JP4412485B2 - Monolithic composite of silicone rubber and substrate and method for producing the same - Google Patents
Monolithic composite of silicone rubber and substrate and method for producing the same Download PDFInfo
- Publication number
- JP4412485B2 JP4412485B2 JP2004357865A JP2004357865A JP4412485B2 JP 4412485 B2 JP4412485 B2 JP 4412485B2 JP 2004357865 A JP2004357865 A JP 2004357865A JP 2004357865 A JP2004357865 A JP 2004357865A JP 4412485 B2 JP4412485 B2 JP 4412485B2
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- JP
- Japan
- Prior art keywords
- silicone rubber
- resin
- rubber composition
- integrally molded
- molded composite
- 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.)
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- 229920002379 silicone rubber Polymers 0.000 title claims description 88
- 239000004945 silicone rubber Substances 0.000 title claims description 87
- 239000000758 substrate Substances 0.000 title claims description 33
- 239000002131 composite material Substances 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000000203 mixture Substances 0.000 claims description 43
- 229920005989 resin Polymers 0.000 claims description 40
- 239000011347 resin Substances 0.000 claims description 40
- 239000000463 material Substances 0.000 claims description 28
- 239000011521 glass Substances 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 238000007259 addition reaction Methods 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 229920001971 elastomer Polymers 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 150000001451 organic peroxides Chemical class 0.000 claims description 10
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 10
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 9
- 238000002485 combustion reaction Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- 229920005668 polycarbonate resin Polymers 0.000 claims description 6
- 239000004431 polycarbonate resin Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 230000009182 swimming Effects 0.000 claims description 5
- 229920005992 thermoplastic resin Polymers 0.000 claims description 5
- 229920001187 thermosetting polymer Polymers 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 229920006015 heat resistant resin Polymers 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 description 23
- -1 polybutylene terephthalate Polymers 0.000 description 21
- 239000002585 base Substances 0.000 description 17
- 239000010410 layer Substances 0.000 description 15
- 238000001723 curing Methods 0.000 description 14
- 229920001296 polysiloxane Polymers 0.000 description 13
- 239000010408 film Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 125000003342 alkenyl group Chemical group 0.000 description 9
- 150000002430 hydrocarbons Chemical group 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000011282 treatment Methods 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 125000000962 organic group Chemical group 0.000 description 5
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 5
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000009189 diving Effects 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000005388 dimethylhydrogensiloxy group Chemical group 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 210000002445 nipple Anatomy 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 125000005372 silanol group Chemical group 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 229920001893 acrylonitrile styrene Polymers 0.000 description 2
- 238000013006 addition curing Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011067 equilibration Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000009965 odorless effect Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920009441 perflouroethylene propylene Polymers 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920002620 polyvinyl fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 230000009967 tasteless effect Effects 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- ZICNIEOYWVIEQJ-UHFFFAOYSA-N (2-methylbenzoyl) 2-methylbenzenecarboperoxoate Chemical compound CC1=CC=CC=C1C(=O)OOC(=O)C1=CC=CC=C1C ZICNIEOYWVIEQJ-UHFFFAOYSA-N 0.000 description 1
- AGKBXKFWMQLFGZ-UHFFFAOYSA-N (4-methylbenzoyl) 4-methylbenzenecarboperoxoate Chemical compound C1=CC(C)=CC=C1C(=O)OOC(=O)C1=CC=C(C)C=C1 AGKBXKFWMQLFGZ-UHFFFAOYSA-N 0.000 description 1
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 1
- PEVRKKOYEFPFMN-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene;1,1,2,2-tetrafluoroethene Chemical group FC(F)=C(F)F.FC(F)=C(F)C(F)(F)F PEVRKKOYEFPFMN-UHFFFAOYSA-N 0.000 description 1
- QYXVDGZUXHFXTO-UHFFFAOYSA-L 3-oxobutanoate;platinum(2+) Chemical compound [Pt+2].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O QYXVDGZUXHFXTO-UHFFFAOYSA-L 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004944 Liquid Silicone Rubber Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 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
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IOMSYMSQXIKSQG-UHFFFAOYSA-N bis[(2-methylpropan-2-yl)oxy] 2-pentylpropanediperoxoate Chemical compound CC(C)(C)OOOC(=O)C(CCCCC)C(=O)OOOC(C)(C)C IOMSYMSQXIKSQG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 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
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- NYMPGSQKHIOWIO-UHFFFAOYSA-N hydroxy(diphenyl)silicon Chemical class C=1C=CC=CC=1[Si](O)C1=CC=CC=C1 NYMPGSQKHIOWIO-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000013532 laser treatment Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/10—Applications used for bottles
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Fixing For Electrophotography (AREA)
- Medical Preparation Storing Or Oral Administration Devices (AREA)
Description
本発明は、シリコーンゴムと基材とが強固に接着した一体成形体及びその一体成形体を得る製造方法に関し、より詳しくは、表面を改質した金属、ガラス、有機樹脂等の基材とシリコーンゴムとの一体成形物及びその一体成形物を得る製造方法に関するものである。 The present invention relates to an integrally molded body in which silicone rubber and a substrate are firmly bonded, and a manufacturing method for obtaining the integrally molded body. More specifically, the present invention relates to a surface-modified base material such as metal, glass, organic resin, and silicone. The present invention relates to an integral molded product with rubber and a manufacturing method for obtaining the integral molded product.
シリコーンゴムと金属、ガラス、有機樹脂等の各種基材との一体成型品は、シリコーンゴムの耐熱性などから各種ガスケットなどでの自動車用部品、レンジの窓枠シール、ポットのパッキン等の家電類、複写機・プリンターの定着機周辺等幅広い分野に使用されてきた。また、シリコーンゴムの安全性及び透明性・着色性などから哺乳瓶などの乳児用品、ゴーグル等のダイビング用品、シャワーキャップ等のトイレタリー用品などにも広く使用されている。このようなシリコーンゴムと各種基材との一体成形体を得るにはシリコーンゴムに接着性を付与する方法、基材の表面をプライマーなどで改質する方法、硬化したシリコーンゴムと基材を接着剤で貼り合わせる方法、２色成形により成形する方法などが知られている。 Integrated products of silicone rubber and various base materials such as metal, glass, and organic resin are used for home appliances such as automotive parts such as gaskets, range window frame seals, and pot packing due to the heat resistance of silicone rubber. It has been used in a wide range of fields such as around copiers and printer fixing machines. In addition, it is widely used for baby products such as baby bottles, diving products such as goggles, and toiletry products such as shower caps because of the safety and transparency / coloring properties of silicone rubber. In order to obtain such an integrally molded body of silicone rubber and various substrates, a method of imparting adhesiveness to the silicone rubber, a method of modifying the surface of the substrate with a primer, etc., and bonding the cured silicone rubber to the substrate A method of pasting with an agent and a method of molding by two-color molding are known.
しかしながら、シリコーンゴムに接着性を付与する方法は、カーボンファンクショナルシラン（ＣＦシラン）など反応性の高い接着助剤を添加するために、耐熱性の低下や圧縮永久歪の悪化に加え、金型に接着してしまうため成形性が著しく低下してしまうという問題があった。基材表面をプライマーで改質する方法は、プライマー塗布工程での塗りむらや乾燥むらによる接着不良だけでなく塗布・乾燥・焼付け等の煩雑な工程や溶剤を使用することによる作業環境の悪化も大きな問題であった。プライマー以外に基材表面を改質する方法としては、紫外線照射法、コロナ放電処理、プラズマ処理、サンドブラスト処理、クロム酸混液処理等が挙げられるが、これらはいずれも表面改質としては不十分なものであった。また、作業環境が危険を伴うものであったり、設備が大規模、高価であるといった経済上の問題も見られた。一方、接着剤による貼り合わせ方法は、まずシリコーンゴムを接着させることが困難で、可能であっても接着剤自体の耐熱性や耐寒性が不十分で接着剤破壊に到ることが頻繁であった。また、２色成形による方法は、成形機への投資が莫大なわりに、成形サイクルが長く、効率が悪いという問題があった。 However, the method of imparting adhesiveness to silicone rubber is to add a highly reactive adhesion assistant such as carbon functional silane (CF silane), and in addition to lowering heat resistance and worsening compression set, As a result, the moldability is remarkably lowered. The method of modifying the surface of the substrate with a primer not only causes poor adhesion due to uneven coating and drying during the primer application process, but also complicated processes such as coating, drying and baking, and deterioration of the work environment due to the use of solvents. It was a big problem. Examples of methods for modifying the substrate surface other than the primer include ultraviolet irradiation, corona discharge treatment, plasma treatment, sand blast treatment, chromic acid mixed solution treatment, etc., but these are insufficient as surface modification. It was a thing. There were also economic problems such as dangerous work environments and large and expensive equipment. On the other hand, in the bonding method using an adhesive, it is difficult to adhere silicone rubber first, and even if possible, the adhesive itself is insufficient in heat resistance and cold resistance, and often causes adhesive destruction. It was. In addition, the two-color molding method has a problem that the molding cycle is long and the efficiency is low, although the investment in the molding machine is enormous.
なお、本発明に関連する先行文献としては下記のものが挙げられる。
本発明は、上記事情に鑑みなされたもので、金属、ガラス、樹脂等の基材とシリコーンゴムとが強固に接着し一体化した複合体及びその製造方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composite in which a base material such as metal, glass, or resin and silicone rubber are firmly bonded and integrated, and a method for manufacturing the same.
本発明者は、上記目的を達成するため鋭意検討を重ねた結果、金属、ガラス、樹脂等の基材表面で有機ケイ素化合物を燃焼させることにより、表面にシラノール基を有する酸化ケイ素皮膜を形成し、この皮膜と接触させながらシリコーンゴムを硬化させることで、基材とゴムとが強固に接着し、一体化した複合体が得られることを見出した。 As a result of intensive studies to achieve the above object, the present inventor forms a silicon oxide film having a silanol group on the surface by burning an organosilicon compound on the surface of a substrate such as metal, glass or resin. It was found that by curing the silicone rubber while being in contact with this film, the base material and the rubber were firmly bonded and an integrated composite was obtained.
従って、本発明は、下記のシリコーンゴムと基材とが一体化した複合体及びその複合体を得る製造方法を提供する。
請求項１：
熱可塑性樹脂、熱硬化性樹脂、金属及びガラスから選ばれた材料により形成され、かつ、表面に有機ケイ素化合物の燃焼により形成された酸化ケイ素皮膜を有する基材に対し、該基材表面の酸化ケイ素皮膜上に常温で液状又は生ゴム状のシリコーンゴム組成物層を形成し、これを硬化してシリコーンゴムと基材とを接着、一体化させてなるシリコーンゴムと基材との一体成形複合体。
請求項２：
シリコーンゴムが、付加反応硬化型又は有機過酸化物硬化型シリコーンゴム組成物の硬化物である請求項１記載の一体成形複合体。
請求項３：
基材が金属製の芯金、金属製のベルト、耐熱樹脂製のベルト又はフッ素系樹脂のチューブであり、シリコーンゴムが付加反応硬化型シリコーンゴム組成物の硬化物であって、デュロメータＡによるゴム硬度４０以下のシリコーンゴムであり、一体成形複合体が電子写真式画像形成装置用の定着ロール又は定着ベルトである請求項１記載の一体成形複合体。
請求項４：
基材がガラス、ポリカーボネート樹脂又はアクリル樹脂製レンズであり、該基材の周囲に形成されるフレーム部が付加反応硬化型シリコーンゴム組成物を硬化させたシリコーンゴムであり、一体成形複合体がスイミングゴーグル又は水中メガネである請求項１記載の一体成形複合体。
請求項５：
基材がガラス又はポリカーボネート樹脂製のボトル又はボトルのネック部であり、吸引部が付加反応硬化型シリコーンゴム組成物を硬化させたシリコーンゴムであり、一体成形複合体が乳児用哺乳瓶である請求項１記載の一体成形複合体。
請求項６：
熱可塑性樹脂、熱硬化性樹脂、金属及びガラスから選ばれた材料により形成された基材の表面に、有機ケイ素化合物の燃焼による酸化ケイ素皮膜を形成し、その後、この酸化ケイ素皮膜上に常温で液状又は生ゴム状のシリコーンゴム組成物層を形成し、これを硬化させることを特徴とするシリコーンゴムと基材との一体成形複合体の製造方法。
請求項７：
シリコーンゴム組成物が付加反応硬化型又は有機過酸化物硬化型シリコーンゴム組成物である請求項６記載の一体成形複合体の製造方法。
Accordingly, the present invention provides a composite in which the following silicone rubber and substrate are integrated, and a production method for obtaining the composite.
Claim 1:
Oxidation of the substrate surface with respect to a substrate formed of a material selected from thermoplastic resin, thermosetting resin, metal and glass and having a silicon oxide film formed on the surface by combustion of an organosilicon compound Forming a liquid or raw rubber-like silicone rubber composition layer on a silicon film at room temperature and curing it to bond and integrate the silicone rubber and the base material. .
Claim 2 :
Silicone rubber, addition reaction curable or organic peroxide curable cured product in which it claims 1 Symbol placement integrally molded composite of the silicone rubber composition.
Claim 3 :
The base material is a metal core, a metal belt, a heat-resistant resin belt, or a fluororesin tube, and the silicone rubber is a cured product of an addition reaction curable silicone rubber composition, and rubber by durometer A The integrally molded composite according to claim 1, which is a silicone rubber having a hardness of 40 or less, and the integrally molded composite is a fixing roll or a fixing belt for an electrophotographic image forming apparatus.
Claim 4 :
The base material is a lens made of glass, polycarbonate resin, or acrylic resin, the frame portion formed around the base material is silicone rubber obtained by curing the addition reaction curable silicone rubber composition, and the integrally molded composite is swimming The integrally molded composite according to claim 1, which is goggles or underwater glasses.
Claim 5 :
The base material is a glass or polycarbonate resin bottle or bottle neck, the suction part is a silicone rubber obtained by curing an addition reaction curable silicone rubber composition, and the integrally formed composite is an infant baby bottle Item 1. An integrally molded composite according to Item 1.
Claim 6 :
A silicon oxide film is formed by burning an organosilicon compound on the surface of a substrate formed of a material selected from a thermoplastic resin, a thermosetting resin, a metal and glass , and then at room temperature on the silicon oxide film. A method for producing an integrally molded composite of silicone rubber and a substrate, wherein a liquid or raw rubber-like silicone rubber composition layer is formed and cured.
According to claim 7:
The method for producing an integrally molded composite according to claim 6, wherein the silicone rubber composition is an addition reaction curable type or an organic peroxide curable type silicone rubber composition.
本発明のシリコーンゴムと基材との一体化した複合体は、各種ガスケット等の自動車用部品、レンジの窓枠シール、ポットのパッキン等の家電類、複写機・プリンターの定着機周辺、特に電子写真式画像形成用の定着ローラや定着ベルト、哺乳瓶等の乳児用品、スイミングゴーグル、水中メガネ等のダイビング用品、シャワーキャップ等のトイレタリー用品など幅広い分野で有効に利用することができる。 The composite of the silicone rubber and the base material of the present invention includes automotive parts such as various gaskets, household appliances such as range window frame seals, pot packings, around the fixing machine of copying machines and printers, especially electronic It can be effectively used in a wide range of fields such as fixing rollers and fixing belts for photographic image formation, baby items such as baby bottles, diving items such as swimming goggles and underwater glasses, and toiletry items such as shower caps.
本発明のシリコーンゴムと基材との一体成形複合体において、基材は、金属、ガラス、有機樹脂である。
具体的に金属としては、鉄、アルミニウム、マグネシウム、ニッケル、クロム、金、銀銅、亜鉛、ステンレス等である。
In integrally molded composite of silicone rubber and the substrate of the present invention, the substrate is a metal, glass, Ru organic resin der.
Specific metal, Ru iron, aluminum, magnesium, nickel, chromium, gold, silver-copper, zinc, stainless steel or the like Ah.
有機樹脂としては、熱可塑性樹脂、熱硬化性樹脂のいずれでもよく、ポリアミド樹脂、ポリブチレンテレフタレート（ＰＢＴ）樹脂、ポリエチレンテレフタレート樹脂（ＰＥＴ）樹脂、ポリカーボネート（ＰＣ）樹脂、ポリフェニレンスルヒド（ＰＰＳ）樹脂、ポリフェニレンオキサイド（ＰＰＯ）樹脂、ポリスルフォン樹脂、ポリエーテルスルフォン樹脂、ポリイミド樹脂、ポリエーテルイミド樹脂、ポリアクリル樹脂、ポリエチレン樹脂、ポリスチレン樹脂、アクリロニトリル−ブタジエン−スチレン（ＡＢＳ）樹脂、アクリロニトリル−スチレン（ＡＳ）樹脂、エチレン−テトラフルオロエチレン共重合体、ポリフッ化ビニル樹脂、テトラフルオロエチレン−パーフルオロエーテル共重合体、テトラフルオロエチレン−ヘキサフルオロプロピレン重合体、ポリテトラフルオロエチレン樹脂、ポリフッ化ビニリデン樹脂、エチレンポリトリフルオロクロロエチレン樹脂、エポキシ樹脂、フェノール樹脂、尿素樹脂等が挙げられる。 The organic resin may be either a thermoplastic resin or a thermosetting resin. Polyamide resin, polybutylene terephthalate (PBT) resin, polyethylene terephthalate resin (PET) resin, polycarbonate (PC) resin, polyphenylene sulfide (PPS) resin , Polyphenylene oxide (PPO) resin, polysulfone resin, polyether sulfone resin, polyimide resin, polyetherimide resin, polyacryl resin, polyethylene resin, polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) ) Resin, ethylene-tetrafluoroethylene copolymer, polyvinyl fluoride resin, tetrafluoroethylene-perfluoroether copolymer, tetrafluoroethylene-hexafluoro Propylene polymers, polytetrafluoroethylene resin, polyvinylidene fluoride resin, ethylene polytrifluorochloroethylene resins, epoxy resins, phenol resins, urea resins, and the like.
これら基材と一体成形複合体を形成するシリコーンゴムは、通常シリコーンゴムと呼ばれるものであれば、いかなるものでもよいが、特に付加反応硬化型又は有機過酸化物硬化型のシリコーンゴム組成物の硬化物が好ましい。
ここで、付加反応硬化型のシリコーンゴム組成物としては、
（１）一分子中に少なくとも２個のケイ素原子に結合したアルケニル基を含有するオルガノポリシロキサン １００質量部
（２）一分子中に少なくとも２個、好ましくは３個以上のケイ素原子に結合した水素原子を含有するオルガノハイドロジェンポリシロキサン ０．１〜３０質量部
（３）付加反応触媒 触媒量
を主成分とする常温下で液状又は生ゴム状の組成物であり、加熱すると硬化してゴム状弾性体になるものである。
The silicone rubber that forms the integrally molded composite with these substrates may be any silicone rubber composition as long as it is usually called silicone rubber, but in particular, curing of an addition reaction curing type or organic peroxide curing type silicone rubber composition. Things are preferred.
Here, as an addition reaction curable silicone rubber composition,
(1) Organopolysiloxane containing an alkenyl group bonded to at least two silicon atoms in one molecule 100 parts by mass (2) Hydrogen bonded to at least two, preferably three or more silicon atoms in one molecule 0.1 to 30 parts by mass of an organohydrogenpolysiloxane containing atoms (3) Addition reaction catalyst A liquid or raw rubber-like composition at room temperature with a catalytic amount as a main component, and cures when heated to give a rubbery elasticity It's something to become a body.
（１）成分のオルガノポリシロキサンは付加反応硬化型シリコーンゴム組成物のベースポリマーであり、このオルガノポリシロキサンのケイ素原子に結合する有機基は、好ましくは炭素数１〜１２、より好ましくは１〜８の置換又は非置換の一価炭化水素基であり、具体的にはメチル、エチル、プロピル等のアルキル基などの脂肪族飽和炭化水素基、ビニル、アリル、プロペニル、ブテニル等のアルケニル基などの脂肪族不飽和炭化水素基、フェニル、キシリル等のアリール基、ベンジル基等のアラルキル基、３，３，３−トリフルオロプロピル等のハロゲン置換、シアノ基置換炭化水素基などから選ばれ、全有機基のうち７０モル％以上がメチル基であることが好ましい。ケイ素原子に結合する各有機基は異なっていても同一であってもよいが、分子中に少なくとも平均２個のアルケニル基を含んでいることが必要である。この（１）成分のオルガノポリシロキサンは分子鎖両末端がトリオルガノシロキシ基で封鎖され、主鎖がジオルガノシロキサン単位の繰り返しからなる直鎖状であることが好ましいが、一部分岐していてもよい。このオルガノポリシロキサンは当業者にとって公知の方法によって製造される。例えば、その製造方法は、オルガノシクロポリシロキサンとヘキサオルガノジシロキサンとをアルカリ又は酸触媒の存在下に平衡化反応を行うことによって得ることができる。 The organopolysiloxane (1) is a base polymer of an addition reaction curable silicone rubber composition, and the organic group bonded to the silicon atom of the organopolysiloxane is preferably 1 to 12 carbon atoms, more preferably 1 to 1 carbon atoms. 8 substituted or unsubstituted monovalent hydrocarbon groups, specifically, aliphatic saturated hydrocarbon groups such as alkyl groups such as methyl, ethyl, and propyl, and alkenyl groups such as vinyl, allyl, propenyl, and butenyl. Selected from aliphatic unsaturated hydrocarbon groups, aryl groups such as phenyl and xylyl, aralkyl groups such as benzyl groups, halogen substitution such as 3,3,3-trifluoropropyl, cyano group-substituted hydrocarbon groups, etc. It is preferable that 70 mol% or more of groups is a methyl group. Each organic group bonded to the silicon atom may be different or the same, but it is necessary that the molecule contains at least two alkenyl groups on average. The organopolysiloxane of component (1) is preferably a straight chain in which both ends of the molecular chain are blocked with triorganosiloxy groups and the main chain is composed of repeating diorganosiloxane units. Good. This organopolysiloxane is produced by methods known to those skilled in the art. For example, the production method can be obtained by conducting an equilibration reaction of organocyclopolysiloxane and hexaorganodisiloxane in the presence of an alkali or an acid catalyst.
（２）成分のオルガノハイドロジェンポリシロキサンは架橋剤として作用するものであり、分子中に少なくとも２個、好ましくは３個以上のケイ素原子に結合した水素原子（ＳｉＨ基）を有するものであれば、直鎖状、環状、分岐状、三次元網状などいずれの分子構造のものであってもよく、このオルガノハイドロジェンポリシロキサンとしては、１，１，３，３−テトラメチルジシロキサン、１，３，５，７−テトラメチルシクロテトラシロキサン、トリス（ジメチルハイドロジェンシロキシ）メチルシラン、両末端トリメチルシロキシ基封鎖メチルハイドロジェンポリシロキサン、両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルポリシロキサン、両末端ジメチルハイドロジェンシロキシ基封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、両末端トリメチルシロキシ基封鎖メチルハイドロジェンシロキサン・ジフェニルシロキサン共重合体、両末端トリメチルシロキシ基封鎖メチルハイドロジェンシロキサン・ジフェニルシロキサン・ジメチルシロキサン共重合体、（ＣＨ3）2ＨＳｉＯ1/2単位とＳｉＯ4/2単位とからなる共重合体、（ＣＨ3）2ＨＳｉＯ1/2単位とＳｉＯ4/2単位と（Ｃ6Ｈ5）3ＳｉＯ3/2単位とからなる共重合体等が挙げられる。 The component (2), organohydrogenpolysiloxane, acts as a crosslinking agent and has at least two, preferably three or more hydrogen atoms bonded to silicon atoms (SiH groups) in the molecule. , Linear, cyclic, branched, and three-dimensional network structures may be used. Examples of the organohydrogenpolysiloxane include 1,1,3,3-tetramethyldisiloxane, 3,5,7-tetramethylcyclotetrasiloxane, tris (dimethylhydrogensiloxy) methylsilane, both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane, both ends trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, Both end dimethylhydrogensiloxy group blocked dimethyl Lisiloxane, both ends dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer, both ends trimethylsiloxy group-blocked methylhydrogensiloxane Diphenylsiloxane / dimethylsiloxane copolymer, a copolymer comprising (CH 3 ) 2 HSiO 1/2 units and SiO 4/2 units, (CH 3 ) 2 HSiO 1/2 units and SiO 4/2 units ( Examples thereof include copolymers composed of C 6 H 5 ) 3 SiO 3/2 units.
このオルガノハイドロジェンポリシロキサンの配合量は、（１）成分のオルガノポリシロキサン１００質量部に対して０．１〜３０質量部、特に０．２〜２０質量部とすることが好ましい。また、このオルガノハイドロジェンポリシロキサンは、（１）成分中のケイ素原子に結合したアルケニル基に対する（２）成分中のケイ素原子に結合した水素原子（即ち、ＳｉＨ基）がモル比で０．１〜１０、好ましくは０．５〜５程度となるように配合することもできる。 The compounding amount of the organohydrogenpolysiloxane is preferably 0.1 to 30 parts by mass, particularly preferably 0.2 to 20 parts by mass with respect to 100 parts by mass of the organopolysiloxane (1). The organohydrogenpolysiloxane has a molar ratio of hydrogen atoms (that is, SiH groups) bonded to silicon atoms in the component (2) to alkenyl groups bonded to silicon atoms in the component (1) in a molar ratio of 0.1. -10, preferably about 0.5-5.
（３）成分の付加反応触媒としては、白金黒、塩化第２白金、塩化白金酸、塩化白金酸と１価アルコールとの反応物、塩化白金酸とオレフィン類との錯体、白金ビスアセトアセテート等の白金系触媒、パラジウム系触媒、ロジウム系触媒等が挙げられる。なおこの付加反応触媒の配合量は触媒量とすることができ、通常、白金族金属量として、（１）成分に対し０．１〜１，０００ｐｐｍ、特に１〜５００ｐｐｍである。 (3) Component addition reaction catalysts include platinum black, platinous chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohol, complexes of chloroplatinic acid and olefins, platinum bisacetoacetate, etc. Platinum-based catalysts, palladium-based catalysts, rhodium-based catalysts, and the like. In addition, the compounding quantity of this addition reaction catalyst can be made into a catalyst quantity, and is 0.1-1,000 ppm with respect to (1) component normally as a platinum group metal quantity, Especially 1-500 ppm.
また、有機過酸化物硬化型のシリコーンゴムとしては、
（４）１分子中に少なくとも平均２個以上のアルケニル基を有するオルガノポリシロキサン １００質量部
（５）有機過酸化物 触媒量
を主成分とする常温下で液状又は生ゴム状の組成物であり、加熱すると硬化してゴム状弾性体になるものである。
In addition, as organic peroxide curing type silicone rubber,
(4) 100 parts by mass of an organopolysiloxane having at least two alkenyl groups on average in one molecule
(5) Organic peroxide The composition is a liquid or raw rubber-like composition at room temperature with a catalytic amount as a main component, and cures to become a rubber-like elastic body when heated.
ここで、（４）成分のオルガノポリシロキサンは、有機過酸化物硬化型シリコーンゴム組成物のベースポリマーであり、このオルガノポリシロキサンのケイ素原子に結合する有機基は、好ましくは炭素数１〜１２、より好ましくは１〜８の置換又は非置換の一価炭化水素基であり、具体的にはメチル、エチル、プロピル等のアルキル基などの脂肪族飽和炭化水素基、ビニル、アリル、プロペニル、ブテニル等のアルケニル基などの脂肪族不飽和炭化水素基、フェニル、キシリル等のアリール基、ベンジル基等のアラルキル基、３，３，３−トリフルオロプロピル等のハロゲン置換、シアノ基置換炭化水素基などから選ばれ、全Ｒのうち０．０１〜１０モル％はアルケニル基であり、特にアルケニル基とメチル基との合計が全有機基の７０％以上であることが好ましい。ケイ素原子に結合する各有機基は異なっていても同一であってもよいが、分子中に少なくとも平均２個のアルケニル基を含んでいることが必要である。この（４）成分のオルガノポリシロキサンは主鎖がジオルガノシロキサン単位の繰り返しからなり、分子鎖両末端がトリオルガノシロキシ基で封鎖された直鎖状であることが好ましいが、一部分岐したものであってもよい。このオルガノポリシロキサンは当業者にとって公知の方法によって製造される。例えば、その製造方法は、オルガノシクロポリシロキサンとヘキサオルガノジシロキサンとをアルカリ又は酸触媒の存在下に平衡化反応を行うことによって得ることができる。 Here, the organopolysiloxane of the component (4) is a base polymer of the organic peroxide curable silicone rubber composition, and the organic group bonded to the silicon atom of the organopolysiloxane is preferably 1 to 12 carbon atoms. More preferably, it is a substituted or unsubstituted monovalent hydrocarbon group of 1 to 8, specifically, an aliphatic saturated hydrocarbon group such as an alkyl group such as methyl, ethyl or propyl, vinyl, allyl, propenyl, butenyl. Aliphatic unsaturated hydrocarbon groups such as alkenyl groups, aryl groups such as phenyl and xylyl, aralkyl groups such as benzyl groups, halogen substitution such as 3,3,3-trifluoropropyl, cyano group substituted hydrocarbon groups, etc. Of the total R, 0.01 to 10 mol% is an alkenyl group. In particular, the total of alkenyl groups and methyl groups is 70% or more of all organic groups. It is preferable that. Each organic group bonded to the silicon atom may be different or the same, but it is necessary that the molecule contains at least two alkenyl groups on average. The organopolysiloxane of component (4) is preferably a straight chain in which the main chain is composed of repeating diorganosiloxane units and both ends of the molecular chain are blocked with triorganosiloxy groups. There may be. This organopolysiloxane is produced by methods known to those skilled in the art. For example, the production method can be obtained by conducting an equilibration reaction of organocyclopolysiloxane and hexaorganodisiloxane in the presence of an alkali or an acid catalyst.
（５）成分の有機過酸化物とは、（４）成分の架橋反応を促進するための触媒として使用されるもので、従来公知のものとすればよいが、例えばベンゾイルパーオキサイド、２，４−ジクロロベンゾイルパーオキサイド、ｐ−メチルベンゾイルパーオキサイド、ｏ−メチルベンゾイルパーオキサイド、２，４−ジクミルパーオキサイド、２，５−ジメチル−ビス（２，５−ｔ−ブチルパーオキシ）ヘキサン、ジ−ｔ−ブチルパーオキサイド、ｔ−ブチルパーベンゾエート、１，１−ビス（ｔ−ブチルパーオキシカルボキシ）ヘキサン等が挙げられるが、特にこれらに限定されるものではない。 The component (5) organic peroxide is used as a catalyst for accelerating the crosslinking reaction of the component (4) and may be a conventionally known one. For example, benzoyl peroxide, 2, 4 -Dichlorobenzoyl peroxide, p-methylbenzoyl peroxide, o-methylbenzoyl peroxide, 2,4-dicumyl peroxide, 2,5-dimethyl-bis (2,5-t-butylperoxy) hexane, di Examples include -t-butyl peroxide, t-butyl perbenzoate, 1,1-bis (t-butylperoxycarboxy) hexane, and the like, but are not particularly limited thereto.
なお、添加量は、硬化速度に応じて適宜選択すればよいが、通常は（４）成分に対し、０．１〜１０質量部、好ましくは０．２〜２質量部の範囲とすればよい。 In addition, what is necessary is just to select suitably according to a cure rate, However, Usually, what is necessary is just to make it the range of 0.1-10 mass parts with respect to (4) component, Preferably it is 0.2-2 mass parts. .
上述した成分の他、本発明のシリコーンゴム組成物にヒュームドシリカ、沈降シリカ等の補強性充填材、ヘキサメチルジシラザン、シラノール基含有の重合度が１００以下の低分子量ジメチルシロキサン、シラノール基含有シラン、アルコキシ基含有シラン、ヘキサアルキルジシラザン等の分散助剤、珪藻土、石英粉末、溶融石英粉末、クレー、アルミナ、タルク等の無機充填剤、ベンガラ、酸化チタン、酸化セリウム、酸化亜鉛、炭酸亜鉛、炭酸カルシウム、水酸化カルシウム、炭酸マグネシウム、酸化マグネシウム等の耐熱、耐油向上剤、カーボンブラック、群青等の着色のための顔料、離型剤、その他、通常のシリコーンゴム組成物に添加される添加剤を用途等に応じ、適宜配合することができる。更に接着性をより強固にさせる目的で、ＣＦシランや各種ＳｉＨ基含有化合物等の接着助剤を加えてもよい。 In addition to the components described above, the silicone rubber composition of the present invention includes fumed silica, reinforcing filler such as precipitated silica, hexamethyldisilazane, low molecular weight dimethylsiloxane having a silanol group-containing degree of polymerization of 100 or less, and silanol group-containing. Dispersing aids such as silane, alkoxy group-containing silane, hexaalkyldisilazane, diatomaceous earth, quartz powder, fused silica powder, inorganic fillers such as clay, alumina, talc, bengara, titanium oxide, cerium oxide, zinc oxide, zinc carbonate , Calcium carbonate, calcium hydroxide, magnesium carbonate, magnesium oxide and other heat and oil resistance improvers, carbon black, ultramarine pigments, mold release agents, and other additives added to normal silicone rubber compositions An agent can be appropriately blended depending on the application. Further, for the purpose of further strengthening the adhesion, an adhesion aid such as CF silane or various SiH group-containing compounds may be added.
本発明においては、上記基材とシリコーンゴムとを有機ケイ素化合物の燃焼により形成された酸化ケイ素皮膜を介して接着、一体化するもので、この場合、酸化ケイ素皮膜の形成は、基材の表面を有機ケイ素化合物を含む燃料ガスの火炎で吹き付け処理することにより、基材表面の改質を行う方法による。このような有機ケイ素化合物としては、テトラメチルシラン、トリメチルクロロシラン、ジメチルジクロロシラン、メチルトリクロロシラン、テトラメトキシシラン、トリメトキシラン、テトラエトキシシラン、メチルトリメトキシシラン、ジメチルジメトキシシラン、トリメチルメトキシシラン、フェニルトリクロロシラン、ジフェニルジクロロシラン、フェニルトリメトキシシラン、ジフェニルジメトキシシラン等が挙げられる。なお、これら有機ケイ素化合物に加え、火炎のコントロールを容易にするために、プロパンガスや天然ガス等の炭化水素ガス、水素、酸素、空気等の引火性ガスを混合してもよい。 In the present invention, the base material and the silicone rubber are bonded and integrated through a silicon oxide film formed by burning an organosilicon compound. In this case, the silicon oxide film is formed on the surface of the base material. the by treating spraying flame of a fuel gas containing an organic silicon compound, Ru good to a method of performing modification of the substrate surface. Examples of such organosilicon compounds include tetramethylsilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, tetramethoxysilane, trimethoxylane, tetraethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and phenyl. Examples include trichlorosilane, diphenyldichlorosilane, phenyltrimethoxysilane, diphenyldimethoxysilane, and the like. In addition to these organosilicon compounds, a hydrocarbon gas such as propane gas or natural gas, or a flammable gas such as hydrogen, oxygen, or air may be mixed in order to easily control the flame.
上記燃焼ガスの火炎を基材表面に吹き付ける時間としては、０．１〜５０秒の範囲、好ましくは、０．３〜３０秒の範囲である。０．１秒未満では、表面処理が不十分かつ不均一であり、５０秒を超えると、表面改質する基材にダメージを与えてしまうおそれがある。この場合、形成される酸化ケイ素皮膜の厚さは、表面の分子官能基に変化が生じる程度であれば特に制限はなく、通常１０μｍ以下（例えば０．００１〜１０μｍ、特に０．００２〜５μｍ程度）の皮膜で十分であり、１０μｍを超えるような厚い皮膜を形成する必要はない。
このようなケイ素化合物の燃焼による表面改質方法としては、特に特開２００３−２３８７１０号公報で開示されているような方法が効果的である。
The time for spraying the flame of the combustion gas onto the substrate surface is in the range of 0.1 to 50 seconds, preferably in the range of 0.3 to 30 seconds. If it is less than 0.1 seconds, the surface treatment is insufficient and non-uniform, and if it exceeds 50 seconds, the substrate to be surface-modified may be damaged. In this case, the thickness of the formed silicon oxide film is not particularly limited as long as the molecular functional group on the surface is changed, and is usually 10 μm or less (for example, 0.001 to 10 μm, particularly about 0.002 to 5 μm). ) Is sufficient, and it is not necessary to form a thick film exceeding 10 μm.
As such a surface modification method by burning a silicon compound, a method as disclosed in Japanese Patent Application Laid-Open No. 2003-238710 is particularly effective.
次いで、上記シリコーンゴム組成物の硬化物（シリコーンゴム）と、有機ケイ素化合物の燃焼処理により表面処理された基材とが一体化した複合体を得る方法において、シリコーンゴム組成物層をこの基材上に形成する方法は、ディッピング、コーティング、注入成形、圧縮成形、射出成形等いかなる方法でもよいが、取り扱いの容易さ、生産性等の点から、注入成形、圧縮成形、射出成形が好ましい。これらはいずれの場合も、表面処理した基材を金型内に設置し、硬化性のシリコーンゴム組成物を金型内で基材と接触させながら硬化させることで一体複合体が得られる。表面処理した部分のみが接着するため、金型離型が良好で、かつバリ取りなどの後工程も用意である。 Next, in a method for obtaining a composite in which a cured product of the above-mentioned silicone rubber composition (silicone rubber) and a substrate surface-treated by a combustion treatment of an organosilicon compound are obtained, the silicone rubber composition layer is formed from the substrate. Any method such as dipping, coating, injection molding, compression molding, and injection molding may be used as the method for forming the upper layer. However, injection molding, compression molding, and injection molding are preferable from the viewpoint of ease of handling, productivity, and the like. In any case, an integrated composite is obtained by placing a surface-treated substrate in a mold and curing the curable silicone rubber composition in contact with the substrate in the mold. Since only the surface-treated part adheres, mold release is good and a post-process such as deburring is also prepared.
シリコーンゴム組成物の硬化条件としては、上述した付加反応硬化型あるいは有機過酸化物硬化型シリコーンゴム組成物の場合、６０〜２３０℃で５秒〜２時間、好ましくは８０〜２１０℃で１０秒〜１時間である。６０℃未満では、硬化に時間がかかりすぎ、２３０℃を超えると、金型にシリコーンゴム組成物を充填する前に硬化してしまったり、硬化したシリコーンゴムが劣化したりしてしまうおそれがある。 As the curing conditions for the silicone rubber composition, in the case of the addition reaction curable type or organic peroxide curable type silicone rubber composition described above, 60 to 230 ° C. for 5 seconds to 2 hours, preferably 80 to 210 ° C. for 10 seconds. ~ 1 hour. If it is less than 60 ° C., it takes too much time to cure, and if it exceeds 230 ° C., it may be cured before filling the mold with the silicone rubber composition or the cured silicone rubber may be deteriorated. .
本発明のシリコーンゴムと基材との一体化複合体は、既存のシリコーンゴムと金属、ガラスや樹脂が接触しながら用いられているほぼすべての用途に適用可能であるが、特に哺乳瓶等の乳幼児用品、スイミングゴーグル、水中眼鏡等のダイビング用品、更にはプリンター、複写機等の電子式写真装置の定着装置（定着ローラ、定着ベルト）に好適である。 The integrated composite of the silicone rubber and the substrate of the present invention can be applied to almost all uses where the existing silicone rubber and metal, glass or resin are used in contact with each other. Suitable for infant supplies, swimming goggles, diving equipment such as underwater glasses, and fixing devices (fixing rollers, fixing belts) for electronic photographic devices such as printers and copying machines.
ダイビング用品は、シリコーンゴムが、無味無臭で生理的に不活性、更に透明性に優れ、かつ着色も容易であることからデザイン性にも優れるため、ゴーグル、水中眼鏡のストラップ及び周囲部、シュノーケルのマウスピース部などに用いられている。水中眼鏡やゴーグルのメガネ部（レンズ）はガラス又は透明なポリカーボネート樹脂又はアクリル樹脂であり、これら樹脂を有機シラン化合物の燃焼による表面処理後、シリコーンゴム組成物、特に付加硬化型のシリコーンゴム組成物を接触させながら硬化させることにより、透明メガネ部（レンズ）と周囲のゴム部（フレーム）が一体化したスイミングゴーグル又は水中メガネを得ることができる。 For diving equipment, silicone rubber is tasteless, odorless, physiologically inert, excellent in transparency, and easy to color, so it is also excellent in design, so goggles, straps and surroundings of underwater glasses, snorkeling It is used for the mouthpiece part. Glasses (lenses) of underwater glasses and goggles are made of glass or transparent polycarbonate resin or acrylic resin, and these resins are subjected to surface treatment by burning an organosilane compound, and then a silicone rubber composition, particularly an addition-curing silicone rubber composition. By making it harden while being in contact, swimming goggles or underwater glasses in which the transparent glasses part (lens) and the surrounding rubber part (frame) are integrated can be obtained.
乳幼児用品についても、同様にシリコーンゴムが無味無臭で生理的に不活性であることから、哺乳瓶用乳首や赤ちゃん用おしゃぶりなどに使用されている。これらの基材はガラスや有機樹脂が主で、有機樹脂の中でも透明性の点からポリカーボネート樹脂が広く使用されている。これらのガラスや有機樹脂を有機シラン化合物の燃焼による表面処理後、シリコーンゴム組成物、特に付加硬化型のシリコーンゴム組成物を基材の表面処理部に接触させながら硬化させることにより、ゴム性乳首部と周囲部が一体化した哺乳瓶用乳首や赤ちゃん用おしゃぶりを得ることができる。 Similarly, since silicone rubber is tasteless and odorless and physiologically inactive, it is used for baby bottle nipples and baby pacifiers. These base materials are mainly glass or organic resin, and among organic resins, polycarbonate resin is widely used from the viewpoint of transparency. After surface treatment of these glass and organic resin by the combustion of an organosilane compound, a silicone rubber composition, in particular, an addition-curing type silicone rubber composition is cured while being in contact with the surface treatment portion of the substrate, thereby making a rubber nipple A nipple for baby bottles and a baby pacifier in which the part and the peripheral part are integrated can be obtained.
また、電子写真式画像形成装置の定着装置に用いられる定着ロール、定着ベルト用としても、本発明のシリコーンゴムとの一体化複合体は効果的に利用できる。ここでシリコーンゴムは、芯金、又は耐熱性樹脂あるいは金属薄膜からなる無端ベルト基材にシリコーンゴム層が介在され、更にこのシリコーンゴム層上にフッ素系樹脂コーティング剤又はフッ素系樹脂チューブなどによるフッ素系樹脂層が表層として形成されたフッ素系樹脂被覆定着ロール又は定着ベルトのシリコーンゴム層として使用される。この場合、芯金又はベルトの材質、寸法等はロールの種類に応じて適宜選定し得る。芯金の材質としては、アルミニウム、ステンレス、鉄等があり、ベルトの基材としては、アルミニウム、ニッケル、ポリイミド、ポリエーテルイミド等が主として用いられる。フッ素系樹脂チューブとしては市販品を使用し得、この場合は、例えば、ポリテトラフルオロエチレン樹脂（ＰＴＦＥ）、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体樹脂（ＰＦＡ）、フッ化エチレン−プロピレン共重合体樹脂（ＦＥＰ）、ポリフッ化ビニリデン樹脂（ＰＶＤＦ）、ポリフッ化ビニル樹脂等が一般的である。これら、芯金、ベルト基材とフッ素樹脂チューブ（内面）の両方又は一方の表面を有機シラン化合物による燃焼処理を実施した後、金型内に設置し、両者の間にシリコーンゴム組成物、特に付加反応硬化型シリコーンゴム組成物を充填し、硬化させることにより、芯金又はベルト基材とフッ素樹脂チューブの間にシリコーンゴム弾性層を有する定着装置用のロール又はベルトを得ることができる。この時、シリコーンゴム組成物の硬化条件は特に制限されないが、１００〜１８０℃、好ましくは１２０〜１６０℃で３分〜１時間硬化させ、更に１８０〜２２０℃で、１〜１２時間ポストキュアすることが好ましい。得られるシリコーンゴム組成物の硬化物のデュロメータＡによるゴム硬度は４０以下であることが好ましい。 Also, the integrated composite with the silicone rubber of the present invention can be effectively used for a fixing roll and a fixing belt used in a fixing device of an electrophotographic image forming apparatus. Here, the silicone rubber has a silicone rubber layer interposed on an endless belt base material made of a core metal, a heat-resistant resin or a metal thin film, and further a fluorine resin coating agent or a fluorine resin tube on the silicone rubber layer. It is used as a silicone rubber layer of a fluororesin-coated fixing roll or fixing belt having a base resin layer formed as a surface layer. In this case, the material, dimensions, and the like of the core bar or belt can be appropriately selected according to the type of roll. As the material of the core metal, there are aluminum, stainless steel, iron and the like, and as the base material of the belt, aluminum, nickel, polyimide, polyetherimide and the like are mainly used. Commercially available products can be used as the fluororesin tube. In this case, for example, polytetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), fluorinated ethylene-propylene copolymer. Polymer resin (FEP), polyvinylidene fluoride resin (PVDF), polyvinyl fluoride resin, etc. are common. These core metal, the belt base material and the fluororesin tube (inner surface) or one of the surfaces is subjected to a combustion treatment with an organosilane compound and then placed in a mold, and a silicone rubber composition, especially between them By filling and curing the addition reaction curable silicone rubber composition, a roll or belt for a fixing device having a silicone rubber elastic layer between the core metal or belt substrate and the fluororesin tube can be obtained. At this time, the curing condition of the silicone rubber composition is not particularly limited, but is cured at 100 to 180 ° C., preferably 120 to 160 ° C. for 3 minutes to 1 hour, and further post-cured at 180 to 220 ° C. for 1 to 12 hours. It is preferable. It is preferable that the rubber hardness by the durometer A of the hardened | cured material of the obtained silicone rubber composition is 40 or less.
なお、上記フッ素系樹脂被覆定着ロール又は定着ベルトのシリコーンゴム層の厚さは適宜選定されるが、定着ロールは、通常、０．１〜５０ｍｍ、好ましくは０．３〜３０ｍｍであり、定着ベルトは、通常、０．０２〜１ｍｍ、好ましくは０．０５〜０．８ｍｍである。 The thickness of the silicone rubber layer of the fluororesin-coated fixing roll or fixing belt is appropriately selected. The fixing roll is usually 0.1 to 50 mm, preferably 0.3 to 30 mm. Is usually 0.02 to 1 mm, preferably 0.05 to 0.8 mm.
なお、フッ素系樹脂チューブは、有機シラン化合物の燃焼により表面処理される前に、従来より行われているコロナ放電処理、ナトリウムナフタレン法、液体アンモニア法、スパッタエッチング法、エキシマレーザー処理等により、シリコーンゴムの接着を更に強固にすることも効果的である。更に、接着耐久性を向上させるために、プライマー処理を使用してもよい。 In addition, before the surface treatment by the combustion of the organosilane compound, the fluorine-based resin tube is treated with silicone by a corona discharge treatment, a sodium naphthalene method, a liquid ammonia method, a sputter etching method, an excimer laser treatment, etc. that are conventionally performed. It is also effective to further strengthen the adhesion of rubber. Furthermore, primer treatment may be used to improve the adhesion durability.
このフッ素系樹脂層の厚さは適宜選定されるが、０．１〜１００μｍ、特に１〜５０μｍとすることが好ましく、０．１μｍより薄いとロールの硬度が小さくなり、供給される紙がスリップする場合があり、１００μｍより厚いとロールの硬度が高くなり、ニップ幅が取れず、定着後の画像が不良となる場合がある。
The thickness of the fluororesin layer is appropriately selected, but it is preferably 0.1 to 100 μm, particularly preferably 1 to 50 μm. If it is thinner than 0.1 μm, the hardness of the roll becomes small and the supplied paper slips. If the thickness is greater than 100 μm, the hardness of the roll increases, the nip width cannot be obtained, and the image after fixing may be defective.
以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
［実施例及び比較例］
次の各テストピース（市販品、長さ５０ｍｍ×幅２５ｍｍ）について、テトラメチルシラン、テトラメトキシシランと空気の混合ガス（モル比＝０．００００１：０．０００００１：１、即ち、テトラメチルシランを０．００１モル％、テトラメトキシシランを０．０００１モル％濃度で含有する空気混合ガス）を基材表面上でガス流量：１ｍ3／ｈｒで約０．５秒間燃焼処理を実施した。
テストピース：ステンレス、アルミニウム、ガラス、ポリアミド樹脂、ＰＥＴ樹脂
この表面処理された基材の先端２５ｍｍ×１０ｍｍ以外の部分をテフロン（商品名）テープでシールした。このテストピース上に付加反応硬化型シリコーンゴム組成物（ＫＥ１９５０−５０Ａ／Ｂ、配合比（質量）１００／１００、信越化学工業（株）製）を塗布し、硬化条件を１２０℃／１０分としてプレスキュアを行い、更に１５０℃／２時間オーブンキュアを行った。
接着試験は、ゴムと基材を引っ張る１８０度ピール試験によって行い、ゴム破壊：１００％を○、ゴム破壊と界面剥離混在を△、界面剥離１００％を×とした。
比較例として、燃焼処理を実施せずに同様の接着試験を実施したものを記載した。
[Examples and Comparative Examples]
For each of the following test pieces (commercial product, length 50 mm × width 25 mm), a mixed gas of tetramethylsilane, tetramethoxysilane and air (molar ratio = 0.00001: 0.000001: 1, ie, tetramethylsilane was added) An air mixed gas containing 0.001 mol% and tetramethoxysilane at a concentration of 0.0001 mol%) was burned on the substrate surface at a gas flow rate of 1 m 3 / hr for about 0.5 seconds.
Test piece: stainless steel, aluminum, glass, polyamide resin, PET resin A portion other than the tip 25 mm × 10 mm of the surface-treated substrate was sealed with Teflon (trade name) tape. On this test piece, an addition reaction curable silicone rubber composition (KE1950-50A / B, blending ratio (mass) 100/100, manufactured by Shin-Etsu Chemical Co., Ltd.) is applied, and the curing condition is 120 ° C./10 minutes. Press cure was performed, followed by oven cure at 150 ° C./2 hours.
The adhesion test was performed by a 180-degree peel test in which the rubber and the substrate were pulled. Rubber breakage: 100%, ○, rubber breakage and interfacial debonding mixed, and interfacial delamination 100%.
As a comparative example, the same adhesion test was carried out without carrying out the combustion treatment.
次に、直径１５ｍｍ、長さ２５０ｍｍ、厚さ５０μｍのＰＦＡ樹脂チューブの内側及び直径１０ｍｍ×長さ３００ｍｍのアルミニウムシャフトの表面を、テトラメチルシラン、テトラメトキシシランと空気との混合物（モル比＝０．００００１：０．０００００１：１、即ち、テトラメチルシランを０．００１モル％、テトラメトキシシランを０．０００１モル％濃度で含有する空気混合ガス）をそれぞれガス流量：１ｍ3／ｈｒで２秒間燃焼処理させた。これを金型内に固定し、チューブとシャフトとの間に付加反応硬化型液状シリコーンゴム組成物（ＫＥ１３７５Ａ／Ｂ、信越化学工業（株）製）を１００対１００（質量比）で混合したものを充填し、１５０℃で３０分加熱硬化、更に２００℃で４時間ポストキュアし、アルミニウムシャフトの外周面上にシリコーンゴム層が形成され、このシリコーンゴム層の外周面上に、更にフッ素樹脂層が形成された定着ロールを得た。この定着ロールを電子写真複写機に装着してＡ４サイズの複写紙を１，０００万枚連続複写後、芯金及び表層であるフッ素樹脂層を剥がそうとしたところ、いずれもシリコーンゴム層にて１００％ゴム凝集破壊となった。
同様に燃焼処理をしないチューブとシャフトの間に上記と同じシリコーンゴム組成物を充填し、硬化させて得た定着ロールを複写機に装着して連続複写を実施しようとしたが、通紙５枚目で表面にしわが発生し、９枚目でチューブが剥がれてしまったため、試験を中止した。
Next, the inside of a PFA resin tube having a diameter of 15 mm, a length of 250 mm, and a thickness of 50 μm and the surface of an aluminum shaft having a diameter of 10 mm × length of 300 mm were mixed with tetramethylsilane, tetramethoxysilane and air (molar ratio = 0). 0.0001: 0.000001: 1, that is, an air mixed gas containing 0.001 mol% of tetramethylsilane and 0.0001 mol% of tetramethoxysilane) for 2 seconds at a gas flow rate of 1 m 3 / hr, respectively. Burned. This is fixed in a mold, and an addition reaction curable liquid silicone rubber composition (KE1375A / B, manufactured by Shin-Etsu Chemical Co., Ltd.) is mixed at a ratio of 100 to 100 (mass ratio) between the tube and the shaft. And is cured by heating at 150 ° C. for 30 minutes and further post-cured at 200 ° C. for 4 hours. A silicone rubber layer is formed on the outer peripheral surface of the aluminum shaft, and a fluororesin layer is further formed on the outer peripheral surface of the silicone rubber layer. As a result, a fixing roll in which was formed was obtained. When this fixing roll was installed in an electrophotographic copying machine and 10 million copies of A4 size copy paper were continuously copied, the core metal and the fluororesin layer as the surface layer were peeled off. 100% rubber cohesive failure occurred.
Similarly, the same silicone rubber composition as above was filled between a tube and a shaft not subjected to combustion treatment, and the fixing roll obtained by curing was mounted on a copying machine to carry out continuous copying. The test was stopped because the surface was wrinkled by the eyes and the tube peeled off at the ninth sheet.
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| JP2004357865A JP4412485B2 (en) | 2004-12-10 | 2004-12-10 | Monolithic composite of silicone rubber and substrate and method for producing the same |
| CN2005101217172A CN1837269B (en) | 2004-12-10 | 2005-12-09 | Integrally molded composite of silicone rubber and base material and its manufacturing method |
| KR1020050120293A KR101194455B1 (en) | 2004-12-10 | 2005-12-09 | An Integrally Molded Composite Body of a Silicone Rubber and a Substrate, and the Preparation Process Thereof |
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| JP2007178721A (en) * | 2005-12-28 | 2007-07-12 | Synztec Co Ltd | Fixing rotator |
| JP4995480B2 (en) * | 2006-04-26 | 2012-08-08 | 株式会社カネカ | Composite molded body |
| JP4761067B2 (en) * | 2006-11-27 | 2011-08-31 | 信越化学工業株式会社 | Airbag coating cloth |
| JP5158474B2 (en) * | 2007-07-05 | 2013-03-06 | 住友電工ファインポリマー株式会社 | Roller and belt for image forming apparatus |
| KR101049927B1 (en) * | 2009-09-04 | 2011-07-15 | 선우에이엠씨주식회사 | Silicone coated plastic bonding sheet and method of making same |
| FR2964646B1 (en) * | 2010-09-13 | 2014-06-13 | Sgd Sa | GLASS CONTAINER AND METHOD OF MANUFACTURING THE SAME |
| CN102512327A (en) * | 2011-12-15 | 2012-06-27 | 佘庆琛 | Safe silica gel glass feeding bottle and production process thereof |
| JP5984187B2 (en) * | 2013-04-22 | 2016-09-06 | 信越化学工業株式会社 | Pellicle and photomask assembly |
| JP2015123656A (en) * | 2013-12-26 | 2015-07-06 | 信越ポリマー株式会社 | Shape retaining sheet and method of producing shape retaining sheet |
| CN106573708B (en) * | 2014-05-02 | 2020-11-10 | 满趣健公司 | Anti-biting kettle nozzle |
| CN105086855B (en) * | 2014-05-09 | 2018-12-21 | 深圳光启创新技术有限公司 | The adhesive method and flexible absorbing material of silicon rubber and object |
| JP6134889B2 (en) * | 2014-09-29 | 2017-05-31 | 住友理工株式会社 | Silicone rubber composition, crosslinked silicone rubber, integral molded body, and method for producing integral molded body |
| WO2016056038A1 (en) * | 2014-10-07 | 2016-04-14 | 有限会社コーキ・エンジニアリング | Slidable medical silicone rubber, gasket using said rubber, and prefilled syringe using said gasket |
| CN105131669B (en) * | 2015-08-13 | 2018-07-06 | 岳胜武 | A kind of one-component inorganic agent for handling PC bonding addition-type silicon rubbers and preparation method thereof |
| CN105287225A (en) * | 2015-11-19 | 2016-02-03 | 黄克锋 | Novel anti-falling jelly glass milk bottle manufacturing method |
| WO2017094703A1 (en) | 2015-11-30 | 2017-06-08 | 住友理工株式会社 | Elastic roller for electrophotographic device, and method for manufacturing said roller |
| JP6585535B2 (en) | 2016-03-29 | 2019-10-02 | 住友理工株式会社 | Silicone rubber composition and crosslinked silicone rubber |
| KR102082890B1 (en) | 2019-04-16 | 2020-02-28 | 주식회사 만컴퍼니 | Method for testing bonding line of smart phone and apparatus therefor |
| CN110339537A (en) * | 2019-05-27 | 2019-10-18 | 滁州君越高分子新材料有限公司 | A kind of swimming cap production technology |
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| JP3494039B2 (en) * | 1998-11-06 | 2004-02-03 | 信越化学工業株式会社 | Silicone rubber composition for heat fixing roll and heat fixing roll |
| JP2004008540A (en) | 2002-06-07 | 2004-01-15 | Koshin Baby Co Ltd | Nursing bottle |
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| KR101194455B1 (en) | 2012-10-24 |
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