、保護基であるトリメチルシリル基1モルあたり、少なくとも1モル以上のメタノール等の一価アルコール、水又はこれらの混合物を加えて加熱することにより、加アルコール分解により脱保護させる工程。
(X,Y)2−3(Si,Al)4O10(OH)2Z1/3・nH2O (A)
(但し、Xは、Al、Fe(III)、Mn(III)、又は、Cr(III)であり、Yは、Mg、Fe(II)、Ni、Zn、又はLiであり、Zは、K、Na、又はCaである)このような無機系水溶性高分子として、具体的には、ベントナイト、モンモリロナイト、パイデライト、ノントロナイト、サポナイト、ヘクトライト、ケイ酸アルミニウムマグネシウム、及び無水ケイ酸が例示され、これらは天然物及び合成物のいずれであってもよい。
表面処理粉体を、1100℃の温度、酸素雰囲気下で、シリカ表面に化学結合する疎水性基をCO2に熱分解した後、微量炭素分析装置(Horiba製「EMIAー110」)により、有機物(wt%)を求めた。
表面処理粉体の試料0.5gに、メタノールと水の混合溶液(25℃)100mlを加え、シェーカーで30分間振り混ぜた後、一晩静置して混合溶液に対する粉体の浮遊割合を測定した。水−メタノールの比を変えて上記操作を行い、浮遊量が0%となるメタノール濃度(容量%)を疎水化度(%)として求めた。
B型回転粘度計(ビスメトロン粘度計、芝浦システム (株))No.3ローターを使用し、25℃、30rpmで1分後の粘度を測定した。
分光光度計(spectrophotometer U−2010,日立製作所)で、300〜800nmの可視紫外光線透過率を測定した。
専門パネラー10名により、のびの良さ、べたつきのなさ、肌なじみの良さ、白残りの少なさを評価した。なお、評価は以下の基準に従い、5段階評価によりその平均値を記載した。
5:非常に良い
4:良い
3:普通
2:やや悪い
1:悪い
◎:平均点が4.5以上
○:平均点が3.5以上4.5未満
△:平均点が2.5以上3.5未満
×:平均点が2.5未満
トルエン中にオルガノシロキサン誘導体(化合物1)とチタン工業製微粒子酸化チタン(まゆ状、水酸化アルミ処理品、平均粒子径:短軸直径30nm、長軸直径80nm)を順番に添加して撹拌した後、150℃のオーブンでトルエンを乾燥除去し、焼付け処理を行った。その後、粉砕機で粉砕して表面処理粉体を得た。評価結果を下記表1に示す。
実施例1と同種類の微粒子酸化チタン(水酸化アルミ処理品)をメチルハイドロジェンポリシロキサンで表面処理したチタン工業製微粒子酸化チタン(商品名:ST−605EC)を比較例1とした。
実施例1と同種類の微粒子酸化チタン(水酸化アルミ処理品)をステアリン酸で表面処理したチタン工業製微粒子酸化チタンを比較例2とした。
イソドデカン80g中にオルガノシロキサン誘導体(化合物1)を1.5g、石原産業社製微粒子酸化亜鉛(商品名:FZO−50、未処理品、平均粒子径:21nm)30gを順番に添加して撹拌し、さらに該混合物を超音波洗浄器にて約20分かけて均一化した後、吸引ろ過して、固液を分離し、得られた固体分を150℃のオーブンでイソドデカンを乾燥除去し、焼付け処理を行った。その後、粉砕機で粉砕して実施例2の表面処理粉体を得た。
イソドデカン80g中にオルガノシロキサン誘導体(化合物1)を1.5g、石原産業社製酸化チタン(商品名:TTO−S−4、水酸化アルミ処理、ステアリン酸被覆品、平均粒子径:短軸直径10〜20nm、長軸直径50〜100nm)30gを順番に添加して撹拌し、さらに該混合物を超音波洗浄器にて約20分かけて均一化した後、吸引ろ過して、固液を分離し、得られた固体分を150℃のオーブンでイソドデカンを乾燥除去し、焼付け処理を行った。その後、粉砕機で粉砕して実施例3の表面処理粉体を得た。
イソドデカン80g中にオルガノシロキサン誘導体(化合物1)を1.5g、テイカ製酸化亜鉛(商品名:MZ−300、未処理品、平均粒子径:35nm)30gを順番に添加して撹拌し、さらに該混合物を超音波洗浄器にて約20分かけて均一化した後、吸引ろ過して、固液を分離し、得られた固体分を150℃のオーブンでイソドデカンを乾燥除去し、焼付け処理を行った。その後、粉砕機で粉砕して実施例4の表面処理粉体を得た。
実施例4で使用したテイカ製未処理酸化亜鉛MZ−300を比較例4とした。
実施例4と同様の酸化亜鉛をジメチコン・メチコンコポリマーで表面処理したテイカ製酸化亜鉛MZY−303Sを比較例4とした。
実施例1及び比較例1の表面処理微粒子酸化チタンを、それぞれ微粒子酸化チタン/環状シリコーン(東レ・ダウコーニング社製SH245)/シリコーン系分散剤(東レ・ダウコーニング社製ES−5612)/1mmφジルコニアビーズ=40g/50g/10g/300gの配合割合で250mLガラスマヨネーズ瓶に採取し、ペイントコンディショナー(レッドデビル社製)を使用して2時間分散した。得られた各スラリーを石英ガラス板上へ10μmの膜厚で塗布し、形成した膜の波長300nm〜800nmにおける透過率曲線を測定した。測定結果を図1に示す。実施例5の表面処理粉体を用いた場合は比較例5よりも透明性がやや低かったものの、十分な使用レベルであることが確認された。また、スラリーの粘度を測定したところ、実施例5は280mPa.sであったのに対し、比較例5は120mPa.sであった。両者ともに環状シリコーンへの分散性に優れていた。さらに、室温で17ヶ月保管した場合の保存安定性を比較した結果、両者ともに濃度上昇及びケーキングは起きないことを確認した。
実施例1及び比較例2の表面処理微粒子酸化チタンを、それぞれ微粒子酸化チタン/水添ポリイソブテン(日油製パールリーム4)/有機系分散剤(日清オイリオ社製サラコスHS−6C)/1mmφジルコニアビーズ=55g/40g/5g/300gの配合割合で250mLガラスマヨネーズ瓶に採取し、ペイントコンディショナー(レッドデビル社製)を使用して2時間分散した。得られた各スラリーを石英ガラス板上へ10μmの膜厚で塗布し、形成した膜の波長300nm〜800nmにおける透過率曲線を測定した。測定結果を図2に示す。実施例6のスラリーの透過率は、比較例6のスラリーの透過率と同程度であることが分かった。また、スラリーの粘度を測定したところ、実施例6は940mPa.sであったのに対し、比較例6は440mPa.sと環状シリコーン分散体と比較するとやや粘度が高かったものの、両者ともに使用レベルであった。
実施例2及びその未処理の微粒子酸化亜鉛FZO−50を、それぞれ微粒子酸化亜鉛/環状シリコーン(東レ・ダウコーニング社製SH245)/シリコーン系分散剤(東レ・ダウコーニング社製ES−5612)/0.8mmφジルコニアビーズ=18g/10.5g/1.5g/120gの配合割合で225mLガラスマヨネーズ瓶に採取し、ペイントシェーカー(浅田鉄工社製)を使用して15時間分散した。得られた各スラリーの粘度は実施例7が2000mPa.sであったのに対し、未処理の比較例7は粉が濡れたのみで液状とならず、粘度の測定は不可能であった。
実施例4と比較例3及び4の微粒子酸化亜鉛を、それぞれ微粒子酸化亜鉛/環状シリコーン(東レ・ダウコーニング社製SH245)/シリコーン系分散剤(東レ・ダウコーニング社製ES−5612)/0.8mmφジルコニアビーズ=18g/10.5g/1.5g/120gの配合割合で225mLガラスマヨネーズ瓶に採取し、ペイントシェーカー(浅田鉄工社製)を使用して15時間分散した。得られた各スラリーの粘度は実施例10が1000mPa.sであったのに対し、比較例3を使用した比較例8は粉が濡れたのみで液状とならず粘度の測定は不可であり、比較例9のシリコーン処理品は150mPa.sであった。
実施例5及び比較例5の環状シリコーン分散体を用いて表3に示すサンスクリーン剤を調製したところ、べたつきのなさに有意差がないものの、のびの良さ、肌なじみの良さ、及び白残りの少なさについては実施例9の方が優れていた。
実施例5及び比較例5の環状シリコーン分散体を用いて表4に示すサンスクリーン剤を調製したところ、のびの良さに有意差がないものの、べたつきのなさ、肌なじみの良さ、及び白残りの少なさについては実施例10の方が優れていた。
実施例8及び比較例9の環状シリコーン分散体を用いて表5に示すサンスクリーン剤を調製したところ、のびの良さに有意差がないものの、べたつきのなさ、肌なじみの良さ、及び白残りの少なさについては実施例11の方が優れていた。
(成分)
相A
1)シリコーン乳化剤(注1) 4質量部
2)カプリリルメチコン(注2) 16質量部
3)メトキシケイヒ酸エチルヘキシル 7質量部
4)サリチル酸エチルヘキシル 2.5質量部
5)シリコーンレジン(注3) 2質量部
6)シリコーン架橋体(注4) 3質量部
7)酢酸トコフェロール 0.5質量部
相B
8)アスコルビルリン酸ナトリウム 0.5質量部
9)グリセリン 8質量部
10)塩化ナトリウム 0.7質量部
11)精製水 39.8質量部
相C
12)酸化チタン(注5) 5.6質量部
13)黄色酸化鉄(注6) 0.25質量部
14)赤色酸化鉄(注7) 0.1質量部
15)黒色酸化鉄(注8) 0.05質量部
16)フェニルトリメチコン(注9) 9.2質量部
17)実施例4の酸化亜鉛 0.8質量部
注1:ダウコーニング社製、5200 FORMULATION AID
注2:ダウコーニング社製、FZ−3196
注3:ダウコーニング社製、MQ−1640 FLAKE RESIN
注4:ダウコーニング社製、9701 COSMETIC POWDER
注5:三好化成工業製、SI−チタンCR−50−Z
注6:三好化成工業製、SA−IOY−8
注7:三好化成工業製、SA−IOR−8
注8:三好化成工業製、SA−IOB−8
注9:東レ・ダウコーニング社製、SH556
1.成分1〜7を混合する。
2.成分8〜11を混合する。
3.成分12〜17を混合する。
4.工程1で得られる相Aと工程3で得られる相Cを混合する。
5.工程4で得られる混合物を撹拌しながら工程2で得られる相Bをゆっくり加え乳化する。
(成分)
相A
1)メトキシケイ皮酸エチルヘキシル 6.0質量部
2)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 1.5質量部
3)シクロペンタシロキサン 5質量部
4)アクリル変性シリコーン(注1) 3質量部
5)ジメチコン(6cs) 1質量部
6)トリオクタノイン 1質量部
7)シリコーン架橋体(注2) 3質量部
8)ポリシリコーン13(注3) 2質量部
9)実施例8の酸化亜鉛スラリー 10質量部
10)実施例2の酸化チタンスラリー 2質量部
相B
11)塩化ナトリウム 1質量部
12)パンテノール 0.5質量部
13)精製水 61.95質量部
14)グリセリン 2質量部
15)防腐剤 0.05質量部
注1:東レ・ダウコーニング社製FA4001CM SILICONE ACRYLATE
注2:ダウコーニング社製9040 SILICONE ELASTOMER BLEND
注3:東レ・ダウコーニング社製FZ−2233
1.成分1〜10を混合する。
2.成分11〜15を混合する。
3.工程1で得られる相Aに工程2で得られる相Bを加えて乳化する。
(成分)
相A
1)実施例4の酸化亜鉛 15質量部
2)イソドデカン 8.75質量部
3)シリコーン系分散剤(注1) 1.25質量部
4)メトキシケイ皮酸エチルヘキシル 10質量部
5)シリコーン乳化剤(注2) 0.5質量部
6)イソドデカン 30質量部
7)シリコーン架橋体(注3) 3質量部
8)シリコーンレジン(注4) 1質量部
相B
9)メチルパラベン 0.1質量部
10)エタノール 5質量部
相C
11)1,3−ブチレングリコール 3質量部
12)精製水 22.4質量部
注1:ダウコーニング社製ES−5612 FORMULATION AID
注2:ダウコーニング社製ES−5300 FORMULATION AID
注3:ダウコーニング社製EL−8050ID SILICONE ORGANIC ELASTOMER BLEND
注4:ダウコーニング社製MQ−1640 SILICONE FLAKE RESIN
1.成分1〜3を混合する。
2.成分4〜8を混合する。
3.成分9及び10を混合する。
4.成分11及び12を混合する。
5.工程1〜3で得られる相A及び相Bを混合する。
6.工程5で得られる混合物に工程4で得られる相Cを加えて乳化する。
Claims (11)
- (a)透過電子顕微鏡を用いて測定した平均粒子径が5〜100nmの無機微粒子と、
(b)1種類以上のカルボン酸変性シリコーン(ただし、デンドリマー構造を有するオルガノシロキシ基を有するものを除く)と
を含み、前記無機微粒子の表面の一部又は全部が、前記カルボン酸変性シリコーンで処理されている、表面処理粉体。 - 前記無機微粒子が金属酸化物微粒子である、請求項1に記載の表面処理粉体。
- 前記金属酸化物微粒子が、酸化チタン微粒子又は酸化亜鉛微粒子である、請求項2に記載の表面処理粉体。
- 前記一般式(1)において、R1及びR2が−O−Si(R4)3で表される基(R4は炭素数1〜6のアルキル基である)であり、R3が炭素数1〜10の1価炭化水素基であり、qが6〜20の整数である、請求項4に記載の表面処理粉体。
- 前記カルボン酸変性シリコーンが、前記無機微粒子100質量部に対して2〜10質量部含まれる、請求項1〜5のいずれか一項に記載の表面処理粉体。
- 請求項1〜6のいずれか一項に記載の表面処理粉体と、
(c)分散溶媒と
を含む、スラリー組成物。 - 請求項1〜6のいずれか一項に記載の表面処理粉体を含む化粧料用原料。
- 請求項8に記載の化粧料用原料を含む化粧料。
- 皮膚用化粧料である、請求項9に記載の化粧料。
- メークアップ化粧料又はサンスクリーン剤である、請求項10に記載の化粧料。
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