JP2017523283A - シリコーンエラストマー組成物 - Google Patents
シリコーンエラストマー組成物 Download PDFInfo
- Publication number
- JP2017523283A JP2017523283A JP2017502222A JP2017502222A JP2017523283A JP 2017523283 A JP2017523283 A JP 2017523283A JP 2017502222 A JP2017502222 A JP 2017502222A JP 2017502222 A JP2017502222 A JP 2017502222A JP 2017523283 A JP2017523283 A JP 2017523283A
- Authority
- JP
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- Prior art keywords
- units
- silicone
- linear organopolysiloxane
- reaction product
- group
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 235
- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 86
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 349
- 239000012530 fluid Substances 0.000 claims abstract description 200
- 238000006459 hydrosilylation reaction Methods 0.000 claims abstract description 103
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 77
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 36
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 35
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 230000001953 sensory effect Effects 0.000 claims abstract description 14
- 125000000524 functional group Chemical group 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
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- 125000001931 aliphatic group Chemical group 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 41
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
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- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 18
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- 238000009835 boiling Methods 0.000 description 12
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 11
- 229920001451 polypropylene glycol Polymers 0.000 description 11
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 10
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000008346 aqueous phase Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
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- 241000894007 species Species 0.000 description 8
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 125000000129 anionic group Chemical group 0.000 description 7
- 230000003750 conditioning effect Effects 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 230000002209 hydrophobic effect Effects 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 229920002050 silicone resin Polymers 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000004166 Lanolin Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- 238000000265 homogenisation Methods 0.000 description 6
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- 150000003839 salts Chemical class 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
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- 238000010586 diagram Methods 0.000 description 5
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- 125000000962 organic group Chemical group 0.000 description 5
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- 238000010998 test method Methods 0.000 description 5
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- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
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- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 4
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
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- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
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- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 3
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- OTOIBUHBRMYFLY-UHFFFAOYSA-N trimethyl-[(2,4,4,6,6-pentamethyl-1,3,5,2,4,6-trioxatrisilinan-2-yl)oxy]silane Chemical compound C[Si](C)(C)O[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 OTOIBUHBRMYFLY-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229940113164 trimyristin 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
- 229960001947 tripalmitin Drugs 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 239000010723 turbine oil Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
- 239000010679 vetiver oil Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 239000008170 walnut oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000010698 whale oil Substances 0.000 description 1
- 239000010497 wheat germ oil Substances 0.000 description 1
- 239000009637 wintergreen oil Substances 0.000 description 1
- 230000029663 wound healing Effects 0.000 description 1
- 229940075420 xanthine Drugs 0.000 description 1
- 239000008096 xylene 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
- VNTDZUDTQCZFKN-UHFFFAOYSA-L zinc 2,2-dimethyloctanoate Chemical compound [Zn++].CCCCCCC(C)(C)C([O-])=O.CCCCCCC(C)(C)C([O-])=O VNTDZUDTQCZFKN-UHFFFAOYSA-L 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- 229940105125 zinc myristate Drugs 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- GAWWVVGZMLGEIW-GNNYBVKZSA-L zinc ricinoleate Chemical compound [Zn+2].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O.CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O GAWWVVGZMLGEIW-GNNYBVKZSA-L 0.000 description 1
- 229940100530 zinc ricinoleate 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
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-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
Images
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Abstract
Description
組成物は、広範囲の濃度にわたり、独特のレオロジー的、視覚的、及び感覚的特性を呈することができる。このような組成物の化学的、及びしたがって物理的特性は、組成物を皮膚に適用した際に、親水性又は疎水性の挙動、有機的相溶性又は不相溶性、及び/又は様々な視覚的特性を呈するように、変更することができる。例えば、特定の組成物によって、構成成分の蓄積効果よりも有意な、望ましい特性を付与することができる。粘液性シリコーン流体及びシリコーンエラストマーを選択することによって、レオロジーを変更し、感覚認知を改善し、視覚的効果を変えることができ、組成物の持続性を高めることができる。
粘液性シリコーン流体は、粘液性を呈するシリコーン流体である。本明細書で使用する「粘液性」は、シリコーン流体のレオロジー特性を説明するもので、流体が一定に増大する剪断力を加えられた際に、流体は、垂直方向に観察される、増大する垂直応力を呈する。例えば、粘液性シリコーン流体がX−Y平面で剪断応力を受けると、Z方向(剪断力の平面に対して垂直又は法線方向)の力が生じる。シリコーン流体の粘液性レオロジーは、制御ストレスレオメーター(controlled stress rheometer)を使用して測定することができる。このようなレオメーターは、TA Instruments AR 1000−N(109 Lukens Drive,New Castle Del.19720)のように市販されている。典型的には、流体試料を、平らなディスク(レオメーターに装着)と、ロードセルを備えた固定プレートとの間に保持する。調節された量の力(トルク)を、ディスクに装着されたシャウトに加え、試料に剪断応力を受けさせる。トルクを増大させ、ディスクが速度を上げながら回転すると、剪断速度として記録される。試料は剪断応力を受けるので、垂直応力が、ロードセルによって記録される。レオロジー特性の結果と評価は、垂直剪断速度(単位秒−1)に対する垂直応力(単位パスカル)のプロットとして報告される。他の実施形態において、剪断速度に対する垂直応力のプロットが、方程式y=3.6x(式中、yは垂直応力であり、xは剪断速度である)を使用して作成したグラフ上の限界線の上方にある場合、流体は粘液性であるとみなされる。しかしながら、結果はこのような種類の報告に限定されず、当該技術分野において認められた任意の方法を使用して報告又は評価することができる。
ヒドロシリル化反応生成物は、第1及び第2の直鎖オルガノポリシロキサンの反応生成物である。別の言い方をすると、ヒドロシリル化反応生成物は、第1及び第2の直鎖オルガノポリシロキサンのヒドロシリル化反応から生成される。典型的には、ヒドロシリル化反応生成物それ自体は、直鎖である。様々な実施形態において、用語「直鎖」によって、第1の直鎖オルガノポリシロキサン、第2の直鎖オルガノポリシロキサン、ヒドロシリル化反応生成物、及び/又は粘液性シリコーン流体自体が、<1重量%、<0.5重量%、<0.1重量%、又は<0.01重量%のT単位及びQ単位、すなわち、それぞれ式(置換基−SiO3/2)及び(SiO4/2)を有するシロキシ単位を含むことが説明される。他の実施形態において、用語「直鎖」によって、第1の直鎖オルガノポリシロキサン、第2の直鎖オルガノポリシロキサン、ヒドロシリル化反応生成物、及び/又は粘液性シリコーン流体自体が、分枝化又は高度に分枝化していないことが説明される。更に他の実施形態において、第1の直鎖オルガノポリシロキサン、第2の直鎖オルガノポリシロキサン、ヒドロシリル化反応生成物、及び/又は粘液性シリコーン流体自体のそれぞれの主鎖は直鎖として、例えば、分枝化又は高度に分枝化していないものとして説明される。例えば、第1の直鎖オルガノポリシロキサン、第2の直鎖オルガノポリシロキサン、ヒドロシリル化反応生成物、及び/又は粘液性シリコーン流体自体のそれぞれの主鎖は典型的には直鎖である一方で、主鎖は、主鎖に結合した、1つ以上の環状置換基、芳香族置換基、又は非直鎖置換基を有してもよい。このような摘要において、第1の直鎖オルガノポリシロキサン、第2の直鎖オルガノポリシロキサン、ヒドロシリル化反応生成物、及び/又は粘液性シリコーン流体自体並びにそれぞれの主鎖は、依然として、本明細書で使用する「直鎖」とみなされる。更に、上記で使用した用語「分枝化した」及び「高度に分枝化した」は、当業者によって理解されるように使用される。
第1の直鎖オルガノポリシロキサンは、それぞれM単位及びD単位としても既知の、(R1R2R3SiO1/2)単位及び(R4R5SiO2/2)単位を含む。R1〜R5の少なくとも1つがアルケニル基である限り、R1〜R5のそれぞれは独立して炭化水素基である。炭化水素基は、メチル、エチル、プロピル、ブチル、ペンチル及びヘキシル等の、1〜20、2〜15、3〜10、5〜10個等の炭素原子を有するアルキル基、シクロヘキシル及びシクロヘプチル等のシクロアルキル基、フェニル、トリル及びキシリル等の、6〜12個の炭素原子を有するアリール基、ベンジル及びフェニルエチル等の、7〜20個の炭素原子を有するアラルキル基とすることができる。炭化水素基はまた、ビニル、アリル、ブテニル、ペンテニル、ヘキセニル及びデセニル、典型的にはビニル又はヘキセニル基等の、2〜20個の炭素原子を有するアルケニル基とすることができる。あるいは、炭化水素基は、1個以上のハロゲン原子を含んでもよい。上記の任意及び全ての値又はその間の値の範囲も使用してもよいことが企図される。
第2の直鎖オルガノポリシロキサンは、(R6R7R8SiO1/2)単位及び(R9R10SiO2/2)単位を含む。R6〜R10の少なくとも1つが水素原子である限り、R6〜R10のそれぞれは独立して炭化水素基である。炭化水素基は、上記のいずれかとすることができる。
粘液性シリコーン流体はまた、1種以上の任意選択の化合物を含んでもよい。あるいは、ヒドロシリル化反応生成物は、第1の直鎖オルガノポリシロキサン、第2の直鎖オルガノポリシロキサン、及び1種以上の下記の任意選択の化合物の、例えば前述のヒドロシリル化触媒存在下での反応生成物として更に定義することができる。あるいは、第1の直鎖オルガノポリシロキサンは、第2の直鎖オルガノポリシロキサンとの反応の前に、任意選択の化合物と反応させてもよい。他の実施形態において、第2の直鎖オルガノポリシロキサンは、第1の直鎖オルガノポリシロキサンとの反応の前に任意選択の化合物と反応させてもよく、依然として第2の直鎖オルガノポリシロキサンの一般的説明の範囲内にある。例えば、一実施形態において、第1のタイプの第2の直鎖オルガノポリシロキサンを任意選択の化合物と反応させ、第2のタイプの第2の直鎖オルガノポリシロキサンを生成することができる。あるいは、この第1のタイプの第2の直鎖オルガノポリシロキサンを、広範な第2の直鎖オルガノポリシロキサンの(第1)種と記述することができる。一実施形態において、第2の直鎖オルガノポリシロキサンは、第1種の第2の直鎖オルガノポリシロキサンと、モノ末端脂肪族不飽和炭化水素基を有する化合物又は本明細書に記載の他の任意選択の化合物のいずれかと、の反応生成物を含む。
粘液性シリコーン流体はまた、キャリア流体を含む。キャリア流体は、典型的には、シリコーン流体、有機溶媒、有機油、及びこれらの組み合わせから選択される。好適なキャリア流体としては、直鎖及び環状の両方のシリコーン、有機油、有機溶媒、及びこれらの組み合わせが挙げられる。具体的な溶媒の例は、米国特許第6,200,581号に見いだすことができ、本記載は、これらの溶媒に関連する様々な非限定的実施形態における参照により、本明細書に明示的に援用される。
組成物はまた、ヒドロシリル化反応生成物とは異なるシリコーンエラストマーも含む。より詳細には、シリコーンエラストマー及びヒドロシリル化生成物は同じ化合物ではないが、非常に類似している。シリコーンエラストマーは特に限定されず、当業者によって理解されるように、当該技術分野において既知の任意のものである。シリコーンエラストマーは、典型的には、組成物中に、組成物の100重量部当たり、1〜50、2〜40、3〜30、3〜25、4〜25、5〜25、5〜20、5〜15、5〜10、5〜9、6〜9、又は7〜8重量部の量で存在する。上記の任意及び全ての値又はその間の値の範囲も使用してもよいことが企図される。
好適なシリコーンエラストマーは、(A)≡Si−H含有ポリシロキサンと、(B)白金触媒存在下のα,ω−ジエンと、(C)低分子量直鎖又は環状ポリシロキサンと、の間の架橋反応によって調製することができる。シリコーンエラストマーは、低分子量ポリシロキサンによって、剪断力下で膨潤することができる。65〜98重量%の低分子量ポリシロキサンを含有するエラストマーは安定であり、広範囲の粘度を有する、均質なシリコーンペーストを形成する。
別の好適なシリコーンエラストマーを、オルガノハイドロジェンシロキサン、α,ω−不飽和ポリオキシアルキレン、及びヒドロシリル化触媒、それぞれ構成成分A)、B)、及びC)のヒドロシリル化反応生成物として得ることができる。用語「ヒドロシリル化」とは、触媒(例えば、構成成分C))の存在下、ケイ素結合水素を含有する有機ケイ素化合物(例えば、構成成分A))を脂肪族不飽和を含有する化合物(例えば、構成成分B))に付加するという意味である。ヒドロシリル化反応は、当該技術分野において既知であり、任意のこのような既知の方法又は技術を用い、構成成分A)、B)、及びC)のヒドロシリル化反応を行って、シリコーン有機エラストマーを調製することができる。
H2C=CHCH2O(C2H4O)c’H、H2C=CHCH2O(C2H4O)c’CH3、H2C=CHCH2O(C2H4O)c’C(O)CH3、H2C=CHCH2O(C2H4O)c’(C3H6O)d’H、H2C=CHCH2O(C2H4O)c’(C3H6O)d’CH3、H2C=C(CH3)CH2O(C2H4O)c’H、H2C=CC(CH3)2O(C2H4O)c’H、H2C=C(CH3)CH2O(C2H4O)c’CH3、H2C=C(CH3)CH2O(C2H4O)c’C(O)CH3、H2C=C(CH3)CH2O(C2H4O)c’(C3H6O)d’H、H2C=C(CH3)CH2O(C2H4O)c’(C3H6O)d’CH3、HC≡CCH2O(C2H4O)c’H、HC≡CCH2O(C2H4O)c’CH3、HC≡CCH2O(C2H4O)c’(C3H6O)d’H、HC≡CCH2O(C2H4O)c’(C3H6O)d’CH3、及びHC≡CCH2O(C2H4O)c’C(O)CH3が挙げられ、式中、c’及びd’は上記定義のとおりである。
別の好適なシリコーンエラストマーは、A)平均式:(R1 3SiO0.5)v(R2 2SiO)x(R2HSiO)y(式中、R1は水素又はR2であり、R2は一価のヒドロカルビルであり、vは≧2、xは≧0、かつyは≧2である)のシロキシ単位を含むオルガノハイドロジェンシロキサンと、B)平均式:R3O−[(C2H4O)c(C3H6O)d(C4H8O)e]−R3(式中、R3は、2〜12個の炭素原子を含有する一価の不飽和脂肪族炭化水素基であり、「c」は0〜50であり、「d」は0〜100であり、かつ「e」は0〜100であり、ただし、(d+e)/(c+d+e)の比は>0.5)を有する第1のポリオキシアルキレンと、C)ヒドロシリル化触媒と、D)平均式:R3O−[(C2H4O)c’(C3H6O)d’(C4H8O)e]−R4(式中、R3は、2〜12個の炭素原子を含有する一価の不飽和脂肪族炭化水素基であり、c’は>4、d’及び「e」は0〜100の範囲で変動してもよく、かつR4は水素、アシル基、又は1〜8個の炭素を含有する一価の炭化水素基である)を有する第2のポリオキシアルキレンとを、疎水性のキャリア流体の存在下で反応させることによって、得ることができる。
粘液性シリコーン流体は、エマルションとして提供してもよい。本明細書で使用する「エマルション」は、水連続性エマルション(例えば水中油型、又は水中シリコーンエマルション)、油、又はシリコーン連続性エマルション(油中水型エマルション又はシリコーン中水型エマルション)、又は多層エマルション(水/油/水、油/水/油型、水/シリコーン/水、又はシリコーン/水/シリコーン)について説明する。粘液性シリコーン流体は、撹拌、均質化、及びソナレーティング(sonalating)の、例えば、バッチ、半連続的、又は連続プロセス等の、当該技術の任意の方法を用い、エマルションとして提供することができる。
本組成物はまた、1種以上の下記の樹脂及び/又はコポリマーを含んでもよい。あるいは、ヒドロシリル化反応生成物は、第1及び第2の直鎖オルガノポリシロキサン、並びに1種以上の下記の樹脂及び/又はコポリマーの、例えばヒドロシリル化触媒存在下での反応生成物であってもよい。下記の樹脂及び/又はコポリマーはまた、後述するパーソナルケア組成物において使用することもでき、その場合、組成物に応じ、かつ/又は組成物とは別の様々な量で含まれ得る。
本開示はまた、組成物の形成方法を提供する。この方法は、第1及び第2の直鎖オルガノポリシロキサンを、ヒドロシリル化触媒及びキャリア流体の存在下、ヒドロシリル化反応を介して反応させ、粘液性シリコーン流体、例えば、アルケニル基又はSi−H官能基を含むヒドロシリル化反応生成物を生成することを含む。この方法は、反応に先立ち、第1の直鎖オルガノポリシロキサン、第2の直鎖オルガノポリシロキサン、ヒドロシリル化触媒、及びキャリア流体を1つにまとめる工程を含んでもよい。典型的には、粘液性シリコーン流体は100%の純度で形成されるわけではない。それよりもむしろ、粘液性シリコーン流体は典型的には、キャリア流体の存在下で直接最終固形含量で形成され、かつ/又はより高い固形含量で形成され、その後で追加のキャリア流体によって、所望の、より低い最終用途の固形濃度まで希釈される。換言すれば、この方法は、追加のキャリア流体を、粘液性シリコーン流体及び/又はヒドロシリル化反応生成物に加える工程を含んでもよい。典型的には、ヒドロシリル化反応生成物の生成後に、ヒドロシリル化反応生成物とシリコーンエラストマーとを1つにまとめ、望ましくない副反応及び/又はヒドロシリル化反応生成物の不完全な生成を防止する。
本開示はまた、パーソナルケア組成物も提供し、これはパーソナルケア製品組成物と記述することもできる。パーソナルケア組成物は、上記のシリコーンエラストマー組成物を含む。パーソナルケア組成物は、クリーム、ゲル、粉末、ペースト、又は注ぎやすい液体の形態であってもよい。概して、このような組成物は、室温にて組成物中に固形分が存在しない場合には、簡素なプロペラミキサー、Brookfield逆回転ミキサー、又はホモジナイジングミキサーを用いて、室温で調製することができる。特別な装置又は加工条件は、典型的には必要ない。製造する形態の種類に応じて調製方法は異なるが、こうした方法は当技術分野においては周知である。
本パーソナルケア組成物、及び/又は粘液性シリコーン流体、及び/又は本組成物全体として、(i)有機化合物、(ii)ケイ素原子含有化合物、(iii)有機化合物の混合物、(iv)ケイ素原子含有化合物の混合物、又は(v)有機化合物とケイ素原子含有化合物との混合物等の、他の材料を溶解し、懸濁し、又はその物理的特性を変更するために工業規模で使用される溶媒も含んでもよい。
本開示はまた、パーソナルケア組成物を形成する方法も提供する。方法は、上記のとおりのパーソナルケア製品又は任意の他の同様の化合物を、シリコーンエラストマー組成物と組み合わせることを含む。パーソナルケア製品が、第1及び第2の直鎖オルガノポリシロキサンの反応の前、反応中、及び/又は反応後に存在し得ることが企図される。一実施形態において、粘液性シリコーン流体は、個別に調製された後で、パーソナルケア組成物原料と組み合わせられる。ある種のパーソナルケア原料を流体反応工程(すなわち、ヒドロシリル化反応生成物の生成)時に含ませることができるものの、反応抑制、原料の温度感受性等の様々な因子を制御する必要があり得る。パーソナルケア処方の形成について当該技術分野において既知の技術、例えば、これらに限定されるものではないが、パーソナルケア組成物の形成を容易にするための混合技術、コールドブレンド、又は加熱を使用することができる。本明細書で使用する添加の順は、当該技術分野において既知のものであってもよい。
反応フラスコ中に、以下の物質:830DPのビニル末端シロキサン(すなわち、ジメチルシロキサン、ジメチルビニル末端)7.72g、6個のペンダントSiH部位を有する100DPのシロキサン(すなわち、ジメチル、メチルハイドロジェンシロキサン、トリメチルシロキシ末端)0.344g、2mm2/秒(2cSt)のポリジメチルシロキサン191.92g、及び白金触媒溶液0.080g(全バッチサイズに対してPt約2.0ppmである)、を入れた。攪拌を開始し、反応フラスコを75℃まで加熱した。約20分間の反応時間後、反応混合物が次第に粘稠となったところで、撹拌を停止した。生成物を75℃で更に2時間静置した。
最大容量100gの歯科用ミキサーカップに、以下の成分:エラストマー1を52.49g、及び4.00%固形分の前述の粘液性シリコーン流体17.50g、を入れた。内容物を、Speed Mixer(登録商標)歯科用ミキサー中、2,500rpmで45秒間混合した。これによって、本開示のエラストマー配合物の試料1を形成する。
更にまた、最大容量100gの歯科用ミキサーカップに、エラストマー2を52.51g、及び4.00%固形分の前述の粘液性シリコーン流体17.51gを入れた。再び、内容物を、Speed Mixer(登録商標)歯科用ミキサー中、2,500rpmで45秒間混合した。これによって、本開示のエラストマー配合物の試料2を形成する。
この粘液性シリコーン流体は、粘液性シリコーン流体とポリジメチルシロキサンとの配合物であり、エマルション全体が約1.56重量%の粘液性シリコーン流体を有するように、6.25重量%有効成分とする。この粘液性シリコーン流体を形成するため、反応フラスコ中に、以下の物質:9,500DPのビニル末端シロキサン(すなわち、ジメチルシロキサン、ジメチルビニル末端)12.44g、6個のペンダントSiH部位を有する100DPのシロキサン(すなわち、ジメチル、メチルハイドロジェンシロキサン、トリメチルシロキシ末端)0.13g、2mm2/秒(2cSt)のポリジメチルシロキサン187.42g、及び白金触媒溶液0.080g(全バッチサイズに対してPt約2.0ppmである)、を入れた。攪拌を開始し、反応フラスコを75℃まで加熱した。約40分間の反応時間後、反応混合物が次第に粘稠となったところで、撹拌を停止した。生成物を75℃で更に2時間静置した。
Lightnin(登録商標)ミキサーカップに下記の成分を入れ、水中油型エマルション配合物の油相を形成した:6.25%固形分の前述の粘液性シリコーン流体74.98g、RM−2051増粘剤12.04g、及び2mm2/秒(2cSt)ポリジメチルシロキサン15.02g。次にこの溶液を1,000rpmで10分間混合し、水相を調製した。蒸留水189.00g、グリセリン9.05g、及び抗菌性防腐剤0.27gからなる液相を、磁気撹拌プレート上で5分間混合した。次に水相を、油相を1,000rpmで撹拌しながら、30分間にわたって滴下した。添加終了後、エマルションを10分間1,200rpmで混合し、全体を確実に均質化した。生成物は、スピンドル94番を装着したBrookfield Digital II+粘度計を用い、15のデータポイントにわたって測定するとき、測定粘度は99,146cPである。
Lightnin(登録商標)ミキサーカップに下記の成分を入れ、水中油型エマルション配合物の油相を形成した:前述の実施例2の粘液性シリコーン流体及びシリコーンエラストマーを、最大容量100gの歯科用ミキサーカップ中で組み合わせ、2,000rpmで60秒間混合し、均質な溶液を調製することによって調製した、エラストマー1と6.25%固形分の前述の粘液性シリコーン流体の70:30重量%の配合物75.04g、RM−2051増粘剤12.03g、及び2mm2/秒(2cSt)ポリジメチルシロキサン15.00g。次にこの溶液を1,000rpmで10分間混合し、水相を調製した。蒸留水189.01g、グリセリン9.01g、及び抗菌性防腐剤0.30gからなる液相を、磁気撹拌プレート上で5分間混合した。次に水相を、油相を1,000rpmで撹拌しながら、30分間にわたって滴下した。添加終了後、エマルションを10分間1,200rpmで混合し、全体を確実に均質化した。生成物は、スピンドル94番を装着したBrookfield Digital II+粘度計を用い、単一のデータポイントで測定するとき、測定粘度は91,200cPである。総有効成分含量は、エラストマー1及び粘液性シリコーン流体の有効成分含量を計算に入れると、約3.27%である。
試料3及び4は、3点試験法の形態で、官能パネルに提出された。8人の参加者のうち7人が、正しい試料を明らかにすることができ、99.0%信頼区間(CI)を満たしたことから、粘液性シリコーン流体の25%水中油型エマルションと、シリコーンエラストマーと粘液性シリコーン流体との70:30配合物の25%水中油型エマルションとの間には、感知可能な差異がある。この官能パネルの結果は、配合された(乳化された)試料においてもなお、粘液性シリコーン流体を含有するエラストマー試料と含有しない試料との差異を、著しいレオロジー的な差異により、検査員が感知できることを示している。特に、これらの官能パネルにおいて、対照はなかった。構成成分を、顕著な差異有/差異無の系列で、直接互いに比較した。
粘液性シリコーン流体をシリコーンエラストマーに添加すると、シリコーンエラストマーのレオロジーに顕著な影響を及ぼす。この効果を、配合試料の粘度によって追跡し、粘液性シリコーン流体を様々な濃度でシリコーンエラストマーに添加した影響と、これらの配合物の経時的な相対安定性の両方を測定した。配合物は、最大容量100gの歯科用ミキサーカップ中で、様々な重量比のエラストマー(ジメチコーン及びジメチコーンのクロスポリマー)及び粘液性シリコーン流体、例えば、25:75、50:50、及び75:25、並びに直接比較用の未希釈のエラストマー(ジメチコーン及びジメチコーンのクロスポリマー)試料を組み合わせることによって、調製した。これらの混合物を、2,000rpmで60秒間混合し、確実に均質化した。粘度の測定値は、付属品のスピンドル91番を装着したBrookfield Digital II+粘度計を、15点の加重平均分析に使用して得た。配合物の平均粘度は、時間の関数として図5に示す。
この実施例は、エラストマー2を70%及び粘液性シリコーン流体30%の二成分配合物を含む。この実施例は、標準的な有機エラストマーによる希釈にも関わらず、粘液性シリコーン流体の挙動が残存することを示す。
この実施例は、粘液性シリコーン流体の挙動がエマルション形態でも残存することを示す。粘液性シリコーン流体のエラストマー配合物への添加の影響を示すため、粘液性シリコーン流体の25重量%エマルションを、レオロジー特性について評価した。この粘液性シリコーン流体は、100DPのSiH含有シロキサン0.13g、9,500DPのビニル末端シリコーンガム12.44g、2mm2/秒(2cSt)のPDMS 187.42g、及び白金触媒0.08gの反応によって生成した。この反応は70℃で約40分間、ゲル化が起こるまで進行し、その後、試料を70℃の恒温槽に2時間の硬化時間の間移した。
この実施例は、エラストマー3のクロスポリマー(又はエラストマー又は親水性エラストマー)と粘液性シリコーン流体の増大する濃度との比較である。下記の表に示したデータは、(エラストマー3の)未希釈のエラストマー及び粘液性シリコーン流体を有する配合物の水吸収/相溶性を示す。このデータは、粘液性シリコーン流体を親水性エラストマーに加えても、乳化エラストマーの水との相溶性を低下させないことを示している。
Claims (15)
- カスタマイズ可能な官能特性を有するシリコーンエラストマー組成物であって、前記シリコーンエラストマー組成物は、
A)粘液性シリコーン流体と、
B)シリコーンエラストマーと、
を含み、
前記A)粘液性シリコーン流体は、
(1)ヒドロシリル化反応生成物と、
(2)キャリア流体と、
を含み、
前記(1)ヒドロシリル化反応生成物は、
(a)第1の直鎖オルガノポリシロキサンと、
(b)第2の直鎖オルガノポリシロキサンと、
のヒドロシリル化反応生成物であり、
前記(a)第1の直鎖オルガノポリシロキサンは、(R1R2R3SiO1/2)単位及び(R4R5SiO2/2)単位(式中、R1〜R5のそれぞれは、少なくとも1つのR1〜R5がアルケニル基である限り、独立して炭化水素基である)を含み、
前記(a)第1の直鎖オルガノポリシロキサンは1重量%未満のT単位及びQ単位を含み、
前記(a)第1の直鎖オルガノポリシロキサンの重合度は100〜15,000であり、
前記(b)第2の直鎖オルガノポリシロキサンは、(R6R7R8SiO1/2)単位及び(R9R10SiO2/2)単位(式中、R6〜R10のそれぞれは、少なくとも1つのR6〜R10が水素原子である限り、独立して炭化水素基、ポリエーテル基、シロキサン基、又はポリオール基である)を含み、
前記(b)第2の直鎖オルガノポリシロキサンは1重量%未満のT単位及びQ単位を含み、
前記(b)第2の直鎖オルガノポリシロキサンの重合度は4〜1,000であり、
前記(2)キャリア流体は、シリコーン流体、有機溶媒、有機油、及びこれらの組み合わせから選択され、
前記(1)ヒドロシリル化反応生成物はアルケニル基又はSi−H官能基を含み、
前記(1)ヒドロシリル化反応生成物は、前記A)粘液性シリコーン流体の100重量部当たり3〜30重量部の量で存在し、
前記A)粘液性シリコーン流体は、一定に増大する剪断力を加えられた際に、垂直方向に観察される増大する垂直応力を呈し、
前記B)シリコーンエラストマーは、前記(1)ヒドロシリル化反応生成物とは異なる、
シリコーンエラストマー組成物。 - 前記第1の直鎖オルガノポリシロキサンがビニル末端であるか、あるいはジメチルビニル末端である、請求項1に記載のシリコーンエラストマー組成物。
- 前記第2の直鎖オルガノポリシロキサンが、2〜10個のペンダントSiH部位を有するか、あるいは6個のペンダントSiH部位を有する、請求項1又は2に記載のシリコーンエラストマー組成物。
- 前記第2の直鎖オルガノポリシロキサンが、ジメチル、メチルハイドロジェンシロキサン、トリメチルシロキシ末端である、請求項1〜3のいずれか一項に記載のシリコーンエラストマー組成物。
- 前記ヒドロシリル化反応生成物がビニル官能基を含み、前記第1及び第2の直鎖オルガノポリシロキサンのSi−Hに対するビニルのモル比が、それぞれ1より大きい、請求項1〜4のいずれか一項に記載のシリコーンエラストマー組成物。
- 前記ヒドロシリル化反応生成物がSi−H官能基を含み、前記第1及び第2の直鎖オルガノポリシロキサンのSi−Hに対するビニルのモル比が、それぞれ1未満である、請求項1〜4のいずれか一項に記載のシリコーンエラストマー組成物。
- 前記ヒドロシリル化反応生成物が、前記粘液性シリコーン流体の100重量部当たり3〜30重量部の量で存在する、請求項1〜6のいずれか一項に記載のシリコーンエラストマー組成物。
- 前記キャリア流体がシリコーン流体であるか、あるいはポリジメチルシロキサンである、請求項1〜7のいずれか一項に記載のシリコーンエラストマー組成物。
- 剪断速度に対する垂直応力のプロットが、グラフ上の限界線の上方にあり、前記限界線は方程式y=3.6x(式中、yは垂直応力であり、xは剪断速度である)を使用して作成される、請求項1〜8のいずれか一項に記載のシリコーンエラストマー組成物。
- 前記シリコーンエラストマーが、SiH含有ポリシロキサンとα,ω−ジエンとの反応生成物である、請求項1〜9のいずれか一項に記載のシリコーンエラストマー組成物。
- 請求項1〜10のいずれか一項に記載のシリコーンエラストマー組成物を含む、パーソナルケア組成物。
- A)粘液性シリコーン流体とB)シリコーンエラストマーとを含むパーソナルケア組成物であって、
前記A)粘液性シリコーンは、
(1)ヒドロシリル化反応生成物と、
(2)キャリア流体と、
を含み、
前記(1)ヒドロシリル化反応生成物は、
(a)第1の直鎖オルガノポリシロキサンと、
(b)第2の直鎖オルガノポリシロキサンと、
のヒドロシリル化反応生成物であり、
前記(a)第1の直鎖オルガノポリシロキサンは、(R1R2R3SiO1/2)単位及び(R4R5SiO2/2)単位(式中、R1〜R5のそれぞれは、少なくとも1つのR1〜R5がアルケニル基である限り、独立して炭化水素基である)を含み、
前記(a)第1の直鎖オルガノポリシロキサンは1重量%未満のT単位及びQ単位を含み、
前記(a)第1の直鎖オルガノポリシロキサンの重合度は100〜15,000であり、
前記(b)第2の直鎖オルガノポリシロキサンは、(R6R7R8SiO1/2)単位及び(R9R10SiO2/2)単位(式中、R6〜R10のそれぞれは、少なくとも1つのR6〜R10が水素原子である限り、独立して炭化水素基、ポリエーテル基、シロキサン基、又はポリオール基である)を含み、
前記(b)第2の直鎖オルガノポリシロキサンは1重量%未満のT単位及びQ単位を含み、
前記(b)第2の直鎖オルガノポリシロキサンの重合度は4〜1,000であり、
前記(2)キャリア流体は、シリコーン流体、有機溶媒、有機油、及びこれらの組み合わせから選択され、
前記(1)ヒドロシリル化反応生成物はアルケニル基又はSi−H官能基を含み、
前記(1)ヒドロシリル化反応生成物は、前記A)粘液性シリコーン流体の100重量部当たり3〜30重量部の量で存在し、
前記A)粘液性シリコーン流体は、一定に増大する剪断力を加えられた際に、垂直方向に観察される増大する垂直応力を呈する、
パーソナルケア組成物。 - シリコーンエラストマー組成物を形成する方法であって、
前記方法は、
第1の直鎖オルガノポリシロキサンと第2の直鎖オルガノポリシロキサンとを、ヒドロシリル化触媒及びキャリア流体の存在下、ヒドロシリル化反応を介して反応させ、アルケニル基又はSi−H官能基を含むヒドロシリル化反応生成物を生成することと、
前記ヒドロシリル化反応生成物を、前記ヒドロシリル化反応生成物とは異なるシリコーンエラストマーと組み合わせ、シリコーンエラストマー組成物を形成することと、
を含み、
前記第1の直鎖オルガノポリシロキサンは、(R1R2R3SiO1/2)単位及び(R4R5SiO2/2)単位(式中、R1〜R5のそれぞれは、少なくとも1つのR1〜R5がアルケニル基である限り、独立して炭化水素基である)を含み、
前記第1の直鎖オルガノポリシロキサンは1重量%未満のT単位及びQ単位を含み、
前記第1の直鎖オルガノポリシロキサンの重合度は100〜15,000であり、
前記第2の直鎖オルガノポリシロキサンは、(R6R7R8SiO1/2)単位及び(R9R10SiO2/2)単位(式中、R6〜R10のそれぞれは、少なくとも1つのR6〜R10が水素原子である限り、独立して炭化水素基、ポリエーテル基、シロキサン基、又はポリオール基である)を含み、
前記第2の直鎖オルガノポリシロキサンは1重量%未満のT単位及びQ単位を含み、
前記第2の直鎖オルガノポリシロキサンの重合度は4〜1,000であり、
前記キャリア流体は、シリコーン流体、有機溶媒、有機油、及びこれらの組み合わせから選択され、
前記ヒドロシリル化反応生成物は、前記粘液性シリコーン流体の100重量部当たり3〜30重量部の量で存在し、
前記粘液性シリコーン流体は、一定に増大する剪断力を加えられた際に、垂直方向に観察される増大する垂直応力を呈する、
シリコーンエラストマー組成物を形成する方法。 - 前記第2の直鎖オルガノポリシロキサンが、第1種の前記第2の直鎖オルガノポリシロキサンと、モノ末端脂肪族不飽和炭化水素基を有する化合物と、の反応生成物を含む、請求項13に記載の方法。
- i)前記第1の直鎖オルガノポリシロキサンがビニル末端であり、かつ/又は
ii)前記第2の直鎖オルガノポリシロキサンが2〜10個のペンダントSiH部位を有する、
請求項13又は14に記載の方法。
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TWI792498B (zh) * | 2020-12-30 | 2023-02-11 | 中國大陸商北京康美特科技股份有限公司 | 反應性有機矽觸變劑、有機矽封裝膠和led元件 |
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WO2016014127A1 (en) | 2016-01-28 |
US20170165190A1 (en) | 2017-06-15 |
JP2017523285A (ja) | 2017-08-17 |
US10500151B2 (en) | 2019-12-10 |
CN106536634A (zh) | 2017-03-22 |
US10172781B2 (en) | 2019-01-08 |
CN106536634B (zh) | 2020-03-17 |
KR101916655B1 (ko) | 2018-11-08 |
JP6405034B2 (ja) | 2018-10-17 |
DE112015003369T5 (de) | 2017-03-30 |
US20170360690A9 (en) | 2017-12-21 |
EP3171946A1 (en) | 2017-05-31 |
CN106795373B (zh) | 2020-06-05 |
KR20170020492A (ko) | 2017-02-22 |
JP6334807B2 (ja) | 2018-05-30 |
CN106795373A (zh) | 2017-05-31 |
US20170174885A1 (en) | 2017-06-22 |
WO2016014128A1 (en) | 2016-01-28 |
WO2016014128A9 (en) | 2017-02-02 |
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