JP7442438B2 - Adhesive compositions, adhesives for electronic parts, and adhesives for display elements - Google Patents
Adhesive compositions, adhesives for electronic parts, and adhesives for display elements Download PDFInfo
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- JP7442438B2 JP7442438B2 JP2020502728A JP2020502728A JP7442438B2 JP 7442438 B2 JP7442438 B2 JP 7442438B2 JP 2020502728 A JP2020502728 A JP 2020502728A JP 2020502728 A JP2020502728 A JP 2020502728A JP 7442438 B2 JP7442438 B2 JP 7442438B2
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- adhesive composition
- mass
- meth
- adhesive
- nitrogen
- Prior art date
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- 230000001070 adhesive effect Effects 0.000 title claims description 186
- 239000000853 adhesive Substances 0.000 title claims description 185
- 239000000203 mixture Substances 0.000 title claims description 132
- 239000000178 monomer Substances 0.000 claims description 89
- 150000001875 compounds Chemical class 0.000 claims description 44
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 41
- 238000005259 measurement Methods 0.000 claims description 29
- 229920005989 resin Polymers 0.000 claims description 25
- 239000011347 resin Substances 0.000 claims description 25
- 125000004122 cyclic group Chemical group 0.000 claims description 21
- 239000003505 polymerization initiator Substances 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 229920001187 thermosetting polymer Polymers 0.000 claims description 14
- 238000013008 moisture curing Methods 0.000 claims description 8
- 125000003368 amide group Chemical group 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 2
- -1 polyethylene terephthalate Polymers 0.000 description 64
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 60
- 238000001723 curing Methods 0.000 description 32
- 230000014759 maintenance of location Effects 0.000 description 19
- 239000003822 epoxy resin Substances 0.000 description 16
- 229920000647 polyepoxide Polymers 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 13
- 125000000524 functional group Chemical group 0.000 description 13
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000007822 coupling agent Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 6
- 238000005286 illumination Methods 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 229920006026 co-polymeric resin Polymers 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 230000001678 irradiating effect Effects 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 229920002799 BoPET Polymers 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- PFHLXMMCWCWAMA-UHFFFAOYSA-N [4-(4-diphenylsulfoniophenyl)sulfanylphenyl]-diphenylsulfanium Chemical compound C=1C=C([S+](C=2C=CC=CC=2)C=2C=CC=CC=2)C=CC=1SC(C=C1)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 PFHLXMMCWCWAMA-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 150000004292 cyclic ethers Chemical group 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000000532 dioxanyl group Chemical group 0.000 description 3
- 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 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 229920001780 ECTFE Polymers 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- 229920000577 Nylon 6/66 Polymers 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- TZYHIGCKINZLPD-UHFFFAOYSA-N azepan-2-one;hexane-1,6-diamine;hexanedioic acid Chemical compound NCCCCCCN.O=C1CCCCCN1.OC(=O)CCCCC(O)=O TZYHIGCKINZLPD-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001768 cations Chemical group 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000004643 cyanate ester Substances 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 230000005661 hydrophobic surface Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920001230 polyarylate Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229940042596 viscoat Drugs 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- PEVRKKOYEFPFMN-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene;1,1,2,2-tetrafluoroethene Chemical group FC(F)=C(F)F.FC(F)=C(F)C(F)(F)F PEVRKKOYEFPFMN-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical group C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-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
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- FLKHVLRENDBIDB-UHFFFAOYSA-N 2-(butylcarbamoyloxy)ethyl prop-2-enoate Chemical compound CCCCNC(=O)OCCOC(=O)C=C FLKHVLRENDBIDB-UHFFFAOYSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
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- 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 1
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
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- 125000003277 amino group Chemical group 0.000 description 1
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000005345 chemically strengthened glass Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical class [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- URQUNWYOBNUYJQ-UHFFFAOYSA-N diazonaphthoquinone Chemical compound C1=CC=C2C(=O)C(=[N]=[N])C=CC2=C1 URQUNWYOBNUYJQ-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000005400 gorilla glass Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000006502 nitrobenzyl group Chemical group 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920003214 poly(methacrylonitrile) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001896 polybutyrate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000005076 polymer ester Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005554 polynitrile Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel 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
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2463/00—Presence of epoxy resin
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、接着剤組成物、該接着剤組成物を用いた電子部品用接着剤及び表示素子用接着剤に関する。 The present invention relates to an adhesive composition, an adhesive for electronic components, and an adhesive for display elements using the adhesive composition.
従来より、接着剤組成物として、紫外線又は電子線等の活性エネルギー線により硬化するものが広く使用されている。このような接着剤組成物は電子機器分野をはじめとして、広い分野で用いられている。 Conventionally, adhesive compositions that are cured by active energy rays such as ultraviolet rays or electron beams have been widely used. Such adhesive compositions are used in a wide range of fields including the field of electronic equipment.
特許文献１には、硬化性成分として、活性メチレン基を有するラジカル重合性化合物（Ａ）、および水素引き抜き作用のあるラジカル重合開始剤（Ｂ）を含有することを特徴とする活性エネルギー線硬化型接着剤組成物に関する発明が記載されており、２以上の部材、特に偏光子と透明保護フィルム層との接着性が向上することが示されている。
特許文献２には、特定のモノアクリレートと、有機化合物と、光開始剤とを含有する光硬化性粘着剤を用いた接着方法に関する発明が記載されており、該光硬化性粘着剤は、空気中でも迅速に硬化することが示されている。
特許文献３には、（ａ１）特定のアルキル（メタ）アクリレートモノマー、（ａ２）分子内に少なくとも１つの窒素原子と１つのエチレン性不飽和結合を有するモノマー、（ａ３）分子内に１つのエチレン性不飽和結合を有する特定のモノマーとを含有する粘着剤組成物により形成される粘着剤層を有する粘着テープ等に関する発明が記載されている。該粘着テープは、高い初期粘着力を維持しつつ、被着体から剥がす際には容易に剥離することが示されている。
Patent Document 1 discloses an active energy ray-curable type characterized by containing a radically polymerizable compound (A) having an active methylene group and a radical polymerization initiator (B) having a hydrogen abstracting action as a curable component. An invention relating to an adhesive composition is described and shown to improve adhesion between two or more members, particularly a polarizer and a transparent protective film layer.
Patent Document 2 describes an invention related to an adhesion method using a photocurable adhesive containing a specific monoacrylate, an organic compound, and a photoinitiator, and the photocurable adhesive is It has been shown that it cures quickly.
Patent Document 3 describes (a1) a specific alkyl (meth)acrylate monomer, (a2) a monomer having at least one nitrogen atom and one ethylenically unsaturated bond in the molecule, and (a3) one ethylene in the molecule. The invention relates to an adhesive tape having an adhesive layer formed from an adhesive composition containing a specific monomer having a sexually unsaturated bond. It has been shown that the adhesive tape can be easily peeled off from an adherend while maintaining a high initial adhesive strength.
近年、接着剤組成物を被着体に塗布した後、活性エネルギー線を２度照射して硬化させる２段階硬化システムが注目されている。１段階目の硬化は、接着剤組成物を基材などの被着体に塗布した後に活性エネルギー線を照射して行う硬化であり、これを初期硬化（仮硬化）ともいう。該初期硬化させた接着剤組成物の初期硬化体上に、別の被着体を積層して仮接着させた後、活性エネルギー線を再度照射して、２段階目の硬化を行う。２段階目の硬化のことを本硬化などという。
１段階目の硬化の際には、被着体同士を仮接着させるために、接着剤組成物の接着力（初期接着力）を高くすること、及び接着剤組成物の初期硬化体の形状保持性が良好であることが必要とされる。しかしながら、上記した従来の接着剤組成物について２段階硬化システムを適用した場合、初期接着力及び形状保持性を両立することが困難であった。
そこで、本発明の課題は、活性エネルギー線を照射した際の初期接着力及び形状保持性の良好な接着剤組成物を提供することにある。
In recent years, a two-step curing system has attracted attention, in which an adhesive composition is applied to an adherend and then cured by irradiating it with active energy rays twice. The first stage of curing is performed by applying active energy rays to the adhesive composition after applying it to an adherend such as a base material, and is also referred to as initial curing (temporary curing). After another adherend is laminated and temporarily bonded onto the initially cured product of the adhesive composition that has been initially cured, active energy rays are irradiated again to perform a second stage of curing. The second stage of curing is called main curing.
During the first stage of curing, the adhesive strength (initial adhesive strength) of the adhesive composition is increased in order to temporarily bond the adherends together, and the shape of the initially cured adhesive composition is maintained. Good quality is required. However, when a two-step curing system is applied to the conventional adhesive composition described above, it is difficult to achieve both initial adhesive strength and shape retention.
Therefore, an object of the present invention is to provide an adhesive composition that exhibits good initial adhesive strength and shape retention when irradiated with active energy rays.
本発明者らは、上記課題を解決するため鋭意検討した。その結果、Ｔｇａ及びＴｇｂ－Ｔｇａの絶対値（｜Ｔｇｂ－Ｔｇａ｜）が一定範囲となる接着剤組成物により上記課題が解決できることを見出し、本発明を完成させた。なお、上記Ｔｇａとは、酸素存在下おいて硬化させた接着剤組成物の硬化物の動的粘弾性測定におけるｔａｎδピーク温度であり、上記Ｔｇｂとは、酸素非存在下おいて硬化させた接着剤組成物の硬化物の動的粘弾性測定におけるｔａｎδピーク温度である。
すなわち、本発明は下記のとおりである。
The present inventors conducted extensive studies to solve the above problems. As a result, the inventors found that the above-mentioned problems can be solved by using an adhesive composition in which the absolute values of Tga and Tgb-Tga (|Tgb-Tga|) fall within a certain range, and the present invention was completed. The above Tga is the tan δ peak temperature in the dynamic viscoelasticity measurement of the cured product of the adhesive composition cured in the presence of oxygen, and the above Tgb is the peak temperature of the adhesive cured in the absence of oxygen. This is the tan δ peak temperature in the dynamic viscoelasticity measurement of the cured product of the agent composition.
That is, the present invention is as follows.
［１］ラジカル重合性化合物と、光ラジカル重合開始剤とを含む接着剤組成物であって、酸素存在下で硬化させた前記接着剤組成物の硬化物の動的粘弾性測定におけるｔａｎδピーク温度をＴｇａ、酸素非存在下で硬化させた前記接着剤組成物の硬化物の動的粘弾性測定におけるｔａｎδピーク温度をＴｇｂとした場合に、下記式（１）及び（２）を満足する、接着剤組成物。
式（１） ｜Ｔｇｂ－Ｔｇａ｜≦３０℃
式（２） －１５℃≦Ｔｇａ≦３５℃
［２］前記ラジカル重合性化合物全量基準における多官能モノマーの含有量が５質量％以下である、上記［１］に記載の接着剤組成物。
［３］前記ラジカル重合性化合物が窒素含有モノマーを含む、上記［１］又は［２］に記載の接着剤組成物。
［４］前記窒素含有モノマーが環状構造を有する窒素含有モノマーである、上記［３］に記載の接着剤組成物。
［５］前記環状構造を有する窒素含有モノマーが、環状構造を有するアミド基含有モノマーである、上記［４］に記載の接着剤組成物。
［６］前記ラジカル重合性化合物全量基準における前記環状構造を有する窒素含有モノマーの含有量が１０～６０質量％である、上記［４］又は［５］に記載の接着剤組成物。
［７］前記光ラジカル重合開始剤の含有量が、ラジカル重合性化合物１００質量部に対して、０．１質量部以上２．０質量部以下である、上記［１］～［６］のいずれかに記載の接着剤組成物。
［８］さらに熱硬化性樹脂及び湿気硬化性樹脂から選択される１種以上を含有する、上記［１］～［７］のいずれかに記載の接着剤組成物。
［９］上記［１］～［８］のいずれかに記載の接着剤組成物からなる電子部品用接着剤。
［１０］上記［１］～［８］のいずれかに記載の接着剤組成物からなる表示素子用接着剤。
[1] An adhesive composition containing a radical polymerizable compound and a photoradical polymerization initiator, the tan δ peak temperature in dynamic viscoelasticity measurement of a cured product of the adhesive composition cured in the presence of oxygen. An adhesive that satisfies the following formulas (1) and (2), where Tga is the tan δ peak temperature in the dynamic viscoelasticity measurement of the cured product of the adhesive composition cured in the absence of oxygen. agent composition.
Formula (1) |Tgb-Tga|≦30℃
Formula (2) -15℃≦Tga≦35℃
[2] The adhesive composition according to [1] above, wherein the content of the polyfunctional monomer based on the total amount of the radically polymerizable compound is 5% by mass or less.
[3] The adhesive composition according to [1] or [2] above, wherein the radically polymerizable compound contains a nitrogen-containing monomer.
[4] The adhesive composition according to [3] above, wherein the nitrogen-containing monomer has a cyclic structure.
[5] The adhesive composition according to [4] above, wherein the nitrogen-containing monomer having a cyclic structure is an amide group-containing monomer having a cyclic structure.
[6] The adhesive composition according to [4] or [5] above, wherein the content of the nitrogen-containing monomer having a cyclic structure is 10 to 60% by mass based on the total amount of the radically polymerizable compound.
[7] Any of the above [1] to [6], wherein the content of the photoradical polymerization initiator is 0.1 parts by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the radically polymerizable compound. The adhesive composition according to claim 1.
[8] The adhesive composition according to any one of [1] to [7] above, further containing one or more selected from thermosetting resins and moisture-curing resins.
[9] An adhesive for electronic components comprising the adhesive composition according to any one of [1] to [8] above.
[10] An adhesive for display elements comprising the adhesive composition according to any one of [1] to [8] above.
本発明によれば、活性エネルギー線を照射した際の初期接着力及び形状保持性の良好な接着剤組成物を提供することができる。 According to the present invention, it is possible to provide an adhesive composition that exhibits good initial adhesive strength and shape retention when irradiated with active energy rays.
［接着剤組成物］
本発明の接着剤組成物は、ラジカル重合性化合物と、光ラジカル重合開始剤とを含む接着剤組成物である。該接着剤組成物は、酸素存在下で硬化させた前記接着剤組成物の硬化物の動的粘弾性測定におけるｔａｎδピーク温度をＴｇａ、酸素非存在下で硬化させた前記接着剤組成物の硬化物の動的粘弾性測定におけるｔａｎδピーク温度をＴｇｂとした場合に、下記式（１）及び（２）を満足する、接着剤組成物である。
式（１） ｜Ｔｇｂ－Ｔｇａ｜≦３０℃
式（２） －１５℃≦Ｔｇａ≦３５℃
[Adhesive composition]
The adhesive composition of the present invention is an adhesive composition containing a radically polymerizable compound and a radical photopolymerization initiator. The adhesive composition has a tan δ peak temperature of Tga in the dynamic viscoelasticity measurement of the cured product of the adhesive composition cured in the presence of oxygen, and a cure of the adhesive composition cured in the absence of oxygen. The adhesive composition satisfies the following formulas (1) and (2), where Tgb is the tan δ peak temperature in the dynamic viscoelasticity measurement of the object.
Formula (1) |Tgb-Tga|≦30℃
Formula (2) -15℃≦Tga≦35℃
本発明において、酸素存在下での硬化とは、後述する２段階硬化システムにおける１段階目の硬化と同様の環境下で行う硬化であり、基材などの被着体に接着剤組成物を塗布した後に、該接着剤組成物に対して活性エネルギー線を照射して行う初期硬化（仮硬化）のことを意味している。すなわち、被着体に塗布された接着剤組成物の被着体に接する側と反対側が大気中に開放されている状態での硬化を意味する。
本発明において、酸素非存在下での硬化とは、接着剤組成物を被着体同士で挟み込んで行う硬化のことを意味し、２段階硬化システムにおける２段回目の硬化（本硬化）と同様の環境下で行う硬化のことを意味する。
本発明において、初期接着力とは、初期硬化（仮硬化）させた接着剤組成物の接着力を意味し、本接着力とは、本硬化させた際の接着剤組成物の接着力を意味する。また、形状保持性とは、仮硬化させた接着剤組成物の形状保持性を意味する。
In the present invention, curing in the presence of oxygen refers to curing performed in the same environment as the first stage curing in a two-stage curing system described below, in which the adhesive composition is applied to an adherend such as a base material. This refers to initial curing (temporary curing) performed by irradiating the adhesive composition with active energy rays after the adhesive composition has been cured. That is, it means curing in a state where the side of the adhesive composition applied to the adherend is exposed to the atmosphere, and the side opposite to the side in contact with the adherend is exposed to the atmosphere.
In the present invention, curing in the absence of oxygen means curing performed by sandwiching the adhesive composition between adherends, and is similar to the second curing (main curing) in a two-step curing system. This refers to curing performed under an environment of
In the present invention, the initial adhesive strength means the adhesive strength of the adhesive composition after initial curing (temporary curing), and the actual adhesive strength means the adhesive strength of the adhesive composition after main curing. do. Moreover, shape retention means the shape retention of the adhesive composition which was temporarily hardened.
本発明の接着剤組成物は、式（１）で表されるように、Ｔｇｂ－Ｔｇａの絶対値である｜Ｔｇｂ－Ｔｇａ｜が３０℃以下である。これは、接着剤組成物を酸素存在下で硬化させた場合と酸素非存在下で硬化させた場合とで、硬化の進行の度合いの差が小さいことを意味し、換言すれば、酸素存在下の硬化の際に、重合阻害が生じ難いことを意味する。本発明の接着剤組成物の｜Ｔｇｂ－Ｔｇａ｜が３０℃を超えると、初期接着力が低くなりやすい。接着剤組成物の初期接着力を高める観点から、｜Ｔｇｂ－Ｔｇａ｜は好ましくは２５℃以下であり、より好ましくは２２℃以下であり、更に好ましくは２０℃以下であり、そして好ましくは０℃以上である。 As expressed by formula (1), the adhesive composition of the present invention has an absolute value of Tgb-Tga, |Tgb-Tga|, of 30° C. or less. This means that the difference in the degree of curing progress is small when the adhesive composition is cured in the presence of oxygen and in the absence of oxygen. This means that polymerization inhibition is unlikely to occur during curing. When |Tgb-Tga| of the adhesive composition of the present invention exceeds 30°C, the initial adhesive strength tends to be low. From the viewpoint of increasing the initial adhesive strength of the adhesive composition, |Tgb-Tga| is preferably 25°C or less, more preferably 22°C or less, even more preferably 20°C or less, and preferably 0°C. That's all.
本発明の接着剤組成物は、式（２）で表されるように、Ｔｇａが－１５℃以上３５℃以下である。Ｔｇａが－１５℃未満の場合は、接着剤組成物の形状保持性が悪くなる。Ｔｇａが３５℃を超える場合、硬化が進行し過ぎて接着剤組成物の初期接着力が低くなる。Ｔｇａは、好ましい下限が－１０℃、より好ましい下限が－５℃であり、好ましい上限が３０℃、より好ましい上限が２７℃である。
本発明の接着剤組成物は、上記式（１）及び（２）を同時に満足することにより、初期接着力及び形状保持性を良好に両立させることが可能となる。
As expressed by formula (2), the adhesive composition of the present invention has a Tga of -15°C or more and 35°C or less. If Tga is less than -15°C, the shape retention of the adhesive composition will be poor. When Tga exceeds 35°C, curing progresses too much and the initial adhesive strength of the adhesive composition becomes low. A preferable lower limit of Tga is -10°C, a more preferable lower limit is -5°C, a preferable upper limit is 30°C, and a more preferable upper limit is 27°C.
By satisfying the above formulas (1) and (2) at the same time, the adhesive composition of the present invention can achieve both good initial adhesive strength and shape retention.
本発明の接着剤組成物のＴｇｂは特に限定されないが、好ましい下限が０℃、より好ましい下限が５℃であり、好ましい上限が６０℃、より好ましい上限が５２℃、さらに好ましい上限が５０℃である。 The Tgb of the adhesive composition of the present invention is not particularly limited, but a preferable lower limit is 0°C, a more preferable lower limit is 5°C, a preferable upper limit is 60°C, a more preferable upper limit is 52°C, and an even more preferable upper limit is 50°C. be.
上記式（１）における｜Ｔｇｂ－Ｔｇａ｜、及び式（２）のＴｇａは、後述する接着剤組成物に含有される１又は２以上のラジカル重合性化合物の種類、量などにより調整することができる。 |Tgb−Tga| in the above formula (1) and Tga in formula (2) can be adjusted by the type, amount, etc. of one or more radically polymerizable compounds contained in the adhesive composition described below. can.
（Ｔｇａ、Ｔｇｂの測定方法）
Ｔｇａは、酸素存在下で硬化させた接着剤組成物の硬化物の動的粘弾性測定におけるｔａｎδピーク温度である。Ｔｇａは以下のように測定することができる。
被着体に接着剤組成物を塗布した後、接着剤組成物の被着体に接する側と反対側が大気中に開放された状態、すなわち酸素存在下で、接着剤組成物に対して活性エネルギー線を照射することにより得た硬化物について、動的粘弾性測定を行うことで、Ｔｇａを求めることができる。上記被着体としては、加熱により変形しないものであれば、特に制限されず、材質が金属であることが好ましく、また測定の容易さの観点から、動的粘弾性の測定冶具（材質はＳＵＳ製）を被着体として用いてもよい。なお、Ｔｇａ及びＴｇｂは、実施例に記載の方法で測定することができる。
活性エネルギー線の照射は、ＬＥＤランプにて、照度１０００ｍＷ／ｃｍ２、積算光量１０００ｍＪ／ｃｍ２の条件で行う。ＬＥＤランプの波長は、光ラジカル重合開始剤の吸収波長域に応じて適宜選択され、例えば波長４０５ｎｍのランプを用いる。また、動的粘弾性測定は、せん断法にて、測定温度－１００～２００℃、昇温速度３℃／分、歪み量０．８％、周波数１Ｈｚ、の条件で行う。
(Measurement method of Tga and Tgb)
Tga is the tan δ peak temperature in the dynamic viscoelasticity measurement of the cured product of the adhesive composition cured in the presence of oxygen. Tga can be measured as follows.
After applying the adhesive composition to the adherend, active energy is applied to the adhesive composition in a state where the side of the adhesive composition in contact with the adherend and the opposite side are exposed to the atmosphere, that is, in the presence of oxygen. Tga can be determined by performing dynamic viscoelasticity measurement on the cured product obtained by irradiating the cured product. The above-mentioned adherend is not particularly limited as long as it does not deform when heated; it is preferably made of metal, and from the viewpoint of ease of measurement, a dynamic viscoelasticity measuring jig (made of SUS may be used as the adherend. Note that Tga and Tgb can be measured by the methods described in Examples.
Irradiation with active energy rays is performed using an LED lamp under the conditions of an illumination intensity of 1000 mW/cm 2 and an integrated light amount of 1000 mJ/cm 2 . The wavelength of the LED lamp is appropriately selected depending on the absorption wavelength range of the photoradical polymerization initiator, and for example, a lamp with a wavelength of 405 nm is used. Further, dynamic viscoelasticity measurement is performed using a shear method under the conditions of a measurement temperature of -100 to 200°C, a temperature increase rate of 3°C/min, a strain amount of 0.8%, and a frequency of 1Hz.
Ｔｇｂは、酸素非存在下で硬化させた接着剤組成物の硬化物の動的粘弾性測定におけるｔａｎδピーク温度である。Ｔｇｂは以下のように測定することができる。
接着剤組成物を２枚の離型ポリエチレンテレフタレートフィルムの間に挟み込んだ測定試料を準備する。該測定試料に対して、活性エネルギー線を照射することにより得た、接着剤組成物の硬化物について、動的粘弾性測定を行うことで、Ｔｇｂを求めることができる。上記測定試料は、厚みが変わらないように、テープ等により固定してもよい。
活性エネルギー線の照射は、ＬＥＤランプにて、照度４ｍＷ／ｃｍ２、積算光量３０００ｍＪ／ｃｍ２の条件で行う。ＬＥＤランプの波長は、光ラジカル重合開始剤の吸収波長域に応じて適宜選択され、例えば波長４０５ｎｍのランプを用いる。また、動的粘弾性測定は、せん断法にて、測定温度－１００～２００℃、昇温速度３℃／分、歪み量０．８％、周波数１Ｈｚ、の条件で行う。
Tgb is the tan δ peak temperature in the dynamic viscoelasticity measurement of the cured product of the adhesive composition cured in the absence of oxygen. Tgb can be measured as follows.
A measurement sample is prepared in which an adhesive composition is sandwiched between two release polyethylene terephthalate films. Tgb can be determined by performing dynamic viscoelasticity measurement on a cured adhesive composition obtained by irradiating the measurement sample with active energy rays. The measurement sample may be fixed with tape or the like so that its thickness does not change.
Irradiation with active energy rays is performed using an LED lamp under the conditions of an illumination intensity of 4 mW/cm 2 and an integrated light amount of 3000 mJ/cm 2 . The wavelength of the LED lamp is appropriately selected depending on the absorption wavelength range of the photoradical polymerization initiator, and for example, a lamp with a wavelength of 405 nm is used. Further, dynamic viscoelasticity measurement is performed using a shear method under the conditions of a measurement temperature of -100 to 200°C, a temperature increase rate of 3°C/min, a strain amount of 0.8%, and a frequency of 1Hz.
（ラジカル重合性化合物）
本発明の接着剤組成物は、ラジカル重合性化合物を含有する。ラジカル重合性化合物は、光重合性を有するラジカル重合性化合物であればよく、分子中に、ラジカル反応性官能基を有する化合物であれば特に限定されない。ラジカル反応性官能基としては、例えば、（メタ）アクリロイル基、ビニル基、スチリル基、アリル基などが挙げられる。
なお、本明細書において、上記「（メタ）アクリロイル基」とは、アクリロイル基又はメタクリロイル基を意味する。他の類似する表現も同様とする。
(Radical polymerizable compound)
The adhesive composition of the present invention contains a radically polymerizable compound. The radically polymerizable compound may be any radically polymerizable compound having photopolymerizability, and is not particularly limited as long as it is a compound having a radically reactive functional group in the molecule. Examples of the radically reactive functional group include (meth)acryloyl group, vinyl group, styryl group, and allyl group.
In addition, in this specification, the said "(meth)acryloyl group" means an acryloyl group or a methacryloyl group. The same applies to other similar expressions.
ラジカル重合性化合物は、一つのラジカル反応性官能基を有する単官能モノマー、二以上のラジカル反応性官能基を有する多官能モノマーの一方又は両方を含んでもよいが、接着剤組成物の初期接着力を向上させる観点から、多官能モノマーの量は少ない方が好ましく、含有しないことがより好ましい。多官能モノマーの量を少なくすることにより、Ｔｇａ及びＴｇｂが大きくなりすぎるのを防止することができる。具体的には、ラジカル重合性化合物全量基準における多官能モノマーの含有量は５質量％以下であることが好ましく、２質量％以下であることがより好ましく、０．５質量％以下であることが更に好ましく、０．２質量％以下であることが更に好ましく、０質量％であることが更に好ましい。 The radically polymerizable compound may contain one or both of a monofunctional monomer having one radically reactive functional group and a polyfunctional monomer having two or more radically reactive functional groups, but the initial adhesive strength of the adhesive composition From the viewpoint of improving the polyfunctional monomer, it is preferable that the amount of the polyfunctional monomer is small, and it is more preferable that it is not contained. By reducing the amount of polyfunctional monomer, it is possible to prevent Tga and Tgb from becoming too large. Specifically, the content of the polyfunctional monomer based on the total amount of radically polymerizable compounds is preferably 5% by mass or less, more preferably 2% by mass or less, and preferably 0.5% by mass or less. It is more preferably 0.2% by mass or less, even more preferably 0% by mass.
＜窒素含有モノマー＞
本発明のラジカル重合性化合物は、窒素含有モノマーを含むことが好ましい。窒素含有モノマーを用いることにより、Ｔｇａ及び｜Ｔｇｂ－Ｔｇａ｜を上記した範囲に調整しやすくなり、接着剤組成物の初期接着力及び形状保持性が良好になる。これは、窒素含有モノマーを用いることにより、接着剤組成物を酸素存在下で重合する際に、重合阻害を受けにくくなるためと推察される。
また、接着剤組成物が、窒素含有モノマーを含む場合は、１段階目で活性エネルギー線を照射した後でも、徐々に硬化が進行する傾向がある。そのため、得られる接着剤組成物が初期接着力により一層優れるものとなる。
窒素含有モノマーは、窒素原子及びラジカル反応性官能基を有するモノマーであればよい。窒素含有モノマーは、一つのラジカル反応性官能基を有する単官能モノマー、二以上のラジカル反応性官能基を有する多官能モノマーの一方又は両方を含んでもよいが、接着剤組成物の初期接着力を高める観点から、多官能モノマーは少ない方が好ましく、含有しないことがより好ましい。具体的には、上記したとおり、ラジカル重合性化合物全量基準における多官能モノマーの含有量を好ましくは５質量％以下、より好ましくは２質量％以下、更に好ましくは０．５質量％以下、更に好ましくは０．２質量％以下、更に好ましくは０質量％となるように調整すればよい。
窒素含有モノマーは、鎖状の窒素含有モノマー及び環状構造を有する窒素含有モノマーの一方又は両方を含有してもよいが、接着剤組成物の初期接着力及び形状保持性を良好とする観点から、環状構造を有する窒素含有モノマーを含むことが好ましく、鎖状の窒素含有モノマーと、環状構造を有する窒素含有モノマーとを併用することがより好ましい。鎖状の窒素含有モノマーを含有することにより、得られる接着剤組成物の｜Ｔｇｂ－Ｔｇａ｜を上記した所定の範囲に調整しやすくなる。一方、環状構造を有する窒素含有モノマーを含むことにより、光照射時の反応性が高くなり、初期接着性により一層優れるものとなる。
<Nitrogen-containing monomer>
The radically polymerizable compound of the present invention preferably contains a nitrogen-containing monomer. By using a nitrogen-containing monomer, Tga and |Tgb-Tga| can be easily adjusted within the above-mentioned ranges, and the initial adhesive strength and shape retention of the adhesive composition are improved. This is presumably because the use of a nitrogen-containing monomer makes the adhesive composition less susceptible to polymerization inhibition when polymerizing in the presence of oxygen.
Furthermore, when the adhesive composition contains a nitrogen-containing monomer, curing tends to proceed gradually even after irradiation with active energy rays in the first step. Therefore, the resulting adhesive composition has even better initial adhesive strength.
The nitrogen-containing monomer may be any monomer having a nitrogen atom and a radically reactive functional group. The nitrogen-containing monomer may include one or both of a monofunctional monomer having one radically reactive functional group and a polyfunctional monomer having two or more radically reactive functional groups; From the viewpoint of increasing the number of polyfunctional monomers, it is preferable that there are fewer polyfunctional monomers, and it is more preferable that they are not contained. Specifically, as described above, the content of the polyfunctional monomer based on the total amount of the radically polymerizable compound is preferably 5% by mass or less, more preferably 2% by mass or less, still more preferably 0.5% by mass or less, and even more preferably may be adjusted to 0.2% by mass or less, more preferably 0% by mass.
The nitrogen-containing monomer may contain one or both of a chain nitrogen-containing monomer and a nitrogen-containing monomer having a cyclic structure, but from the viewpoint of improving the initial adhesive strength and shape retention of the adhesive composition, It is preferable to include a nitrogen-containing monomer having a cyclic structure, and it is more preferable to use a chain nitrogen-containing monomer and a nitrogen-containing monomer having a cyclic structure in combination. By containing the chain nitrogen-containing monomer, |Tgb-Tga| of the resulting adhesive composition can be easily adjusted to the above-mentioned predetermined range. On the other hand, by including a nitrogen-containing monomer having a cyclic structure, the reactivity upon irradiation with light increases, resulting in even more excellent initial adhesiveness.
鎖状の窒素含有モノマーとしては、例えば、ジメチルアミノ（メタ）アクリレート、ジエチルアミノ（メタ）アクリレート、アミノメチル（メタ）アクリレート、アミノエチル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート等の鎖状のアミノ基含有モノマー、ジアセトンアクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ，Ｎ－ジエチルアクリルアミド、Ｎ－イソプロピルアクリルアミド、Ｎ－ヒドロキシエチルアクリルアミド、アクリルアミド、メタクリルアミド等の鎖状のアミド基含有モノマー、１，２－エタンジオール１－アクリラート２－（Ｎ－ブチルカルバマート）などの鎖状のウレタン基含有モノマー、アクリロニトリル等が挙げられる。
環状構造を有する窒素含有モノマーとしては、Ｎ－ビニルピロリドン、Ｎ－ビニルカプロラクタム、Ｎ－アクリロイルモルホリンなどが挙げられ、中でもＮ－ビニルピロリドン、Ｎ－ビニルカプロラクタムなどの環状構造を有するアミド基含有モノマーを用いることが好ましい。
Examples of chain nitrogen-containing monomers include chain nitrogen-containing monomers such as dimethylamino (meth)acrylate, diethylamino (meth)acrylate, aminomethyl (meth)acrylate, aminoethyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate. Amino group-containing monomer, chain-shaped amide group-containing monomer such as diacetone acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, N-hydroxyethylacrylamide, acrylamide, methacrylamide, etc., 1. Examples include linear urethane group-containing monomers such as 2-ethanediol 1-acrylate 2-(N-butyl carbamate), acrylonitrile, and the like.
Examples of nitrogen-containing monomers having a cyclic structure include N-vinylpyrrolidone, N-vinylcaprolactam, N-acryloylmorpholine, etc. Among them, amide group-containing monomers having a cyclic structure such as N-vinylpyrrolidone and N-vinylcaprolactam are used. It is preferable to use
ラジカル重合性化合物全量基準における窒素含有モノマーの含有量は、接着剤組成物の初期接着力及び形状保持性を良好とする観点、および｜Ｔｇｂ－Ｔｇａ｜を上記した所定の範囲に調整しやすくなる観点から、好ましくは１０質量％以上、より好ましくは４０質量％以上、更に好ましくは７０質量％以上である。また、同様の観点から、ラジカル重合性化合物全量基準における窒素含有モノマーの含有量は、好ましくは９５質量％以下、より好ましくは９０質量％以下ある。 The content of the nitrogen-containing monomer based on the total amount of the radically polymerizable compound is determined from the viewpoint of improving the initial adhesive strength and shape retention of the adhesive composition, and making it easier to adjust |Tgb-Tga| to the above-mentioned predetermined range. From this point of view, the content is preferably 10% by mass or more, more preferably 40% by mass or more, and even more preferably 70% by mass or more. Further, from the same viewpoint, the content of the nitrogen-containing monomer based on the total amount of radically polymerizable compounds is preferably 95% by mass or less, more preferably 90% by mass or less.
ラジカル重合性化合物全量基準における環状構造を有する窒素含有モノマーの含有量は、接着剤組成物の初期接着力及び形状保持性を良好とする観点、および｜Ｔｇｂ－Ｔｇａ｜を上記した所定の範囲に調整しやすくなる観点から、好ましくは１０質量％以上、より好ましくは２０質量％以上、更に好ましくは３０質量％以上である。また、同様の観点から、ラジカル重合性化合物全量基準における環状構造を有する窒素含有モノマーの含有量は、好ましくは６０質量％以下であり、より好ましくは５０質量％以下である。 The content of the nitrogen-containing monomer having a cyclic structure based on the total amount of the radically polymerizable compound is determined from the viewpoint of improving the initial adhesive strength and shape retention of the adhesive composition, and from the viewpoint of keeping |Tgb-Tga| within the above-mentioned predetermined range. From the viewpoint of easy adjustment, the content is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more. Further, from the same viewpoint, the content of the nitrogen-containing monomer having a cyclic structure based on the total amount of radically polymerizable compounds is preferably 60% by mass or less, and more preferably 50% by mass or less.
鎖状の窒素含有モノマーと環状構造を有する窒素含有モノマーとを併用する場合は、接着剤組成物の初期接着力及び形状保持性を良好とする観点から、鎖状の窒素含有モノマーに対する環状構造を有する窒素含有モノマーの質量は０．３～２．０であることが好ましく、０．５～１．０であることが好ましい。 When a chain nitrogen-containing monomer and a nitrogen-containing monomer having a cyclic structure are used together, from the viewpoint of improving the initial adhesive strength and shape retention of the adhesive composition, the cyclic structure for the chain nitrogen-containing monomer is The mass of the nitrogen-containing monomer is preferably 0.3 to 2.0, more preferably 0.5 to 1.0.
＜窒素含有モノマー以外のモノマー＞
本発明のラジカル重合性化合物は、上記した窒素含有モノマー以外のモノマー（以下、窒素非含有モノマーともいう）を含むことが好ましい。
窒素非含有モノマーは、一つのラジカル反応性官能基を有する単官能モノマー、二以上のラジカル反応性官能基を有する多官能モノマーの一方又は両方を含んでもよいが、接着剤組成物の初期接着力を高める観点から、多官能モノマーは少ない方が好ましく、含有しないことがより好ましい。具体的には、上記したとおり、ラジカル重合性化合物全量基準における多官能モノマーの含有量を好ましくは５質量％以下、より好ましくは２質量％以下、更に好ましくは０．５質量％以下、更に好ましくは０．２質量％以下、更に好ましくは０質量％となるように調整すればよい。
窒素非含有モノマーとしては、ラジカル反応性官能基を有する化合物であれば特に制限されないが、（メタ）アクリロイル基を有するモノマー（以下、アクリルモノマーともいう）が好ましい。
アクリルモノマーとしては、例えば、アルキル（メタ）アクリレート、脂環構造含有（メタ）アクリレート、芳香環含有（メタ）アクリレートなどが挙げられる。
また、アクリルモノマーは、環状エーテル基、水酸基、カルボキシル基などの官能基を有するモノマーであってもよい。
中でも、アクリルモノマーとしては、アルキル（メタ）アクリレート、芳香環含有（メタ）アクリレート、環状エーテル基含有（メタ）アクリレートが好ましい。
<Monomer other than nitrogen-containing monomer>
The radically polymerizable compound of the present invention preferably contains monomers other than the above-mentioned nitrogen-containing monomers (hereinafter also referred to as non-nitrogen-containing monomers).
The nitrogen-free monomer may include one or both of a monofunctional monomer having one radically reactive functional group and a polyfunctional monomer having two or more radically reactive functional groups, but the initial adhesive strength of the adhesive composition From the viewpoint of increasing the polyfunctional monomer, it is preferable that there is a small amount of the polyfunctional monomer, and it is more preferable that it is not contained. Specifically, as described above, the content of the polyfunctional monomer based on the total amount of the radically polymerizable compound is preferably 5% by mass or less, more preferably 2% by mass or less, still more preferably 0.5% by mass or less, and even more preferably may be adjusted to 0.2% by mass or less, more preferably 0% by mass.
The nitrogen-free monomer is not particularly limited as long as it is a compound having a radically reactive functional group, but a monomer having a (meth)acryloyl group (hereinafter also referred to as an acrylic monomer) is preferred.
Examples of the acrylic monomer include alkyl (meth)acrylates, alicyclic structure-containing (meth)acrylates, aromatic ring-containing (meth)acrylates, and the like.
Further, the acrylic monomer may be a monomer having a functional group such as a cyclic ether group, a hydroxyl group, or a carboxyl group.
Among these, as the acrylic monomer, alkyl (meth)acrylates, aromatic ring-containing (meth)acrylates, and cyclic ether group-containing (meth)acrylates are preferred.
アルキル（メタ）アクリレートとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ｎ－ペンチル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ミリスチル（メタ）アクリレート、イソミリスチル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート等が挙げられ、これらの中でも、アルキル基の炭素数が１～１０であるアルキル（メタ）アクリレートが好ましく、ｎ－ブチル（メタ）アクリレート、イソデシルアクリレートなどがより好ましい。 Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, and n-pentyl (meth)acrylate. Acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, myristyl (meth)acrylate, Examples include isomyristyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, etc. Among these, alkyl (meth)acrylates in which the alkyl group has 1 to 10 carbon atoms are preferred, and n-butyl (Meth)acrylate, isodecyl acrylate, etc. are more preferred.
脂環構造含有（メタ）アクリレートとしては、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート等が挙げられる。 Examples of the alicyclic structure-containing (meth)acrylate include cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and the like.
芳香環含有（メタ）アクリレートとしては、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート等が挙げられる。これらの中でも、フェノキシエチル（メタ）アクリレートが好ましい。 Examples of the aromatic ring-containing (meth)acrylate include benzyl (meth)acrylate and phenoxyethyl (meth)acrylate. Among these, phenoxyethyl (meth)acrylate is preferred.
環状エーテル基含有（メタ）アクリレートとしては、エポキシ環、オキセタン環、テトラヒドロフラン環、ジオキソラン環、ジオキサン環を有する（メタ）アクリレートが挙げられる。中でも、テトラヒドロフラン環又はジオキサン環を有する（メタ）アクリレートが好ましい。テトラヒドロフラン環を有する（メタ）アクリレートとしては、例えば、テトラヒドロフルフリル（メタ）アクリレートなどが挙げられる。ジオキサン環を有する（メタ）アクリレートとしては、環状トリメチロールプロパンホルマールアクリレートなどが挙げられる。 Examples of the cyclic ether group-containing (meth)acrylates include (meth)acrylates having an epoxy ring, an oxetane ring, a tetrahydrofuran ring, a dioxolane ring, and a dioxane ring. Among these, (meth)acrylates having a tetrahydrofuran ring or a dioxane ring are preferred. Examples of the (meth)acrylate having a tetrahydrofuran ring include tetrahydrofurfuryl (meth)acrylate. Examples of the (meth)acrylate having a dioxane ring include cyclic trimethylolpropane formal acrylate.
水酸基含有アクリルモノマーとしては、２－ヒドロキシエチル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等が挙げられる。 Examples of the hydroxyl group-containing acrylic monomer include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.
カルボキシル基含有アクリルモノマーとしては、アクリル酸、メタクリル酸、ω－カルボキシ－ポリカプロラクトンモノ（メタ）アクリレート等が挙げられる。 Examples of the carboxyl group-containing acrylic monomer include acrylic acid, methacrylic acid, and ω-carboxy-polycaprolactone mono(meth)acrylate.
上記以外のアクリルモノマーとして、二以上の（メタ）アクリロイル基を有する多官能アクリルモノマーを用いてもよい。
多官能アクリルモノマーとしては、例えば、１，４－ブタンジオールジ（メタ）アクリレート、１，３－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、１，１０－デカンジオールジ（メタ）アクリレート、２－ｎ－ブチル－２－エチル－１，３－プロパンジオールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレートなどが挙げられる。
As an acrylic monomer other than the above, a polyfunctional acrylic monomer having two or more (meth)acryloyl groups may be used.
Examples of polyfunctional acrylic monomers include 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 1,9-nonane. Diol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, Tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, etc. Can be mentioned.
上記例示したアクリルモノマーの中でも、ｎ－ブチル（メタ）アクリレート、イソデシル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、２－フェノキシエチル（メタ）アクリレートからなる群から選択される１又は２以上の単官能のアクリルモノマーが好ましい。
これら単官能のアクリルモノマーと、上記した窒素含有モノマーを併用することで、Ｔｇａ及び｜Ｔｇｂ－Ｔｇａ｜を上記した所定の範囲に調整しやすくなり、接着剤組成物の初期接着力及び形状保持性が良好になりやすい。
Among the acrylic monomers exemplified above, one or more selected from the group consisting of n-butyl (meth)acrylate, isodecyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and 2-phenoxyethyl (meth)acrylate. Monofunctional acrylic monomers are preferred.
By using these monofunctional acrylic monomers and the nitrogen-containing monomers mentioned above, it becomes easier to adjust Tga and |Tgb-Tga| to the above-mentioned predetermined ranges, and the initial adhesive strength and shape retention of the adhesive composition are improved. tends to be good.
ラジカル重合性化合物全量基準における窒素非含有モノマーの含有量は、接着剤組成物の初期接着力及び形状保持性を良好とする観点から、好ましくは５質量％以上、より好ましくは１０質量％以上であり、そして好ましくは１００質量％以下であり、より好ましくは７０質量％以下、更に好ましくは５０質量％以下ある。 The content of the nitrogen-free monomer based on the total amount of the radically polymerizable compound is preferably 5% by mass or more, more preferably 10% by mass or more, from the viewpoint of improving the initial adhesive strength and shape retention of the adhesive composition. The content is preferably 100% by mass or less, more preferably 70% by mass or less, even more preferably 50% by mass or less.
＜光ラジカル重合開始剤＞
本発明の接着剤組成物は、光ラジカル重合開始剤を含有する。光ラジカル重合開始剤を含有させると、活性エネルギー線を照射することで、上記ラジカル重合性化合物の重合反応が進行する。
上光ラジカル重合開始剤としては、例えば、ベンゾフェノン系化合物、アセトフェノン系化合物、アシルフォスフィンオキサイド系化合物、チタノセン化合物、オキシムエステル系化合物、ベンゾインエーテル系化合物、チオキサントン、マレイミド系化合物等の光ラジカル重合開始剤が挙げられる。光ラジカル重合開始剤は、単独で用いてもよく、２種以上を併用して用いてもよい。
<Photoradical polymerization initiator>
The adhesive composition of the present invention contains a photoradical polymerization initiator. When a photoradical polymerization initiator is contained, the polymerization reaction of the radically polymerizable compound proceeds by irradiation with active energy rays.
Examples of photoradical polymerization initiators include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthone, maleimide compounds, etc. Examples include agents. The photoradical polymerization initiators may be used alone or in combination of two or more.
上記光ラジカル重合開始剤の含有量は、特に限定されないが、上記ラジカル重合性化合物１００質量部に対して、好ましくは０．１質量部以上であり、より好ましくは０．３質量部以上であり、そして好ましくは２質量部以下であり、より好ましくは１質量部以下である。これら光ラジカル重合開始剤の含有量がこれら下限値以上であると、重合反応が進行しやすく、これら上限値以下であると接着剤組成物の保存安定性が良好となる。 The content of the photoradical polymerization initiator is not particularly limited, but is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, based on 100 parts by mass of the radically polymerizable compound. , and preferably 2 parts by mass or less, more preferably 1 part by mass or less. When the content of these photoradical polymerization initiators is at least these lower limits, the polymerization reaction tends to proceed, and when it is at most these upper limits, the storage stability of the adhesive composition is good.
＜熱硬化性樹脂、湿気硬化性樹脂＞
本発明の接着剤組成物は、本発明の効果を害しない範囲で、上記したラジカル重合性化合物以外の成分として、熱硬化性樹脂及び湿気硬化性樹脂から選択される１種以上を含有してもよい。
<Thermosetting resin, moisture curing resin>
The adhesive composition of the present invention may contain one or more selected from thermosetting resins and moisture-curing resins as components other than the above-mentioned radically polymerizable compound, within a range that does not impair the effects of the present invention. Good too.
熱硬化性樹脂としては、例えば、エポキシ樹脂、フェノール樹脂、尿素樹脂、メラミン樹脂などが挙げられ、中でもエポキシ樹脂が好ましい。
エポキシ樹脂としては、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、ビフェニル型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、ビフェノール型エポキシ樹脂、ナフタレン型エポキシ樹脂、フルオレン型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、アントラセン型エポキシ樹脂、アダマンタン骨格を有するエポキシ樹脂、トリシクロデカン骨格を有するエポキシ樹脂、及びトリアジン核を骨格に有するエポキシ樹脂等が挙げられる。
Examples of thermosetting resins include epoxy resins, phenol resins, urea resins, and melamine resins, of which epoxy resins are preferred.
Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, biphenyl epoxy resin, biphenyl novolac epoxy resin, biphenol epoxy resin, and naphthalene epoxy resin. Resin, fluorene type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, anthracene type epoxy resin, epoxy resin having an adamantane skeleton, epoxy resin having a tricyclodecane skeleton, and triazine nucleus Examples include epoxy resins having a skeleton.
熱硬化性樹脂を用いる場合は、熱硬化剤を接着剤組成物に含有させることが好ましい。熱硬化剤としては、特に限定されず、シアネートエステル化合物（シアネートエステル硬化剤）、フェノール化合物（フェノール熱硬化剤）、アミン化合物（アミン熱硬化剤）、チオール化合物（チオール熱硬化剤）、イミダゾール化合物、ホスフィン化合物、酸無水物、活性エステル化合物及びジシアンジアミド等が挙げられる。
また、熱硬化性樹脂としてエポキシ樹脂を使用する場合は、光カチオン重合開始剤を接着剤組成物に含有させてもよい。これにより、１段階目で活性エネルギー線を照射した後でも、徐々に硬化が進行しやすくなる。その結果、得られる接着性組成物が初期接着力により一層優れたものとなる。
When using a thermosetting resin, it is preferable to include a thermosetting agent in the adhesive composition. Thermosetting agents are not particularly limited, and include cyanate ester compounds (cyanate ester curing agents), phenol compounds (phenol thermosetting agents), amine compounds (amine thermosetting agents), thiol compounds (thiol thermosetting agents), and imidazole compounds. , phosphine compounds, acid anhydrides, active ester compounds, and dicyandiamide.
Furthermore, when using an epoxy resin as the thermosetting resin, a photocationic polymerization initiator may be included in the adhesive composition. Thereby, even after irradiation with active energy rays in the first stage, curing tends to proceed gradually. As a result, the resulting adhesive composition has even better initial adhesive strength.
上記光カチオン重合開始剤は、光照射によりプロトン酸又はルイス酸を発生するものであれば特に限定されず、イオン性光酸発生型であってもよいし、非イオン性光酸発生型であってもよい。 The photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or Lewis acid upon irradiation with light, and may be an ionic photoacid generating type or a nonionic photoacid generating type. It's okay.
上記イオン性光酸発生型の光カチオン重合開始剤としては、例えば、次のものが挙げられる。すなわち、カチオン部分が芳香族スルホニウム、芳香族ヨードニウム、芳香族ジアゾニウム、芳香族アンモニウム、又は、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅカチオンであり、アニオン部分がＢＦ４ －、ＰＦ６ －、ＳｂＦ６ －、又は、（ＢＸ４）－で構成されるオニウム塩等が挙げられる。前記Ｘは、少なくとも２つ以上のフッ素又はトリフルオロメチル基で置換されたフェニル基を表す。 Examples of the ionic photoacid generating type photocationic polymerization initiator include the following. That is, the cation moiety is aromatic sulfonium, aromatic iodonium, aromatic diazonium, aromatic ammonium, or (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe cation, Examples include onium salts in which the anion moiety is composed of BF 4 − , PF 6 − , SbF 6 − , or (BX 4 ) − . The X represents a phenyl group substituted with at least two fluorine or trifluoromethyl groups.
上記芳香族スルホニウム塩としては、例えば、ビス（４－（ジフェニルスルホニオ）フェニル）スルフィドビスヘキサフルオロホスフェート、ビス（４－（ジフェニルスルホニオ）フェニル）スルフィドビスヘキサフルオロアンチモネート、ビス（４－（ジフェニルスルホニオ）フェニル）スルフィドビステトラフルオロボレート、ビス（４－（ジフェニルスルホニオ）フェニル）スルフィドテトラキス（ペンタフルオロフェニル）ボレート、ジフェニル－４－（フェニルチオ）フェニルスルホニウムヘキサフルオロホスフェート、ジフェニル－４－（フェニルチオ）フェニルスルホニウムヘキサフルオロアンチモネート、ジフェニル－４－（フェニルチオ）フェニルスルホニウムテトラフルオロボレート、ジフェニル－４－（フェニルチオ）フェニルスルホニウムテトラキス（ペンタフルオロフェニル）ボレート、トリフェニルスルホニウムヘキサフルオロホスフェート、トリフェニルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムテトラフルオロボレート、トリフェニルスルホニウムテトラキス（ペンタフルオロフェニル）ボレート、ビス（４－（ジ（４－（２－ヒドロキシエトキシ））フェニルスルホニオ）フェニル）スルフィドビスヘキサフルオロホスフェート、ビス（４－（ジ（４－（２－ヒドロキシエトキシ））フェニルスルホニオ）フェニル）スルフィドビスヘキサフルオロアンチモネート、ビス（４－（ジ（４－（２－ヒドロキシエトキシ））フェニルスルホニオ）フェニル）スルフィドビステトラフルオロボレート、ビス（４－（ジ（４－（２－ヒドロキシエトキシ））フェニルスルホニオ）フェニル）スルフィドテトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。 Examples of the aromatic sulfonium salts include bis(4-(diphenylsulfonio)phenyl)sulfide bishexafluorophosphate, bis(4-(diphenylsulfonio)phenyl)sulfide bishexafluoroantimonate, and bis(4-(diphenylsulfonio)phenyl)sulfide bishexafluoroantimonate. diphenylsulfonio)phenyl) sulfide bistetrafluoroborate, bis(4-(diphenylsulfonio)phenyl)sulfidetetrakis(pentafluorophenyl)borate, diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate, diphenyl-4-( Phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4-(phenylthio)phenylsulfonium tetrafluoroborate, diphenyl-4-(phenylthio)phenylsulfonium tetrakis(pentafluorophenyl)borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexa Fluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, bis(4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl)sulfide bishexafluorophosphate, Bis(4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl)sulfide bishexafluoroantimonate, bis(4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl ) sulfide bistetrafluoroborate, bis(4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl)sulfide tetrakis(pentafluorophenyl)borate, and the like.
上記芳香族ジアゾニウム塩としては、例えば、フェニルジアゾニウムヘキサフルオロホスフェート、フェニルジアゾニウムヘキサフルオロアンチモネート、フェニルジアゾニウムテトラフルオロボレート、フェニルジアゾニウムテトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。 Examples of the aromatic diazonium salt include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis(pentafluorophenyl)borate.
上記芳香族アンモニウム塩としては、例えば、１－ベンジル－２－シアノピリジニウムヘキサフルオロホスフェート、１－ベンジル－２－シアノピリジニウムヘキサフルオロアンチモネート、１－ベンジル－２－シアノピリジニウムテトラフルオロボレート、１－ベンジル－２－シアノピリジニウムテトラキス（ペンタフルオロフェニル）ボレート、１－（ナフチルメチル）－２－シアノピリジニウムヘキサフルオロホスフェート、１－（ナフチルメチル）－２－シアノピリジニウムヘキサフルオロアンチモネート、１－（ナフチルメチル）－２－シアノピリジニウムテトラフルオロボレート、１－（ナフチルメチル）－２－シアノピリジニウムテトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。 Examples of the aromatic ammonium salt include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, and 1-benzyl-2-cyanopyridinium hexafluoroantimonate. -2-cyanopyridinium tetrakis(pentafluorophenyl)borate, 1-(naphthylmethyl)-2-cyanopyridinium hexafluorophosphate, 1-(naphthylmethyl)-2-cyanopyridinium hexafluoroantimonate, 1-(naphthylmethyl) -2-cyanopyridinium tetrafluoroborate, 1-(naphthylmethyl)-2-cyanopyridinium tetrakis(pentafluorophenyl)borate, and the like.
上記（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ塩としては、例えば、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ（ＩＩ）ヘキサフルオロホスフェート、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ（ＩＩ）ヘキサフルオロアンチモネート、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ（ＩＩ）テトラフルオロボレート、（２，４－シクロペンタジエン－１－イル）（（１－メチルエチル）ベンゼン）－Ｆｅ（ＩＩ）テトラキス（ペンタフルオロフェニル）ボレート等が挙げられる。 As the above (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe salt, for example, (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene )-Fe(II) hexafluorophosphate, (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe(II) hexafluoroantimonate, (2,4-cyclopentadien-1 -yl)((1-methylethyl)benzene)-Fe(II) tetrafluoroborate, (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe(II) tetrakis(penta Examples include fluorophenyl) borate and the like.
上記非イオン性光酸発生型の光カチオン重合開始剤としては、例えば、ニトロベンジルエステル、スルホン酸誘導体、リン酸エステル、フェノールスルホン酸エステル、ジアゾナフトキノン、Ｎ－ヒドロキシイミドスホナート等が挙げられる。 Examples of the nonionic photoacid-generating photocationic polymerization initiator include nitrobenzyl esters, sulfonic acid derivatives, phosphoric esters, phenolsulfonic esters, diazonaphthoquinone, N-hydroxyimidosulfonate, and the like.
光カチオン重合開始剤は、単独で用いてもよく、２種以上を併用して用いてもよい。
上記光カチオン重合開始剤の含有量は、上記熱硬化性樹脂１００質量部に対して、好ましい下限が０．１質量部、好ましい上限が１０質量部である。
The photocationic polymerization initiators may be used alone or in combination of two or more.
The preferable lower limit of the content of the photocationic polymerization initiator is 0.1 parts by weight and the preferable upper limit is 10 parts by weight based on 100 parts by weight of the thermosetting resin.
湿気硬化性樹脂としては、例えば、湿気硬化性ウレタン樹脂、架橋性シリル基を有する樹脂などが挙げられ、中でも湿気硬化性ウレタン樹脂が好ましい。湿気硬化性ウレタン樹脂は、ウレタン結合とイソシアネート基とを有し、分子内のイソシアネート基が、水分と反応して硬化する。イソシアネート基は分子の末端に有することが好ましい。
湿気硬化性ウレタン樹脂は、ラジカル反応性官能基を有してもよい。なお、湿気硬化性ウレタン樹脂がラジカル反応性官能基を有する場合は、上記したラジカル重合性化合物には含まず、湿気硬化性ウレタン樹脂として扱う。
湿気硬化性ウレタン樹脂は、１分子中に２個以上の水酸基を有するポリオール化合物と、１分子中に２個以上のイソシアネート基を有するポリイソシアネート化合物とを反応させることにより得ることができる。
Examples of the moisture-curable resin include moisture-curable urethane resins and resins having crosslinkable silyl groups, and moisture-curable urethane resins are preferred among them. Moisture-curable urethane resin has a urethane bond and an isocyanate group, and the isocyanate group in the molecule reacts with moisture to be cured. It is preferable to have an isocyanate group at the end of the molecule.
The moisture-curable urethane resin may have a radically reactive functional group. In addition, when the moisture-curable urethane resin has a radically reactive functional group, it is not included in the above-mentioned radically polymerizable compounds and is treated as a moisture-curable urethane resin.
A moisture-curable urethane resin can be obtained by reacting a polyol compound having two or more hydroxyl groups in one molecule with a polyisocyanate compound having two or more isocyanate groups in one molecule.
湿気硬化性樹脂を用いる場合は、湿気硬化時の硬化速度を向上させる観点から、湿気硬化促進剤を接着剤組成物に含有させることが好ましい。湿気硬化促進剤としては、例えば、モルホリン骨格を有する化合物、ピペリジン骨格を有する化合物、ピペラジン骨格を有する化合物等が挙げられる。 When using a moisture curable resin, it is preferable to include a moisture curing accelerator in the adhesive composition from the viewpoint of improving the curing speed during moisture curing. Examples of the moisture curing accelerator include compounds having a morpholine skeleton, compounds having a piperidine skeleton, and compounds having a piperazine skeleton.
＜その他の成分＞
本発明の接着剤組成物には、上記したラジカル重合性化合物、光ラジカル重合開始剤、必要に応じて配合される熱硬化性樹脂、湿気硬化性樹脂、湿気硬化促進剤など以外に、本発明の効果を阻害しない範囲で、その他の成分として、カップリング剤、充填材、遮光剤、着色剤、イオン液体、溶剤、金属含有粒子、反応性希釈剤等の添加剤を含んでもよい。
<Other ingredients>
In addition to the above-mentioned radical polymerizable compound, photoradical polymerization initiator, thermosetting resin, moisture curable resin, moisture curing accelerator, etc., which are blended as necessary, the adhesive composition of the present invention may contain the following ingredients: Other components may include additives such as coupling agents, fillers, light shielding agents, colorants, ionic liquids, solvents, metal-containing particles, and reactive diluents, as long as they do not impede the effects of the above.
カップリング剤としては、例えば、シランカップリング剤、チタネート系カップリング剤、アルミネート系カップリング剤、ジルコネート系カップリング剤等が挙げられる。カップリング剤を用いることにより、接着剤組成物の接着性を向上させることができる。なかでも、接着性や耐クリープ性を向上させる効果に特に優れることから、シランカップリング剤が好ましい。上記カップリング剤は、単独で用いられてもよいし、２種以上が組み合わせて用いられてもよい。 Examples of the coupling agent include silane coupling agents, titanate coupling agents, aluminate coupling agents, and zirconate coupling agents. By using a coupling agent, the adhesive properties of the adhesive composition can be improved. Among these, silane coupling agents are preferred because they are particularly effective in improving adhesiveness and creep resistance. The above coupling agents may be used alone or in combination of two or more.
充填剤としては、例えば、シリカ、タルク、酸化チタン、酸化亜鉛等が挙げられる。充填材を含有させることにより、接着剤組成物の塗布性や形状保持性を調整することができる。なかでも、得られる接着剤組成物がＵＶ光透過性に優れるものとなることから、シリカが好ましい。これらの充填剤は、単独で用いられてもよいし、２種以上を組み合わせて用いられてもよい。上記充填剤は、疎水性表面処理がなされていてもよい。疎水性表面処理としては、シリル化処理、アルキル化処理、エポキシ化処理等が挙げられる。 Examples of fillers include silica, talc, titanium oxide, zinc oxide, and the like. By containing the filler, the applicability and shape retention of the adhesive composition can be adjusted. Among these, silica is preferred because the resulting adhesive composition has excellent UV light transmittance. These fillers may be used alone or in combination of two or more. The filler may be subjected to hydrophobic surface treatment. Examples of the hydrophobic surface treatment include silylation treatment, alkylation treatment, and epoxidation treatment.
遮光剤としては、例えば、酸化鉄、チタンブラック、アニリンブラック、シアニンブラック、フラーレン、カーボンブラック、樹脂被覆型カーボンブラック等が挙げられる。また、上記遮光剤は、黒色を呈するものでなくてもよく、可視光領域の光を透過させ難い能力を有する材料であれば、シリカ、タルク、酸化チタン等、充填剤として挙げた材料も上記遮光剤に含まれる。なかでも、チタンブラックが好ましい。接着剤組成物に、遮光剤を含有させることにより、遮光性に優れるものとなって表示素子の光漏れを防止することができる。 Examples of the light shielding agent include iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, and resin-coated carbon black. In addition, the above-mentioned light-shielding agent does not have to be black, and the above-mentioned materials such as silica, talc, and titanium oxide may also be used as long as they have the ability to hardly transmit light in the visible light range. Contained in sunscreens. Among them, titanium black is preferred. By incorporating a light shielding agent into the adhesive composition, the adhesive composition has excellent light shielding properties and can prevent light leakage from the display element.
本発明の接着剤組成物を製造する方法としては、例えば、遊星式撹拌機、ホモディスパー、ホモミキサー、万能ミキサー、プラネタリーミキサー、ニーダー、３本ロール等の混合機を用いて、各成分を混合する方法が挙げられる。 As a method for producing the adhesive composition of the present invention, for example, each component is mixed using a mixer such as a planetary stirrer, a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three-roll mixer. An example is a method of mixing.
本発明の接着剤組成物を用いて接着することが可能な被着体としては、金属、ガラス、プラスチック等の各種の被着体が挙げられる。
上記被着体の形状としては、例えば、フィルム状、シート状、板状、パネル状、トレイ状、ロッド（棒状体）状、箱体状、筐体状等が挙げられる。
Examples of adherends that can be bonded using the adhesive composition of the present invention include various adherends such as metal, glass, and plastic.
Examples of the shape of the adherend include a film, a sheet, a plate, a panel, a tray, a rod, a box, and a housing.
上記金属としては、例えば、鉄鋼、ステンレス鋼、アルミニウム、銅、ニッケル、クロムやその合金等が挙げられる。
上記ガラスとしては、例えば、アルカリガラス、無アルカリガラス、石英ガラス、化学強化ガラス（ゴリラガラス）等が挙げられる。
上記プラスチックとしては、例えば、高密度ポリエチレン、超高分子量ポリエチレン、アイソタクチックポリプロピレン、シンジオタクチックポリプロピレン、エチレンプロピレン共重合体樹脂等のポリオレフィン系樹脂や、ナイロン６（Ｎ６）、ナイロン６６（Ｎ６６）、ナイロン４６（Ｎ４６）、ナイロン１１（Ｎ１１）、ナイロン１２（Ｎ１２）、ナイロン６１０（Ｎ６１０）、ナイロン６１２（Ｎ６１２）、ナイロン６／６６共重合体（Ｎ６／６６）、ナイロン６／６６／６１０共重合体（Ｎ６／６６／６１０）、ナイロンＭＸＤ６（ＭＸＤ６）、ナイロン６Ｔ、ナイロン６／６Ｔ共重合体、ナイロン６６／ＰＰ共重合体、ナイロン６６／ＰＰＳ共重合体等のポリアミド系樹脂や、ポリブチレンテレフタレート（ＰＢＴ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンイソフタレート（ＰＥＩ）、ＰＥＴ／ＰＥＩ共重合体、ポリアリレート（ＰＡＲ）、ポリブチレンナフタレート（ＰＢＮ）、液晶ポリエステル、ポリオキシアルキレンジイミドジ酸／ポリブチレートテレフタレート共重合体等の芳香族ポリエステル系樹脂や、ポリアクリロニトリル（ＰＡＮ）、ポリメタクリロニトリル、アクリロニトリル／スチレン共重合体（ＡＳ）、メタクリロニトリル／スチレン共重合体、メタクリロニトリル／スチレン／ブタジエン共重合体等のポリニトリル系樹脂や、ポリカーボネートや、ポリメタクリル酸メチル（ＰＭＭＡ）、ポリメタクリル酸エチル酢酸ビニル（ＥＶＡ）等のポリメタクリレート系樹脂や、ポリビニルアルコール（ＰＶＡ）、ビニルアルコール／エチレン共重合体（ＥＶＯＨ）、ポリ塩化ビニリデン（ＰＶＤＣ）、ポリ塩化ビニル（ＰＶＣ）、塩化ビニル／塩化ビニリデン共重合体、塩化ビニリデン／メチルアクリレート共重合体等のポリビニル系樹脂や、ポリテトラフルオロエチレン樹脂（ＰＴＦＥ）、テトラフルオロエチレン－パーフルオロアルキルビニルエーテル共重合体樹脂（ＰＦＡ）、テトラフルオロエチレン－ヘキサフルオロプロピレン共重合体樹脂（ＦＥＰ）、ポリクロロトリフルオロエチレン共重合体樹脂（ＰＣＴＦＥ）、エチレン－テトラフルオロエチレン共重合体樹脂（ＥＴＦＥ）、エチレン－クロロトリフルオロエチレン共重合体樹脂（ＥＣＴＦＥ）、ポリフッ化ビニリデン樹脂（ＰＶＤＦ）等のフッ素樹脂が挙げられる。
Examples of the metal include steel, stainless steel, aluminum, copper, nickel, chromium, and alloys thereof.
Examples of the glass include alkali glass, non-alkali glass, quartz glass, chemically strengthened glass (gorilla glass), and the like.
Examples of the above-mentioned plastics include polyolefin resins such as high-density polyethylene, ultra-high molecular weight polyethylene, isotactic polypropylene, syndiotactic polypropylene, and ethylene propylene copolymer resins, and nylon 6 (N6) and nylon 66 (N66). , nylon 46 (N46), nylon 11 (N11), nylon 12 (N12), nylon 610 (N610), nylon 612 (N612), nylon 6/66 copolymer (N6/66), nylon 6/66/610 Polyamide resins such as copolymer (N6/66/610), nylon MXD6 (MXD6), nylon 6T, nylon 6/6T copolymer, nylon 66/PP copolymer, nylon 66/PPS copolymer, Polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET/PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, polyoxyalkylene diimide diacid /Aromatic polyester resins such as polybutyrate terephthalate copolymer, polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile/styrene copolymer (AS), methacrylonitrile/styrene copolymer, methacrylonitrile / Polynitrile resins such as styrene/butadiene copolymer, polycarbonate, polymethacrylate resins such as polymethyl methacrylate (PMMA), polyethyl vinyl acetate (EVA), polyvinyl alcohol (PVA), and vinyl alcohol. / Polyvinyl resins such as ethylene copolymer (EVOH), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride/vinylidene chloride copolymer, vinylidene chloride/methyl acrylate copolymer, polytetrafluoro Ethylene resin (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), polychlorotrifluoroethylene copolymer resin (PCTFE), Examples include fluororesins such as ethylene-tetrafluoroethylene copolymer resin (ETFE), ethylene-chlorotrifluoroethylene copolymer resin (ECTFE), and polyvinylidene fluoride resin (PVDF).
また、上記被着体としては、表面に金属メッキ層を有する複合材料も挙げられ、該複合材料のメッキの下地材としては、例えば、上述した、金属、ガラス、プラスチック等が挙げられる。
更に、上記被着体としては、金属表面を不動態化処理することにより不導態皮膜を形成した材料も挙げられ、該不動態化処理としては、例えば、加熱処理、陽極酸化処理等が挙げられる。特に、国際アルミニウム合金名が６０００番台の材質であるアルミニウム合金等の場合は、上記不動態化処理として硫酸アルマイト処理やリン酸アルマイト処理を行うことで、接着性を向上させることができる。
Further, examples of the adherend include a composite material having a metal plating layer on the surface, and examples of the base material for plating the composite material include metal, glass, plastic, etc. as described above.
Furthermore, examples of the above-mentioned adherend include materials in which a passivation film is formed by passivating the metal surface, and examples of the passivation treatment include heat treatment, anodizing treatment, etc. It will be done. In particular, in the case of aluminum alloys having international aluminum alloy names in the 6000 range, adhesion can be improved by performing sulfuric acid alumite treatment or phosphoric acid alumite treatment as the passivation treatment.
本発明の接着剤組成物は、電子部品用接着剤や表示素子用接着剤として特に好適に用いることができる。上記電子部品としては、特に限定されないが、例えば、半導体チップ、センサーなどが挙げられる。上記表示素子としては、特に限定されないが、液晶表示素子、有機ＥＬ表示素子などが挙げられる。
本発明の接着剤組成物からなる電子部品用接着剤、及び、本発明の接着剤組成物からなる表示素子用接着剤もまた、それぞれ本発明の１つである。
The adhesive composition of the present invention can be particularly suitably used as an adhesive for electronic components or an adhesive for display elements. Examples of the electronic components include, but are not limited to, semiconductor chips, sensors, and the like. Examples of the display element include, but are not particularly limited to, liquid crystal display elements, organic EL display elements, and the like.
An adhesive for electronic components made of the adhesive composition of the present invention and an adhesive for display elements made of the adhesive composition of the present invention are also each part of the present invention.
以下に、実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。 EXAMPLES The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited to these Examples.
［各実施例、比較例で用いた材料］
（ラジカル重合性化合物）
（１）窒素非含有モノマー
・ブチルアクリレート 日本触媒社製
・イソデシルアクリレート 大阪有機化学工業株式会社製
・フェノキシエチルアクリレート 大阪有機化学工業株式会社製
・テトラヒドロフルフリルアルコール アクリル酸多量体エステル 大阪有機化学工業株式会社製「ビスコート＃１５０Ｄ」
・環状トリメチロールプロパンホルマールアクリレート 大阪有機化学工業株式会社製「ＣＴＦＡ」
・ポリプロピレングリコール（＃７００）ジアクリレート 新中村化学株式会社製「ＡＰＧ－７００」
・多官能（メタ）アクリレート ダイセル・オルネクス社製「ＥＢＥＣＲＹＬ８４０２」
（２－１）鎖状の窒素含有モノマー
・１，２－エタンジオール１－アクリラート２－（Ｎ－ブチルカルバマート） ＣＡＳ．Ｎｏ．６３２２５－５３－６ 大阪有機化学工業株式会社製「ビスコート＃２１６」
（２－２）環状構造を有する窒素含有モノマー
・Ｎ－ビニル－ε－カプロラクタム 東京化成工業株式会社製「ＮＶＣ」
（光ラジカル重合開始剤）
・ＢＡＳＦ社製「Ｉｒｇａｃｕｒｅ ＴＰＯ」
・ＢＡＳＦ社製「Ｉｒｇａｃｕｒｅ ３７９ＥＧ」
（３）湿気硬化性樹脂 以下の方法により合成したポリエステル骨格ウレタンを用いた。
ポリオール化合物（水酸基価：２１２ｍｇＫＯＨ、ダイセル化学社製、「Ｐｌａｃｃｅｌ２０５Ｕ」、ポリカプロラクトンポリオール）を１００質量部と、０．０１質量部のジブチル錫ジラウレートとを５００ｍＬ容のセパラブルフラスコに入れ、真空下（２０ｍｍＨｇ以下）、１００℃で３０分間撹拌し、混合した。その後常圧とし、ポリイソシアネート化合物としてジフェニルメタンジイソシアネート（日曹商事社製、「Ｐｕｒｅ ＭＤＩ」）１００質量部を入れ、８０℃で３時間撹拌して反応させ、ポリエステル骨格ウレタン（重量平均分子量６３００）を得た。
[Materials used in each example and comparative example]
(Radical polymerizable compound)
(1) Nitrogen-free monomer - butyl acrylate Made by Nippon Shokubai Co., Ltd. Isodecyl acrylate Made by Osaka Organic Chemical Industry Co., Ltd. Phenoxyethyl acrylate Made by Osaka Organic Chemical Industry Co., Ltd. Tetrahydrofurfuryl alcohol Acrylic acid polymer ester Osaka Organic Chemical Industry Co., Ltd. "Viscoat #150D" manufactured by Co., Ltd.
・Cyclic trimethylolpropane formal acrylate “CTFA” manufactured by Osaka Organic Chemical Industry Co., Ltd.
・Polypropylene glycol (#700) diacrylate “APG-700” manufactured by Shin Nakamura Chemical Co., Ltd.
・Multifunctional (meth)acrylate “EBECRYL8402” manufactured by Daicel Allnex
(2-1) Chain-shaped nitrogen-containing monomer/1,2-ethanediol 1-acrylate 2-(N-butyl carbamate) CAS. No. 63225-53-6 “Viscoat #216” manufactured by Osaka Organic Chemical Industry Co., Ltd.
(2-2) Nitrogen-containing monomer with cyclic structure N-vinyl-ε-caprolactam “NVC” manufactured by Tokyo Chemical Industry Co., Ltd.
(Photoradical polymerization initiator)
・“Irgacure TPO” manufactured by BASF
・“Irgacure 379EG” manufactured by BASF
(3) Moisture-curable resin A polyester skeleton urethane synthesized by the following method was used.
100 parts by mass of a polyol compound (hydroxyl value: 212 mg KOH, manufactured by Daicel Chemical Co., Ltd., "Placcel 205U", polycaprolactone polyol) and 0.01 part by mass of dibutyltin dilaurate were placed in a 500 mL separable flask, and the mixture was heated under vacuum ( 20 mmHg or less) and 100° C. for 30 minutes to mix. Thereafter, the pressure was reduced to normal pressure, and 100 parts by mass of diphenylmethane diisocyanate (manufactured by Nisso Shoji Co., Ltd., "Pure MDI") was added as a polyisocyanate compound, and the reaction was stirred for 3 hours at 80°C to form a polyester skeleton urethane (weight average molecular weight 6300). Obtained.
［実施例１～１２、比較例１～６］
表１、２に記載された配合比に従い、各材料を、遊星式撹拌装置（シンキー社製、「あわとり練太郎」）にて撹拌した後、セラミック３本ロールにて均一に混合して実施例１～９、比較例１～６の接着剤組成物を得た。該接着剤組成物について後述する各評価を行い、結果を表１、２に示した。
[Examples 1 to 12, Comparative Examples 1 to 6]
According to the compounding ratios listed in Tables 1 and 2, each material was stirred using a planetary stirring device ("Awatori Rentaro", manufactured by Shinky Co., Ltd.), and then uniformly mixed using three ceramic rolls. Adhesive compositions of Examples 1 to 9 and Comparative Examples 1 to 6 were obtained. Each evaluation described below was performed on the adhesive composition, and the results are shown in Tables 1 and 2.
各実施例、比較例の接着剤組成物について、以下のとおり評価した。
［Ｔｇａ］
動的粘弾性測定装置（アイティー計測制御社製「ＤＶＡ－２００」）のせん断測定冶具（Ｉパーツ）の一方の面に、接着剤組成物を５ｍｍ×１０ｍｍの領域に厚さ０．４ｍｍとなるように塗布した。該塗布した接着剤組成物に対して、酸素存在下で、ＬＥＤランプにて、波長４０５ｎｍ、照度１０００ｍＷ／ｃｍ２、積算光量１０００ｍＪ／ｃｍ２の条件で活性エネルギー線を照射して、接着剤組成物を硬化させた。その後、該硬化した接着剤組成物上に、せん断測定冶具（第１のＬパーツ）を取り付けた。次いで、せん断測定冶具（第２のＬパーツ）に、接着剤組成物を５ｍｍ×１０ｍｍの領域に厚さ０．４ｍｍとなるように塗布した。該塗布した接着剤組成物に対して、上記と同様の条件で活性エネルギー線を照射して、接着剤組成物を硬化させた。その後、該硬化した接着剤組成物上に、上記せん断測定冶具（Ｉパーツ）の上記接着剤組成物を塗布していない面を接着させ、Ｔｇａ評価用試料を作製した。
なお、上記ＬＥＤランプは、以下のものを使用した。
ＨＯＹＡ ＣＡＮＤＥＯ ＯＰＴＲＯＮＩＣＳ ＣＯＲＰＯＲＡＴＩＯＮ製 ＵＶ－ＬＥＤ ＬＩＧＨＴ ＳＯＵＲＣＥ 「ＥＸＥＣＵＲＥ－Ｈ－１ＶＣＩＩ」、ヘッドユニットとして「Ｈ－１ＶＨ－０１」を用いた。
上記のとおり作製したＴｇａ評価用試料を用いて、動的粘弾性測定装置（アイティー計測制御社製「ＤＶＡ－２００」）にて、以下の条件で測定されたｔａｎδピーク温度を、Ｔｇａとした。
＜条件＞
せん断法
測定温度－１００～２００℃
昇温速度３℃／分
歪み量０．８％
周波数１Ｈｚ
The adhesive compositions of each Example and Comparative Example were evaluated as follows.
[Tga]
The adhesive composition was applied to a 5 mm x 10 mm area with a thickness of 0.4 mm on one side of the shear measurement jig (I part) of a dynamic viscoelasticity measurement device (IT Keizai Control Co., Ltd. "DVA-200"). I applied it to make it look like this. The applied adhesive composition was irradiated with active energy rays using an LED lamp in the presence of oxygen at a wavelength of 405 nm, an illumination intensity of 1000 mW/cm 2 , and an integrated light amount of 1000 mJ/cm 2 to determine the adhesive composition. Hardened things. Thereafter, a shear measurement jig (first L part) was attached onto the cured adhesive composition. Next, the adhesive composition was applied to a shear measurement jig (second L part) in a 5 mm x 10 mm area to a thickness of 0.4 mm. The applied adhesive composition was irradiated with active energy rays under the same conditions as above to cure the adhesive composition. Thereafter, the surface of the shear measurement jig (part I) on which the adhesive composition was not applied was adhered onto the cured adhesive composition to prepare a sample for Tga evaluation.
Note that the following LED lamps were used.
A UV-LED LIGHT SOURCE "EXECURE-H-1VCII" manufactured by HOYA CANDEO OPTRONICS CORPORATION and "H-1VH-01" were used as the head unit.
Using the Tga evaluation sample prepared as described above, the tan δ peak temperature was measured under the following conditions with a dynamic viscoelasticity measuring device (IT Keisakusho Co., Ltd. "DVA-200"), which was defined as Tga. .
<Conditions>
Shear method Measurement temperature -100 to 200℃
Heating rate: 3℃/min Strain amount: 0.8%
Frequency 1Hz
［Ｔｇｂ］
離型ポリエチレンテレフタレートフィルム（離型ＰＥＴフィルム ニッパ社製「５０×１－Ｅ」）に厚さ１００μｍとなるように接着剤組成物を塗布し、該塗布した接着時組成物上に、別の離型ＰＥＴフィルムを積層し、２枚の離型ＰＥＴフィルムに厚さ１００μｍの接着剤組成物が挟み込まれた積層体を作製した。積層体の一部を、テープ（積水化学社製、スパットライトテープＮｏ．７３３）で固定して、積層体の厚みを変動し難くした。該積層体に対して、ＬＥＤランプにて、波長４０５ｎｍ、照度４ｍＷ／ｃｍ２、積算光量３０００ｍＪ／ｃｍ２の条件で活性エネルギー線を照射して、接着剤組成物を硬化させた。その後、積層体を５ｍｍ×１０ｍｍの大きさに切断して、２枚の離型ＰＥＴフィルムを剥がした試料を、動的粘弾性測定装置（アイティー計測制御社製「ＤＶＡ－２００」）のせん断測定冶具に取り付け、以下の条件で測定されたｔａｎδピーク温度を、Ｔｇｂとした。
なおＬＥＤランプはＴｇａの測定に使用したものと同様のものを使用した。
＜条件＞
せん断法
測定温度－１００～２００℃
昇温速度３℃／分
歪み量０．８％
周波数１Ｈｚ
[Tgb]
An adhesive composition is applied to a release polyethylene terephthalate film (release PET film "50x1-E" manufactured by Nipper Co., Ltd.) to a thickness of 100 μm, and another release agent is applied on the applied adhesive composition. The molded PET films were laminated to produce a laminate in which a 100 μm thick adhesive composition was sandwiched between two molded PET films. A part of the laminate was fixed with tape (Spat Light Tape No. 733, manufactured by Sekisui Chemical Co., Ltd.) to make the thickness of the laminate difficult to vary. The adhesive composition was cured by irradiating the laminate with active energy rays using an LED lamp under the conditions of a wavelength of 405 nm, an illumination intensity of 4 mW/cm 2 , and an integrated light amount of 3000 mJ/cm 2 . After that, the laminate was cut into a size of 5 mm x 10 mm, the two release PET films were peeled off, and the sample was subjected to shearing with a dynamic viscoelasticity measuring device (“DVA-200” manufactured by IT Keizai Control Co., Ltd.). The tan δ peak temperature, which was attached to a measurement jig and measured under the following conditions, was defined as Tgb.
Note that the LED lamp used was the same as that used for the measurement of Tga.
<Conditions>
Shear method Measurement temperature -100 to 200℃
Heating rate 3℃/min Strain amount 0.8%
Frequency 1Hz
［初期接着力（仮接着力）］
アルミニウム基板（２５ｍｍ×１００ｍｍ）に、３ｍｍ（半径）×０．４ｍｍ（厚さ）となるように、接着剤組成物を円形状に塗布した。その後、該接着剤組成物に対して、酸素存在下で、波長４０５ｎｍ、照度１０００ｍＷ／ｃｍ２、積算光量１０００ｍＪ／ｃｍ２の条件で活性エネルギー線を照射して、接着剤組成物を硬化させた。次いで、該接着剤組成物上にガラス板（２５ｍｍ×１００ｍｍ）を載置して、接着剤組成物を挟み込んだ後、ガラス板の上から２００ｇの重りを乗せて、初期接着力評価用試料を作製した。
得られた初期接着力評価用試料について、引張試験機オートグラフＡＧ－Ｘ（島津製作所）を用い、２５℃、５０％ＲＨ雰囲気下でせん断方向に１２．７ｍｍ／分の速度で引張り、アルミニウム基板とガラス板とが剥がれる際の強度を測定して、これを初期接着力とし、以下の基準で評価した。
Ａ・・３ＭＰａ超
Ｂ・・２ＭＰａ超３ＭＰａ以下
Ｃ・・１ＭＰａ超２ＭＰａ以下
Ｄ・・１ＭＰａ以下
[Initial adhesive strength (temporary adhesive strength)]
The adhesive composition was applied in a circular shape to an aluminum substrate (25 mm x 100 mm) with dimensions of 3 mm (radius) x 0.4 mm (thickness). Thereafter, the adhesive composition was irradiated with active energy rays in the presence of oxygen at a wavelength of 405 nm, an illumination intensity of 1000 mW/cm 2 , and an integrated light amount of 1000 mJ/cm 2 to cure the adhesive composition. . Next, a glass plate (25 mm x 100 mm) was placed on the adhesive composition to sandwich the adhesive composition, and then a 200 g weight was placed on top of the glass plate to form a sample for evaluating initial adhesive strength. Created.
The obtained initial adhesive force evaluation sample was pulled at a speed of 12.7 mm/min in the shear direction at 25° C. and in a 50% RH atmosphere using a tensile tester Autograph AG-X (Shimadzu Corporation), and then applied to an aluminum substrate. The strength when the glass plate was peeled off was measured, and this was taken as the initial adhesive strength, which was evaluated based on the following criteria.
A... More than 3 MPa B... More than 2 MPa and less than 3 MPa C... More than 1 MPa and less than 2 MPa D... Less than 1 MPa
［本接着力］
上記初期接着力評価において作製する初期接着力評価用試料を用いて以下の手順で評価した。
初期接着力評価用試料のガラス板側から、再度、波長４０５ｎｍ、照度１０００ｍＷ／ｃｍ２、積算光量１０００ｍＪ／ｃｍ２の条件で活性エネルギー線を照射して、本接着力評価用試料を作製した。
得られた本接着力評価用試料について、引張試験機オートグラフＡＧ－Ｘ（島津製作所）を用い、２５℃、５０％ＲＨ雰囲気下でせん断方向に１２．７ｍｍ／分の速度で引張り、アルミニウム基板とガラス板とが剥がれる際の強度を測定して、これを本接着力とし、以下の基準で評価した。
Ａ・・４．５ＭＰａ超
Ｂ・・２．６ＭＰａ超４．５ＭＰａ以下
Ｃ・・２ＭＰａ超２．６ＭＰａ以下
Ｄ・・２ＭＰａ以下
[Real adhesive strength]
The initial adhesive strength evaluation sample prepared in the above initial adhesive strength evaluation was used to evaluate according to the following procedure.
The glass plate side of the initial adhesive force evaluation sample was again irradiated with active energy rays under the conditions of a wavelength of 405 nm, an illumination intensity of 1000 mW/cm 2 , and an integrated light amount of 1000 mJ/cm 2 to prepare a final adhesive force evaluation sample.
The obtained sample for evaluation of adhesive force was pulled at a speed of 12.7 mm/min in the shear direction in an atmosphere of 25° C. and 50% RH using a tensile tester Autograph AG-X (Shimadzu Corporation), and then applied to an aluminum substrate. The strength when the glass plate was peeled off was measured, and this was taken as the actual adhesive strength, which was evaluated based on the following criteria.
A... More than 4.5 MPa B... More than 2.6 MPa and less than 4.5 MPa C... More than 2 MPa and less than 2.6 MPa D... Less than 2 MPa
［形状保持性］
上記した初期接着力評価において、２００ｇの重りを乗せる代わりに、１ｋｇの重りを乗せて、重りを乗せた後の接着剤組成物の厚みを測定し、形状保持性を評価した。
Ａ・・厚み０．３ｍｍ超０．４ｍｍ以下
Ｂ・・厚み０．２ｍｍ超０．３ｍｍ以下
Ｃ・・厚み０．１ｍｍ超０．２ｍｍ以下
Ｄ・・厚み０．１ｍｍ以下
[Shape retention]
In the initial adhesive strength evaluation described above, a 1 kg weight was placed instead of a 200 g weight, and the thickness of the adhesive composition after the weight was placed was measured to evaluate shape retention.
A: Thickness over 0.3 mm and 0.4 mm or less B: Thickness over 0.2 mm and 0.3 mm or less C: Thickness over 0.1 mm and 0.2 mm or less D: Thickness 0.1 mm or less
各実施例に示すとおり、Ｔｇａ及び｜Ｔｇｂ－Ｔｇａ｜が所定の範囲である本発明の接着剤組成物は、初期接着力及び形状保持性が共に良好であった。一方、各比較例に示すとおり、本発明の要件を満足しない各比較例の接着剤組成物は、初期接着力及び形状保持性の少なくとも一方が悪い結果となった。 As shown in each example, the adhesive composition of the present invention in which Tga and |Tgb-Tga| were within the predetermined ranges had good initial adhesive strength and shape retention. On the other hand, as shown in each comparative example, the adhesive composition of each comparative example that did not satisfy the requirements of the present invention had poor results in at least one of initial adhesive strength and shape retention.
Claims (9)
前記ラジカル重合性化合物が窒素含有モノマー（但し、３－（メタ）アクリロイルオキシ－２－ヒドロキシプロピル基を末端に有するものを除く）を含み、
前記窒素含有モノマーの含有量が前記ラジカル重合性化合物全量基準に対して１０質量％以上９５質量％以下であり、
酸素存在下で硬化させた前記接着剤組成物の硬化物の動的粘弾性測定におけるｔａｎδピーク温度をＴｇａ、
酸素非存在下で硬化させた前記接着剤組成物の硬化物の動的粘弾性測定におけるｔａｎδピーク温度をＴｇｂとした場合に、
下記式（１）及び（２）を満足する、接着剤組成物。
式（１） ｜Ｔｇｂ－Ｔｇａ｜≦３０℃
式（２） －１５℃≦Ｔｇａ≦３５℃ An adhesive composition comprising a radically polymerizable compound and a radical photopolymerization initiator,
The radically polymerizable compound contains a nitrogen-containing monomer (excluding those having a 3-(meth)acryloyloxy-2-hydroxypropyl group at the end) ,
The content of the nitrogen-containing monomer is 10% by mass or more and 95% by mass or less based on the total amount of the radically polymerizable compound,
The tan δ peak temperature in the dynamic viscoelasticity measurement of the cured product of the adhesive composition cured in the presence of oxygen is Tga,
When the tan δ peak temperature in the dynamic viscoelasticity measurement of the cured product of the adhesive composition cured in the absence of oxygen is defined as Tgb,
An adhesive composition satisfying the following formulas (1) and (2).
Formula (1) |Tgb-Tga|≦30℃
Formula (2) -15℃≦Tga≦35℃
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| JP2024023935A JP2024045653A (en) | 2018-12-21 | 2024-02-20 | Adhesive compositions, adhesives for electronic parts, and adhesives for display elements |
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| JP2018240383 | 2018-12-21 | ||
| PCT/JP2019/049630 WO2020130043A1 (en) | 2018-12-21 | 2019-12-18 | Adhesive composition, adhesive for electronic component, and adhesive for display element |
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| KR (1) | KR20210104056A (en) |
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| WO2016163153A1 (en) | 2015-04-09 | 2016-10-13 | 協立化学産業株式会社 | Photocurable adhesive composition |
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| WO2019073979A1 (en) | 2017-10-11 | 2019-04-18 | セメダイン株式会社 | Photocurable adhesive composition, and bonding method |
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| JP5801435B2 (en) | 2014-04-03 | 2015-10-28 | 日東電工株式会社 | Active energy ray-curable adhesive composition, polarizing film and method for producing the same, optical film and image display device |
| JP2016074893A (en) * | 2014-10-03 | 2016-05-12 | 積水化学工業株式会社 | Photo-and moisture-curable resin composition, electronic component adhesive, and display element adhesive |
| CN105219316B (en) * | 2015-11-12 | 2017-09-19 | 四川厚生天佐药业有限公司 | A kind of high adhesiveness energy medical polyacrylate pressure-sensitive adhesive sticks agent |
| JP6156607B1 (en) | 2015-12-08 | 2017-07-05 | セメダイン株式会社 | Adhesion method using photocurable adhesive |
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- 2019-12-18 KR KR1020217018558A patent/KR20210104056A/en not_active Application Discontinuation
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Patent Citations (7)
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| JP2015108115A (en) | 2013-10-24 | 2015-06-11 | 昭和電工株式会社 | Active energy ray-curable adhesive composition |
| JP2016089174A (en) | 2014-11-04 | 2016-05-23 | 積水化学工業株式会社 | Photo-and moisture-curable resin composition, adhesive for electronic component, and adhesive for display element |
| WO2016163152A1 (en) | 2015-04-06 | 2016-10-13 | 協立化学産業株式会社 | Photocurable adhesive composition |
| WO2016163153A1 (en) | 2015-04-09 | 2016-10-13 | 協立化学産業株式会社 | Photocurable adhesive composition |
| WO2017183333A1 (en) | 2016-04-20 | 2017-10-26 | 日東電工株式会社 | Active-energy-ray-curable adhesive composition, laminated polarizing film, method for producing same, laminated optical film, and image display device |
| WO2019069872A1 (en) | 2017-10-04 | 2019-04-11 | 日本化薬株式会社 | Uv-curable adhesive composition, cured product thereof, and method for manufacturing optical member employing uv-curable adhesive composition |
| WO2019073979A1 (en) | 2017-10-11 | 2019-04-18 | セメダイン株式会社 | Photocurable adhesive composition, and bonding method |
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| CN113195661A (en) | 2021-07-30 |
| TW202033695A (en) | 2020-09-16 |
| WO2020130043A1 (en) | 2020-06-25 |
| KR20210104056A (en) | 2021-08-24 |
| JPWO2020130043A1 (en) | 2021-11-11 |
| JP2024045653A (en) | 2024-04-02 |
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