JP6304803B2 - Method for producing resin composition - Google Patents
Method for producing resin composition Download PDFInfo
- Publication number
- JP6304803B2 JP6304803B2 JP2014007383A JP2014007383A JP6304803B2 JP 6304803 B2 JP6304803 B2 JP 6304803B2 JP 2014007383 A JP2014007383 A JP 2014007383A JP 2014007383 A JP2014007383 A JP 2014007383A JP 6304803 B2 JP6304803 B2 JP 6304803B2
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- filler
- producing
- rubber
- manufacturing
- 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.)
- Active
Links
- 239000011342 resin composition Substances 0.000 title claims description 96
- 238000004519 manufacturing process Methods 0.000 title claims description 55
- 239000000945 filler Substances 0.000 claims description 84
- 239000003822 epoxy resin Substances 0.000 claims description 58
- 229920000647 polyepoxide Polymers 0.000 claims description 58
- -1 styrene olefin Chemical class 0.000 claims description 35
- 239000002245 particle Substances 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 24
- 239000000853 adhesive Substances 0.000 claims description 22
- 230000001070 adhesive effect Effects 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 229920001971 elastomer Polymers 0.000 claims description 19
- 239000005060 rubber Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 15
- 239000007870 radical polymerization initiator Substances 0.000 claims description 11
- 229920000800 acrylic rubber Polymers 0.000 claims description 10
- 239000010419 fine particle Substances 0.000 claims description 10
- 239000012766 organic filler Substances 0.000 claims description 10
- 229920000058 polyacrylate Polymers 0.000 claims description 10
- 229920001187 thermosetting polymer Polymers 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- 229920002379 silicone rubber Polymers 0.000 claims description 6
- 239000004945 silicone rubber Substances 0.000 claims description 6
- 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 5
- 230000002209 hydrophobic effect Effects 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims 1
- 239000004973 liquid crystal related substance Substances 0.000 description 28
- 238000000034 method Methods 0.000 description 24
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 12
- 229920003986 novolac Polymers 0.000 description 11
- 239000000758 substrate Substances 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 10
- 239000007983 Tris buffer Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 10
- 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
- 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 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011256 inorganic filler Substances 0.000 description 6
- 229910003475 inorganic filler Inorganic materials 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011109 contamination Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000010526 radical polymerization reaction Methods 0.000 description 5
- 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 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910001868 water Inorganic materials 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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 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
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000003999 initiator Substances 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
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 4
- 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 3
- 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 3
- QCBSYPYHCJMQGB-UHFFFAOYSA-N 2-ethyl-1,3,5-triazine Chemical compound CCC1=NC=NC=N1 QCBSYPYHCJMQGB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- 229930192627 Naphthoquinone Natural products 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229910002026 crystalline silica Inorganic materials 0.000 description 3
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000005350 fused silica glass Substances 0.000 description 3
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 229920003049 isoprene rubber Polymers 0.000 description 3
- 239000000178 monomer Substances 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
- 230000008569 process Effects 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 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
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 2
- 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 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- 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
- 229920006311 Urethane elastomer Polymers 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
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 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
- 229920005549 butyl rubber Polymers 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
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 229940091173 hydantoin Drugs 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 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
- 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
- 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
- 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
- 229920003023 plastic Polymers 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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-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
- 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
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010409 thin film Substances 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
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 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
- 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
- PMOIEAKTNCGZAJ-UHFFFAOYSA-N 1-methoxy-4-[1,2,2-tris(4-methoxyphenyl)-1,2-diphenoxyethyl]benzene Chemical compound O(C1=CC=CC=C1)C(C(C1=CC=C(C=C1)OC)(C1=CC=C(C=C1)OC)OC1=CC=CC=C1)(C1=CC=C(C=C1)OC)C1=CC=C(C=C1)OC PMOIEAKTNCGZAJ-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- VUZNLSBZRVZGIK-UHFFFAOYSA-N 2,2,6,6-Tetramethyl-1-piperidinol Chemical group CC1(C)CCCC(C)(C)N1O VUZNLSBZRVZGIK-UHFFFAOYSA-N 0.000 description 1
- BGCSUUSPRCDKBQ-UHFFFAOYSA-N 2,4,8,10-tetraoxaspiro[5.5]undecane Chemical compound C1OCOCC21COCOC2 BGCSUUSPRCDKBQ-UHFFFAOYSA-N 0.000 description 1
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 1
- SKHBJDDIGYYYMJ-UHFFFAOYSA-N 2,6-ditert-butyl-6-methylcyclohexa-1,3-dien-1-ol Chemical compound CC(C)(C)C1=C(O)C(C)(C(C)(C)C)CC=C1 SKHBJDDIGYYYMJ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- KCCIQVUYNPMYSL-UHFFFAOYSA-N 2-[tert-butyl(dimethyl)silyl]oxy-1,1,2,2-tetraphenylethanol Chemical compound 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 KCCIQVUYNPMYSL-UHFFFAOYSA-N 0.000 description 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical class OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- XSXYESVZDBAKKT-UHFFFAOYSA-N 2-hydroxybenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1O XSXYESVZDBAKKT-UHFFFAOYSA-N 0.000 description 1
- LGWROMGRXCZCLA-UHFFFAOYSA-N 2-hydroxybutanedihydrazide Chemical compound NNC(=O)CC(O)C(=O)NN LGWROMGRXCZCLA-UHFFFAOYSA-N 0.000 description 1
- TZMACLAARXHRRZ-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarbohydrazide Chemical compound NNC(=O)CC(O)(C(=O)NN)CC(=O)NN TZMACLAARXHRRZ-UHFFFAOYSA-N 0.000 description 1
- QXSNXUCNBZLVFM-UHFFFAOYSA-N 2-methyl-1h-imidazole;1,3,5-triazinane-2,4,6-trione Chemical compound CC1=NC=CN1.O=C1NC(=O)NC(=O)N1 QXSNXUCNBZLVFM-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- RJIQELZAIWFNTQ-UHFFFAOYSA-N 2-phenyl-1h-imidazole;1,3,5-triazinane-2,4,6-trione Chemical compound O=C1NC(=O)NC(=O)N1.C1=CNC(C=2C=CC=CC=2)=N1 RJIQELZAIWFNTQ-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- LZHCVNIARUXHAL-UHFFFAOYSA-N 2-tert-butyl-4-ethylphenol Chemical compound CCC1=CC=C(O)C(C(C)(C)C)=C1 LZHCVNIARUXHAL-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 description 1
- SESYNEDUKZDRJL-UHFFFAOYSA-N 3-(2-methylimidazol-1-yl)propanenitrile Chemical compound CC1=NC=CN1CCC#N SESYNEDUKZDRJL-UHFFFAOYSA-N 0.000 description 1
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 1
- SZUPZARBRLCVCB-UHFFFAOYSA-N 3-(2-undecylimidazol-1-yl)propanenitrile Chemical compound CCCCCCCCCCCC1=NC=CN1CCC#N SZUPZARBRLCVCB-UHFFFAOYSA-N 0.000 description 1
- HENCHDCLZDQGIQ-UHFFFAOYSA-N 3-[3,5-bis(2-carboxyethyl)-2,4,6-trioxo-1,3,5-triazinan-1-yl]propanoic acid Chemical compound OC(=O)CCN1C(=O)N(CCC(O)=O)C(=O)N(CCC(O)=O)C1=O HENCHDCLZDQGIQ-UHFFFAOYSA-N 0.000 description 1
- JCUMQTAAEUDUPK-UHFFFAOYSA-N 3-[3-(2-carboxyethyl)-2,4,6-trioxo-1,3,5-triazinan-1-yl]propanoic acid Chemical compound OC(=O)CCN1C(=O)NC(=O)N(CCC(O)=O)C1=O JCUMQTAAEUDUPK-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- BOTGCZBEERTTDQ-UHFFFAOYSA-N 4-Methoxy-1-naphthol Chemical compound C1=CC=C2C(OC)=CC=C(O)C2=C1 BOTGCZBEERTTDQ-UHFFFAOYSA-N 0.000 description 1
- YKCCXOHQOVXCIG-UHFFFAOYSA-N 5-(1-cyanoethyl)-2-(2-phenylethoxymethyl)imidazole-1,4-dicarbonitrile Chemical compound C(#N)C(C)C=1N(C(=NC=1C#N)COCCC1=CC=CC=C1)C#N YKCCXOHQOVXCIG-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004255 Butylated hydroxyanisole Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- QDZXJOMXPRWGFG-UHFFFAOYSA-N CCC1=NC=NC=N1.O=C1NC(=O)NC(=O)N1 Chemical compound CCC1=NC=NC=N1.O=C1NC(=O)NC(=O)N1 QDZXJOMXPRWGFG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- XCOBLONWWXQEBS-KPKJPENVSA-N N,O-bis(trimethylsilyl)trifluoroacetamide Chemical compound C[Si](C)(C)O\C(C(F)(F)F)=N\[Si](C)(C)C XCOBLONWWXQEBS-KPKJPENVSA-N 0.000 description 1
- CVTIZMOISGMZRJ-UHFFFAOYSA-N N-Mononitrosopiperazine Chemical compound O=NN1CCNCC1 CVTIZMOISGMZRJ-UHFFFAOYSA-N 0.000 description 1
- CKRZKMFTZCFYGB-UHFFFAOYSA-N N-phenylhydroxylamine Chemical compound ONC1=CC=CC=C1 CKRZKMFTZCFYGB-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- LULCPJWUGUVEFU-UHFFFAOYSA-N Phthiocol Natural products C1=CC=C2C(=O)C(C)=C(O)C(=O)C2=C1 LULCPJWUGUVEFU-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000003490 Thiodipropionic acid Substances 0.000 description 1
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 description 1
- ZFDXZGUFUMAREO-UHFFFAOYSA-N [1-(hydroxymethyl)-2-phenylimidazol-4-yl]methanol Chemical compound OCC1=CN(CO)C(C=2C=CC=CC=2)=N1 ZFDXZGUFUMAREO-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- OFLXLNCGODUUOT-UHFFFAOYSA-N acetohydrazide Chemical compound C\C(O)=N\N OFLXLNCGODUUOT-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 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
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- ALHNLFMSAXZKRC-UHFFFAOYSA-N benzene-1,4-dicarbohydrazide Chemical compound NNC(=O)C1=CC=C(C(=O)NN)C=C1 ALHNLFMSAXZKRC-UHFFFAOYSA-N 0.000 description 1
- WARCRYXKINZHGQ-UHFFFAOYSA-N benzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1 WARCRYXKINZHGQ-UHFFFAOYSA-N 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- UHVCSNKHFBQKBO-UHFFFAOYSA-N benzyl-ethenyl-[2-(3-trimethoxysilylpropylamino)ethyl]azanium;chloride Chemical compound Cl.CO[Si](OC)(OC)CCCNCCN(C=C)CC1=CC=CC=C1 UHVCSNKHFBQKBO-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- VYCDFODYRFOXDA-UHFFFAOYSA-N bis(2,2,6,6-tetramethyl-1-undecoxypiperidin-4-yl) carbonate Chemical compound C1C(C)(C)N(OCCCCCCCCCCC)C(C)(C)CC1OC(=O)OC1CC(C)(C)N(OCCCCCCCCCCC)C(C)(C)C1 VYCDFODYRFOXDA-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 1
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 1
- 229940043253 butylated hydroxyanisole Drugs 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- HJMZMZRCABDKKV-UHFFFAOYSA-N carbonocyanidic acid Chemical compound OC(=O)C#N HJMZMZRCABDKKV-UHFFFAOYSA-N 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- FOAFCAUCIZMBJM-UHFFFAOYSA-N cyclohexane-1,1,2-tricarbohydrazide Chemical compound NNC(=O)C1CCCCC1(C(=O)NN)C(=O)NN FOAFCAUCIZMBJM-UHFFFAOYSA-N 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- LPLAXQKUDSKKAU-UHFFFAOYSA-N cyclohexane-1,4-dicarbohydrazide Chemical compound NNC(=O)C1CCC(C(=O)NN)CC1 LPLAXQKUDSKKAU-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- MZRQZJOUYWKDNH-UHFFFAOYSA-N diphenylphosphoryl-(2,3,4-trimethylphenyl)methanone Chemical compound CC1=C(C)C(C)=CC=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MZRQZJOUYWKDNH-UHFFFAOYSA-N 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005886 esterification reaction Methods 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 239000010408 film Substances 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
- OXAGUPFRAIIDLT-UHFFFAOYSA-N heptanedihydrazide Chemical compound NNC(=O)CCCCCC(=O)NN OXAGUPFRAIIDLT-UHFFFAOYSA-N 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 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
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000005641 methacryl 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
- 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
- FPLYNRPOIZEADP-UHFFFAOYSA-N octylsilane Chemical compound CCCCCCCC[SiH3] FPLYNRPOIZEADP-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 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
- 230000035699 permeability Effects 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 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
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene 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
- 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
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 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
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000012321 sodium triacetoxyborohydride 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
- 238000003860 storage Methods 0.000 description 1
- 230000035882 stress Effects 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
- HVYVMSPIJIWUNA-UHFFFAOYSA-N triphenylstibine Chemical compound C1=CC=CC=C1[Sb](C=1C=CC=CC=1)C1=CC=CC=C1 HVYVMSPIJIWUNA-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
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Polymerisation Methods In General (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、フィラーの凝集を無くし、該フィラーが高分散された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、フィラーの凝集物が無い為、ジェットディスペンスのような精密塗布作業性に優れ、また、平行でかつ正確なギャップ間距離で接合でき、更に接着強度も高いという特性を有する。従って、特に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 resin composition in which filler aggregation is eliminated and the filler is highly dispersed. Since the resin composition obtained by this method is free of filler aggregates, it is excellent in precision coating workability such as jet dispensing, and can be joined at a parallel and accurate distance between gaps, and further has high adhesive strength. Has characteristics. Therefore, it is particularly 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。
Conventionally, resin compositions used for electronic components, for example, resins for substrates, adhesives for semiconductor elements and substrates, heat-resistant film and copper foil adhesives for flexible substrates, etc., thermosetting epoxy resin compositions Things 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.
しかし、近年では、半導体パッケージを初めとする電子部品の小型化への要望に伴い、複数の電子部品を積層して多層の半導体チップ積層体とする３次元実装技術の開発が進んできている。また、半導体チップ積層体等の電子部品を更に小型化させる研究が進められている。これに伴い、例えば半導体チップは極めて薄い薄膜となり、更に半導体チップには微細な配線が形成されるようになってきた。このような３次元実装の半導体チップ積層体においては、各半導体チップを損傷なく、かつ、均一なギャップ間距離で水平を保って積層することが求められている。
このような用途に用いる場合には、上記フィラーの分散性が非常に重要な要求特性となる。すなわち高充填されたフィラーに凝集物が多いと、ギャップ間距離を厚くせざるを得ず、薄膜積層を困難とし、また水平な積層にも妨げとなる。
However, in recent years, along with a demand for downsizing of electronic components such as semiconductor packages, development of a three-dimensional mounting technique in which a plurality of electronic components are stacked to form a multilayer semiconductor chip stacked body has been advanced. In addition, research for further downsizing electronic components such as semiconductor chip laminates is underway. Accordingly, for example, the semiconductor chip has become an extremely thin thin film, and fine wiring has been formed on the semiconductor chip. In such a three-dimensionally mounted semiconductor chip stacked body, it is required to stack each semiconductor chip without damage and with a uniform distance between gaps.
When used in such applications, the dispersibility of the filler is a very important required characteristic. That is, if the highly filled filler contains a large amount of aggregates, the gap distance must be increased, making thin film stacking difficult and hindering horizontal stacking.
この課題を解決する為に、例えば平均粒子径の異なる２種のフィラーを、ボールミルを用いて分散する方法が開示されている（特許文献２）。しかしこの方法は、ボールミルのような特殊な分散装置を必要とするものであり、またボールミルでは製造する樹脂組成物の粘度の制約を受けるといった課題を有する為、更なる改良が求められている。 In order to solve this problem, for example, a method of dispersing two types of fillers having different average particle diameters using a ball mill is disclosed (Patent Document 2). However, this method requires a special dispersing device such as a ball mill, and the ball mill has a problem that it is restricted by the viscosity of the resin composition to be produced. Therefore, further improvement is required.
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、フィラーの凝集を無くし、該フィラーが高分散された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、フィラーの凝集物が無い為、ジェットディスペンスのような精密塗布作業性に優れ、また、平行でかつ正確なギャップ間距離で接合でき、更に接着強度も高いという特性を有する。従って、特に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 resin composition in which filler aggregation is eliminated and the filler is highly dispersed. Since the resin composition obtained by this method is free of filler aggregates, it is excellent in precision coating workability such as jet dispensing, and can be joined at a parallel and accurate distance between gaps, and further has high adhesive strength. Has characteristics. Therefore, it is particularly suitable as an adhesive for electronic parts such as semiconductors.
本発明者らは、鋭意検討の結果、平均粒子径異なる２種類のフィラー（フィラー（ａ）、フィラー（ｂ））を用い、硬化性化合物（ｃ）中に分散する前に、前記フィラー（ａ）とフィラー（ｂ）を攪拌混合することによって、フィラーの分散性を高め、非常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 two types of fillers (filler (a) and filler (b)) having different average particle diameters, and before dispersing in the curable compound (c), the filler (a ) And filler (b) are stirred and mixed to increase the dispersibility of the filler, and it has been found that a very excellent resin composition can be provided, 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]のフィラー（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、前記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）中にフィラー（ａ）及びフィラー（ｂ）を分散する前に、フィラー（ａ）とフィラー（ｂ）を攪拌混合する工程を有する樹脂組成物の製造方法、
３μｍ ≦ Ａ ≦ ２０μｍ ・・・ （Ｉ）
０．０００５×Ａ ≦ Ｂ ≦ ０．０２０×Ａ ・・・ （ＩＩ）
２）
上記（ａ）が、有機フィラーである上記１）に記載の樹脂組成物の製造方法、
３）
上記（ｂ）が、シリカ及び／又はアルミナである上記１）又は２）に記載の樹脂組成物の製造方法、
４）
上記（ａ）が疎水性フィラーであり、上記（ｂ）が親水性フィラーである上記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（ａ）が、アクリルゴム、スチレンゴム、スチレンオレフィンゴム、及びシリコーンゴムからなる群より選択される１又は２以上のゴム微粒子である上記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）
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５部以上５０部未満である上記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）
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１部以上２０部未満である上記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）
上記硬化性化合物（ｃ）が、エポキシ樹脂、（メタ）アクリル化エポキシ樹脂及び部分（メタ）アクリル化エポキシ樹脂から選択される１種もしくは２種以上であり、更に熱硬化剤（ｄ）を含有する上記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）
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８）に記載の樹脂組成物の製造方法、
１０）
上記熱硬化剤（ｄ）が有機酸ヒドラジド化合物である上記８）又は９）に記載の樹脂組成物の製造方法、
１１）
更に熱ラジカル重合開始剤（ｅ）を含有する上記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、
１２）
更にシランカップリング剤（ｆ）を含有する、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、
１３）
上記１）乃至１２）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、
１４）
上記１）乃至１２）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 filler (a) having an average particle size A [μm], a filler (b) having an average particle size B [μm], and a curable compound (c), wherein the A [μm] And B [μm] satisfy the conditions represented by the following formulas (I) and (II) and before the filler (a) and the filler (b) are dispersed in the curable compound (c), the filler ( a) a process for producing a resin composition comprising a step of stirring and mixing the filler (b);
3 μm ≦ A ≦ 20 μm (I)
0.0005 × A ≦ B ≦ 0.020 × A (II)
2)
The method for producing a resin composition according to 1) above, wherein (a) is an organic filler,
3)
The method for producing a resin composition according to 1) or 2) above, wherein (b) is silica and / or alumina,
4)
The method for producing a resin composition according to any one of 1) to 3) above, wherein (a) is a hydrophobic filler, and (b) is a hydrophilic filler,
5)
The resin according to any one of 1) to 4), wherein (a) is one or more rubber fine particles selected from the group consisting of acrylic rubber, styrene rubber, styrene olefin rubber, and silicone rubber. Production method of the composition,
6)
The method for producing a resin composition according to any one of 1) to 5) above, wherein the content of (a) when the total amount of the resin composition is 100 parts by mass is 5 parts or more and less than 50 parts,
7)
The method for producing a resin composition according to any one of 1) to 6) above, wherein the content of (b) when the total amount of the resin composition is 100 parts by mass is 1 part or more and less than 20 parts,
8)
The curable compound (c) is one or more selected from an epoxy resin, a (meth) acrylated epoxy resin and a partial (meth) acrylated epoxy resin, and further contains a thermosetting agent (d). The method for producing a resin composition according to any one of 1) to 7) above,
9)
The method for producing a resin composition according to 8) above, wherein the curable compound (c) is a (meth) acrylic esterified product of resorcin diglycidyl ether,
10)
The method for producing a resin composition according to 8) or 9) above, wherein the thermosetting agent (d) is an organic acid hydrazide compound,
11)
Furthermore, the manufacturing method of the resin composition as described in any one of said 1) thru | or 10) containing a thermal radical polymerization initiator (e),
12)
Furthermore, the manufacturing method of the resin composition as described in any one of said 1) thru | or 11) containing a silane coupling agent (f),
13)
An adhesive for electronic parts obtained by the method for producing a resin composition according to any one of 1) to 12) above,
14)
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 12) above,
About.
本発明の製造方法によって得られる樹脂組成物は、フィラーの凝集物が無い為、精密性が重要である、水平で狭ギャップ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。また、フィラーの凝集物が無いことは、高接着強度にも寄与するものである。 Since the resin composition obtained by the production method of the present invention has no filler agglomerates, precision is important, and an extremely advantageous effect is exhibited in electronic components that require horizontal and narrow gap properties. The absence of filler aggregates also contributes to high adhesive strength.
本発明は、平均粒子径の異なる２種類のフィラー（フィラー（ａ）、フィラー（ｂ））を用い、硬化性化合物（ｃ）中に分散する前に、前記（ａ）と（ｂ）を攪拌混合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。
２種類のフィラー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、２種類のフィラーをそれぞれ添加し、攪拌混合し、その後２本ロール等の混練器によってフィラーを分散する方法が一般的である。しかし、この方法では、２種の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フィラー（ａ）と平均粒子径の小さいフィラー（ｂ）を、事前に攪拌混合することによって、フィラー（ａ）の表面にフィラー（ｂ）を付着させることができ、これを硬化性化合物（ｃ）中に分散することによって、最終的に凝集物のない樹脂組成物の製造を可能にするものである。
なお、フィラー（ａ）とフィラー（ｂ）の攪拌混合は、プラネタリーミキサーやジェットミル粉砕機等を用いて行うことができる。
The present invention uses two types of fillers (filler (a) and filler (b)) having different average particle diameters, and stirs (a) and (b) before dispersing in the curable compound (c). It is a manufacturing method of the resin composition characterized by having the process to mix.
When producing a resin composition containing two kinds of fillers, for example, two kinds of fillers are respectively added to a curable compound such as an epoxy resin, stirred and mixed, and then filled with a kneader such as two rolls. The method of dispersing is generally used. However, in this method, the two kinds of fillers are independently dispersed in the curable compound and do not interact with each other.
In the present invention, the filler (b) can be attached to the surface of the filler (a) by previously stirring and mixing the filler (a) having a large average particle size and the filler (b) having a small average particle size. By dispersing this in the curable compound (c), it becomes possible to finally produce a resin composition free from aggregates.
The stirring and mixing of the filler (a) and the filler (b) can be performed using a planetary mixer, a jet mill pulverizer, or the like.
また本発明の樹脂組成物の製造方法に用いられるフィラー（ａ）及びフィラー（ｂ）の平均粒子径は以下の数式を満たす。すなわち、フィラー（ａ）の平均粒子径をＡ[μｍ]とし、フィラー（ｂ）の平均粒子径をＢ[μｍ]とした場合に、Ａ[μｍ]及びＢ[μｍ]が、下記数式（Ｉ）、（ＩＩ）で表される条件を満たす。
３μｍ ≦ Ａ ≦ ２０μｍ ・・・ （Ｉ）
０．０００５×Ａ ≦ Ｂ ≦ ０．０２×Ａ ・・・ （ＩＩ）
[数式（Ｉ）に関して]
数式（Ｉ）は、平均粒子径の大きいフィラー（ａ）の、平均粒子径を規定している。すなわち、フィラー（ａ）の平均粒子径は、３μｍ以上２０μｍ以下である。フィラー平均粒子径が小さいと、その凝集力が高くなる傾向がある。従って、３μｍ未満である場合、本発明の効果が十分に得られない。また、フィラーの平均粒子径が大きすぎると、凝集していなくても、液晶表示セルの製造には不向きとなる。平均粒子径の更に好ましい範囲は、３μｍ以上１５μｍ以下であり、特に好ましくは、４μｍ以上１０μｍ以下である。
[数式（ＩＩ）に関して]
数式（ＩＩ）は、フィラー（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、フィラー（ａ）の平均粒子径の２０００分の１以上１０００分の２０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（ａ）の粒子とフィラー（ａ）の粒子の間に効率良く入り込み、フィラー（ａ）の分散性を高める効果を発現する。また、フィラー（ａ）が有機フィラーの場合には、外的応力によって形状が変形することがあるが、フィラー（ｂ）が上記範囲であれば、その変形に追従することが可能であって、フィラー（ａ）から剥離することもない。フィラー（ｂ）の平均粒子径は、更に好ましくは、１０００分の２以上１０００分の１５以下であり、特に好ましくは、１０００分の５以上１０００分の１０以下である。
Moreover, the average particle diameter of the filler (a) used for the manufacturing method of the resin composition of this invention and a filler (b) satisfy | fills the following numerical formula. That is, when the average particle diameter of the filler (a) is A [μm] and the average particle diameter of the filler (b) is B [μm], A [μm] and B [μm] are expressed by the following formula (I ) And (II).
3 μm ≦ A ≦ 20 μm (I)
0.0005 × A ≦ B ≦ 0.02 × A (II)
[Regarding Formula (I)]
Formula (I) defines the average particle size of the filler (a) having a large average particle size. That is, the average particle diameter of the filler (a) is 3 μm or more and 20 μm or less. When the filler average particle size is small, the cohesive force tends to increase. Therefore, when it is less than 3 μm, the effect of the present invention cannot be sufficiently obtained. On the other hand, if the average particle size of the filler is too large, it becomes unsuitable for the production of a liquid crystal display cell even if it does not aggregate. A more preferable range of the average particle diameter is 3 μm or more and 15 μm or less, and particularly preferably 4 μm or more and 10 μm or less.
[Regarding Formula (II)]
Formula (II) shows the relationship between the average particle diameters of the filler (a) and the filler (b). That is, the average particle diameter of the filler (b) is 1/2000 to 20/1000 of the average particle diameter of the filler (a). When the average particle diameter of the filler (b) is within this range, the filler (a) and the filler (a) are efficiently inserted between the filler (a) and the filler (a). . Further, when the filler (a) is an organic filler, the shape may be deformed by an external stress, but if the filler (b) is in the above range, the deformation can be followed, It does not peel from the filler (a). The average particle diameter of the filler (b) is more preferably 2/1000 to 15/1000, and particularly preferably 5/1000 to 10/1000.
本明細書において平均粒子径は、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 this specification, the average particle diameter 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.
上記フィラー（ａ）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 (a) 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.
上記シリコーンゴムとしてはＫＭＰ−５９４、ＫＭＰ−５９７、ＫＭＰ−５９８（信越化学工業製）、トレフィルＲＴＭＥ−５５００、９７０１、ＥＰ−２００１（東レダウコーニング社製）が好ましく、ウレタンゴムとしてはＪＢ−８００Ｔ、ＨＢ−８００ＢＫ（根上工業株式会社）、スチレンゴムとしてはラバロンＲＴＭＴ３２０Ｃ、Ｔ３３１Ｃ、ＳＪ４４００、ＳＪ５４００、ＳＪ６４００、ＳＪ４３００Ｃ、ＳＪ５３００Ｃ、ＳＪ６３００Ｃ（三菱化学製）が好ましく、スチレンオレフィンゴムとしてはセプトンＲＴＭＳＥＰＳ２００４、ＳＥＰＳ２０６３が好ましい。なお本明細書中、上付きの「ＲＴＭ」は登録商標を意味する。 As the silicone rubber, KMP-594, KMP-597, KMP-598 (manufactured by Shin-Etsu Chemical Co., Ltd.), Trefil RTM E-5500, 9701, EP-2001 (manufactured by Toray Dow Corning) are preferable, and as the urethane rubber, JB- 800T, HB-800BK (Negami Kogyo Co., Ltd.), Lavalon RTM T320C, T331C, SJ4400, SJ5400, SJ6400, SJ4300C, SJ5300C, SJ6300C (Mitsubishi Chemical) are preferable as the styrene rubber, and Septon RTM SEPS2004 as the styrene olefin rubber. SEPS 2063 is preferred. In the present specification, the superscript “RTM” means a registered trademark.
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。 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.
フィラー（ａ）として好ましいものは有機フィラーである。
有機フィラーの中で好ましいものは、アクリルゴム、スチレンゴム、スチレンオレフィンゴム、及びシリコーンゴムからなる群より選択される１又は２以上のゴム微粒子であり、更に好ましいものは、アクリルゴム及び／又はシリコーンゴムである。
有機フィラーとして特に好ましいものは、ＫＭＰ−５９４、ＫＭＰ−５９７、ＫＭＰ−５９８（信越化学工業製）、ＡＦＸ−８、ＡＦＸ−１５（積水化成品工業製）、ＪＢ−８００Ｔ、ＨＢ−８００ＢＫ（根上工業製）である。
A preferable filler (a) is an organic filler.
Among the organic fillers, preferred are one or more rubber fine particles selected from the group consisting of acrylic rubber, styrene rubber, styrene olefin rubber, and silicone rubber, and more preferred are acrylic rubber and / or silicone. It is rubber.
Particularly preferable organic fillers are KMP-594, KMP-597, KMP-598 (manufactured by Shin-Etsu Chemical Co., Ltd.), AFX-8, AFX-15 (manufactured by Sekisui Plastics Co., Ltd.), JB-800T, HB-800BK (Negami). Industrial).
上記フィラー（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、ゼフィアックＲＴＭＦ−３２５、Ｆ−３４０、Ｆ−３５１（アイカ工業株式会社製）、パラロイドＥＸＬ−２６５５（呉羽化学工業株式会社製）などが挙げられる。
The filler (b) means an organic filler and / or an inorganic filler.
Examples of the organic filler include Zefiac RTMF-325, F-340, F-351 (manufactured by Aika Industry Co., Ltd.), Paraloid EXL-2655 (manufactured by Kureha Chemical Industry Co., Ltd.), and the like.
上記無機フィラーの例としては、上記フィラー（ａ）に挙げたものと同様のものが挙げられる。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。
As an example of the said inorganic filler, the thing similar to what was mentioned to the said filler (a) is mentioned. 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.
フィラー（ａ）とフィラー（ｂ）の表面極性について、フィラー（ａ）が疎水性であって、フィラー（ｂ）が親水性である場合は、本願発明の好ましい態様の一つである。硬化性樹脂（ｃ）は、比較的極性の高いものである為、疎水性のフィラー（ａ）の表面を親水性のフィラー（ｂ）によって保護することによって、より高い分散性が得られる為である。
ここで、親水性とは、表面が水酸基、アミノ基などの水素結合性水酸基を有する官能基で構成されているか金属酸化物などの水素結合受容成分であるものをいう。また疎水性とは、親水性表面をジメチルジクロロシラン、ヘキサメチルジシラザン、オクチルシラン、シリコーンオイルまたは末端に非極性の官能基を有するカップリング剤などで化学的に結合させたものをいう。
About the surface polarity of a filler (a) and a filler (b), when a filler (a) is hydrophobic and a filler (b) is hydrophilic, it is one of the preferable aspects of this invention. Since the curable resin (c) has a relatively high polarity, higher dispersibility can be obtained by protecting the surface of the hydrophobic filler (a) with the hydrophilic filler (b). is there.
Here, the hydrophilic property means that the surface is composed of a functional group having a hydrogen bonding hydroxyl group such as a hydroxyl group or an amino group or is a hydrogen bond accepting component such as a metal oxide. Hydrophobic means that the hydrophilic surface is chemically bonded with dimethyldichlorosilane, hexamethyldisilazane, octylsilane, silicone oil or a coupling agent having a nonpolar functional group at the terminal.
フィラー（ａ）の樹脂組成物中の含有量としては、樹脂組成物の総量を１００質量部とした場合に、５〜５０質量部である場合が好ましく、７〜４０である場合がより好ましく、１０〜３０である場合が更に好ましい。
また、フィラー（ｂ）の樹脂組成物中の含有量としては、樹脂組成物の総量を１００質量部とした場合に、１〜２０質量部である場合が好ましく、２〜１５である場合がより好ましく、３〜１０である場合が更に好ましい。
As content in the resin composition of a filler (a), when the total amount of a resin composition is 100 mass parts, the case where it is 5-50 mass parts is preferable, and the case where it is 7-40 is more preferable, More preferably, it is 10-30.
Moreover, as content in the resin composition of a filler (b), when the total amount of a resin composition is 100 mass parts, the case where it is 1-20 mass parts is preferable, and the case where it is 2-15 is more. The case of 3 to 10 is more preferable.
本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。
この硬化性樹脂としては、エポキシ樹脂、（メタ）アクリル化エポキシ樹脂、（メタ）アクリル酸エステルのモノマー、（メタ）アクリル酸エステルのオリゴマー、部分（メタ）アクリル化エポキシ樹脂等を挙げることができる。また、接着剤用途の場合には、上記のうち、エポキシ樹脂、（メタ）アクリル化エポキシ樹脂及び部分（メタ）アクリル化エポキシ樹脂から選択される１種もしくは２種以上からなる硬化性樹脂である場合が特に好ましい。 例えば、エポキシ樹脂、エポキシ樹脂と（メタ）アクリル化エポキシ樹脂の混合物、（メタ）アクリル化エポキシ樹脂、部分（メタ）アクリル化エポキシ樹脂等が挙げられる。特に液晶表示セル用接着剤として用いる場合であり、液晶と直接接触する部分で使用する場合には、液晶に対する汚染性、溶解性が低いものが好ましく、好適なエポキシ樹脂の例としては、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が、これらに限定されるものではない。（メタ）アクリロイル化エポキシ樹脂、部分（メタ）アクリロイル化エポキシ樹脂は、エポキシ樹脂と（メタ）アクリル酸の周知の反応により得ることができる。例えば、エポキシ樹脂に所定の当量比の（メタ）アクリル酸と触媒（例えば、ベンジルジメチルアミン、トリエチルアミン、ベンジルトリメチルアンモニウムクロライド、トリフェニルホスフィン、トリフェニルスチビン等）と、重合防止剤（例えば、メトキノン、ハイドロキノン、メチルハイドロキノン、フェノチアジン、ジブチルヒドロキシトルエン等）を添加して、例えば８０〜１１０℃でエステル化反応を行うことにより得られる。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、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、より好ましいも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。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。
The resin composition obtained by the production method of the present invention contains a curable compound (c).
Examples of the curable resin include epoxy resins, (meth) acrylated epoxy resins, (meth) acrylate monomers, (meth) acrylate oligomers, and partial (meth) acrylated epoxy resins. . Moreover, in the case of adhesive use, among the above, it is a curable resin composed of one or more selected from epoxy resins, (meth) acrylated epoxy resins and partial (meth) acrylated epoxy resins. The case is particularly preferred. Examples thereof include an epoxy resin, a mixture of an epoxy resin and a (meth) acrylated epoxy resin, a (meth) acrylated epoxy resin, and a partial (meth) acrylated epoxy resin. Especially when it is used as an adhesive for liquid crystal display cells, and when used in a portion that is in direct contact with the liquid crystal, those having low contamination and solubility in the liquid crystal are preferred. Examples of suitable epoxy resins include 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 novolac type epoxy resin, bisphenol F novolac 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 resin, phenol novolac type epoxy resin having triphenolmethane skeleton, etc. Bifunctional phenols diglycidyl ethers of bifunctional alcohols diglycidyl ethers of, and their halides, but like hydrogenated product, but is not limited thereto. The (meth) acryloylated epoxy resin and the partially (meth) acryloylated epoxy resin can be obtained by a well-known reaction between an epoxy resin and (meth) acrylic acid. For example, (meth) acrylic acid in a predetermined equivalent ratio to an epoxy resin and a catalyst (for example, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenylphosphine, triphenylstibine, etc.) and a polymerization inhibitor (for example, methoquinone, Hydroquinone, methylhydroquinone, phenothiazine, dibutylhydroxytoluene, etc.) are added, and the esterification reaction is performed at 80 to 110 ° C., for example. 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, diglycidyl ethers of difunctional phenols, difunctional alcohols Diglycidyl ether compound, and their halides, and the like hydrogenated product. Of these, bisphenol type epoxy resin and novolac type epoxy resin are more preferable from the viewpoint of liquid crystal contamination. 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.
本発明の製造方法で得られる樹脂組成物には、さらに必要に応じて、（メタ）アクリル酸エステルのモノマー及び／又はオリゴマーを使用しても良い。そのようなモノマー、オリゴマーとしては、例えば、ジペンタエリスリトールと（メタ）アクリル酸の反応物、ジペンタエリスリトール・カプロラクトンと（メタ）アクリル酸の反応物等が挙げられるが、特に制限されるものではない。 In the resin composition obtained by the production method of the present invention, a monomer and / or oligomer of (meth) acrylic acid ester may be further used as necessary. Examples of such a monomer or oligomer include a reaction product of dipentaerythritol and (meth) acrylic acid, a reaction product of dipentaerythritol / caprolactone and (meth) acrylic acid, and the like. Absent.
本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。
この熱硬化剤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、固形の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、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、特に好ましくはマロン酸ジヒドラジド、セバシン酸ジヒドラジドである。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 is not particularly limited, and examples thereof include polyvalent amines, polyhydric phenols, hydrazide compounds, and the like, but solid organic acid hydrazide is 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, from the balance of curing reactivity and latency, isophthalic acid dihydrazide, malonic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, tris (1-hydrazinocarbonylmethyl) isocyanurate, tris (2-hydrazinocarbonylethyl) Isocyanurate and tris (3-hydrazinocarbonylpropyl) isocyanurate, particularly preferably malonic acid dihydrazide and sebacic acid dihydrazide. 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.
本発明の製造方法で得られる樹脂組成物は、更に熱ラジカル重合開始剤（ｅ）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−０７０、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。
上記（ｅ）熱ラジカル重合開始剤として、好ましいのは、分子内に酸素−酸素結合（−Ｏ−Ｏ−）又は窒素−窒素結合（−Ｎ＝Ｎ−）を有さない熱ラジカル重合開始剤である。分子内に酸素−酸素結合（−Ｏ−Ｏ−）や窒素−窒素結合（−Ｎ＝Ｎ−）を有する熱ラジカル重合開始剤は、ラジカル発生時に多量の酸素や窒素を発するため、樹脂組成物中に気泡を残した状態で硬化し、接着強度等の特性を低下させる虞がある。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）が特に好適である。具体的には、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 further contain a thermal radical polymerization initiator (e). 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-070, 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.
The above (e) thermal radical polymerization initiator is preferably a thermal radical polymerization initiator having no oxygen-oxygen bond (—O—O—) or nitrogen-nitrogen bond (—N═N—) in the molecule. It is. Since the thermal radical polymerization initiator having an oxygen-oxygen bond (—O—O—) or a nitrogen-nitrogen bond (—N═N—) in the molecule emits a large amount of oxygen or nitrogen when a radical is generated, the resin composition There exists a possibility that it hardens | cures in the state which left the bubble inside, and characteristics, such as adhesive strength, may be reduced. Particularly preferred are benzopinacol-based thermal radical polymerization initiators (including those obtained by chemically modifying benzopinacol). Specifically, 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-tetraphenyl Ethane, 1,2-bis (t-butyldimethylsiloxy) -1,1,2,2-tetraphenylethane, 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, and the like are preferable, and preferably 1- Hydroxy-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, 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, especially The Mashiku 1, 2- bis (trimethylsiloxy) -1,1, 2,2-tetraphenyl ethane.
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.
（ｅ）熱ラジカル重合開始剤は粒径を細かくし、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電子部品製造時に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。 (E) It is preferable that the thermal radical polymerization initiator has a fine particle size and is uniformly dispersed. The average particle size is preferably 5 μm or less, and 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 manufacturing a narrow gap electronic component. 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).
（ｅ）熱ラジカル重合開始剤の含有量としては、本発明で製造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。 (E) The content of the thermal radical polymerization initiator is preferably 0.0001 to 10 parts by mass, more preferably 0 when the total amount of the resin composition produced 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.
本発明の製造方法で得られる樹脂組成物は、（ｆ）シランカップリング剤を用いて、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 by using (f) a silane coupling agent. 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 (all manufactured by BASF), Sequol 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 particularly preferably 0.01 to 0.2% by mass in the total amount of the resin composition. .
上記硬化促進剤としては、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。
Examples of the curing accelerator include organic acids and imidazoles.
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-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5 -Methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole and the like.
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%.
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接着し、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 opposite to each other at a predetermined interval, the periphery is bonded 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。次いで事前に混合した成分（ａ）及び（ｂ）、また必要に応じて、成分（ｄ）、（ｅ）、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) mixed in advance, and components (d) and (e), an antifoaming agent, a leveling agent, a solvent and the like are added as necessary, and a known mixing device, for example, two Mix uniformly with a roll, 3 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、フィラーの凝集物が無い為、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、また液晶表示セルのセルギャップ不良を引き起こさない。また、液晶の差込への耐性も良好であり、液晶滴下工法における基板の貼り合せ工程、加熱工程においても液晶が差し込んだり、決壊したりする現象をおこさない。従って、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。また、保存安定性にも優れる為、液晶表示セルの製造に適している。更に、その硬化物は接着強度、耐熱性、耐湿性等の各種硬化物特性にも優れる、特に透湿度は非常に低い。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 no filler aggregate, it is excellent in coating workability such as dispensing and screen printing, and does not cause a cell gap defect of a liquid crystal display cell. Moreover, the tolerance to the insertion of the liquid crystal is also good, and the phenomenon that the liquid crystal is inserted or broken in the substrate bonding step and the heating step in the liquid crystal dropping method is not caused. Therefore, 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. Moreover, since it is excellent also in storage stability, it is suitable for manufacture of a liquid crystal display cell. Furthermore, the cured product is excellent in various cured product properties such as adhesive strength, heat resistance, and moisture resistance, and particularly has a very low moisture permeability. 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全アクリル化物の合成]
レゾルシンジグリシジルエーテル１８１．２ｇ（ＥＸ−２０１：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。得られたエポキシアクリレートの反応性基当量は理論値で１８３である。
[Synthesis Example 1]
[Synthesis of total acrylate of resorcin diglycidyl ether]
Resorcin diglycidyl ether 181.2 g (EX-201: 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. The reactive group equivalent of the obtained epoxy acrylate is 183 in theory.
[合成例２]
[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の合成]
市販ベンゾピナコール（東京化成製）１００部（０．２８モル）をジメチルホルムアルデヒド３５０部に溶解させた。これに塩基触媒としてピリジン３２部（０．４モル）、シリル化剤としてＢＳＴＦＡ（信越化学工業製）１５０部（０．５８モル）を加え７０℃まで昇温し、２時間攪拌した。得られた反応液を冷却し、攪拌しながら、水２００部を入れ、生成物を沈殿させると共に未反応シリル化剤を失活させた。沈殿した生成物をろ別分離した後十分に水洗した。次いで得られた生成物をアセトンに溶解し、水を加えて再結晶させ、精製した。目的の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を１０５．６部（収率８８．３％）得た。
ＨＰＬＣ(高速液体クロマトグラフィー）で分析した結果、純度は９９．０％（面積百分率）であった。
[Synthesis Example 2]
[Synthesis of 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane]
100 parts (0.28 mol) of commercially available benzopinacol (manufactured by Tokyo Chemical Industry) was dissolved in 350 parts of dimethylformaldehyde. To this was added 32 parts (0.4 mol) of pyridine as a base catalyst and 150 parts (0.58 mol) of BSTFA (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silylating agent, and the mixture was heated to 70 ° C. and stirred for 2 hours. The obtained reaction solution was cooled and stirred while adding 200 parts of water to precipitate the product and deactivate the unreacted silylating agent. The precipitated product was separated by filtration and thoroughly washed with water. Subsequently, the obtained product was dissolved in acetone, recrystallized by adding water and purified. 105.6 parts (yield 88.3%) of the desired 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane were obtained.
As a result of analysis by HPLC (high performance liquid chromatography), the purity was 99.0% (area percentage).
[実施例１〜７、比較例１〜４]
下記表１に示す量の成分（ａ）、（ｂ）等を用い、樹脂組成物の製造を行った。製造方法は以下に示す通りである。
まず、熱混合し、冷却した成分（ｃ）に成分（ｆ）を添加し攪拌した。その後成分（ａ）、（ｂ）、（ｄ）及び（ｅ）を順次添加し、３本ロールにより均一に混合した。
なお、実施例１〜７、比較例３〜４においては、成分（ａ）、（ｂ）を事前混合し、それを成分（ｃ）と（ｆ）の混合物に添加したが、比較例１〜２ では、成分（ｃ）と（ｆ）の混合物に対して、成分（ａ）、（ｂ）をこの順で添加し、混合したものである。
また、成分（ａ）と（ｂ）の事前混合は、（ａ）：（ｂ）＝７５：１８の比率で混ぜ合わせたものをジェットミル粉砕機を用いて３ｐａｓｓ行った。
[Examples 1-7, Comparative Examples 1-4]
Using the amounts of components (a) and (b) shown in Table 1 below, resin compositions were produced. The manufacturing method is as follows.
First, the component (f) was added to the component (c) that had been heat-mixed and cooled, and stirred. Thereafter, components (a), (b), (d), and (e) were sequentially added and mixed uniformly with three rolls.
In Examples 1 to 7 and Comparative Examples 3 to 4, components (a) and (b) were premixed and added to the mixture of components (c) and (f). In 2, the components (a) and (b) are added in this order to the mixture of the components (c) and (f) and mixed.
In addition, premixing of components (a) and (b) was performed 3 passes using a jet mill pulverizer by mixing them in a ratio of (a) :( b) = 75: 18.
実施例１〜４、比較例１で調製した樹脂組成物について、以下の評価を行った。結果を表２にまとめる。 The following evaluations were performed on the resin compositions prepared in Examples 1 to 4 and Comparative Example 1. The results are summarized in Table 2.
[ろ過性試験]
凝集物の存在を評価する方法として、ろ過性試験を実施した。
これは、上記実施例１〜４、比較例１で調整した樹脂組成物４ｇを６ｍｍΦの６３５メッシュの金属メッシュでろ過し、時間とろ過できる量を測定する方法である。凝集物の多い樹脂組成物は次第にメッシュが詰まってくるため、ろ過速度が遅くなるが、分散されている樹脂組成物は一定の速度でろ過することができる。
ろ過性の評価
○：樹脂組成物４ｇが一定の速度でろ過できる。
△：樹脂組成物４ｇが徐々に速度が遅くなるがろ過できる。
×：樹脂組成物４ｇがろ過できず詰まってしまう。
[Filterability test]
A filterability test was performed as a method for evaluating the presence of aggregates.
This is a method of filtering 4 g of the resin composition prepared in Examples 1 to 4 and Comparative Example 1 with a metal mesh of 635 mesh of 6 mmΦ, and measuring the time and the amount that can be filtered. The resin composition having a large amount of agglomerates gradually clogs the mesh, and thus the filtration rate becomes slow. However, the dispersed resin composition can be filtered at a constant rate.
Evaluation of filterability ○: 4 g of the resin composition can be filtered at a constant rate.
(Triangle | delta): Although resin resin 4g becomes slow slowly, it can filter.
X: The resin composition 4 g cannot be filtered and is clogged.
[接着強度試験]
凝集物が存在すると樹脂組成物中でのフィラーの均一性がなくなるため接着強度が低下するが、均一に分散されている樹脂組成物はフィラーの偏りがなくなるため接着強度が向上する。
樹脂組成物１００ｇにスペーサーとして直径３μｍのグラスファイバー（ＰＦ−３０Ｓ：日本電気硝子株式会社製）１ｇを添加して混合撹拌を行う。この樹脂組成物を５０ｍｍ×５０ｍｍのガラス基板上に塗布し、その樹脂組成物上に１．５ｍｍ×１．５ｍｍのガラス片を貼り合わせ、１２０℃オーブンに１時間投入して硬化させた。そのガラス片のせん断接着強度をボンドテスター（ＳＳ−３０ＷＤ：西進商事株式会社製）を使用して測定した。その結果を表２に示す。
[Adhesive strength test]
When aggregates are present, the uniformity of the filler in the resin composition is lost and the adhesive strength is lowered. However, the uniformly dispersed resin composition is free from the unevenness of the filler, so that the adhesive strength is improved.
As a spacer, 1 g of glass fiber (PF-30S: manufactured by Nippon Electric Glass Co., Ltd.) having a diameter of 3 μm is added to 100 g of the resin composition and mixed and stirred. This resin composition was applied onto a 50 mm × 50 mm glass substrate, a 1.5 mm × 1.5 mm piece of glass was bonded to the resin composition, and cured in a 120 ° C. oven for 1 hour. The shear adhesive strength of the glass piece was measured using a bond tester (SS-30WD: manufactured by Seishin Shoji Co., Ltd.). The results are shown in Table 2.
表２の結果より、本発明によって得られた樹脂組成物には、凝集物がなく、ろ過速度が落ちない結果となった。これに対し、比較例の樹脂組成物は凝集物の存在から、ろ過性が徐々に落ちていることが分かる。
また、本発明の樹脂組成物は接着強度についても、優れることが確認された。
From the results shown in Table 2, the resin composition obtained according to the present invention had no aggregates, and the filtration rate did not decrease. On the other hand, it turns out that the filterability of the resin composition of the comparative example is gradually lowered due to the presence of the aggregate.
Moreover, it was confirmed that the resin composition of this invention is excellent also about adhesive strength.
本発明の方法によって得られた樹脂組成物は、フィラーの凝集物が無い為、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、また電子部品のギャップ不良を引き起こさない。更に接着強度等のような接着剤としての一般的な特性においても優れる為、長期信頼性に優れる電子部品の製造を容易にすることができる。 Since the resin composition obtained by the method of the present invention has no filler agglomerates, it is excellent in coating workability such as dispensing and screen printing, and does not cause gap defects in electronic parts. Furthermore, since it is excellent also in general characteristics as an adhesive such as adhesive strength, it is possible to easily manufacture an electronic component having excellent long-term reliability.
Claims (13)
３μｍ≦Ａ≦２０μｍ・・・ （１）
０．０００５×Ａ≦Ｂ≦０．０２０×Ａ・・・（２） A method for producing a resin composition comprising an organic filler (a) having an average particle size A [μm], a filler (b) having an average particle size B [μm], and a curable compound (c), wherein the A [μm ] And B [μm] satisfy the conditions represented by the following formulas (1) and (2), and before the filler (a) and the filler (b) are dispersed in the curable compound (c), the filler The manufacturing method of the resin composition which has a dry process which stirs and mixes (a) and a filler (b).
3 μm ≦ A ≦ 20 μm (1)
0.0005 × A ≦ B ≦ 0.020 × A (2)
The resin composition obtained by the manufacturing method of the resin composition as described in any one of Claims 1 thru | or 11.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014007383A JP6304803B2 (en) | 2014-01-20 | 2014-01-20 | Method for producing resin composition |
| TW103140189A TW201529654A (en) | 2014-01-20 | 2014-11-20 | Method for producing resin composition |
| KR1020140184414A KR102226486B1 (en) | 2014-01-20 | 2014-12-19 | Method for preparing resin composition, adhesive for electronic component, and electronic component |
| CN201510025793.7A CN104789166A (en) | 2014-01-20 | 2015-01-19 | Method for preparing resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014007383A JP6304803B2 (en) | 2014-01-20 | 2014-01-20 | Method for producing resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2015134887A JP2015134887A (en) | 2015-07-27 |
| JP6304803B2 true JP6304803B2 (en) | 2018-04-04 |
Family
ID=53554364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014007383A Active JP6304803B2 (en) | 2014-01-20 | 2014-01-20 | Method for producing resin composition |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6304803B2 (en) |
| KR (1) | KR102226486B1 (en) |
| CN (1) | CN104789166A (en) |
| TW (1) | TW201529654A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018163921A1 (en) | 2017-03-06 | 2018-09-13 | デクセリアルズ株式会社 | Resin composition, method for producing resin composition, and structure |
| JP7066998B2 (en) | 2017-08-23 | 2022-05-16 | デクセリアルズ株式会社 | Spacer-containing tape |
| WO2020175273A1 (en) * | 2019-02-26 | 2020-09-03 | 富士フイルム株式会社 | Adhesive for endoscope, cured product thereof, endoscope, and method for producing same |
| JP6744693B2 (en) * | 2019-09-02 | 2020-08-19 | 日本化薬株式会社 | Method for producing resin composition |
| TWI784669B (en) | 2020-08-19 | 2022-11-21 | 南韓商Ｌｇ化學股份有限公司 | Adhesive resin composition and adhesive film for semiconductor |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2676849B2 (en) * | 1988-11-19 | 1997-11-17 | 三菱化学株式会社 | Silica composite fine particles |
| JPH0558698A (en) * | 1991-06-18 | 1993-03-09 | Isuzu Motors Ltd | Production of artificial marble |
| JP2878497B2 (en) | 1991-09-30 | 1999-04-05 | イビデン株式会社 | Manufacturing method of adhesive for electroless plating |
| JP3415292B2 (en) | 1994-10-07 | 2003-06-09 | ジャパンエポキシレジン株式会社 | Epoxy resin composition for semiconductor encapsulation |
| JP3737207B2 (en) * | 1996-07-23 | 2006-01-18 | 京セラケミカル株式会社 | How to mix powder |
| AU2003289247A1 (en) * | 2002-12-13 | 2004-07-09 | Dow Corning Toray Silicone Co., Ltd. | Composite cured silicone powder, method for production thereof and aqueous composition |
| JP5343450B2 (en) * | 2007-08-29 | 2013-11-13 | 日立化成株式会社 | Adhesive film and adhesive sheet for fixing semiconductor elements |
| JP2010014771A (en) * | 2008-07-01 | 2010-01-21 | Nippon Kayaku Co Ltd | Thermosetting liquid crystal sealing material for liquid crystal dropping method and liquid crystal display cell using the same |
| JP5393292B2 (en) * | 2009-06-26 | 2014-01-22 | 日本化薬株式会社 | Liquid crystal sealing agent for liquid crystal dropping method and liquid crystal display cell using the same |
| KR101618397B1 (en) * | 2009-07-01 | 2016-05-04 | 니폰 가야꾸 가부시끼가이샤 | Liquid crystal sealing agent for liquid crystal dropping method and liquid crystal display cell using same |
| JP5589364B2 (en) * | 2009-11-20 | 2014-09-17 | 住友ベークライト株式会社 | Silicone rubber fine particle-containing epoxy resin composition, prepreg, metal-clad laminate, printed wiring board, and semiconductor device |
| JP5589363B2 (en) * | 2009-11-20 | 2014-09-17 | 住友ベークライト株式会社 | Silicone rubber fine particle-containing epoxy resin composition, prepreg, metal-clad laminate, printed wiring board, and semiconductor device |
| JP2011241279A (en) * | 2010-05-17 | 2011-12-01 | Shin Kobe Electric Mach Co Ltd | Epoxy resin composition and prepreg, laminated board, and wiring board |
| JP5943672B2 (en) * | 2012-03-28 | 2016-07-05 | クラレノリタケデンタル株式会社 | Dental composite inorganic filler |
-
2014
- 2014-01-20 JP JP2014007383A patent/JP6304803B2/en active Active
- 2014-11-20 TW TW103140189A patent/TW201529654A/en unknown
- 2014-12-19 KR KR1020140184414A patent/KR102226486B1/en active IP Right Grant
-
2015
- 2015-01-19 CN CN201510025793.7A patent/CN104789166A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| KR20150087090A (en) | 2015-07-29 |
| CN104789166A (en) | 2015-07-22 |
| KR102226486B1 (en) | 2021-03-10 |
| TW201529654A (en) | 2015-08-01 |
| JP2015134887A (en) | 2015-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6478313B2 (en) | Liquid crystal sealant and liquid crystal display cell using the same | |
| JP6304803B2 (en) | Method for producing resin composition | |
| JP6238850B2 (en) | Liquid crystal sealant and liquid crystal display cell using the same | |
| JP6253638B2 (en) | Liquid crystal sealant and liquid crystal display cell using the same | |
| JP2016109997A (en) | Liquid crystal sealant and liquid crystal cells using the same | |
| JP2016024243A (en) | Liquid crystal sealant and liquid crystal cell using the same | |
| JP6289372B2 (en) | Liquid crystal sealant and liquid crystal display cell using the same | |
| JP6235297B2 (en) | Liquid crystal sealant and liquid crystal display cell using the same | |
| JP6482371B2 (en) | Method for producing resin composition | |
| JP2015200729A (en) | Radiation curable resin composition, cured product, and application thereof | |
| JP6238761B2 (en) | Liquid crystal sealant and liquid crystal display cell using the same | |
| JP2017027043A (en) | Liquid crystal sealant and liquid crystal display cell using the same | |
| JP2017198726A (en) | Sealant for liquid crystal optical element and liquid crystal optical element using the same | |
| JP2018022052A (en) | Liquid crystal sealant and liquid crystal display cell using the same | |
| JP6744693B2 (en) | Method for producing resin composition | |
| JP6584132B2 (en) | Method for producing resin composition | |
| JP2016038509A (en) | Liquid crystal sealing agent and liquid crystal display cell having the same | |
| JP6465741B2 (en) | Liquid crystal sealant and liquid crystal display cell using the same | |
| JP2016109996A (en) | Liquid crystal sealant and liquid crystal cells using the same | |
| JP6366069B2 (en) | Method for producing resin composition | |
| JP2017219604A (en) | Liquid crystal sealant and liquid crystal display cell using the same | |
| JP6465740B2 (en) | Liquid crystal sealant and liquid crystal display cell using the same | |
| JP2018022055A (en) | Liquid crystal sealant and liquid crystal display cell using the same | |
| JP2017198725A (en) | Sealant for liquid crystal optical element and liquid crystal optical element using the same | |
| JP2016206474A (en) | Liquid crystal sealant and liquid crystal display cell using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160721 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20170127 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170131 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170308 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170406 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170522 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170802 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170914 |
|
| 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: 20180301 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20180302 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6304803 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R157 | Certificate of patent or utility model (correction) |
Free format text: JAPANESE INTERMEDIATE CODE: R157 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |