KR100803646B1 - 유기 수지용 첨가제 및 유기 수지 조성물 - Google Patents
유기 수지용 첨가제 및 유기 수지 조성물 Download PDFInfo
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- KR100803646B1 KR100803646B1 KR1020010069663A KR20010069663A KR100803646B1 KR 100803646 B1 KR100803646 B1 KR 100803646B1 KR 1020010069663 A KR1020010069663 A KR 1020010069663A KR 20010069663 A KR20010069663 A KR 20010069663A KR 100803646 B1 KR100803646 B1 KR 100803646B1
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- 229920005989 resin Polymers 0.000 title claims abstract description 106
- 239000011347 resin Substances 0.000 title claims abstract description 106
- 239000000654 additive Substances 0.000 title claims abstract description 40
- 239000011342 resin composition Substances 0.000 title claims description 34
- 230000000996 additive effect Effects 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 31
- -1 dimethylsiloxy Chemical group 0.000 claims abstract description 25
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 6
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- 150000004706 metal oxides Chemical class 0.000 claims description 5
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 2
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
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- 229910004298 SiO 2 Inorganic materials 0.000 description 2
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- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
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- 229910052618 mica group Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
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- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
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- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
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- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
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- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- OIAUFEASXQPCFE-UHFFFAOYSA-N formaldehyde;1,3-xylene Chemical compound O=C.CC1=CC=CC(C)=C1 OIAUFEASXQPCFE-UHFFFAOYSA-N 0.000 description 1
- HDNHWROHHSBKJG-UHFFFAOYSA-N formaldehyde;furan-2-ylmethanol Chemical compound O=C.OCC1=CC=CO1 HDNHWROHHSBKJG-UHFFFAOYSA-N 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
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- 230000009477 glass transition Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
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- 239000004700 high-density polyethylene Substances 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000005386 organosiloxy group Chemical group 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
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- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
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- 238000009966 trimming Methods 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
형 | 화학식 | SiH%[중량%] | 점도[mPa·s] |
A1 | HMe2SiO(Me2SiO)60SiMe2H | 0.044 | 60 |
A2 | Me3SiO(Me2SiO)540(MeHSiO)10SiMe3 | 0.025 | 3,200 |
A3 | HMe2SiO(Me2SiO)1700SiMe2H | 0.002 | 1,000,000 |
A4 | Me2SiO(MeHSiO)50SiMe3 | 1.59 | 20 |
A5 | Me3SiO(Me2SiO)500SiMe3 | 0 | 2,700 |
실시예 1 | 실시예 2 | 실시예 3 | 비교 실시예 1 | 비교 실시예 2 | |
유기 수지용 첨가제 | D1 | D2 | D3 | D4 | D5 |
액상 오가노폴리실록산 | A1 | A2 | A3 | A4 | A5 |
200-메쉬 통과% (중량%) | 51 | 80 | 83 | 30 | 81 |
실시예 4 | 실시예 5 | 실시예 6 | 비교 실시예 3 | 비교 실시예 4 | 비교 실시예 5 | |
유기 수지용 첨가제 | D1 | D2 | D3 | D4 | D5 | 없음 |
물의 접촉각(°) | 106 | 106 | 104 | 99 | 103 | 96 |
동마찰계수 | 0.21 | 0.15 | 0.09 | 1.35 | 0.45 | 1.43 |
한계 PV값 (kgf/㎠·㎝/sec) | 400 | 400 | 400 | 400 | 390 | 400 |
성형품의 외관 | 양호 | 양호 | 다소 양호 [약간의 블리딩(bleeding)] | 불량 (블리딩) | 불량 (블리딩) | 양호 |
금형 표면의 외관 | 양호 | 양호 | 양호 | 불량 | 불량 | 양호 |
실시예 7 | 비교 실시예 6 | |
유기 수지용 첨가제 | D2 | 없음 |
물 접촉각(°) | 104 | 94 |
동마찰계수 | 0.09 | 1.75 |
한계 PV값((kgf/㎠·㎝/sec) | 370 | 430 |
성형품의 외관 | 양호 | 양호 |
금형 표면의 외관 | 양호 | 양호 |
Claims (17)
- 규소 결합된 수소 원자의 함량이 0.001중량% 이상 1.5중량% 이하이고 디메틸실옥시 반복 단위가 50개 이상인 액상 오가노폴리실록산(A)과 무기 분말(B)을 성분(A) 100중량부당 성분(B) 50 내지 250중량부의 양으로 함유하는 분말을 포함하는 유기 수지용 첨가제.
- 제1항에 있어서, 성분(A)의 25℃에서의 점도가 40 내지 100,000,000mPa·s인 유기 수지용 첨가제.
- 제1항에 있어서, 성분(B)이 금속 산화물 분말인 유기 수지용 첨가제.
- 제1항에 있어서, 성분(B)이 실리카 분말인 유기 수지용 첨가제.
- 삭제
- 유기 수지(I)와 규소 결합된 수소 원자의 함량이 0.001중량% 이상 1.5중량% 이하이고 디메틸실옥시 반복 단위가 50개 이상인 액상 오가노폴리실록산(A)과 무기 분말(B)을 성분(A) 100중량부당 성분(B) 50 내지 250중량부의 양으로 함유하는 분말을 포함하는 유기 수지용 첨가제(II)를 포함하는 유기 수지 조성물.
- 제6항에 있어서, 성분(A)의 25℃에서의 점도가 40 내지 100,000,000mPa·s인 유기 수지 조성물.
- 제6항에 있어서, 성분(B)이 금속 산화물 분말인 유기 수지 조성물.
- 제6항에 있어서, 성분(B)이 실리카 분말인 유기 수지 조성물.
- 삭제
- 제6항에 있어서, 성분(I)이 열가소성 유기 수지인 유기 수지 조성물.
- 제6항에 있어서, 성분(II)의 함량이 성분(I) 100중량부당 0.1 내지 50중량부인 유기 수지 조성물.
- 제1항에 있어서, 성분(A)이 규소 결합된 수소 원자를 0.005 내지 0.5중량% 포함하는 유기 수지용 첨가제.
- 제1항에 있어서, 성분(A)의 25℃에서의 점도가 100 내지 1,000,000mPa·s인 유기 수지용 첨가제.
- 제1항에 있어서, 성분(B)가, BET 비표면적이 100㎡/g 이상인 실리카 분말인 유기 수지용 첨가제.
- 제1항에 있어서, 성분(A) 100중량부당 성분(B) 75 내지 150중량부를 포함하는 유기 수지용 첨가제.
- 제1항에 있어서, 입자 크기가 0.1 내지 500㎛인 유기 수지용 첨가제.
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JP2000342775A JP4885351B2 (ja) | 2000-11-10 | 2000-11-10 | 有機樹脂用添加剤および有機樹脂組成物 |
JPJP-P-2000-00342775 | 2000-11-10 |
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EP (1) | EP1205519B1 (ko) |
JP (1) | JP4885351B2 (ko) |
KR (1) | KR100803646B1 (ko) |
CA (1) | CA2361866C (ko) |
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US6907176B2 (en) * | 2002-06-24 | 2005-06-14 | Dow Corning Corporation | Planar optical waveguide assembly and method of preparing same |
JP5162879B2 (ja) * | 2006-10-27 | 2013-03-13 | 住友大阪セメント株式会社 | 金属酸化物粒子−シリコーン樹脂複合体とそれを備えた光学部材及び発光装置並びに金属酸化物粒子−シリコーン樹脂複合体の製造方法 |
JP2010031271A (ja) * | 2008-07-02 | 2010-02-12 | Yazaki Corp | シリコーン表面処理水酸化マグネシウム |
KR102348911B1 (ko) | 2019-08-07 | 2022-01-11 | 다우 실리콘즈 코포레이션 | 액체 폴리다이오르가노실록산을 포함하는 고체 담체 성분, 및 고체 담체 성분의 제조 및 사용 방법 |
CN112654673B (zh) | 2019-08-07 | 2023-09-01 | 美国陶氏有机硅公司 | 包含液体聚有机硅氧烷的固体载体组分及制备和使用该固体载体组分的方法 |
JP7109604B2 (ja) | 2019-08-07 | 2022-07-29 | ダウ シリコーンズ コーポレーション | 木材プラスチック複合体の形成における、アルケニル官能性ポリジオルガノシロキサン組成物及びその使用方法 |
CN114174437B (zh) | 2019-08-07 | 2023-07-14 | 美国陶氏有机硅公司 | 聚二有机硅氧烷组合物及其在形成木塑复合材料中的使用方法 |
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JP4885351B2 (ja) | 2012-02-29 |
JP2002146193A (ja) | 2002-05-22 |
EP1205519A1 (en) | 2002-05-15 |
KR20020036744A (ko) | 2002-05-16 |
EP1205519B1 (en) | 2004-08-18 |
CA2361866A1 (en) | 2002-05-10 |
US6660807B2 (en) | 2003-12-09 |
CA2361866C (en) | 2010-03-09 |
US20020151633A1 (en) | 2002-10-17 |
DE60104964D1 (de) | 2004-09-23 |
DE60104964T2 (de) | 2005-08-18 |
MXPA01011469A (es) | 2002-12-17 |
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