JP6366069B2 - Method for producing resin composition - Google Patents
Method for producing resin composition Download PDFInfo
- Publication number
- JP6366069B2 JP6366069B2 JP2015096394A JP2015096394A JP6366069B2 JP 6366069 B2 JP6366069 B2 JP 6366069B2 JP 2015096394 A JP2015096394 A JP 2015096394A JP 2015096394 A JP2015096394 A JP 2015096394A JP 6366069 B2 JP6366069 B2 JP 6366069B2
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- mass
- producing
- radical polymerization
- filler
- 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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- 239000011342 resin composition Substances 0.000 title claims description 82
- 238000004519 manufacturing process Methods 0.000 title claims description 52
- 239000003822 epoxy resin Substances 0.000 claims description 45
- 229920000647 polyepoxide Polymers 0.000 claims description 45
- 150000001875 compounds Chemical class 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 37
- 239000007870 radical polymerization initiator Substances 0.000 claims description 36
- 239000000945 filler Substances 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 229920001187 thermosetting polymer Polymers 0.000 claims description 15
- AGXAFZNONAXBOS-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethyl)phenyl]methyl]oxirane Chemical compound C=1C=CC(CC2OC2)=CC=1CC1CO1 AGXAFZNONAXBOS-UHFFFAOYSA-N 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 40
- -1 acryl Chemical group 0.000 description 33
- 238000003860 storage Methods 0.000 description 17
- 239000000758 substrate Substances 0.000 description 15
- 210000004027 cell Anatomy 0.000 description 14
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 13
- 239000007983 Tris buffer Substances 0.000 description 11
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 11
- 239000010419 fine particle Substances 0.000 description 11
- 229920003986 novolac Polymers 0.000 description 11
- MFEWNFVBWPABCX-UHFFFAOYSA-N 1,1,2,2-tetraphenylethane-1,2-diol Chemical class C=1C=CC=CC=1C(C(O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(O)C1=CC=CC=C1 MFEWNFVBWPABCX-UHFFFAOYSA-N 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- 238000011109 contamination Methods 0.000 description 9
- 238000001723 curing Methods 0.000 description 9
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000005060 rubber Substances 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229920000800 acrylic rubber Polymers 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 239000011256 inorganic filler Substances 0.000 description 6
- 229910003475 inorganic filler Inorganic materials 0.000 description 6
- 229920000058 polyacrylate Polymers 0.000 description 6
- 239000003999 initiator Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010526 radical polymerization reaction Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 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 4
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 4
- CSFWPUWCSPOLJW-UHFFFAOYSA-N lawsone Chemical compound C1=CC=C2C(=O)C(O)=CC(=O)C2=C1 CSFWPUWCSPOLJW-UHFFFAOYSA-N 0.000 description 4
- 239000012766 organic filler Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 125000006850 spacer group Chemical group 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 3
- QCBSYPYHCJMQGB-UHFFFAOYSA-N 2-ethyl-1,3,5-triazine Chemical compound CCC1=NC=NC=N1 QCBSYPYHCJMQGB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- 229930192627 Naphthoquinone Natural products 0.000 description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N Resorcinol Natural products OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 229910002026 crystalline silica Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000005350 fused silica glass Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 229920003049 isoprene rubber Polymers 0.000 description 3
- 150000002791 naphthoquinones Chemical class 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- WTKVMIIQXATOJO-UHFFFAOYSA-N trimethyl-(1,1,2,2-tetraphenyl-2-trimethylsilyloxyethoxy)silane Chemical compound C=1C=CC=CC=1C(C(O[Si](C)(C)C)(C=1C=CC=CC=1)C=1C=CC=CC=1)(O[Si](C)(C)C)C1=CC=CC=C1 WTKVMIIQXATOJO-UHFFFAOYSA-N 0.000 description 3
- ZNGSVRYVWHOWLX-KHFUBBAMSA-N (1r,2s)-2-(methylamino)-1-phenylpropan-1-ol;hydrate Chemical compound O.CN[C@@H](C)[C@H](O)C1=CC=CC=C1.CN[C@@H](C)[C@H](O)C1=CC=CC=C1 ZNGSVRYVWHOWLX-KHFUBBAMSA-N 0.000 description 2
- TWDFSQNRBYNLAA-UHFFFAOYSA-N 1,1,2,2-tetraphenyl-2-triethylsilyloxyethanol Chemical compound OC(C(C1=CC=CC=C1)(C1=CC=CC=C1)O[Si](CC)(CC)CC)(C1=CC=CC=C1)C1=CC=CC=C1 TWDFSQNRBYNLAA-UHFFFAOYSA-N 0.000 description 2
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 description 2
- OBGBGHKYJAOXRR-UHFFFAOYSA-N 2-methoxy-1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C(OC)=CC(=O)C2=C1 OBGBGHKYJAOXRR-UHFFFAOYSA-N 0.000 description 2
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- MJVAVZPDRWSRRC-UHFFFAOYSA-N Menadione Chemical compound C1=CC=C2C(=O)C(C)=CC(=O)C2=C1 MJVAVZPDRWSRRC-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- 239000007874 V-70 Substances 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229940091173 hydantoin Drugs 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000005051 trimethylchlorosilane Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- VAAVXQPHWGURFL-UHFFFAOYSA-N (1,2-diethoxy-1,2,2-triphenylethyl)benzene Chemical compound C=1C=CC=CC=1C(C(OCC)(C=1C=CC=CC=1)C=1C=CC=CC=1)(OCC)C1=CC=CC=C1 VAAVXQPHWGURFL-UHFFFAOYSA-N 0.000 description 1
- WSYHCVAGLRXMPP-UHFFFAOYSA-N (1,2-dimethoxy-1,2,2-triphenylethyl)benzene Chemical compound C=1C=CC=CC=1C(C(OC)(C=1C=CC=CC=1)C=1C=CC=CC=1)(OC)C1=CC=CC=C1 WSYHCVAGLRXMPP-UHFFFAOYSA-N 0.000 description 1
- ARJBLMGEDUINDZ-UHFFFAOYSA-N (1,2-diphenoxy-1,2,2-triphenylethyl)benzene Chemical compound C=1C=CC=CC=1C(C(OC=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)(C=1C=CC=CC=1)OC1=CC=CC=C1 ARJBLMGEDUINDZ-UHFFFAOYSA-N 0.000 description 1
- MDJZGXRFYKPSIM-JCYAYHJZSA-N (2r,3r)-2,3-dihydroxybutanedihydrazide Chemical compound NNC(=O)[C@H](O)[C@@H](O)C(=O)NN MDJZGXRFYKPSIM-JCYAYHJZSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- FZFFWZJDHRTEMQ-UHFFFAOYSA-N 1,1,2,2-tetraphenyl-2-trimethylsilyloxyethanol Chemical compound OC(C(C1=CC=CC=C1)(C1=CC=CC=C1)O[Si](C)(C)C)(C1=CC=CC=C1)C1=CC=CC=C1 FZFFWZJDHRTEMQ-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- ROFVGYAMRSGUSQ-UHFFFAOYSA-N 1-(2-bromoethyl)piperazine;hydrobromide Chemical compound Br.BrCCN1CCNCC1 ROFVGYAMRSGUSQ-UHFFFAOYSA-N 0.000 description 1
- XTNYHSVRWXRDFR-UHFFFAOYSA-N 1-[1,2-dimethoxy-1,2,2-tris(4-methylphenyl)ethyl]-4-methylbenzene Chemical compound COC(C(C1=CC=C(C=C1)C)(C1=CC=C(C=C1)C)OC)(C1=CC=C(C=C1)C)C1=CC=C(C=C1)C XTNYHSVRWXRDFR-UHFFFAOYSA-N 0.000 description 1
- XZKLXPPYISZJCV-UHFFFAOYSA-N 1-benzyl-2-phenylimidazole Chemical compound C1=CN=C(C=2C=CC=CC=2)N1CC1=CC=CC=C1 XZKLXPPYISZJCV-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- XZBIXDPGRMLSTC-UHFFFAOYSA-N formohydrazide Chemical compound NNC=O XZBIXDPGRMLSTC-UHFFFAOYSA-N 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- OXAGUPFRAIIDLT-UHFFFAOYSA-N heptanedihydrazide Chemical compound NNC(=O)CCCCCC(=O)NN OXAGUPFRAIIDLT-UHFFFAOYSA-N 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000010410 layer 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
- 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
- 230000000873 masking effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- IFZUFHWISBKFJP-UHFFFAOYSA-N n'-[4-[dimethoxy(methyl)silyl]oxybutyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)OCCCCNCCN IFZUFHWISBKFJP-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- DRRZZMBHJXLZRS-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]cyclohexanamine Chemical compound CO[Si](C)(OC)CCCNC1CCCCC1 DRRZZMBHJXLZRS-UHFFFAOYSA-N 0.000 description 1
- VMFUMDXVTKTZQY-UHFFFAOYSA-N naphthalene-1-carbohydrazide Chemical compound C1=CC=C2C(C(=O)NN)=CC=CC2=C1 VMFUMDXVTKTZQY-UHFFFAOYSA-N 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- LGYJSPMYALQHBL-UHFFFAOYSA-N pentanedihydrazide Chemical compound NNC(=O)CCCC(=O)NN LGYJSPMYALQHBL-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- DDOVHJODVHQLCS-UHFFFAOYSA-N pyridine-2,6-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=N1 DDOVHJODVHQLCS-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 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
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 239000007787 solid 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
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- UTADZBVVSYSYTG-UHFFFAOYSA-N tert-butyl(methyl)silane Chemical compound C[SiH2]C(C)(C)C UTADZBVVSYSYTG-UHFFFAOYSA-N 0.000 description 1
- WRWQRNWWCINRPO-UHFFFAOYSA-N tert-butyl-[2-[tert-butyl(dimethyl)silyl]oxy-1,1,2,2-tetraphenylethoxy]-dimethylsilane Chemical compound C(C)(C)(C)[Si](OC(C(C1=CC=CC=C1)(C1=CC=CC=C1)O[Si](C)(C)C(C)(C)C)(C1=CC=CC=C1)C1=CC=CC=C1)(C)C WRWQRNWWCINRPO-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 235000019303 thiodipropionic acid Nutrition 0.000 description 1
- JREYOWJEWZVAOR-UHFFFAOYSA-N triazanium;[3-methylbut-3-enoxy(oxido)phosphoryl] phosphate Chemical compound [NH4+].[NH4+].[NH4+].CC(=C)CCOP([O-])(=O)OP([O-])([O-])=O JREYOWJEWZVAOR-UHFFFAOYSA-N 0.000 description 1
- MPQVYFJXQMBTHQ-UHFFFAOYSA-N triethyl-(1,1,2,2-tetraphenyl-2-triethylsilyloxyethoxy)silane Chemical compound C(C)[Si](OC(C(C1=CC=CC=C1)(C1=CC=CC=C1)O[Si](CC)(CC)CC)(C1=CC=CC=C1)C1=CC=CC=C1)(CC)CC MPQVYFJXQMBTHQ-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、樹脂組成物の製造方法、及びその方法によって得られる電子部品用接着剤に関する。より詳細には、保存安定性に優れる１液型樹脂組成物の製造方法に関する。この方法によって得られる樹脂組成物は、保存安定性が良好な為、ジェットディスペンスのような精密塗布作業性に優れ、半導体のような電子部品用接着剤として好適である。 The present invention relates to a method for producing a resin composition and an adhesive for electronic components obtained by the method. More specifically, the present invention relates to a method for producing a one-component resin composition having excellent storage stability. Since the resin composition obtained by this method has good storage stability, it has excellent precision coating workability such as jet dispensing and is suitable as an adhesive for electronic parts such as semiconductors.
従来より、電子部品に使用される樹脂組成物、例えば基板用の樹脂、半導体素子と基板の接着剤、フレキシブル基板における耐熱フィルムと銅箔の接着剤等には、熱硬化型のエポキシ系、アクリル系の樹脂組成物が適用されている。
このエポキシ系樹脂組成物は、主にエポキシ樹脂、硬化剤、フィラーによって構成されており、特にフィラーは８０質量％程度を占める程に高充填されている（特許文献１）。これは、応力を逃がし、熱によるソリ等の変形を抑えたり、接着強度を向上させたりする等の目的でなされているものである。アクリル系樹脂組成物は従来の光硬化だけでなく、熱硬化性も注目されており、熱ラジカル重合開始剤を使用することも検討されている。
Conventionally, resin compositions used in electronic components, such as resins for substrates, adhesives for semiconductor elements and substrates, heat-resistant film and copper foil adhesives for flexible substrates, etc., are thermosetting epoxy-based, acrylic System resin compositions are applied.
This epoxy resin composition is mainly composed of an epoxy resin, a curing agent, and a filler. In particular, the filler is highly filled to account for about 80% by mass (Patent Document 1). This is done for the purpose of releasing stress, suppressing deformation such as warpage due to heat, and improving adhesive strength. Acrylic resin compositions are attracting attention not only for conventional photocuring but also for thermosetting properties, and the use of thermal radical polymerization initiators is also being studied.
しかし、熱ラジカル重合開始剤は脱泡時にかかる温度の影響で脱泡直後もしくは室温保管時にゲル化するといった課題を抱えており、作業性を著しく低下させていた。 However, the thermal radical polymerization initiator has a problem that it gelates immediately after defoaming or at room temperature storage due to the influence of the temperature at the time of defoaming, and the workability is remarkably lowered.
本発明は、樹脂組成物の製造方法、及びその方法によって得られる電子部品用接着剤に関する。より詳細には、保存安定性良好な１液型樹脂組成物の製造方法に関する。この方法によって得られる樹脂組成物は、保存安定性が良好な為、ジェットディスペンスのような精密塗布作業性に優れるという特性を有する。従って、特に半導体のような１液型電子部品用接着剤として好適である。 The present invention relates to a method for producing a resin composition and an adhesive for electronic components obtained by the method. More specifically, the present invention relates to a method for producing a one-component resin composition having good storage stability. Since the resin composition obtained by this method has good storage stability, it has the property of being excellent in precision coating workability such as jet dispensing. Therefore, it is particularly suitable as an adhesive for a one-pack type electronic component such as a semiconductor.
本発明者らは、鋭意検討の結果、平均粒子径異なる熱ラジカル重合開始剤（ａ）とフィラー（ｂ）を用い、硬化性化合物（ｃ）中に分散する前に、熱ラジカル重合開始剤（ａ）とフィラー（ｂ）を複合化することによって、保存安定性に優れた樹脂組成物の提供が可能であることを発見し本発明に至ったものである。
なお、本明細書中、「（メタ）アクリル」とは「アクリル及び／又はメタクリル」を意味し、「（メタ）アクリロイル基」とは「アクリロイル基及び/又はメタクリロイル基」を意味する。
As a result of intensive studies, the present inventors have used a thermal radical polymerization initiator (a) and a filler (b) having different average particle diameters, and before dispersing in the curable compound (c), a thermal radical polymerization initiator ( It has been found that by combining a) and filler (b), it is possible to provide a resin composition having excellent storage stability, and the present invention has been achieved.
In the present specification, “(meth) acryl” means “acryl and / or methacryl”, and “(meth) acryloyl group” means “acryloyl group and / or methacryloyl group”.
すなわち本発明は、
１）
平均粒子径Ａ[μｍ]の熱ラジカル重合開始剤（ａ）、平均粒子径Ｂ[μｍ]のフィラー（ｂ）及び硬化性化合物（ｃ）を含有する樹脂組成物の製造方法であって、Ａ[μｍ]及びＢ[μｍ]が、下記式（Ｉ）及び（ＩＩ）で表される条件を満たし、かつ硬化性化合物（ｃ）中に熱ラジカル重合開始剤（ａ）とフィラー（ｂ）を分散する前に、熱ラジカル重合開始剤（ａ）とフィラー（ｂ）を複合化する工程を有する樹脂組成物の製造方法、
０．５μｍ ≦ Ａ ≦ ３μｍ ・・・ （Ｉ）
０．００５×Ａ ≦ Ｂ ≦ ０．３×Ａ ・・・ （ＩＩ）
２）
上記（ｂ）が、シリカ及び／又はアルミナである上記１）に記載の樹脂組成物の製造方法、
３）
樹脂組成物の総量を１００質量部としたときの（ａ）の含有量が０．０００１質量部以上１０部質量部未満である上記１）または２）に記載の樹脂組成物の製造方法、
４）
樹脂組成物の総量を１００質量部としたときの（ｂ）の含有量が０．００００５質量部以上２０質量部未満である上記１）乃至３）のいずれか一項に記載の樹脂組成物の製造方法、
５）
上記硬化性化合物（ｃ）が（メタ）アクリル化エポキシ樹脂である上記１）乃至４）のいずれか一項に記載の樹脂組成物の製造方法、
６）
上記硬化性化合物（ｃ）がレゾルシンジグリシジルエーテルの（メタ）アクリルエステル化物である上記１）乃至５）のいずれか一項に記載の樹脂組成物の製造方法、
７）
更に熱硬化剤（ｄ）を含有する上記１）乃至６）のいずれか一項に記載の樹脂組成物の製造方法、
８）
上記熱硬化剤（ｄ）が有機酸ジヒドラジドである上記１）乃至７）のいずれか一項に記載の樹脂組成物の製造方法、
９）
更にシランカップリング剤（ｅ）を含有する、上記１）乃至８）のいずれか一項に記載の樹脂組成物の製造方法、
１０）
更にエポキシ樹脂（ｆ）を含有する、上記１）乃至９）のいずれか一項に記載の樹脂組成物の製造方法、
１１）
上記１）乃至１０）のいずれか一項に記載の樹脂組成物の製造方法で得られる電子部品用接着剤、
１２）
上記１）乃至１１）のいずれか一項に記載の樹脂組成物の製造方法で得られる樹脂組成物を硬化して得られる硬化物接着された電子部品、
に関する。
That is, the present invention
1)
A method for producing a resin composition comprising a thermal radical polymerization initiator (a) having an average particle size A [μm], a filler (b) having an average particle size B [μm], and a curable compound (c), comprising: [μm] and B [μm] satisfy the conditions represented by the following formulas (I) and (II), and the thermal radical polymerization initiator (a) and the filler (b) are added to the curable compound (c). A method for producing a resin composition having a step of combining a thermal radical polymerization initiator (a) and a filler (b) before being dispersed;
0.5 μm ≦ A ≦ 3 μm (I)
0.005 × A ≦ B ≦ 0.3 × A (II)
2)
The method for producing a resin composition according to 1), wherein (b) is silica and / or alumina,
3)
The method for producing a resin composition according to 1) or 2) above, wherein the content of (a) when the total amount of the resin composition is 100 parts by mass is 0.0001 parts by mass or more and less than 10 parts by mass,
4)
The resin composition according to any one of 1) to 3) above, wherein the content of (b) when the total amount of the resin composition is 100 parts by mass is 0.00005 parts by mass or more and less than 20 parts by mass. Production method,
5)
The method for producing a resin composition according to any one of 1) to 4), wherein the curable compound (c) is a (meth) acrylated epoxy resin,
6)
The method for producing a resin composition according to any one of 1) to 5), wherein the curable compound (c) is a (meth) acrylic esterified product of resorcin diglycidyl ether,
7)
Furthermore, the manufacturing method of the resin composition as described in any one of said 1) thru | or 6) containing a thermosetting agent (d),
8)
The method for producing a resin composition according to any one of 1) to 7), wherein the thermosetting agent (d) is an organic acid dihydrazide,
9)
Furthermore, the manufacturing method of the resin composition as described in any one of said 1) thru | or 8) containing a silane coupling agent (e),
10)
Furthermore, the manufacturing method of the resin composition as described in any one of said 1) thru | or 9) containing an epoxy resin (f),
11)
An adhesive for electronic parts obtained by the method for producing a resin composition according to any one of 1) to 10) above,
12)
A cured product-bonded electronic component obtained by curing the resin composition obtained by the method for producing a resin composition according to any one of 1) to 11) above,
About.
本発明の製造方法によって得られる樹脂組成物は、保存安定性が良好な為、精密性が要求される電子部品において、非常に有利な効果を発揮する。 Since the resin composition obtained by the production method of the present invention has good storage stability, it exhibits a very advantageous effect in electronic parts that require precision.
本発明は、平均粒子径の異なる熱ラジカル重合開始剤（ａ）とフィラー（ｂ）を用い、硬化性化合物（ｃ）中に分散する前に、熱ラジカル重合開始剤（ａ）とフィラー（ｂ）を複合化する工程を有することを特徴とする樹脂組成物の製造方法である。
熱硬化剤、硬化促進剤、熱ラジカル重合開始剤、フィラー等を含有する樹脂組成物を製造する場合、例えばエポキシ樹脂のような硬化性化合物中に、熱ラジカル重合開始剤、フィラー等をそれぞれ添加し、攪拌混合し、その後２本ロール等の混練器によって分散する方法が一般的である。しかし、この方法では、熱ラジカル重合開始剤とフィラーがそれぞれ独立して、硬化性化合物中に分散され、相互に作用することはない。
本発明は、平均粒子径の大きい熱ラジカル重合開始剤（ａ）と平均粒子径の小さいフィラー（ｂ）を事前に複合化し、これを硬化性化合物（ｃ）中に分散することによって、最終的に保存安定性樹脂組成物の製造を可能にするものである。
複合化とは、微粒子（子粒子）をそれより大きなサイズの粒子（母粒子）上に分散、固定化することを言い、上記特許文献２に記載のようにホソカワミクロン製ノビルタを使用することにより実現することができる。
本発明では熱ラジカル重合開始剤の表面にフィラーを複合化しているため、室温では樹脂と熱ラジカル重合開始剤が接触することなく、熱ラジカル重合開始剤が融点に達したときに複合化が壊れ、樹脂と熱硬ラジカル剤が接触する。そのため、融点以下での保存安定性は良好であり、硬化温度では従来通りの反応性を示す。
The present invention uses a thermal radical polymerization initiator (a) and a filler (b) having different average particle diameters, and before being dispersed in the curable compound (c), the thermal radical polymerization initiator (a) and the filler (b A process for compounding a resin composition.
When manufacturing a resin composition containing a thermosetting agent, a curing accelerator, a thermal radical polymerization initiator, a filler, etc., for example, a thermal radical polymerization initiator, a filler, etc. are added to a curable compound such as an epoxy resin. In general, the mixture is stirred and mixed and then dispersed by a kneader such as a two-roller. However, in this method, the thermal radical polymerization initiator and the filler are independently dispersed in the curable compound and do not interact with each other.
In the present invention, the thermal radical polymerization initiator (a) having a large average particle size and the filler (b) having a small average particle size are combined in advance and dispersed in the curable compound (c), thereby finally In addition, it makes it possible to produce a storage-stable resin composition.
Compounding refers to dispersing and immobilizing fine particles (child particles) on larger particles (mother particles), and is realized by using Hosokawa Micron Nobilta as described in Patent Document 2 above. can do.
In the present invention, since the filler is combined on the surface of the thermal radical polymerization initiator, the resin is not contacted with the thermal radical polymerization initiator at room temperature, and the composite is broken when the thermal radical polymerization initiator reaches the melting point. The resin and the thermosetting radical agent come into contact. Therefore, the storage stability below the melting point is good, and the conventional reactivity is exhibited at the curing temperature.
平均粒子径Ａ[μｍ]の熱ラジカル重合開始剤（ａ）、平均粒子径Ｂ[μｍ]のフィラー（ｂ）及び硬化性化合物（ｄ）を含有する樹脂組成物の製造方法であって、Ａ[μｍ]及びＢ[μｍ]が、下記式（Ｉ）及び（ＩＩ）で表される条件を満たし、かつ硬化性化合物（ｃ）中に熱ラジカル重合開始剤（ａ）とフィラー（ｂ）を分散する前に、熱ラジカル重合開始剤（ａ）とフィラー（ｂ）を複合化する工程を有する樹脂組成物の製造方法。
０．５μｍ ≦ Ａ ≦ ３μｍ ・・・ （Ｉ）
０．００５×Ａ ≦ Ｂ ≦ ０．３×Ａ ・・・ （ＩＩ）
[数式（Ｉ）に関して]
数式（Ｉ）は、平均粒子径の大きい熱ラジカル重合開始剤（ａ）の平均粒子径を規定している。すなわち、熱硬ラジカル剤（ａ）の平均粒子径は、０．５μｍ以上３μｍ以下である。平均粒子径が小さいと、保存安定性が悪くなる傾向がある。従って、０．５μｍ未満である場合、本発明の効果が十分に得られない場合がある。また、平均粒子径が大きすぎると、液晶表示セルのギャップより大きくなりギャップ不良を起こす可能性がある。平均粒子径の更に好ましい範囲は、１μｍ以上３μｍ以下であり、特に好ましくは、１μｍ以上２μｍ以下である。
[数式（ＩＩ）に関して]
数式（ＩＩ）は、熱ラジカル重合開始剤（ａ）とフィラー（ｂ）の平均粒子径の関係を示したものである。すなわち、フィラー（ｂ）の平均粒子径は、熱ラジカル重合開始剤（ａ）の平均粒子径の１０００分の５以上１０００分の３００以下である。フィラー（ｂ）の平均粒子径がこの範囲である場合には、フィラー（ｂ）の粒子は熱ラジカル重合開始剤（ａ）の粒子との静電引力が強まり、熱ラジカル重合開始剤（ａ）の表面に引き寄せられ、熱ラジカル重合開始剤（ａ）と硬化性化合物（ｃ）の間に効率よく入り込む。フィラー（ｂ）の平均粒子径は、更に好ましくは、１０００分の５以上１０００分の２００以下であり、特に好ましくは、１０００分の８以上１０００分の１００以下である。
A method for producing a resin composition comprising a thermal radical polymerization initiator (a) having an average particle size A [μm], a filler (b) having an average particle size B [μm], and a curable compound (d), comprising: [μm] and B [μm] satisfy the conditions represented by the following formulas (I) and (II), and the thermal radical polymerization initiator (a) and the filler (b) are added to the curable compound (c). A method for producing a resin composition comprising a step of combining a thermal radical polymerization initiator (a) and a filler (b) before dispersion.
0.5 μm ≦ A ≦ 3 μm (I)
0.005 × A ≦ B ≦ 0.3 × A (II)
[Regarding Formula (I)]
Formula (I) defines the average particle size of the thermal radical polymerization initiator (a) having a large average particle size. That is, the average particle diameter of the thermosetting radical agent (a) is 0.5 μm or more and 3 μm or less. When the average particle size is small, the storage stability tends to deteriorate. Therefore, when it is less than 0.5 μm, the effect of the present invention may not be sufficiently obtained. On the other hand, if the average particle size is too large, the gap may be larger than that of the liquid crystal display cell, which may cause a gap defect. A more preferable range of the average particle diameter is 1 μm or more and 3 μm or less, and particularly preferably 1 μm or more and 2 μm or less.
[Regarding Formula (II)]
Formula (II) shows the relationship between the average particle diameters of the thermal radical polymerization initiator (a) and the filler (b). That is, the average particle diameter of the filler (b) is 5/1000 to 300/1000 of the average particle diameter of the thermal radical polymerization initiator (a). When the average particle diameter of the filler (b) is within this range, the particles of the filler (b) have a strong electrostatic attraction with the particles of the thermal radical polymerization initiator (a), and the thermal radical polymerization initiator (a). It is attracted to the surface of the resin and efficiently enters between the thermal radical polymerization initiator (a) and the curable compound (c). The average particle diameter of the filler (b) is more preferably from 5/1000 to 200/1000, and particularly preferably from 8/1000 to 100/1000.
本明細書において平均粒子径は、レーザー回折・散乱式粒度分布測定器（乾式）（株式会社セイシン企業製；ＬＭＳ−３０）により測定することができる。また、市販品であれば、各社カタログにも明記されている。 In the present specification, the average particle size can be measured by a laser diffraction / scattering particle size distribution analyzer (dry type) (manufactured by Seishin Enterprise Co., Ltd .; LMS-30). If it is a commercial product, it is also specified in the catalog of each company.
本願発明の製造方法で得られる樹脂組成物は、熱ラジカル重合開始剤（ａ）を含有しても良い。この熱ラジカル重合開始剤は、加熱によりラジカルを生じ、連鎖重合反応を開始させる化合物であれば特に限定されないが、有機過酸化物、アゾ化合物、ベンゾイン化合物、ベンゾインエーテル化合物、アセトフェノン化合物、ベンゾピナコール等が挙げられ、ベンゾピナコールが好適に用いられる。例えば、有機過酸化物としては、カヤメックＲＴＭＡ、Ｍ、Ｒ、Ｌ、ＬＨ、ＳＰ-３０Ｃ、パーカドックスＣＨ−５０Ｌ、ＢＣ−ＦＦ、カドックスＢ−４０ＥＳ、パーカドックス１４、トリゴノックスＲＴＭ２２−７０Ｅ、２３−Ｃ７０、１２１、１２１−５０Ｅ、１２１−ＬＳ５０Ｅ、２１−ＬＳ５０Ｅ、４２、４２ＬＳ、カヤエステルＲＴＭＰ−７０、ＴＭＰＯ−７０、ＣＮＤ−Ｃ７０、ＯＯ−５０Ｅ、ＡＮ、カヤブチルＲＴＭＢ、パーカドックス１６、カヤカルボンＲＴＭＢＩＣ−７５、ＡＩＣ−７５（以上、化薬アクゾ株式会社製）、パーメックＲＴＭＮ、Ｈ、Ｓ、Ｆ、Ｄ、Ｇ、パーヘキサＲＴＭＨ、ＨＣ、パＴＭＨ、Ｃ、Ｖ、２２、ＭＣ、パーキュアーＲＴＭＡＨ、ＡＬ、ＨＢ、パーブチルＲＴＭＨ、Ｃ、ＮＤ、Ｌ、パークミルＲＴＭＨ、Ｄ、パーロイルＲＴＭＩＢ、ＩＰＰ、パーオクタＲＴＭＮＤ、（以上、日油株式会社製）等などが市販品として入手可能である。また、アゾ化合物としては、ＶＡ−０４４、Ｖ−７０、ＶＰＥ−０２０１、ＶＳＰ−１００１等（以上、和光純薬工業株式会社製）等が市販品として入手可能である。なお、本明細書中、上付きのＲＴＭは登録商標を意味する。
ベンゾピナコール系の熱ラジカル重合開始剤（ベンゾピナコールを化学的に修飾したものを含む）としては、ベンゾピナコール、１, ２−ジメトキシ−１，１, ２，２−テトラフェニルエタン、１, ２−ジエトキシ−１，１, ２，２−テトラフェニルエタン、１, ２−ジフェノキシ−１，１, ２，２−テトラフェニルエタン、１, ２−ジメトキシ−１，１, ２，２−テトラ（４−メチルフェニル）エタン、１, ２−ジフェノキシ−１，１, ２，２−テトラ（４−メトキシフェニル）エタン、１, ２−ビス（トリメチルシロキシ）−１，１, ２，２−テトラフェニルエタン、１, ２−ビス（トリエチルシロキシ）−１，１, ２，２−テトラフェニルエタン、１, ２−ビス（ｔ−ブチルジメチルシロキシ）−１，１, ２，２−テトラフェニルエタン、１−ヒドロキシ−２−トリメチルシロキシ−１，１, ２，２−テトラフェニルエタン、１−ヒドロキシ−２−トリエチルシロキシ−１，１, ２，２−テトラフェニルエタン、１−ヒドロキシ−２−ｔ−ブチルジメチルシロキシ−１，１, ２，２−テトラフェニルエタン等、が挙げられ、好ましくは１−ヒドロキシ−２−トリメチルシロキシ−１，１, ２，２−テトラフェニルエタン、１−ヒドロキシ−２−トリエチルシロキシ−１，１, ２，２−テトラフェニルエタン、１−ヒドロキシ−２−ｔ−ブチルジメチルシロキシ−１，１, ２，２−テトラフェニルエタン、１, ２−ビス（トリメチルシロキシ）−１，１, ２，２−テトラフェニルエタンであり、さらに好ましくは１−ヒドロキシ−２−トリメチルシロキシ−１，１, ２，２−テトラフェニルエタン、１, ２−ビス（トリメチルシロキシ）−１，１, ２，２−テトラフェニルエタンであり、特に好ましくは１, ２−ビス（トリメチルシロキシ）−１，１, ２，２−テトラフェニルエタンである。
上記ベンゾピナコールは東京化成工業株式会社、和光純薬工業株式会社等から市販されている。また、ベンゾピナコールのヒドロキシ基をエーテル化することは、周知の方法によって容易に合成可能である。また、ベンゾピナコールのヒドロキシ基をシリルエーテル化することは、対応するベンゾピナコールと各種シリル化剤をピリジン等の塩基性触媒下で加熱させる方法により合成して得ることができる。シリル化剤としては、一般に知られているトリメチルシリル化剤であるトリメチルクロロシラン（ＴＭＣＳ）、ヘキサメチルジシラザン（ＨＭＤＳ）、Ｎ,Ｏ−ビス（トリメチルシリル）トリフルオロアセトアミド(ＢＳＴＦＡ）やトリエチルシリル化剤としてトリエチルクロロシラン（ＴＥＣＳ）、ｔ−ブチルジメチルシリル化剤としてｔ−ブチルメチルシラン（ＴＢＭＳ）等が挙げられる。これらの試薬はシリコン誘導体メーカー等の市場から容易に入手することが出来る。シリル化剤の反応量としては対象化合物の水酸基１モルに対して１．０〜５．０倍モルが好ましい。さらに好ましくは１．５〜３．０倍モルである。１．０倍モルより少ないと反応効率が悪く、反応時間が長くなるため熱分解を促進してしまう。５．０倍モルより多いと回収の際に分離が悪くなったり、精製が困難になったりしてしまう。
The resin composition obtained by the production method of the present invention may contain a thermal radical polymerization initiator (a). This thermal radical polymerization initiator is not particularly limited as long as it is a compound that generates radicals by heating and initiates a chain polymerization reaction, but is not limited to organic peroxides, azo compounds, benzoin compounds, benzoin ether compounds, acetophenone compounds, benzopinacols, etc. And benzopinacol is preferably used. For example, examples of the organic peroxide include Kayamek RTM A, M, R, L, LH, SP-30C, Parkadox CH-50L, BC-FF, Kadox B-40ES, Parkadox 14, Trigonox RTM 22-70E, 23-C70, 121, 121-50E, 121-LS50E, 21-LS50E, 42, 42LS, Kaya Ester RTM P-70, TMPO-70, CND-C70, OO-50E, AN, Kayabutyl RTM B, Parkardox 16 , Kayacarbon RTM BIC-75, AIC-75 (manufactured by Kayaku Akzo Co., Ltd.), Permec RTM N, H, S, F, D, G, Perhexa RTM H, HC, Pat TMH, C, V, 22, MC, Percure RTM AH, AL, HB, Perbutyl RTM H, C, ND, L, Parkmi Le RTM H, D, Parroyl RTM IB, IPP, Per Octa RTM ND, (manufactured by NOF CORPORATION) and the like are available as commercial products. Moreover, as an azo compound, VA-044, V-70, VPE-0201, VSP-1001, etc. (above, Wako Pure Chemical Industries Ltd. make) etc. are available as a commercial item. In the present specification, the superscript RTM means a registered trademark.
Benzopinacol-based thermal radical polymerization initiators (including those obtained by chemically modifying benzopinacol) include benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2- Diethoxy-1,1,2,2-tetraphenylethane, 1,2-diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra (4- Methylphenyl) ethane, 1,2-diphenoxy-1,1,2,2-tetra (4-methoxyphenyl) ethane, 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane, 1,2-bis (triethylsiloxy) -1,1,2,2-tetraphenylethane, 1,2-bis (t-butyldimethylsiloxy) -1,1,2,2-tetraphenylethane, 1- Loxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-t-butyldimethyl Siloxy-1,1,2,2-tetraphenylethane and the like can be mentioned, preferably 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsiloxy -1,1,2,2-tetraphenylethane, 1-hydroxy-2-tert-butyldimethylsiloxy-1,1,2,2-tetraphenylethane, 1,2-bis (trimethylsiloxy) -1,1 , 2,2-tetraphenylethane, more preferably 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane, particularly preferably 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane is there.
The benzopinacol is commercially available from Tokyo Chemical Industry Co., Ltd., Wako Pure Chemical Industries, Ltd. Moreover, etherification of the hydroxy group of benzopinacol can be easily synthesized by a known method. Moreover, silyl etherification of the hydroxy group of benzopinacol can be obtained by synthesizing by a method in which the corresponding benzopinacol and various silylating agents are heated under a basic catalyst such as pyridine. Examples of silylating agents include trimethylchlorosilane (TMCS), hexamethyldisilazane (HMDS), N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA) and triethylsilylating agents, which are generally known trimethylsilylating agents. Examples of triethylchlorosilane (TECS) and t-butyldimethylsilylating agent include t-butylmethylsilane (TBMS). These reagents can be easily obtained from markets such as silicon derivative manufacturers. The reaction amount of the silylating agent is preferably 1.0 to 5.0 times mol for 1 mol of the hydroxyl group of the target compound. More preferably, it is 1.5-3.0 times mole. When the amount is less than 1.0 times mol, the reaction efficiency is poor and the reaction time is prolonged, so that thermal decomposition is promoted. When the amount is more than 5.0 times mol, separation may be deteriorated during collection or purification may be difficult.
熱ラジカル重合開始剤（ａ）は粒径を細かくし、均一に分散することが好ましい。その平均粒径は、大きすぎると狭ギャップの液晶表示セル製造時に上下ガラス基板を貼り合わせる際のギャップ形成が上手くできない等の不良要因となるため、５μｍ以下が好ましく、より好ましくは３μｍ以下である。また、際限なく細かくしても差し支えないが、通常下限は０．１μｍ程度である。粒径はレーザー回折・散乱式粒度分布測定器（乾式）（株式会社セイシン企業製；ＬＭＳ−３０）により測定できる。 The thermal radical polymerization initiator (a) preferably has a fine particle size and is uniformly dispersed. The average particle size is preferably 5 μm or less, more preferably 3 μm or less, because if the average particle size is too large, it becomes a cause of defects such as inability to successfully form a gap when the upper and lower glass substrates are bonded together during the production of a narrow gap liquid crystal display cell. . Moreover, although it does not matter even if it makes it infinitely small, usually a minimum is about 0.1 micrometer. The particle size can be measured by a laser diffraction / scattering particle size distribution analyzer (dry type) (manufactured by Seishin Enterprise Co., Ltd .; LMS-30).
熱ラジカル重合開始剤（ａ）の含有量としては、本発明で使用される樹脂組成物の総量を１００質量部とした場合、０．０００１〜１０質量部であることが好ましく、さらに好ましくは０．０００５〜５質量部であり、０．００１〜３質量部が特に好ましい。 The content of the thermal radical polymerization initiator (a) is preferably 0.0001 to 10 parts by mass, more preferably 0 when the total amount of the resin composition used in the present invention is 100 parts by mass. .0005 to 5 parts by mass, and 0.001 to 3 parts by mass is particularly preferable.
本願発明の製造方法に用いられるフィラー（ｂ）は、有機フィラー及び／又は無機フィラーを意味する。
有機フィラーとしては、例えばナイロン６、ナイロン１２、ナイロン６６等のポリアミド微粒子、テトラフルオロエチレン、フッ化ビニリデン等のフッ素系微粒子、ポリエチレン、ポリプロピレン等のオレフィン系微粒子、ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステル系微粒子、天然ゴム、イソプレンゴム、アクリルゴム等のゴム微粒子等が挙げられる。このうち好ましいものはゴム微粒子であって、例えば天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）、スチレン・ブタジエンゴム（ＳＢＲ）、ブチルゴム（ＩＩＲ）、二トリルゴム（ＮＢＲ）、エチレン・プロピレンゴム( ＥＰＭ、ＥＰ）、クロロプレンゴム（ＣＲ）、アクリルゴム（ＡＣＭ、ＡＮＭ）、クロロスルホン化ポリエチレンゴム（ＣＳＭ）、ウレタンゴム（ＰＵＲ）、シリコーンゴム（ＳＩ、ＳＲ）、フッ素ゴム（ＦＫＭ、ＦＰＭ）、多硫化ゴム（チオコール）などが挙げられる。これら固形成分（Ｉ）は２種以上を混合して用いても良い。これらのうち、好ましくは、シリコーンゴム、スチレンゴム、スチレンオレフィンゴム、アクリルゴムである。
The filler (b) used in the production method of the present invention means an organic filler and / or an inorganic filler.
Examples of the organic filler include polyamide fine particles such as nylon 6, nylon 12 and nylon 66, fluorine fine particles such as tetrafluoroethylene and vinylidene fluoride, olefin fine particles such as polyethylene and polypropylene, polyester such as polyethylene terephthalate and polyethylene naphthalate. Rubber fine particles such as system fine particles, natural rubber, isoprene rubber, and acrylic rubber. Among these, preferred are rubber fine particles such as natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), butyl rubber (IIR), nitrile rubber (NBR), ethylene.・ Propylene rubber (EPM, EP), chloroprene rubber (CR), acrylic rubber (ACM, ANM), chlorosulfonated polyethylene rubber (CSM), urethane rubber (PUR), silicone rubber (SI, SR), fluoro rubber (FKM) , FPM), polysulfide rubber (thiocol), and the like. These solid components (I) may be used as a mixture of two or more. Of these, silicone rubber, styrene rubber, styrene olefin rubber, and acrylic rubber are preferable.
また、上記アクリルゴムを使用する場合、２種類のアクリルゴムからなるコアシェル構造のアクリルゴムである場合が好ましく、特に好ましくはコア層がｎ−ブチルアクリレートであり、シェル層がメチルメタクリレートであるものが好ましい。これはゼフィアックＲＴＭＦ−３５１としてアイカ工業株式会社から販売されている。 Moreover, when using the said acrylic rubber, the case where it is the case of the acrylic rubber of the core shell structure which consists of two types of acrylic rubbers is preferable, Especially preferably, the core layer is n-butyl acrylate and the shell layer is methyl methacrylate. preferable. This is sold by Aika Industries as Zefiac RTM F-351.
上記無機フィラーの例としては、溶融シリカ、結晶シリカ、シリコンカーバイド、窒化珪素、窒化ホウ素、炭酸カルシウム、炭酸マグネシウム、硫酸バリウム、硫酸カルシウム、マイカ、タルク、クレー、アルミナ、酸化マグネシウム、酸化ジルコニウム、水酸化アルミニウム、水酸化マグネシウム、珪酸カルシウム、珪酸アルミニウム、珪酸リチウムアルミニウム、珪酸ジルコニウム、チタン酸バリウム、硝子繊維、炭素繊維、二硫化モリブデン、アスベスト等が挙げられ、好ましくは溶融シリカ、結晶シリカ、窒化珪素、窒化ホウ素、炭酸カルシウム、硫酸バリウム、硫酸カルシウム、マイカ、タルク、クレー、アルミナ、水酸化アルミニウム、珪酸カルシウム、珪酸アルミニウムであり、更に好ましくは溶融シリカ、結晶シリカ、アルミナ、タルクである。これら無機フィラーは２種以上を混合して用いても良い。
ただし、平均粒子径は上記数式（ＩＩ）を満たすもの、又は、解砕工程を経て、上記数式（ＩＩ）を満たすものとしたものに限られる。また、無機フィラーは様々の方法によって表面処理をされたものでも良いが、未処理のものが好ましい。
このフィラー（ｂ）としては、シリカ又はアルミナが好ましく、特に好ましくはフュームドシリカ、フュームドアルミナである。
フィラー（ｂ）の樹脂組成物中の含有量としては、本願発明の樹脂組成物の総量を１００質量部とした場合に、１〜２０質量部である場合が好ましく、２〜１５質量部である場合がより好ましく、３〜１０質量部である場合が更に好ましい。
なお、本願発明では、上記数式（ＩＩ）を満たす有機フィラー又は無機フィラーが存在すればその効果を奏する為、その他に数式（ＩＩ）を満たさない有機フィラー又は無機フィラーを添加しても良い。
Examples of the inorganic filler include fused silica, crystalline silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, water Aluminum oxide, magnesium hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc., preferably fused silica, crystalline silica, silicon nitride Boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, calcium silicate, aluminum silicate, more preferably fused silica, crystalline silica, aluminum Na, talc. These inorganic fillers may be used in combination of two or more.
However, the average particle size is limited to those satisfying the above formula (II) or those satisfying the above formula (II) through the crushing step. Further, the inorganic filler may be subjected to surface treatment by various methods, but untreated one is preferable.
The filler (b) is preferably silica or alumina, particularly preferably fumed silica or fumed alumina.
As content in the resin composition of a filler (b), when the total amount of the resin composition of this invention is 100 mass parts, the case where it is 1-20 mass parts is preferable, and it is 2-15 mass parts. The case is more preferable, and the case of 3 to 10 parts by mass is still more preferable.
In addition, in this invention, in order to show the effect, if the organic filler or inorganic filler which satisfy | fills said numerical formula (II) exists, you may add the organic filler or inorganic filler which does not satisfy | fill numerical formula (II) to others.
本願発明の製造方法で得られる樹脂組成物は、硬化性化合物（ｃ）を含有する。
この硬化性化合物（ｃ）は、光又は熱によって重合反応するものであれば特に限定されないが、（メタ）アクリロイル基を有する硬化性化合物である場合が特に好ましい。
（メタ）アクリロイル基を有する硬化性化合物は、例えば（メタ）アクリルエステル、エポキシ（メタ）アクリレート等が挙げられる。（メタ）アクリルエステルとしては、ベンジルメタクリレート、シクロヘキシルメタクリレート、グリセロールジメタクリレート、グリセロールトリアクリレート、ＥＯ変性グリセロールトリアクリレート、ペンタエリスリトールアクリレート、トリメチロールプロパントリアクリレート、トリス（アクリロキシエチル）イソシアヌレート、ジペンタエリスリトールヘキサアクリレート、フロログリシノールトリアクリレート等が挙げられる。エポキシ（メタ）アクリレートは、エポキシ樹脂と（メタ）アクリル酸との反応により公知の方法で得られる。原料となるエポキシ樹脂としては、特に限定されるものではないが、２官能以上のエポキシ樹脂が好ましく、例えばビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、ビスフェノールＦノボラック型エポキシ樹脂、脂環式エポキシ樹脂、脂肪族鎖状エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、ヒダントイン型エポキシ樹脂、イソシアヌレート型エポキシ樹脂、トリフェノールメタン骨格を有するフェノールノボラック型エポキシ樹脂、その他、カテコール、レゾルシノール等の二官能フェノール類のジグリシジルエーテル化物、二官能アルコール類のジグリシジルエーテル化物、およびそれらのハロゲン化物、水素添加物などが挙げられる。これらのうち液晶汚染性の観点から、レゾルシン骨格を有するエポキシ樹脂が好ましく、例えばレゾルシンジグリシジルエーテル等である。また、エポキシ基と（メタ）アクリロイル基との比率は限定されるものではなく、工程適合性及び液晶汚染性の観点から適切に選択される。
したがって、好ましい（メタ）アクリロイル基を有する硬化性化合物は、（メタ）アクリロイル基を有し、さらにレゾルシン骨格を有する硬化性化合物であり、例えば、レゾルシンジグリシジルエーテルのアクリル酸エステルやレゾルシンジグリシジルエーテルのメタクリル酸エステルである。
また、硬化性化合物（ｃ）の樹脂組成物中に占める含有率としては、樹脂組成物の総量を１００質量部とした場合に、３０〜９０質量部の範囲内であることが好ましく、さらに好ましくは４０〜８０質量部程度である。
The resin composition obtained by the production method of the present invention contains a curable compound (c).
The curable compound (c) is not particularly limited as long as it undergoes a polymerization reaction by light or heat, but is particularly preferably a curable compound having a (meth) acryloyl group.
Examples of the curable compound having a (meth) acryloyl group include (meth) acrylic ester and epoxy (meth) acrylate. (Meth) acrylic esters include benzyl methacrylate, cyclohexyl methacrylate, glycerol dimethacrylate, glycerol triacrylate, EO-modified glycerol triacrylate, pentaerythritol acrylate, trimethylolpropane triacrylate, tris (acryloxyethyl) isocyanurate, dipentaerythritol. Examples include hexaacrylate and phloroglucinol triacrylate. Epoxy (meth) acrylate is obtained by a known method by a reaction between an epoxy resin and (meth) acrylic acid. Although it does not specifically limit as an epoxy resin used as a raw material, An epoxy resin more than bifunctional is preferable, for example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a phenol novolac type epoxy resin , Cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin , Isocyanurate type epoxy resins, phenol novolac type epoxy resins having a triphenolmethane skeleton, and other difunctional phenolic diglycidyl esters such as catechol and resorcinol Ether compound, bi-functional alcohol diglycidyl ethers of, and their halides, and the like hydrogenated product. Among these, from the viewpoint of liquid crystal contamination, an epoxy resin having a resorcin skeleton is preferable, such as resorcin diglycidyl ether. Further, the ratio of the epoxy group to the (meth) acryloyl group is not limited, and is appropriately selected from the viewpoint of process compatibility and liquid crystal contamination.
Therefore, a preferable curable compound having a (meth) acryloyl group is a curable compound having a (meth) acryloyl group and further having a resorcin skeleton, such as an acrylic acid ester of resorcin diglycidyl ether or resorcin diglycidyl ether. Methacrylic acid ester.
The content of the curable compound (c) in the resin composition is preferably in the range of 30 to 90 parts by mass, more preferably 100 parts by mass when the total amount of the resin composition is 100 parts by mass. Is about 40 to 80 parts by mass.
上記（メタ）アクリロイル基を有する硬化性化合物中には、一分子中に（メタ）アクリロイル基を３個以上有する化合物を含有する場合が好ましい。一分子中に（メタ）アクリロイル基を３個以上有する化合物は、架橋速度（反応速度）が速いため、優れた差込耐性を実現できる。なお、この方法を用いた場合、熱ラジカル重合開始剤等の量を増やして、反応性を向上させる方法とは異なり、ハンドリング性にも優れる。
一分子中に（メタ）アクリロイル基を３個以上有する化合物としては、ＫＡＹＡＲＡＤＲＴＭＰＥＴ−３０、ＤＰＨＡ、ＤＰＣＡ−２０、ＤＰＣＡ−３０、ＤＰＣＡ−６０、ＤＰＣＡ−１２０、ＤＰＥＡ−１２、ＧＰＯ−３０３、ＴＭＰＴＡ、ＴＨＥ-３３０、ＴＰＡ−３２０、ＴＰＡ−３３０、Ｄ−３１０，Ｄ−３３０、ＲＰ−１０４０、ＵＸ−５０００、ＤＰＨＡ−４０Ｈ（以上、日本化薬株式会社製）、ＮＫエステルＲＴＭＡ−９３００、Ａ−９３００−１ＣＬ、Ａ−ＧＬＹ−９Ｅ、Ａ−ＧＬＹ−２０Ｅ、Ａ−ＴＭＭ−３、Ａ−ＴＭＭ−３ＬＭ−Ｎ、Ａ−ＴＭＰＴ、ＡＤ−ＴＭＰ、ＡＴＭ−３５Ｅ、Ａ−ＴＭＭＴ、Ａ−９５５０、Ａ−ＤＰＨ（以上、新中村化学工業株式会社）、ＳＲ２９５、ＳＲ３５０、ＳＲ３５５、ＳＲ３９９、ＳＲ４９４、ＣＤ５０１、ＳＲ５０２、ＣＤ９０２１、ＳＲ９０３５、ＳＲ９０４１（以上、サートマー社製）等を挙げることができる。これらのうち、モル平均分子量が８００以上である場合が好ましく、例えばＫＡＹＡＲＡＤＲＴＭＤＰＣＡ−２０、ＤＰＣＡ−３０、ＤＰＣＡ−６０、ＤＰＥＡ−１２が好ましい。また、分子内にＣ１−Ｃ４アルキレンオキサイド（−Ｏ−Ｒ−Ｏ−）を含有する硬化性化合物である場合が好ましく、ＫＡＹＡＲＡＤＲＴＭＤＰＥＡ−１２が特に好ましい。
The curable compound having a (meth) acryloyl group preferably contains a compound having 3 or more (meth) acryloyl groups in one molecule. Since a compound having three or more (meth) acryloyl groups in one molecule has a high crosslinking rate (reaction rate), excellent insertion resistance can be realized. In addition, when this method is used, it is excellent in handling property unlike the method of increasing the amount of the thermal radical polymerization initiator and the like to improve the reactivity.
As a compound having three or more (meth) acryloyl groups in one molecule, KAYARAD RTM PET-30, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DPEA-12, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, D-310, D-330, RP-1040, UX-5000, DPHA-40H (above, Nippon Kayaku Co., Ltd.), NK Ester RTM A-9300 A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3LM-N, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A -9550, A-DPH (above, Shin-Nakamura Chemical Co., Ltd.), SR295, SR350, SR355, SR399, S R494, CD501, SR502, CD9021, SR9035, SR9041 (above, manufactured by Sartomer) and the like. Among these, the case where a molar average molecular weight is 800 or more is preferable, for example, KAYARAD RTM DPCA-20, DPCA-30, DPCA-60, DPEA-12 are preferable. Moreover, the case where it is a curable compound containing C1-C4 alkylene oxide (—O—R—O—) in the molecule is preferable, and KAYARAD RTM DPEA-12 is particularly preferable.
本願発明の製造方法で得られる樹脂組成物は、熱硬化剤（ｄ）を含有しても良い。
本願発明の熱硬化剤（ｄ）は特に限定されるものではなく、多価アミン類、多価フェノール類、ヒドラジド化合物等を挙げることができるが、有機酸ヒドラジドが特に好適に用いられる。例えば、芳香族ヒドラジドであるサリチル酸ヒドラジド、安息香酸ヒドラジド、１−ナフトエ酸ヒドラジド、テレフタル酸ジヒドラジド、イソフタル酸ジヒドラジド、２，６−ナフトエ酸ジヒドラジド、２，６−ピリジンジヒドラジド、１，２，４−ベンゼントリヒドラジド、１，４，５，８−ナフトエ酸テトラヒドラジド、ピロメリット酸テトラヒドラジド等をあげることが出来る。また、脂肪族ヒドラジド化合物であれば、例えば、ホルムヒドラジド、アセトヒドラジド、プロピオン酸ヒドラジド、シュウ酸ジヒドラジド、マロン酸ジヒドラジド、コハク酸ジヒドラジド、グルタル酸ジヒドラジド、アジピン酸ジヒドラジド、ピメリン酸ジヒドラジド、セバシン酸ジヒドラジド、１，４−シクロヘキサンジヒドラジド、酒石酸ジヒドラジド、リンゴ酸ジヒドラジド、イミノジ酢酸ジヒドラジド、Ｎ，Ｎ’−ヘキサメチレンビスセミカルバジド、クエン酸トリヒドラジド、ニトリロ酢酸トリヒドラジド、シクロヘキサントリカルボン酸トリヒドラジド、１，３−ビス（ヒドラジノカルボノエチル）−５−イソプロピルヒダントイン等のヒダントイン骨格、好ましくはバリンヒダントイン骨格（ヒダントイン環の炭素原子がイソプロピル基で置換された骨格）を有するジヒドラジド化合物、トリス（１−ヒドラジノカルボニルメチル）イソシアヌレート、トリス（２−ヒドラジノカルボニルエチル）イソシアヌレート、トリス（２−ヒドラジノカルボニルエチル）イソシアヌレート、トリス（３−ヒドラジノカルボニルプロピル）イソシアヌレート、ビス（２−ヒドラジノカルボニルエチル）イソシアヌレート等をあげることができる。この熱硬化剤は、単独で用いても２種以上混合しても良い。硬化反応性と潜在性とのバランスから好ましくは、１，３−ビス（ヒドラジノカルボノエチル）−５−イソプロピルヒダントイン、イソフタル酸ジヒドラジド、マロン酸ジヒドラジド、アジピン酸ジヒドラジド、セバシン酸ジヒドラジド、トリス（１−ヒドラジノカルボニルメチル）イソシアヌレート、トリス（２−ヒドラジノカルボニルエチル）イソシアヌレート、トリス（３−ヒドラジノカルボニルプロピル）イソシアヌレートであり、特に好ましくは１，３−ビス（ヒドラジノカルボノエチル）−５−イソプロピルヒダントインである。かかる熱硬化剤を使用する場合の含有量としては、樹脂組成物の総量を１００質量部とした場合に、１〜３０質量部程度である。
The resin composition obtained by the production method of the present invention may contain a thermosetting agent (d).
The thermosetting agent (d) of the present invention is not particularly limited, and examples thereof include polyvalent amines, polyhydric phenols, hydrazide compounds, and the like, and organic acid hydrazides are particularly preferably used. For example, the aromatic hydrazide salicylic acid hydrazide, benzoic acid hydrazide, 1-naphthoic acid hydrazide, terephthalic acid dihydrazide, isophthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 2,6-pyridinedihydrazide, 1,2,4-benzene Examples include trihydrazide, 1,4,5,8-naphthoic acid tetrahydrazide, pyromellitic acid tetrahydrazide and the like. Examples of aliphatic hydrazide compounds include form hydrazide, acetohydrazide, propionic acid hydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, sebacic acid dihydrazide. 1,4-cyclohexanedihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, iminodiacetic acid dihydrazide, N, N'-hexamethylenebissemicarbazide, citric acid trihydrazide, nitriloacetic acid trihydrazide, cyclohexanetricarboxylic acid trihydrazide, 1,3-bis ( Hydantoin skeleton such as hydrazinocarbonoethyl) -5-isopropylhydantoin, preferably valine hydantoin skeleton (where the carbon atom of the hydantoin ring is iso Dihydrazide compounds having a skeleton substituted with a propyl group), tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (3-hydrazinocarbonylpropyl) isocyanurate, bis (2-hydrazinocarbonylethyl) isocyanurate and the like can be mentioned. These thermosetting agents may be used alone or in combination of two or more. Preferably, 1,3-bis (hydrazinocarbonoethyl) -5-isopropylhydantoin, isophthalic acid dihydrazide, malonic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, tris (1) -Hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) isocyanurate, tris (3-hydrazinocarbonylpropyl) isocyanurate, particularly preferably 1,3-bis (hydrazinocarbonoethyl) -5-Isopropylhydantoin. When the thermosetting agent is used, the content is about 1 to 30 parts by mass when the total amount of the resin composition is 100 parts by mass.
本願発明の製造方法で得られる樹脂組成物は、シランカップリング剤（ｅ）を用いて、接着強度向上や耐湿信頼性向上を図ることができる。シランカップリング剤としては、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン、Ｎ−（２−アミノエチル）３−アミノプロピルメチルジメトキシシラン、Ｎ−（２−アミノエチル）３−アミノプロピルメチルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−メルカプトプロピルトリメトキシシラン、ビニルトリメトキシシラン、Ｎ−（２−（ビニルベンジルアミノ）エチル）３−アミノプロピルトリメトキシシラン塩酸塩、３−メタクリロキシプロピルトリメトキシシラン、３−クロロプロピルメチルジメトキシシラン、３−クロロプロピルトリメトキシシラン等が挙げられる。これらのシランカップリング剤はＫＢＭシリーズ、ＫＢＥシリーズ等として信越化学工業株式会社等によって販売されているため、市場から容易に入手可能である。シランカップリング剤の樹脂組成物に占める含有量は、本発明で使用される樹脂組成物の全体を１００質量部とした場合、０．０５〜３質量部が好適である。 The resin composition obtained by the production method of the present invention can improve adhesion strength and moisture resistance reliability using the silane coupling agent (e). As silane coupling agents, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3- Aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-black Propyl methyl dimethoxy silane, 3-chloropropyl trimethoxy silane, and the like. Since these silane coupling agents are sold by Shin-Etsu Chemical Co., Ltd. as KBM series, KBE series, etc., they are easily available from the market. The content of the silane coupling agent in the resin composition is preferably 0.05 to 3 parts by mass when the entire resin composition used in the present invention is 100 parts by mass.
本願発明の製造方法で得られる樹脂組成物は、エポキシ樹脂（ｆ）を添加して、更なる接着強度の向上を図ることができる。用いられるエポキシ樹脂としては、特に限定されるものではないが、２官能以上のエポキシ樹脂が好ましく、例えばビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、ビスフェノールＦノボラック型エポキシ樹脂、脂環式エポキシ樹脂、脂肪族鎖状エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、ヒダントイン型エポキシ樹脂、イソシアヌレート型エポキシ樹脂、トリフェノールメタン骨格を有するフェノールノボラック型エポキシ樹脂、その他、二官能フェノール類のジグリシジルエーテル化物、二官能アルコール類のジグリシジルエーテル化物、およびそれらのハロゲン化物、水素添加物などが挙げられる。これらのうち液晶汚染性の観点より好ましいのはビスフェノール型エポキシ樹脂、ノボラック型エポキシ樹脂である。エポキシ基を有する硬化性樹脂の樹脂組成物中に占める含有量は、樹脂組成物の総量を１００質量部とした場合に、１〜３０質量部程度である。 The resin composition obtained by the production method of the present invention can be further improved in adhesive strength by adding the epoxy resin (f). The epoxy resin used is not particularly limited, but a bifunctional or higher functional epoxy resin is preferable. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, Cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, Isocyanurate type epoxy resins, phenol novolac type epoxy resins having a triphenolmethane skeleton, other diglycidyl ethers of difunctional phenols, difunctional alcohols Diglycidyl ether compound, and their halides, and the like hydrogenated product. Among these, bisphenol type epoxy resin and novolac type epoxy resin are preferable from the viewpoint of liquid crystal contamination. The content of the curable resin having an epoxy group in the resin composition is about 1 to 30 parts by mass when the total amount of the resin composition is 100 parts by mass.
本発明の製造方法で得られる樹脂組成物は上記成分及び必要な場合に含有される成分以外にも、例えば光重合開始剤、ラジカル重合防止剤、硬化促進剤、顔料、レベリング剤、消泡剤、溶剤などを含有するものであってもよい。 The resin composition obtained by the production method of the present invention includes, for example, a photopolymerization initiator, a radical polymerization inhibitor, a curing accelerator, a pigment, a leveling agent, and an antifoaming agent in addition to the above components and components contained when necessary. Further, it may contain a solvent or the like.
上記硬化促進剤は特に限定されるものではなく、有機酸やイミダゾール等を挙げることができる。
有機酸としては、有機カルボン酸や有機リン酸等が挙げられるが、有機カルボン酸である場合が好ましい。具体的には、フタル酸、イソフタル酸、テレフタル酸、トリメリット酸、ベンゾフェノンテトラカルボン酸、フランジカルボン酸等の芳香族カルボン酸、コハク酸、アジピン酸、ドデカン二酸、セバシン酸、チオジプロピオン酸、シクロヘキサンジカルボン酸、トリス（２−カルボキシメチル）イソシアヌレート、トリス（２−カルボキシエチル）イソシアヌレート、トリス（２−カルボキシプロピル）イソシアヌレート、ビス（２−カルボキシエチル）イソシアヌレート等を挙げることができる。
また、イミダゾール化合物としては、２−メチルイミダゾール、２−フェニルイミダゾール、２−ウンデシルイミダゾール、２−ヘプタデシルイミダゾール、２−フェニル−４−メチルイミダゾール、１−ベンジル−２−フェニルイミダゾール、１−ベンジル−２−メチルイミダゾール、１−シアノエチル−２−メチルイミダゾール、１−シアノエチル−２−フェニルイミダゾール、１−シアノエチル−２−ウンデシルイミダゾール、２，４−ジアミノ−６（２’−メチルイミダゾール（１’））エチル−ｓ−トリアジン、２，４−ジアミノ−６（２’−ウンデシルイミダゾール（１’））エチル−ｓ−トリアジン、２ ，４−ジアミノ−６（２ ’−エチル−４−メチルイミダゾール（１’））エチル−ｓ−トリアジン、２，４− ジアミノ−６（２’−メチルイミダゾール（１ ’））エチル−ｓ−トリアジン・イソシアヌル酸付加物、２−メチルイミダゾールイソシアヌル酸の２：３付加物、２−フェニルイミダゾールイソシアヌル酸付加物、２−フェニル−３，５−ジヒドロキシメチルイミダゾール、２−フェニル−４−ヒドロキシメチル−５−メチルイミダゾール、１−シアノエチル−２−フェニル−３，５−ジシアノエトキシメチルイミダゾール等が挙げられる。
硬化促進剤を使用する場合には、樹脂組成物の総量を１００質量部とした場合に、通常０．１〜１０質量％、好ましくは１〜５質量％である。
The said hardening accelerator is not specifically limited, An organic acid, an imidazole, etc. can be mentioned.
Examples of the organic acid include organic carboxylic acids and organic phosphoric acids, but organic carboxylic acids are preferred. Specifically, aromatic carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, benzophenone tetracarboxylic acid, furandicarboxylic acid, succinic acid, adipic acid, dodecanedioic acid, sebacic acid, thiodipropionic acid , Cyclohexanedicarboxylic acid, tris (2-carboxymethyl) isocyanurate, tris (2-carboxyethyl) isocyanurate, tris (2-carboxypropyl) isocyanurate, bis (2-carboxyethyl) isocyanurate and the like. .
Examples of imidazole compounds include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, and 1-benzyl. 2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2′-methylimidazole (1 ′ )) Ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl-4-methylimidazole) (1 ′)) Ethyl-s-triazine, 2,4-diamino-6 (2′- Methylimidazole (1 ′)) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethyl Examples include imidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, and 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole.
When using a hardening accelerator, when the total amount of a resin composition shall be 100 mass parts, it is 0.1-10 mass% normally, Preferably it is 1-5 mass%.
上記光重合開始剤としては、紫外線や可視光の照射によって、ラジカルや酸を発生し、連鎖重合反応を開始させる化合物であれば特に限定されないが、例えば、ベンジルジメチルケタール、１−ヒドロキシシクロヘキシルフェニルケトン、ジエチルチオキサントン、ベンゾフェノン、２−エチルアンスラキノン、２−ヒドロキシ−２−メチルプロピオフェノン、２−メチル−〔４−（メチルチオ）フェニル〕−２−モルフォリノ−１−プロパン、２，４，６−トリメチルベンゾイルジフェニルホスヒンオキサイド、カンファーキノン、９−フルオレノン、ジフェニルジスルヒド等を挙げることができる。具体的には、ＩＲＧＡＣＵＲＥＲＴＭ ６５１、１８４、２９５９、１２７、９０７、３９６、３７９ＥＧ、８１９、７８４、７５４、５００、ＯＸＥ０１、ＯＸＥ０２、ＤＡＲＯＣＵＲＥＲＴＭ１１７３、ＬＵＣＩＲＩＮＲＴＭ ＴＰＯ（いずれもＢＡＳＦ社製）、セイクオールＲＴＭＺ、ＢＺ、ＢＥＥ、ＢＩＰ、ＢＢＩ（いずれも精工化学株式会社製）等を挙げることができる。
また、液晶汚染性の観点から、分子内に（メタ）アクリル基を有するものを使用する事が好ましく、例えば２−メタクリロイルオキシエチルイソシアネートと１−[４−（２−ヒドロキシエトキシ）−フェニル]−２−ヒドロキシ−２メチル−１−プロパン−１−オンとの反応生成物が好適に用いられる。この化合物は国際公開第２００６／０２７９８２号記載の方法にて製造して得ることができる。
光重合開始剤を用いる場合の樹脂組成物総量中の含有率は、通常０．００１〜３質量％、好ましくは０．００２〜２質量％である。
The photopolymerization initiator is not particularly limited as long as it is a compound that generates radicals or acids upon irradiation with ultraviolet rays or visible light, and initiates a chain polymerization reaction. For example, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone , Diethylthioxanthone, benzophenone, 2-ethylanthraquinone, 2-hydroxy-2-methylpropiophenone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propane, 2,4,6- Examples thereof include trimethylbenzoyldiphenylphosphine oxide, camphorquinone, 9-fluorenone, diphenyldisulfide and the like. Specifically, IRGACURE RTM 651, 184, 2959, 127, 907, 396, 379EG, 819, 784, 754, 500, OXE01, OXE02, DAROCURE RTM 1173, LUCIRIN RTM TPO (both manufactured by BASF), Seikol RTM Z, BZ, BEE, BIP, BBI (all of which are manufactured by Seiko Chemical Co., Ltd.) and the like.
Moreover, it is preferable to use what has a (meth) acryl group in a molecule | numerator from a liquid crystal contamination viewpoint, for example, 2-methacryloyloxyethyl isocyanate and 1- [4- (2-hydroxyethoxy) -phenyl]- The reaction product with 2-hydroxy-2methyl-1-propan-1-one is preferably used. This compound can be obtained by the method described in International Publication No. 2006/027982.
The content of the resin composition in the total amount of the photopolymerization initiator is usually 0.001 to 3% by mass, preferably 0.002 to 2% by mass.
上記ラジカル重合防止剤としては、光重合開始剤や熱ラジカル重合開始剤等から発生するラジカルと反応して重合を防止する化合物であれば特に限定されるものではなく、キノン系、ピペリジン系、ヒンダードフェノール系、ニトロソ系等を用いることができる。具体的には、ナフトキノン、２−ヒドロキシナフトキノン、２−メチルナフトキノン、２−メトキシナフトキノン、２，２，６，６，−テトラメチルピペリジン−１−オキシル、２，２，６，６，−テトラメチル−４−ヒドロキシピペリジン−１−オキシル、２，２，６，６，−テトラメチル−４−メトキシピペリジン−１−オキシル、２，２，６，６，−テトラメチル−４−フェノキシピペリジン−１−オキシル、ハイドロキノン、２−メチルハイドロキノン、２−メトキシハイドロキノン、パラベンゾキノン、ブチル化ヒドロキシアニソール、２，６−ジ−ｔ−ブチル−４−エチルフェノール、２，６−ジ−ｔ−ブチルクレゾール、ステアリルβ−（３，５−ジｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、２，２’−メチレンビス（４−エチル−６−ｔ−ブチルフェノール）、４，４’−チオビス−３−メチル−６−ｔ−ブチルフェノール）、４，４’−ブチリデンビス（３−メチル−６−ｔ−ブチルフェノール）、３，９−ビス[１，１−ジメチル−２−[β―（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ]エチル]、２，４，８，１０−テトラオキサスピロ[５，５]ウンデカン、テトラキス−[メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニルプロピオネート）メタン、１，３，５−トリス（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシベンジル）−ｓｅｃ−トリアジン−２，４，６−（１Ｈ，３Ｈ，５Ｈ）トリオン、パラメトキシフェノール、４−メトキシ−１−ナフトール、チオジフェニルアミン、Ｎ−ニトロソフェニルヒドロキシアミンのアルミニウム塩、商品名アデカスタブＬＡ−８１、商品名アデカスタブＬＡ−８２（株式会社アデカ製）等が挙げられるが、これらに限定されるものではない。これらのうちナフトキノン系、ハイドロキノン系、ニトロソ系ピペラジン系のラジカル重合防止剤が好ましく、ナフトキノン、２−ヒドロキシナフトキノン、ハイドロキノン、２，６−ジ−ｔｅｒｔ−ブチル−Ｐ−クレゾール、ポリストップ７３００Ｐ（伯東株式会社製）が更に好ましく、ポリストップ７３００Ｐ（伯東株式会社製）が最も好ましい。
ラジカル重合防止剤は、成分（ｃ）を合成する際に添加する方法や、樹脂組成物の製造時において成分（ｃ）に溶解させる方法があるが、より有効な効果を得る為には樹脂組成物の製造時において成分（ｃ）に溶解させるほうが好ましい。
ラジカル重合防止剤の含有量としては本発明の樹脂組成物総量中、０．０００１〜１質量％が好ましく、０．００１〜０．５質量％が更に好ましく、０．０１〜０．２質量％が特に好ましい。
The radical polymerization inhibitor is not particularly limited as long as it is a compound that prevents polymerization by reacting with radicals generated from a photopolymerization initiator, a thermal radical polymerization initiator, etc., and is not limited to quinone, piperidine, hinders. A dophenol type, a nitroso type, etc. can be used. Specifically, naphthoquinone, 2-hydroxynaphthoquinone, 2-methylnaphthoquinone, 2-methoxynaphthoquinone, 2,2,6,6, -tetramethylpiperidine-1-oxyl, 2,2,6,6, -tetramethyl -4-hydroxypiperidine-1-oxyl, 2,2,6,6, -tetramethyl-4-methoxypiperidine-1-oxyl, 2,2,6,6, -tetramethyl-4-phenoxypiperidine-1- Oxyl, hydroquinone, 2-methylhydroquinone, 2-methoxyhydroquinone, parabenzoquinone, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butylcresol, stearyl β -(3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylene (4-ethyl-6-tert-butylphenol), 4,4′-thiobis-3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3 , 9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl], 2,4,8,10-tetraoxaspiro [ 5,5] undecane, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenylpropionate) methane, 1,3,5-tris (3 ′, 5′- Di-t-butyl-4′-hydroxybenzyl) -sec-triazine-2,4,6- (1H, 3H, 5H) trione, paramethoxyphenol, 4-methoxy-1-naphthol, thiodiphenylamine, N-nitroso Examples include, but are not limited to, an aluminum salt of phenylhydroxyamine, trade name ADK STAB LA-81, trade name ADK STAB LA-82 (manufactured by Adeka Corporation), and the like. Of these, naphthoquinone, hydroquinone, and nitroso piperazine radical polymerization inhibitors are preferred, and naphthoquinone, 2-hydroxynaphthoquinone, hydroquinone, 2,6-di-tert-butyl-P-cresol, Polystop 7300P (Hakuto Co., Ltd.) Company-made) is more preferred, and Polystop 7300P (made by Hakuto Co., Ltd.) is most preferred.
The radical polymerization inhibitor has a method of adding when synthesizing the component (c) and a method of dissolving in the component (c) at the time of production of the resin composition, but in order to obtain a more effective effect, the resin composition It is preferable to dissolve in the component (c) during the production of the product.
The content of the radical polymerization inhibitor is preferably 0.0001 to 1% by mass, more preferably 0.001 to 0.5% by mass, and 0.01 to 0.2% by mass in the total amount of the resin composition of the present invention. Is particularly preferred.
本発明の製造方法によって得られる樹脂組成物は、電子部品用、特に狭ギャップが要求される電子部品用とし、好適に用いられる。狭ギャップが要求される電子部品としては、例えば液晶表示セルを挙げることができる。
液晶表示セルは、基板に所定の電極を形成した一対の基板を所定の間隔に対向配置し、周囲を本発明の樹脂組成物でシールし、その間隙に液晶が封入されたものである。封入される液晶の種類は特に限定されない。ここで、基板とはガラス、石英、プラスチック、シリコン等からなる少なくとも一方に光透過性がある組み合わせの基板から構成される。その製法としては、本発明で得られる樹脂組成物に、グラスファイバー等のスペーサー（間隙制御材）を添加後、該一対の基板の一方にディスペンサー、またはスクリーン印刷装置等を用いて該樹脂組成物を塗布した後、必要に応じて、８０〜１２０℃で仮硬化を行う。その後、該樹脂組成物の堰の内側に液晶を滴下し、真空中にてもう一方のガラス基板を重ね合わせ、ギャップ出しを行う。ギャップ形成後、必要に応じて１０００ｍＪ／ｃｍ２〜６０００ｍＪ／ｃｍ２の紫外線を照射し、その後９０〜１３０℃で１〜２時間硬化することにより本発明の液晶表示セルを得ることができる。このようにして得られた液晶表示セルは、液晶汚染による表示不良が無く、接着性、耐湿信頼性に優れたものである。スペーサとしては、例えばグラスファイバー、シリカビーズ、ポリマービーズ等があげられる。その直径は、目的に応じ異なるが、通常２〜８μｍ、好ましくは４〜７μｍである。その使用量は、本発明の樹脂組成物１００質量％に対し通常０．１〜４質量％、好ましくは０．５〜２質量％、更に、好ましくは０．９〜１．５質量％程度である。
The resin composition obtained by the production method of the present invention is suitably used for electronic parts, particularly for electronic parts that require a narrow gap. As an electronic component requiring a narrow gap, for example, a liquid crystal display cell can be cited.
In the liquid crystal display cell, a pair of substrates each having a predetermined electrode formed on a substrate are arranged to face each other at a predetermined interval, the periphery is sealed with the resin composition of the present invention, and the liquid crystal is sealed in the gap. The kind of liquid crystal to be sealed is not particularly limited. Here, the substrate is composed of a combination of substrates made of at least one of glass, quartz, plastic, silicon, etc. and having light transmission properties. As the production method, after adding a spacer (gap control material) such as glass fiber to the resin composition obtained in the present invention, the resin composition is used on one of the pair of substrates by using a dispenser, a screen printing apparatus or the like. After applying, a temporary curing is performed at 80 to 120 ° C. as necessary. Thereafter, liquid crystal is dropped inside the weir of the resin composition, the other glass substrate is overlaid in a vacuum, and a gap is formed. After gap formation, as required by irradiation with ultraviolet rays of 1000mJ / cm 2 ~6000mJ / cm 2 , it can then obtain a liquid crystal display cell of the present invention by curing for 1-2 hours at 90 to 130 ° C.. The liquid crystal display cell thus obtained does not have a display defect due to liquid crystal contamination, and has excellent adhesion and moisture resistance reliability. Examples of the spacer include glass fiber, silica beads, and polymer beads. The diameter varies depending on the purpose, but is usually 2 to 8 μm, preferably 4 to 7 μm. The amount used is usually 0.1 to 4% by mass, preferably 0.5 to 2% by mass, more preferably about 0.9 to 1.5% by mass with respect to 100% by mass of the resin composition of the present invention. is there.
本発明の樹脂組成物の製造方法は例えば次のような方法が挙げられる。まず、成分（ｃ）（複数の場合は熱混合を行い、冷却する）に必要に応じ、成分（ｆ）を溶解する。次いで事前に複合化した成分（ａ）、（ｂ）、また必要に応じて、成分（ｄ）、（ｅ）、硬化促進剤、消泡剤、レベリング剤、溶剤等を添加し、公知の混合装置、例えば２本ロール、３本ロール等により均一に混合し、金属メッシュにて濾過する。 Examples of the method for producing the resin composition of the present invention include the following methods. First, if necessary, the component (f) is dissolved in the component (c) (in a plurality of cases, heat mixing is performed and cooling is performed). Next, components (a) and (b) combined in advance, and components (d) and (e), a curing accelerator, an antifoaming agent, a leveling agent, a solvent, etc. are added as necessary, and known mixing Mix uniformly with an apparatus, for example, two rolls, three rolls, etc., and filter with a metal mesh.
本発明の製造方法によって得られる樹脂組成物は、保存安定性が良好な為、ディスペンスやスクリーン印刷といった塗布作業性に優れ、安定した液晶表示セルの作成が可能である。また、構成成分の液晶への溶出も極めて少なく、液晶表示セルの表示不良を低減することが可能である。従って、本発明の樹脂組成物を用いることにより、信頼性に優れる液晶表示セルを作成することが可能である。また、本発明の樹脂組成物を用いて作成した液晶表示セルは、電圧保持率が高く、イオン密度が低いという液晶表示セルとして必要な特性も充足される。 Since the resin composition obtained by the production method of the present invention has good storage stability, it is excellent in coating workability such as dispensing and screen printing, and a stable liquid crystal display cell can be produced. Further, the elution of the constituent components into the liquid crystal is extremely small, and display defects of the liquid crystal display cell can be reduced. Therefore, by using the resin composition of the present invention, a liquid crystal display cell having excellent reliability can be produced. Moreover, the liquid crystal display cell produced using the resin composition of the present invention satisfies the characteristics required for a liquid crystal display cell that has a high voltage holding ratio and a low ion density.
本発明の製造方法によって得られる樹脂組成物は、液晶の差し込みへの耐性が高い為、熱のみによる液晶滴下工法への適用も可能であり、生産タクト等の観点から、より好ましい。 Since the resin composition obtained by the production method of the present invention has high resistance to liquid crystal insertion, it can be applied to a liquid crystal dropping method using only heat, and is more preferable from the viewpoint of production tact and the like.
以下、実験例、実施例により本発明を更に詳細に説明するが、本発明は実施例に限定されるものではない。尚、特別の記載のない限り、本文中「部」及び「％」とあるのは質量基準である。 EXAMPLES Hereinafter, although an Example and an Example demonstrate this invention further in detail, this invention is not limited to an Example. Unless otherwise specified, “part” and “%” in the text are based on mass.
［合成例１］
［レゾルシンジグリシジルエーテルのエポキシアクリレートの合成］
レゾルシンジグリシジルエーテル１８１．２ｇ（ナガセケムテックス株式会社製）をトルエン２６６．８ｇに溶解し、これに重合禁止剤としてジブチルヒドロキシトルエン０．８ｇを加え、６０℃まで昇温した。その後、エポキシ基の１００％当量のアクリル酸１１７．５ｇを加え更に８０℃まで昇温し、これに反応触媒であるトリメチルアンモニウムクロライド０．６ｇを添加して、９８℃で約３０時間攪拌し、反応液を得た。この反応液を水洗し、トルエンを留去することにより、目的とするレゾルシンジグリシジルエーテルのエポキシアクリレート２９３ｇを得た。
[Synthesis Example 1]
[Synthesis of Resorcin Diglycidyl Ether Epoxy Acrylate]
Resorcin diglycidyl ether 181.2 g (manufactured by Nagase ChemteX Corporation) was dissolved in 266.8 g of toluene, and 0.8 g of dibutylhydroxytoluene was added thereto as a polymerization inhibitor, and the temperature was raised to 60 ° C. Thereafter, 117.5 g of acrylic acid with 100% equivalent of epoxy group was added and the temperature was further raised to 80 ° C., 0.6 g of trimethylammonium chloride as a reaction catalyst was added thereto, and the mixture was stirred at 98 ° C. for about 30 hours, A reaction solution was obtained. This reaction solution was washed with water, and toluene was distilled off to obtain 293 g of the desired resorcin diglycidyl ether epoxy acrylate.
［製造例１］
［複合化微粒子の製造］
ノビルタＮＯＢ−１３０（ホソカワミクロン株式会社製）にＶ−７０（和光純薬工業株式会社製、２，２’-アゾビス（４−メトキシ−２，４−ジメチルバレロニトリル）、ジェットミルで平均粒径１．８μｍに微粉砕したもの）１００．０ｇとアエロジルＯＸ−５０（日本アエロジル株式会社製、平均粒子径８０ｎｍ）２０．０ｇを投入し、ロータ回転数６０００ｒｐｍで１２０分間運転することにより、目的とする複合化微粒子１１７．２ｇを得た。複合化されていることは、レーザー回折・散乱式粒度分布測定器（乾式）（株式会社セイシン企業製；ＬＭＳ−３０）により、ＯＸ−５０由来の１μｍ以下の微小ピークが消失したことにより確認した。
[Production Example 1]
[Production of composite fine particles]
Novirta NOB-130 (manufactured by Hosokawa Micron Corporation) and V-70 (manufactured by Wako Pure Chemical Industries, Ltd., 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), average particle diameter of 1 with a jet mill 100.0 g) and Aerosil OX-50 (manufactured by Nippon Aerosil Co., Ltd., average particle size 80 nm) 20.0 g are charged and operated at a rotor speed of 6000 rpm for 120 minutes. 117.2 g of composite fine particles were obtained. It was confirmed by the laser diffraction / scattering particle size distribution measuring instrument (dry type) (manufactured by Seishin Enterprise Co., Ltd .; LMS-30) that a minute peak of 1 μm or less derived from OX-50 disappeared. .
[実施例１、比較例１〜４]
下記表１に示す割合で硬化性化合物（ｃ）、エポキシ樹脂（ｆ）、光重合開始剤、を９０℃で加熱溶解させた後、室温まで冷却し、熱ラジカル重合開始剤（ａ）、フィラー（ｂ）、シランカップリング剤（ｅ）、熱硬化剤（ｄ）、硬化促進剤を添加し、攪拌した後、３本ロールミルにて分散させ、金属メッシュ（６３５メッシュ）で濾過し、樹脂組成物実施例１、比較例１〜３を調製した。
なお、実施例１は製造例１に記載の複合化微粒子を使用した。
また比較例１は、事前の複合化をせず、表１に記載したとおりの配合を行った。
[Example 1, Comparative Examples 1 to 4]
After the curable compound (c), the epoxy resin (f), and the photopolymerization initiator are heated and dissolved at 90 ° C. in the proportions shown in Table 1 below, the solution is cooled to room temperature, and the thermal radical polymerization initiator (a), filler (B), a silane coupling agent (e), a thermosetting agent (d), and a curing accelerator are added and stirred, and then dispersed with a three-roll mill, filtered through a metal mesh (635 mesh), and a resin composition Example 1 and Comparative Examples 1-3 were prepared.
In Example 1, the composite fine particles described in Production Example 1 were used.
Moreover, the comparative example 1 performed the mixing | blending as described in Table 1 without carrying out prior compounding.
評価試験は下記の方法で実施した。 The evaluation test was carried out by the following method.
（保存安定性評価）
得られた樹脂組成物１５ｇに５μｍのスペーサＰＦ−５０Ｓ（日本電気硝子株式会社製）０．１５ｇを混ぜた後、自転５００ｒｐｍ、公転１５００ｒｐｍで５分間真空撹拌脱泡した。真空撹拌脱泡装置としては、真空撹拌脱泡ミキサーＶＭＸ−３６０Ｋ（株式会社ＥＭＥ製）を用いた。これを２５℃における粘度変化を測定した。２５℃５０ＲＨ％の条件下で７２時間放置した後の粘度測定を行い、初期粘度に対する粘度増加率を表１に示す。粘度はＥ型粘度計（東機産業株式会社製）を用いて測定した。
(Storage stability evaluation)
After mixing 0.15 g of 5 μm spacer PF-50S (manufactured by Nippon Electric Glass Co., Ltd.) with 15 g of the obtained resin composition, the mixture was degassed by vacuum stirring at 500 rpm for rotation and 1500 rpm for 5 minutes. As a vacuum stirring and defoaming apparatus, a vacuum stirring and defoaming mixer VMX-360K (manufactured by EME Co., Ltd.) was used. The viscosity change at 25 ° C. was measured. Viscosity measurement was performed after standing for 72 hours at 25 ° C. and 50 RH%, and Table 1 shows the rate of increase in viscosity relative to the initial viscosity. The viscosity was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.).
（評価用液晶セルの作成）
透明電極付き基板に配向膜液（ＰＩＡ−５５４０−０５Ａ；チッソ株式会社製）を塗布、焼成し、ラビング処理を施した。この基板に得られた樹脂組成物を貼り合せ後の線幅が１ｍｍとなるようにメインシールおよびダミーシールをディスペンスし、次いで液晶（ＪＣ−５０１５ＬＡ;チッソ株式会社製）の微小滴をシールパターンの枠内に滴下した。更にもう一枚のラビング処理済み基板に面内スペーサ（ナトコスペーサＫＳＥＢ−５２５Ｆ；ナトコ株式会社製；貼り合せ後のギャップ幅５μｍ）を散布、熱固着し、貼り合せ装置を用いて真空中で先の液晶滴下済み基板と貼り合せた。大気開放してギャップ形成した後、シールパターン枠内のみマスクをしてＵＶ照射機により５０ｍＪ／ｃｍ２の紫外線を照射後、オーブンに投入して１２０℃１時間熱硬化させ評価用液晶テストセルを作成した。
(Creation of liquid crystal cell for evaluation)
An alignment film solution (PIA-5540-05A; manufactured by Chisso Corporation) was applied to a substrate with a transparent electrode, baked, and rubbed. The main seal and the dummy seal are dispensed so that the line width after bonding the resin composition obtained on this substrate becomes 1 mm, and then a fine droplet of liquid crystal (JC-5015LA; manufactured by Chisso Corporation) is applied to the seal pattern. It was dripped in the frame. Furthermore, an in-plane spacer (NATOCO SPACER KSEB-525F; manufactured by NATCO; gap width of 5 μm after bonding) is sprayed and thermally fixed on another rubbing-treated substrate, and the substrate is first vacuumed using a bonding apparatus. It was bonded to a liquid crystal dripped substrate. After forming the gap by opening to the atmosphere, masking only the inside of the seal pattern frame and irradiating with 50 mJ / cm 2 of ultraviolet rays with a UV irradiator, putting it in an oven and thermosetting it at 120 ° C. for 1 hour to make a liquid crystal test cell for evaluation Created.
作成した評価用液晶セルのシールの耐差込み性およびシール近傍の液晶配向乱れを偏光顕微鏡にて観察し、シール近傍の液晶配向について以下に示す基準に従って評価を行った。結果を表１に示す。 The insertion resistance of the seal of the prepared liquid crystal cell for evaluation and the liquid crystal alignment disorder near the seal were observed with a polarizing microscope, and the liquid crystal alignment near the seal was evaluated according to the following criteria. The results are shown in Table 1.
[シール近傍の液晶配向の評価]
◎：液晶の配向乱れがシールから０．２ｍｍ未満である。
○：液晶の配向乱れがシールから０．２ｍｍ以上０．４ｍｍ未満である。
△：液晶の配向乱れがシールから０．４ｍｍ以上０．６ｍｍ未満である。
×：液晶の配向乱れがシールから０．６ｍｍ以上である。
[Evaluation of liquid crystal alignment near the seal]
A: The alignment disorder of the liquid crystal is less than 0.2 mm from the seal.
○: The alignment disorder of the liquid crystal is 0.2 mm or more and less than 0.4 mm from the seal.
Δ: The alignment disorder of the liquid crystal is 0.4 mm or more and less than 0.6 mm from the seal.
X: The alignment disorder of the liquid crystal is 0.6 mm or more from the seal.
表１の結果より、粒子を複合化していない比較例１は、保存安定性に劣る結果を示した。また、フィラー（ｂ）を含有しない比較例２、３は保存安定性に不具合を生じており、比較例４は保存安定性は良いものの液晶汚染性に不具合を生じている。これに対し、本願発明に係る実施例１については、安定な保存安定性を実現しながら、液晶汚染性も優れていることが確認される。この結果より、本願発明の樹脂組成物は、保存安定性に優れ、低液晶汚染性も良好であることから液晶表示セルの高信頼性を実現できることが言える。 From the results shown in Table 1, Comparative Example 1 in which the particles were not combined showed results inferior in storage stability. Further, Comparative Examples 2 and 3 which do not contain the filler (b) have a problem in storage stability, and Comparative Example 4 has a problem in liquid crystal contamination although the storage stability is good. On the other hand, in Example 1 according to the present invention, it is confirmed that the liquid crystal contamination is excellent while realizing stable storage stability. From this result, it can be said that the resin composition of the present invention is excellent in storage stability and has good low liquid crystal contamination, so that high reliability of the liquid crystal display cell can be realized.
本願発明の樹脂組成物は保存安定性が良好なため作業性に優れ、さらに低液晶汚染性が良好なため液晶表示セルの信頼性確保にも貢献するものである。 The resin composition of the present invention is excellent in workability because of its good storage stability, and further contributes to ensuring the reliability of liquid crystal display cells because of its good low liquid crystal contamination.
Claims (10)
０．５μｍ≦Ａ≦３μｍ・・・（Ｉ）
０．００５×Ａ≦Ｂ≦０．３×Ａ・・・（ＩＩ） A method for producing a resin composition comprising a thermal radical polymerization initiator (a) having an average particle size A [μm], a filler (b) having an average particle size B [μm], and a curable compound (c), comprising: [μm] and B [μm] satisfy the conditions represented by the following formulas (I) and (II), and the thermal radical polymerization initiator (a) and the filler (b) are added to the curable compound (c). A method for producing a resin composition comprising a step of combining a thermal radical polymerization initiator (a) and a filler (b) before dispersion.
0.5 μm ≦ A ≦ 3 μm (I)
0.005 × A ≦ B ≦ 0.3 × A (II)
Furthermore, the manufacturing method of the resin composition as described in any one of Claims 1 thru | or 9 containing an epoxy resin (f).
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