JP3999751B2 - (メタ)アクリル系重合性液状樹脂組成物の製造方法 - Google Patents
(メタ)アクリル系重合性液状樹脂組成物の製造方法 Download PDFInfo
- Publication number
- JP3999751B2 JP3999751B2 JP2004067387A JP2004067387A JP3999751B2 JP 3999751 B2 JP3999751 B2 JP 3999751B2 JP 2004067387 A JP2004067387 A JP 2004067387A JP 2004067387 A JP2004067387 A JP 2004067387A JP 3999751 B2 JP3999751 B2 JP 3999751B2
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylic
- mass
- liquid
- resin composition
- 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.)
- Expired - Lifetime
Links
- 239000007788 liquid Substances 0.000 title claims description 147
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims description 108
- 239000011342 resin composition Substances 0.000 title claims description 65
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000000178 monomer Substances 0.000 claims description 104
- 239000004014 plasticizer Substances 0.000 claims description 93
- 238000010526 radical polymerization reaction Methods 0.000 claims description 24
- 229920000642 polymer Polymers 0.000 claims description 12
- 239000007870 radical polymerization initiator Substances 0.000 claims description 12
- 230000004580 weight loss Effects 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 description 29
- 229920000178 Acrylic resin Polymers 0.000 description 27
- 239000004925 Acrylic resin Substances 0.000 description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 25
- 239000003431 cross linking reagent Substances 0.000 description 25
- 239000000047 product Substances 0.000 description 24
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 24
- 229920000058 polyacrylate Polymers 0.000 description 20
- 239000006188 syrup Substances 0.000 description 20
- 235000020357 syrup Nutrition 0.000 description 20
- 239000004020 conductor Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- -1 alkylene glycol Chemical compound 0.000 description 15
- 125000005395 methacrylic acid group Chemical group 0.000 description 14
- 239000011231 conductive filler Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 12
- 239000012467 final product Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical class OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 10
- 238000005979 thermal decomposition reaction Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 7
- 239000004593 Epoxy Chemical class 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 125000005907 alkyl ester group Chemical group 0.000 description 6
- 230000000740 bleeding effect Effects 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- DGBIGWXXNGSACT-UHFFFAOYSA-N clonazepam Chemical compound C12=CC([N+](=O)[O-])=CC=C2NC(=O)CN=C1C1=CC=CC=C1Cl DGBIGWXXNGSACT-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- WDIXVQTZULGQNI-UHFFFAOYSA-N 2-ethyl-2-(2-methylbutan-2-ylperoxy)hexanoic acid Chemical compound CCCCC(CC)(C(O)=O)OOC(C)(C)CC WDIXVQTZULGQNI-UHFFFAOYSA-N 0.000 description 2
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 239000000113 methacrylic resin Substances 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 2
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- RLPSARLYTKXVSE-UHFFFAOYSA-N 1-(1,3-thiazol-5-yl)ethanamine Chemical compound CC(N)C1=CN=CS1 RLPSARLYTKXVSE-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- FJGNCDHMLZWTAR-UHFFFAOYSA-N 2-ethyl-2-(2,4,4-trimethylpentan-2-ylperoxy)hexanoic acid Chemical compound CCCCC(CC)(C(O)=O)OOC(C)(C)CC(C)(C)C FJGNCDHMLZWTAR-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- AHWAAQOJHMFNIV-UHFFFAOYSA-N 2-tert-butylperoxy-2-ethylhexanoic acid Chemical compound CCCCC(CC)(C(O)=O)OOC(C)(C)C AHWAAQOJHMFNIV-UHFFFAOYSA-N 0.000 description 1
- NXAFRGRYHSKXJB-UHFFFAOYSA-N 2-tert-butylperoxy-3,5,5-trimethylhexanoic acid Chemical compound CC(C)(C)CC(C)C(C(O)=O)OOC(C)(C)C NXAFRGRYHSKXJB-UHFFFAOYSA-N 0.000 description 1
- VKERWIBXKLNXCY-UHFFFAOYSA-N 3,5,5-trimethyl-2-(2-methylbutan-2-ylperoxy)hexanoic acid Chemical compound CCC(C)(C)OOC(C(O)=O)C(C)CC(C)(C)C VKERWIBXKLNXCY-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- FRBAZRWGNOJHRO-UHFFFAOYSA-N 6-tert-butylperoxycarbonyloxyhexyl (2-methylpropan-2-yl)oxy carbonate Chemical compound CC(C)(C)OOC(=O)OCCCCCCOC(=O)OOC(C)(C)C FRBAZRWGNOJHRO-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 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
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- KRADHMIOFJQKEZ-UHFFFAOYSA-N Tri-2-ethylhexyl trimellitate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(C(=O)OCC(CC)CCCC)C(C(=O)OCC(CC)CCCC)=C1 KRADHMIOFJQKEZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical class [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- QQVHEQUEHCEAKS-UHFFFAOYSA-N diundecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCC QQVHEQUEHCEAKS-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 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
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical class OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- DLSMLZRPNPCXGY-UHFFFAOYSA-N tert-butylperoxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOOC(C)(C)C DLSMLZRPNPCXGY-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229940035024 thioglycerol Drugs 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FJFYFBRNDHRTHL-UHFFFAOYSA-N tris(8-methylnonyl) benzene-1,2,4-tricarboxylate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC(C)C)C(C(=O)OCCCCCCCC(C)C)=C1 FJFYFBRNDHRTHL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
Description
ラジカル重合工程は、本発明によって最も重要な工程であり、(メタ)アクリル系モノマーとラジカル重合開始剤を含む液状可塑剤中で、(メタ)アクリル系モノマーをラジカル重合させて液状樹脂組成物(アクリルシラップ)を製造する点が最も大切である。液状可塑剤は、可塑性(柔軟性)が求められる用途(例えば、熱伝導性材料など)では必須の成分であり、この液状可塑剤を使用する点には何ら問題がなく、簡便に無溶媒とすることができる。しかもこの液状可塑剤中で、(メタ)アクリル系モノマーをラジカル重合させると、特殊な触媒を使用しなくても、メタクリル系モノマーのみならずアクリル系モノマーであっても暴走することなく重合させることができる。アクリル系樹脂は、メタクリル系樹脂に比べて柔軟性(可塑性)に優れているため、アクリル系モノマーをも重合できることは可塑性が求められる用途(熱伝導性材料など)にとっては極めて重要である。
得られる(メタ)アクリル系ポリマーのガラス転移温度は、通常0℃以下程度、好ましくは−30℃以下程度、さらに好ましくは−40℃以下程度である。ガラス転移温度が低いほど、液状樹脂組成物を硬化した最終品の柔軟性を高めることができる。そのため熱伝導性材料にするときの利用価値を高めることができる。またガラス転移温度の低い(メタ)アクリル系ポリマーは、単独ではべたつき感があるため、ハンドリング性を維持するためには溶剤と混合する必要があるところ、本発明の方法によればガラス転移温度の低い(メタ)アクリル系ポリマーであっても、液状可塑剤と混合されているため、ハンドリング性を低下させることなく実質的に無溶媒とすることができる。なおガラス転移温度は、示差走査熱量計によって測定できる。
調製工程では、上記のようにして得られる重合反応混合物に、必要に応じて(メタ)アクリル系モノマー、液状可塑剤などを添加する。成分を適切に調製することによって液状樹脂組成物を得ることができる。なお本発明ではラジカル重合を途中で停止できるため、調製工程は必ずしも必要ではなく、重合反応混合物をそのまま液状樹脂組成物として使用してもよい。
温度計、攪拌機、ガス導入管、還流冷却器および滴下ロートを備えたガラス製容器に、第1の(メタ)アクリル系モノマー[及び必要に応じて第2の(メタ)アクリル系モノマー]、第1の液状可塑剤、連鎖移動剤を仕込み、窒素ガスで反応容器内の気相部分の酸素濃度が0.1質量%以下となる様に置換した(仕込み段階)。所定温度(A)に昇温し、必要に応じて希釈用液状可塑剤で希釈した重合開始剤を滴下ロートから所定時間かけて滴下した(反応開始段階)。次いで所定温度(B)で所定時間、攪拌を継続した(反応継続段階)。必要に応じてさらに重合開始剤を追加し、所定温度(C)で所定時間攪拌を継続した(反応熟成段階)。空気を吹き込み、冷却することによって重合を終了させ、ポリマーA〜Gなどを含有する混合物A〜Gを得た。なおいずれの例でも、重合反応の暴走はなかった。詳細は下記表2の通りである。
上記混合物A〜Fを種々の他の物質と下記表3に示す割合で混合し、下記表3に示す組成の(メタ)アクリル系液状樹脂組成物A〜Gを調製した。なおこれら(メタ)アクリル系液状樹脂組成物のうち、(メタ)アクリル系モノマーを実質的に含有していないもの(0.02質量%程度)は非ラジカル型架橋剤で硬化させるものであるため、“架橋用”に分類する。一方、(メタ)アクリル系モノマーを実質的に含有するものはラジカル重合(熱重合)によって硬化させるものであるため、“重合性”と称する。
メタクリル系重合性液状樹脂組成物A100質量部、ラジカル重合開始剤としてのt−アミルパーオキシ−2−エチルヘキサネート(化薬アクゾ株式会社製、商品名「トリゴノックス121−50E」)1質量部、消泡剤(ビックケミー社製、商品名「A−515」)0.1質量部、酸化アルミニウム(昭和電工株式会社製、品番「AS−10」;熱伝導率30W/m・k)400質量部を均一に混練した後、脱泡した。離型処理を施したPETフィルムを底に敷いたガラスセルに、厚さが1mmとなるように前記脱泡物を注ぎ入れ、温度100℃のオーブンで1時間、次いで温度120℃で1時間加熱して重合(硬化)させた。
メタクリル系重合性液状樹脂組成物Aに代えてアクリル系重合性液状樹脂組成物B〜Eを用いる以外は、実施例1と同様にした。
アクリル系架橋用液状樹脂組成物F100質量部、架橋剤としてのヘキサメチレンジイソシアネート0.35質量部、ウレタン反応促進剤としてのジブチル錫ジラウリレート0.05質量部、消泡剤(ビックケミー社製、商品名「A−515」)0.1質量部、酸化アルミニウム(昭和電工株式界社製、品番「AS−10」;熱伝導率30W/m・k)400質量部を均一に混練した後、脱泡した。離型処理を施したPETフィルムを底に敷いたガラスセルに、厚さが1mmとなるように前記脱泡物を注ぎ入れ、温度80℃のオーブンで1時間、次いで温度100℃で1時間加熱して架橋(硬化)させた。
アクリル系架橋用液状樹脂組成物Fに代えてアクリル系架橋用液状樹脂組成物Gを用いる以外は、比較例1と同様にした。
シート状硬化物を温度130℃のオーブンで168時間加熱し、加熱前後の質量、熱伝導率、硬度をそれぞれ調べた。詳細は、以下の通りである。
加熱前後の質量を測定し、下記式に基づいて質量減量を算出した。
2)熱伝導率
シート状硬化物を厚さ10mmまで積層し、京都電子工業株式会社製の迅速熱伝導率計(品番「QTM−500」)を用いて、該積層物の温度25℃における熱伝導率を測定した。
シート状硬化物を厚さ10mmまで積層し、該積層物の硬度を、JIS K 7312に準じて、高分子計器株式会社製のアスカーゴム硬度計C型を用いて測定した。
シート状硬化物の加熱(130℃)を、加熱時間が504時間になるまでさらに継続し、加熱後の硬度を前記と同様にして調べた。
Claims (2)
- (メタ)アクリル系モノマーとラジカル重合開始剤を含む液状可塑剤中で、(メタ)アクリル系モノマーをラジカル重合させる工程を含み、前記液状可塑剤は、温度150℃で3時間保持した後の質量減量が、5質量%以下であることを特徴とする、(メタ)アクリル系ポリマー、(メタ)アクリル系モノマー、及び液状可塑剤を含む重合性液状樹脂組成物の製造方法。
- 前記(メタ)アクリル系モノマーをラジカル重合させる工程において、前記液状可塑剤の割合は、前記(メタ)アクリル系モノマーと前記液状可塑剤との合計100質量%に対して5質量%〜80質量%である請求項1に記載の重合性液状樹脂組成物の製造方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004067387A JP3999751B2 (ja) | 2004-03-10 | 2004-03-10 | (メタ)アクリル系重合性液状樹脂組成物の製造方法 |
PCT/JP2004/007113 WO2004101678A1 (ja) | 2003-05-19 | 2004-05-19 | 熱伝導性材料用樹脂組成物および熱伝導性材料 |
US10/557,786 US7589147B2 (en) | 2003-05-19 | 2004-05-19 | Resin composition for thermal conductive material and thermal conductive material |
TW093114069A TW200508379A (en) | 2003-05-19 | 2004-05-19 | Resin composition for thermally conductive material and thermally conductive material |
KR1020057021364A KR100731279B1 (ko) | 2003-05-19 | 2004-05-19 | 열전도성 재료용 수지 조성물 및 열전도성 재료 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004067387A JP3999751B2 (ja) | 2004-03-10 | 2004-03-10 | (メタ)アクリル系重合性液状樹脂組成物の製造方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2005255784A JP2005255784A (ja) | 2005-09-22 |
JP3999751B2 true JP3999751B2 (ja) | 2007-10-31 |
Family
ID=35081843
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2004067387A Expired - Lifetime JP3999751B2 (ja) | 2003-05-19 | 2004-03-10 | (メタ)アクリル系重合性液状樹脂組成物の製造方法 |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3999751B2 (ja) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7354835B2 (ja) * | 2019-12-25 | 2023-10-03 | 東洋インキScホールディングス株式会社 | 粘着剤および粘着シート |
-
2004
- 2004-03-10 JP JP2004067387A patent/JP3999751B2/ja not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JP2005255784A (ja) | 2005-09-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2388280B1 (en) | Curable composition, cured object obtained therefrom, and process for producing same | |
KR100715362B1 (ko) | 방열 재료용 수지 조성물 및 방열 재료 | |
JP2009522411A (ja) | ビニルモノマーをフリーラジカル重合する方法 | |
WO2004101678A1 (ja) | 熱伝導性材料用樹脂組成物および熱伝導性材料 | |
JP4652916B2 (ja) | 放熱材用樹脂組成物 | |
CN100386375C (zh) | 导热性材料用树脂组合物和导热性材料 | |
EP3913664A1 (en) | Curable composition and cured material | |
KR102617131B1 (ko) | 경화성 조성물 | |
JP3999751B2 (ja) | (メタ)アクリル系重合性液状樹脂組成物の製造方法 | |
KR20220030103A (ko) | 경화성 조성물 | |
KR20120135827A (ko) | 도로 피복용 도료 조성물 | |
CN112442147B (zh) | 一种低粘度3d用氟树脂及其制备方法和应用 | |
JP4280200B2 (ja) | 放熱材用樹脂組成物 | |
EP3480272B1 (en) | Radical-curable adhesive composition and adhesive | |
US20230312796A1 (en) | Curable Composition | |
JP7231986B2 (ja) | 樹脂組成物およびその硬化物 | |
JP2008201955A (ja) | 多官能(メタ)アクリレートを含有する熱硬化性樹脂組成物 | |
KR101967486B1 (ko) | 긴 측쇄 알킬기를 가지는 이타콘산 에스테르를 포함하는 이형필름용 수지 조성물 | |
EP3712222B1 (en) | Radical-curable adhesive composition, and adhesive | |
JP2005076027A (ja) | 熱硬化性組成物の強化剤を調製する方法 | |
JPH06206942A (ja) | 硬化性樹脂組成物 | |
KR20220012731A (ko) | 경화성 조성물 | |
KR20230120452A (ko) | 적층체 | |
JP2008256957A (ja) | 粘着剤層付き光学積層体 | |
JP2015134868A (ja) | 厚膜シートの製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050915 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20070227 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20070427 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20070529 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20070607 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20070807 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20070809 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 3999751 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100817 Year of fee payment: 3 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100817 Year of fee payment: 3 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110817 Year of fee payment: 4 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120817 Year of fee payment: 5 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120817 Year of fee payment: 5 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130817 Year of fee payment: 6 |
|
EXPY | Cancellation because of completion of term |