WO2022210672A1 - Adhesive sheet - Google Patents
Adhesive sheet Download PDFInfo
- Publication number
- WO2022210672A1 WO2022210672A1 PCT/JP2022/015342 JP2022015342W WO2022210672A1 WO 2022210672 A1 WO2022210672 A1 WO 2022210672A1 JP 2022015342 W JP2022015342 W JP 2022015342W WO 2022210672 A1 WO2022210672 A1 WO 2022210672A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mass
- component
- adhesive layer
- curable
- adhesive sheet
- Prior art date
Links
- 239000000853 adhesive Substances 0.000 title claims abstract description 92
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 92
- 239000012790 adhesive layer Substances 0.000 claims abstract description 142
- 229920005989 resin Polymers 0.000 claims abstract description 122
- 239000011347 resin Substances 0.000 claims abstract description 122
- 239000000203 mixture Substances 0.000 claims abstract description 108
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 74
- 239000011230 binding agent Substances 0.000 claims abstract description 43
- 125000000524 functional group Chemical group 0.000 claims abstract description 29
- 239000004480 active ingredient Substances 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims description 111
- 239000002994 raw material Substances 0.000 claims description 105
- 229920001955 polyphenylene ether Polymers 0.000 claims description 43
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 21
- 239000003505 polymerization initiator Substances 0.000 claims description 20
- 229920005672 polyolefin resin Polymers 0.000 claims description 20
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 16
- 239000010410 layer Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000012787 coverlay film Substances 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000004615 ingredient Substances 0.000 abstract description 3
- 239000007858 starting material Substances 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 description 49
- -1 ethylene, propylene, 1-butene Chemical class 0.000 description 48
- 239000006087 Silane Coupling Agent Substances 0.000 description 28
- 238000010438 heat treatment Methods 0.000 description 21
- 150000002430 hydrocarbons Chemical group 0.000 description 19
- 125000004432 carbon atom Chemical group C* 0.000 description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000010408 film Substances 0.000 description 12
- 239000012948 isocyanate Substances 0.000 description 12
- 150000002513 isocyanates Chemical class 0.000 description 12
- 239000004593 Epoxy Substances 0.000 description 11
- 239000013522 chelant Substances 0.000 description 11
- 239000000178 monomer Substances 0.000 description 11
- 125000001033 ether group Chemical group 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 125000000623 heterocyclic group Chemical group 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229920001721 polyimide Polymers 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 230000001681 protective effect Effects 0.000 description 6
- 229930195734 saturated hydrocarbon Natural products 0.000 description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 125000001046 glycoluril group Chemical group [H]C12N(*)C(=O)N(*)C1([H])N(*)C(=O)N2* 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- HASUCEDGKYJBDC-UHFFFAOYSA-N 1-[3-[[bis(oxiran-2-ylmethyl)amino]methyl]cyclohexyl]-n,n-bis(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC1CC(CN(CC2OC2)CC2OC2)CCC1)CC1CO1 HASUCEDGKYJBDC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical group 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229920001179 medium density polyethylene Polymers 0.000 description 2
- 239000004701 medium-density polyethylene Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 239000005056 polyisocyanate Chemical class 0.000 description 2
- 229920001228 polyisocyanate Chemical class 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000101 thioether group Chemical group 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- JZDQKBZKFIWSNW-UHFFFAOYSA-N (4-methoxyphenyl)-phenyliodanium Chemical compound C1=CC(OC)=CC=C1[I+]C1=CC=CC=C1 JZDQKBZKFIWSNW-UHFFFAOYSA-N 0.000 description 1
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical class O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- BAUSLEQPYWNKPW-UHFFFAOYSA-N 1,3,5-tris(5-isocyanatopentyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C=NCCCCCN1C(=O)N(CCCCCN=C=O)C(=O)N(CCCCCN=C=O)C1=O BAUSLEQPYWNKPW-UHFFFAOYSA-N 0.000 description 1
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical class O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical class C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 1
- HYYJOCXNESGFSB-UHFFFAOYSA-N 1-(oxiran-2-yl)-n-(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CNCC1CO1 HYYJOCXNESGFSB-UHFFFAOYSA-N 0.000 description 1
- 125000006021 1-methyl-2-propenyl group Chemical group 0.000 description 1
- JTINZFQXZLCHNS-UHFFFAOYSA-N 2,2-bis(oxiran-2-ylmethoxymethyl)butan-1-ol Chemical compound C1OC1COCC(CO)(CC)COCC1CO1 JTINZFQXZLCHNS-UHFFFAOYSA-N 0.000 description 1
- GVJRTUUUJYMTNQ-UHFFFAOYSA-N 2-(2,5-dioxofuran-3-yl)acetic acid Chemical compound OC(=O)CC1=CC(=O)OC1=O GVJRTUUUJYMTNQ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- SYIUWAVTBADRJG-UHFFFAOYSA-N 2H-pyran-2,6(3H)-dione Chemical compound O=C1CC=CC(=O)O1 SYIUWAVTBADRJG-UHFFFAOYSA-N 0.000 description 1
- OEENGLRMKHDDBH-UHFFFAOYSA-N 3-[3-aminopropyl(dimethoxy)silyl]oxy-4-phenylhex-5-en-1-amine Chemical compound NCCC[Si](OC)(OC)OC(CCN)C(C=C)C1=CC=CC=C1 OEENGLRMKHDDBH-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- XUKLTPZEKXTPBT-UHFFFAOYSA-N 3-oxatricyclo[5.2.1.01,5]dec-5-ene-2,4-dione Chemical compound C1CC2C=C3C(=O)OC(=O)C13C2 XUKLTPZEKXTPBT-UHFFFAOYSA-N 0.000 description 1
- NMUBRRLYMADSGF-UHFFFAOYSA-N 3-triethoxysilylpropan-1-ol Chemical compound CCO[Si](OCC)(OCC)CCCO NMUBRRLYMADSGF-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- YATIYDNBFHEOFA-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-ol Chemical compound CO[Si](OC)(OC)CCCO YATIYDNBFHEOFA-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical compound CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical class C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- PRKPGWQEKNEVEU-UHFFFAOYSA-N 4-methyl-n-(3-triethoxysilylpropyl)pentan-2-imine Chemical compound CCO[Si](OCC)(OCC)CCCN=C(C)CC(C)C PRKPGWQEKNEVEU-UHFFFAOYSA-N 0.000 description 1
- QKFFSWPNFCXGIQ-UHFFFAOYSA-M 4-methylbenzenesulfonate;tetraethylazanium Chemical compound CC[N+](CC)(CC)CC.CC1=CC=C(S([O-])(=O)=O)C=C1 QKFFSWPNFCXGIQ-UHFFFAOYSA-M 0.000 description 1
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 239000005047 Allyltrichlorosilane Substances 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- IVHVNMLJNASKHW-UHFFFAOYSA-M Chlorphonium chloride Chemical group [Cl-].CCCC[P+](CCCC)(CCCC)CC1=CC=C(Cl)C=C1Cl IVHVNMLJNASKHW-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Chemical class 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical class N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
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- 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
- C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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- 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
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- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/35—Heat-activated
Definitions
- the present invention relates to an adhesive sheet having a curable adhesive layer that does not easily contaminate the surroundings when subjected to heat treatment such as hot press treatment.
- curable adhesives are sometimes used as materials for forming insulating resin layers, sealant layers, adhesive members, etc. of electronic devices.
- Patent Document 1 discloses a thermosetting adhesive sheet containing an epoxy resin, wherein the cured product of the thermosetting adhesive sheet has a storage elastic modulus (x1) of 1 GPa or more at 25°C and a temperature of 100°C. describes a thermosetting adhesive sheet having a storage modulus (x2) of 1 GPa or more.
- this document states that the thermosetting adhesive sheet described in the same document can effectively suppress minute deformation and displacement of an adherend at high temperatures, and can be repeatedly minutely deformed as an adherend. It is also described that even when used to fix an adherend, it is less likely to cause peeling over time.
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide an adhesive sheet having a curable adhesive layer that does not easily contaminate the surroundings when subjected to heat treatment such as hot press treatment.
- the inventors diligently studied to solve the above problems. As a result, for an adhesive sheet having a curable adhesive layer, a raw material composition for the curable adhesive layer containing a predetermined component was used, and the gel fraction of the curable adhesive layer was within a predetermined range. The inventors have found that the adjustment can suppress the exudation of the adhesive component during heat treatment and prevent contamination of the surroundings, leading to the completion of the present invention.
- an adhesive sheet having a curable adhesive layer The raw material composition of the curable adhesive layer contains the following components (A) and (B), and the amount of component (B) is 0.1 mass based on the total amount of active ingredients in the raw material composition. % or more, The adhesive sheet, wherein the curable adhesive layer has a gel fraction of 10% by mass or more.
- component binder resin having a reactive functional group
- B component: cross-linking agent capable of reacting with component (A) [2] described in [1], wherein component (A) is a polyolefin resin adhesive sheet.
- Component (C) is a compound having two or more hydrocarbon groups with double bonds at their terminals
- Adhesive sheet as described.
- the curable adhesive layer is a layer formed from a raw material composition further containing the following component (E) [1] to [ 8] The adhesive sheet according to any one of the above items.
- an adhesive sheet having a curable adhesive layer that hardly contaminates the surroundings when subjected to heat treatment such as hot press treatment is provided.
- FIG. 2 is a schematic diagram (plan view) of a part of a laminate used when evaluating the exudation of an adhesive component.
- FIG. 2 is a schematic diagram showing a cross section taken along line AA of FIG. 1;
- the upper and lower limits can be combined arbitrarily.
- the numerical range is described as “preferably 30 to 100, more preferably 40 to 80”
- the range of "30 to 80” and the range of "40 to 100” are also described in this specification. included in the specified numerical range.
- the numerical range is described as “preferably 30 or more, more preferably 40 or more, and preferably 100 or less, more preferably 80 or less”
- “30 to 80” Ranges and ranges from “40 to 100” are also included in the numerical ranges described herein.
- the description of "60 to 100” means a range of "60 or more and 100 or less”.
- the number average molecular weight (Mn) can be obtained as a standard polystyrene conversion value by performing gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.
- GPC gel permeation chromatography
- THF tetrahydrofuran
- the adhesive sheet of the present invention is an adhesive sheet having a curable adhesive layer, wherein the raw material composition of the curable adhesive layer contains the following components (A) and (B), and (The adhesive sheet contains component B) in an amount of 0.1% by mass or more relative to the total amount of active ingredients in the raw material composition, and the curable adhesive layer has a gel fraction of 10% by mass or more.
- the raw material composition for the curable adhesive layer constituting the adhesive sheet of the present invention contains the above components (A) and (B), and the content of component (B) is the total amount of active ingredients in the raw material composition. is adjusted to 0.1% by mass or more.
- the cross-linking agent (B) is a compound that can react with the binder resin (A), the binder resin (A) and the cross-linking agent are formed in the coating film (curable adhesive layer) obtained by applying the raw material composition. (B) can be reacted to build a crosslinked structure within the curable adhesive layer. As will be described later, by utilizing this reaction, a curable adhesive layer having a gel fraction of 10% by mass or more can be efficiently formed.
- the cross-linking reaction involving the binder resin (A) and the cross-linking agent (B) may be referred to as "curing reaction (I)".
- the raw material composition may contain a curable component other than the binder resin (A) and the cross-linking agent (B) (hereinafter sometimes referred to as "curable component (X)").
- the curable component (X) may be a compound that participates in the curing reaction (I) or a compound that does not participate in the curing reaction (I).
- the curable component (X) can be used for the curing reaction (I) because the curing reaction can be reliably performed a plurality of times and the oozing of the adhesive component in the curable adhesive layer can be suppressed more reliably. Non-participating compounds are preferred.
- the curable component (X) is a compound that participates in the curing reaction (I)
- a step of constructing a crosslinked structure in the curable adhesive layer to produce the adhesive sheet of the present invention and Since the curing reaction (I) is required in both steps of the process of more firmly bonding two adherends using a sheet, curing initiated to build a crosslinked structure within the curable adhesive layer It is necessary to temporarily stop the reaction (I) in the middle, and it is necessary to control the curing reaction (I) to a high degree.
- the adhesive sheet of the present invention can be efficiently produced without highly controlling the curing reaction (I). can be manufactured well.
- curing reaction (II) the curing reaction involving the curable component (X) that does not participate in the curing reaction (I) is sometimes referred to as "curing reaction (II)".
- the curable component (X) includes the following components (C), (D) and (F).
- Component (C) Non-aromatic curable compound that is liquid at 25° C.
- Component (D) Polyphenylene ether resin having a reactive functional group
- Component (F) Silane coupling agent
- the raw material composition used in one aspect of the present invention may further contain the following component (E).
- the raw material composition used in one embodiment of the present invention further contains components other than the above components (A) to (F) within a range that does not impair the effects of the present invention. may contain.
- the total content of the components (A) and (B) is 40% by mass or more with respect to the total amount (100% by mass) of the active ingredients in the raw material composition, 50% by mass or more, 60% by mass or more, 65% by mass or more, or 70% by mass or more, and 100% by mass or less, 99% by mass or less, 95% by mass or less, 90% by mass or less, and 85% by mass or less , or 80% by mass or less.
- the total content of components (A) to (E) is 45% by mass or more with respect to the total amount (100% by mass) of the active ingredients in the raw material composition, 55% by mass or more, 65% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, 90% by mass or more, or 95% by mass or more, and 100% by mass or less, 99.9 % by mass or less, or 99.8% by mass or less.
- the total content of components (A) to (F) is 45 to 100% by mass with respect to the total amount (100% by mass) of the active ingredients in the raw material composition. , 55% by mass or more, 65% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, 90% by mass or more, or 95% by mass or more, and 100% by mass or less, 99. It may be 9% by mass or less, or 99.8% by mass or less.
- a raw material composition (hereinafter, sometimes simply referred to as “raw material composition"), which is a material for forming a curable adhesive layer, contains, as component (A), a binder resin having a reactive functional group (hereinafter, “ It may be described as “binder resin (A)”).
- binder resin (A) By using the raw material composition containing the binder resin (A), it becomes easier to form a curable adhesive layer that does not easily stain the surroundings when subjected to heat treatment such as hot press treatment.
- Binder resin (A) can be used individually by 1 type or in combination of 2 or more types.
- the number average molecular weight (Mn) of the binder resin (A) is not particularly limited. 000 or more, preferably 10,000 to 150,000, more preferably 10,000 to 100,000.
- the number average molecular weight (Mn) of the binder resin (A) can be obtained as a standard polystyrene conversion value by performing gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and specific measurement The conditions are as described above.
- the content of the binder resin (A) contained in the raw material composition (the total amount of these when containing two or more binder resins (A)) is based on the total amount (100% by mass) of the active ingredients in the raw material composition. is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 65% by mass or more, and is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass. 80% by mass or less, and more preferably 80% by mass or less.
- the content of the binder resin (A) is 50% by mass or more, it becomes easier to form a curable adhesive layer that does not easily stain the surroundings when subjected to heat treatment such as hot press treatment.
- binder resin (A) examples include polyolefin-based resins, phenoxy-based resins, polyimide-based resins, polyamideimide-based resins, polyvinyl butyral-based resins, and polycarbonate-based resins. Among these, polyolefin-based resins are preferable as the binder resin (A). When the binder resin (A) is a polyolefin resin, a curable adhesive layer with excellent low dielectric properties can be easily formed.
- the raw material composition may contain other binder resins than the polyolefin resin as other components.
- the content of the other binder resin is preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, and still more preferably 0 to 10 parts by mass with respect to 100 parts by mass of the total polyolefin resin. parts by weight, more preferably 0 to 5 parts by weight.
- a polyolefin resin is a polymer containing repeating units derived from an olefin monomer.
- the polyolefin resin may be a polymer consisting only of repeating units derived from an olefinic monomer, or a repeating unit derived from an olefinic monomer and a monomer copolymerizable with the olefinic monomer. It may be a polymer composed of repeating units derived from
- the olefinic monomer is preferably an ⁇ -olefin having 2 to 8 carbon atoms, more preferably ethylene, propylene, 1-butene, isobutylene, or 1-hexene, and still more preferably ethylene or propylene.
- These olefinic monomers can be used singly or in combination of two or more.
- monomers copolymerizable with olefinic monomers include vinyl acetate, (meth)acrylic acid esters, and styrene.
- (meth)acrylic acid means acrylic acid or methacrylic acid (same below).
- Polyolefin resins include very low density polyethylene (VLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene, polypropylene (PP), ethylene-propylene Copolymers, olefinic elastomers (TPO), ethylene-vinyl acetate copolymers (EVA), ethylene-(meth)acrylic acid copolymers, ethylene-(meth)acrylic acid ester copolymers, and the like.
- VLDPE very low density polyethylene
- LDPE low density polyethylene
- MDPE medium density polyethylene
- HDPE high density polyethylene
- PP polypropylene
- TPO ethylene-propylene Copolymers
- EVA ethylene-vinyl acetate copolymers
- EVA ethylene-(meth)acrylic acid copolymers
- ethylene-(meth)acrylic acid ester copolymers and the like.
- Reactive functional groups contained in the binder resin (A) include a carboxy group, a carboxylic acid anhydride group, a carboxylic acid ester group, a hydroxyl group, an epoxy group, an amide group, an ammonium group, a nitrile group, an amino group, an imide group, and an isocyanate group. group, acetyl group, thiol group, ether group, thioether group, sulfone group, phosphon group, nitro group, urethane group, halogen atom, alkoxysilyl and the like.
- Binder resin (A) is preferably a modified resin.
- the modified resin is a resin into which a reactive functional group is introduced, which is obtained by modifying a resin as a precursor using a modifying agent.
- a modifier used for modifying the binder resin is a compound having a reactive functional group in the molecule. Reactive functional groups include those previously described.
- modified resins include resins into which acid groups have been introduced (acid-modified resins) and resins into which hydroxyl groups have been introduced, and acid-modified resins are preferred.
- acid-modified resins resins into which an acid anhydride structure is introduced are preferable.
- an acid-modified resin as the component (A)
- a curable adhesive layer with excellent low dielectric properties can be easily formed.
- a resin into which an acid anhydride structure is introduced as the acid-modified resin there is a tendency that the pot life of the raw material composition can be easily maintained for a long time.
- the raw material composition may contain, as other components, a binder resin other than the acid-modified resin.
- the content of the other binder resin is preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, and still more preferably 0 to 10 parts by mass with respect to 100 parts by mass of the total amount of the acid-modified resin. parts by weight, more preferably 0 to 5 parts by weight.
- a resin is reacted with an unsaturated carboxylic acid or an unsaturated carboxylic anhydride (hereinafter sometimes referred to as "unsaturated carboxylic acid or the like") to form a carboxy group or a carboxylic anhydride group. is introduced (graft modification).
- unsaturated carboxylic acid or an unsaturated carboxylic anhydride hereinafter sometimes referred to as "unsaturated carboxylic acid or the like
- Unsaturated carboxylic acids to be reacted with the resin include unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, and aconitic acid; maleic anhydride, itaconic anhydride, and glutaconic anhydride. acids, unsaturated carboxylic anhydrides such as citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, and tetrahydrophthalic anhydride; These can be used individually by 1 type or in combination of 2 or more types. Among these, maleic anhydride is preferable because it facilitates the formation of a curable adhesive layer that gives a cured product with higher adhesive strength.
- the amount of the unsaturated carboxylic acid or the like to be reacted with the resin is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, and still more preferably 0.2 to 1 part by mass with respect to 100 parts by mass of the resin. part by mass.
- the method of introducing unsaturated carboxylic acid units or unsaturated carboxylic anhydride units into the resin is not particularly limited.
- a radical generator such as organic peroxides or azonitriles, a resin and an unsaturated carboxylic acid, etc.
- a method of heating and melting above the melting point of the resin to react or a method of reacting the resin and the unsaturated carboxylic acid.
- the resin is graft-copolymerized with an unsaturated carboxylic acid or the like by heating and stirring in the presence of a radical generator.
- a modified polyolefin resin is preferable, and an acid-modified polyolefin resin is more preferable.
- an acid-modified polyolefin resin it becomes easier to form a curable adhesive layer with excellent low dielectric properties and low staining properties.
- a modified polyolefin resin is a polyolefin resin into which a reactive functional group has been introduced, obtained by modifying a polyolefin resin as a precursor using a modifier.
- the raw material composition may contain other binder resins other than the acid-modified polyolefin-based resin as other components.
- the content of the other binder resin is preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, and still more preferably 0 parts by mass with respect to 100 parts by mass of the total amount of the acid-modified polyolefin resin. to 10 parts by weight, more preferably 0 to 5 parts by weight.
- Component (B) Crosslinking agent capable of reacting with component (A)
- the raw material composition contains, as the component (B), a cross-linking agent capable of reacting with the component (A) (hereinafter sometimes referred to as "cross-linking agent (B)").
- cross-linking agent (B) By using the raw material composition containing the cross-linking agent (B), it becomes easier to form a curable adhesive layer that does not easily stain the surroundings when subjected to heat treatment such as hot press treatment.
- a crosslinking agent (B) can be used individually by 1 type or in combination of 2 or more types.
- the molecular weight of the cross-linking agent (B) is preferably 1000 or less, more preferably 800 or less, even more preferably 700 or less, even more preferably 600 or less, and particularly preferably 500 or less.
- the molecular weight of the cross-linking agent (B) is 1000 or less, the collision probability of the reaction with the component (A) increases, making it easier to form a cross-linked structure, and when subjected to heat treatment such as hot press treatment, the surroundings The raw material composition can easily form a curable adhesive layer that is difficult to stain.
- the molecular weight of the cross-linking agent (B) it is usually 100 or more, preferably 200 or more.
- the molecular weight of the cross-linking agent (B) is a formula weight determined from the structural formula of the compound used as the cross-linking agent (B).
- the content of the cross-linking agent (B) (the total amount of these when two or more cross-linking agents (B) are included) is 0.1 mass with respect to the total amount (100 mass%) of the active ingredients in the raw material composition % or more, preferably 0.2 mass % or more, more preferably 0.3 mass % or more, still more preferably 0.5 mass % or more, even more preferably 0.7 mass % or more, particularly preferably 0.7 mass % or more. It is 9% by mass or more, preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less, and even more preferably 2% by mass or less.
- the content of the cross-linking agent (B) is 0.1% by mass or more with respect to the total amount of active ingredients in the raw material composition, so that it has curability that does not easily stain the surroundings when subjected to heat treatment such as hot press treatment. An adhesive layer is easily formed. Further, when the content of the cross-linking agent (B) is 5% by mass or less with respect to the total amount of active ingredients in the raw material composition, a curable adhesive layer having excellent low dielectric properties can be easily formed.
- the content of the cross-linking agent (B) is preferably 0.1 part by mass or more, more preferably 100 parts by mass of component (A) 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 0.8 parts by mass or more, particularly preferably 1.2 parts by mass or more, and preferably 10 parts by mass or less, more It is preferably 7 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less.
- Cross-linking agent (B) is a compound capable of reacting with component (A). Therefore, as the cross-linking agent (B), it is necessary to appropriately select one having a reactive group or a reactive site that is reactive with the reactive functional group in the binder resin (A).
- the cross-linking agent (B) an isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, a metal chelate-based cross-linking agent, an aziridine-based cross-linking agent, or the like can be used.
- one or more selected from isocyanate-based cross-linking agents, epoxy-based cross-linking agents, and metal chelate-based cross-linking agents are preferable from the viewpoint of storage stability.
- a cross-linking agent ( B) is preferably one or more selected from isocyanate-based cross-linking agents, epoxy-based cross-linking agents, and metal chelate-based cross-linking agents.
- An isocyanate-based cross-linking agent is a compound having two or more isocyanate groups in the molecule.
- isocyanate cross-linking agents include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, 1,5-pentamethylene diisocyanate, and 1,6-hexamethylene.
- Epoxy crosslinking agent is a compound having two or more epoxy groups in its molecule.
- Epoxy crosslinking agents include 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-m-xylylenediamine, ethylene glycol diglycidyl ether, 1 ,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidylaniline, diglycidylamine and the like.
- a metal chelate-based cross-linking agent is a chelate compound having metal ions functioning as cross-linking points.
- metal chelate-based cross-linking agents for example, metal chelate compounds whose metal ions are aluminum ions, zirconium ions, titanium ions, zinc ions, iron ions, tin ions, and the like can be used. Among these, aluminum chelate compounds are preferred.
- aluminum chelate compounds include aluminum tris(acetylacetonate), acetylacetonate aluminum bis(ethylacetoacetate), diisopropoxyaluminum monooleyl acetoacetate, monoisopropoxyaluminum bisoleyl acetoacetate, and the like.
- the cross-linking agent (B) is preferably a compound having an isocyanurate skeleton, more preferably a compound having an isocyanurate skeleton and two or more isocyanate groups.
- the cross-linking agent (B) is a compound having an isocyanurate skeleton, a curable adhesive layer with excellent low dielectric properties can be easily formed.
- the raw material composition may contain, as another component, a cross-linking agent other than the compound having an isocyanurate skeleton. good.
- the content of the other cross-linking agent is preferably 0 to 100 parts by mass, more preferably 0 to 50 parts by mass, and still more preferably 100 parts by mass of the total amount of the compound having an isocyanurate skeleton. 0 to 30 parts by weight, more preferably 0 to 10 parts by weight, particularly preferably 0 to 5 parts by weight.
- the cross-linking agent (B) is preferably an isocyanate-based cross-linking agent, which is a compound having two or more isocyanate groups, since a curable adhesive layer having excellent low dielectric properties is easily formed.
- the isocyanurate of the compound is more preferable, and the isocyanurate of 1,5-pentamethylene diisocyanate [1,3,5-tris(5-isocyanatopentyl)-1,3,5-triazine-2,4,6-trione ] or an isocyanurate of 1,6-hexamethylene diisocyanate [1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazine-2,4,6-trione] is more preferable.
- the raw material composition may contain other cross-linking agents other than the isocyanate-based cross-linking agent as other components.
- the content of the other cross-linking agent is preferably 0 to 100 parts by mass, more preferably 0 to 50 parts by mass, and still more preferably 0 parts by mass with respect to 100 parts by mass of the total amount of the isocyanate-based cross-linking agent. to 30 parts by mass, more preferably 0 to 10 parts by mass, and particularly preferably 0 to 5 parts by mass.
- the cross-linking agent (B) is preferably an epoxy-based cross-linking agent, since a curable adhesive layer that does not easily contaminate the surroundings is easily formed when subjected to heat treatment such as hot press treatment.
- the raw material composition may contain other cross-linking agents other than the epoxy-based cross-linking agent as other components.
- the content of the other cross-linking agent is preferably 0 to 100 parts by mass, more preferably 0 to 50 parts by mass, and still more preferably 0 to 100 parts by mass, with respect to 100 parts by mass of the total epoxy cross-linking agent. 30 parts by weight, more preferably 0 to 10 parts by weight, particularly preferably 0 to 5 parts by weight.
- the cross-linking agent (B) is a compound that can react with the binder resin (A), the binder resin (A) and the cross-linking agent are formed in the coating film (curable adhesive layer) obtained by applying the raw material composition. (B) can be reacted to build a crosslinked structure within the curable adhesive layer.
- a curable adhesive layer having a gel fraction of 10% by mass or more can be efficiently formed, and when subjected to heat treatment such as heat press treatment, the surrounding area can be A curable adhesive layer that is difficult to stain is easily formed.
- Component (C) non-aromatic curable compound that is liquid at 25°C
- Component (C) is a non-aromatic curable compound that is liquid at 25° C. (hereinafter sometimes referred to as “curable compound (C)”). Curable compound (C) can be used individually by 1 type or in combination of 2 or more types.
- the curable compound (C) is a curable compound. Therefore, if the curable compound (C) is the curable component (X) that does not participate in the curing reaction (I), the curable adhesive layer containing this curable compound (C) will not participate in the curing reaction (II). It has curability derived from
- the curable compound (C) is a compound that is liquid at 25°C. Therefore, when the curable compound (C) is the curable component (X) that does not participate in the curing reaction (I), the curable adhesive layer containing this curable compound (C) exhibits good wettability during lamination. It has spreadability and is excellent in lamination aptitude.
- "Liquid at 25°C” means having fluidity at 25°C.
- a compound that is liquid at 25° C. is a compound with a viscosity of 2 to 10000 mPa ⁇ s measured at 25° C. and 1.0 rpm using an E-type viscometer.
- the curable compound (C) is a non-aromatic compound.
- a non-aromatic compound means a compound without an aromatic ring. Since the curable compound (C) is a non-aromatic compound, the curable adhesive layer containing the curable compound (C) tends to have excellent low dielectric properties.
- the curable compound (C) is preferably a compound having a heterocyclic skeleton.
- the curable compound (C) is a compound having a heterocyclic skeleton, it becomes easier to form a curable adhesive layer that gives a cured product with excellent adhesive strength and low dielectric properties.
- the raw material composition is a compound having a heterocyclic skeleton, the raw material composition may contain, as other components, a curable compound other than the compound having the heterocyclic skeleton. good.
- the content of the other curable compound is preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, and more preferably 0 to 30 parts by mass, relative to 100 parts by mass of the total amount of the compound having a heterocyclic skeleton. It is preferably 0 to 10 parts by weight, and more preferably 0 to 5 parts by weight.
- the heterocyclic skeleton includes an isocyanurate skeleton and a glycoluril skeleton.
- the heterocyclic skeleton preferably has an n-fold rotation axis as a symmetry element.
- a curable adhesive layer containing such a curable compound (C) having a heterocyclic skeleton tends to have excellent low dielectric properties.
- the molecular weight of the curable compound (C) is preferably 1,000 or less, more preferably 800 or less, still more preferably 650 or less, and even more preferably 500 or less. Curable compounds with a molecular weight of 1,000 or less tend to meet the requirement of being liquid at 25°C. Moreover, the molecular weight of the curable compound (C) is preferably 100 or more, more preferably 200 or more, and even more preferably 275 or more. The curable compound (C) having a molecular weight of 100 or more is difficult to volatilize even when heat treatment is performed when forming the curable adhesive layer or when using the curable adhesive layer. By adding a curable compound (C) having a high molecular weight to the layer, it becomes easier to obtain a cured product having the desired physical properties.
- curable compound (C) for example, a compound having two or more hydrocarbon groups having double bonds at the terminals (hereinafter, this compound may be referred to as "curable compound (C')"). mentioned.
- curable compound (C′) As the curable compound (C), it becomes easier to form a curable adhesive layer that gives a cured product with excellent low dielectric properties.
- the raw material composition in which the component (C) is the curable compound (C') the raw material composition contains, as another component, a curable compound other than the curable compound (C').
- the content of the other curable compound is preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, with respect to 100 parts by mass of the total amount of the curable compound (C'), More preferably 0 to 10 parts by mass, and even more preferably 0 to 5 parts by mass.
- the number of carbon atoms in the hydrocarbon group having a double bond at the end contained in the curable compound (C') is preferably 2-10, more preferably 2-5.
- Hydrocarbon groups having a double bond at the end include vinyl group, allyl group, 3-butenyl group, 4-pentenyl group, 5-hexenyl group, isopropenyl group, 1-methyl-2-propenyl group and vinylbenzyl group. , a vinyl naphthyl group, and the like. Among these, an allyl group is preferred.
- the number of hydrocarbon groups having a double bond at the terminal contained in the curable compound (C') is two or more.
- the number of hydrocarbon groups having a double bond at the terminal is 2 or more, it becomes easier to form a curable adhesive layer that gives a cured product with excellent adhesive strength and heat resistance.
- the number of hydrocarbon groups having a double bond at the end is preferably 2-4, more preferably 2.
- curable compound (C') examples include a curable compound (C') having an isocyanurate skeleton and a curable compound (C') having a glycoluril skeleton.
- curable compound (C') having an isocyanurate skeleton examples include compounds represented by the following formula (1) or (2).
- R 1 and R 2 each independently represent a hydrocarbon group having a double bond at the end;
- R 3 is a saturated hydrocarbon group having 1 to 15 carbon atoms; represents an alkoxy group-substituted alkyl group.
- R 4 to R 6 each independently represent a hydrocarbon group having a double bond at its end.
- hydrocarbon groups having a double bond at the end represented by R 1 , R 2 , R 4 , R 5 and R 6 are as explained above.
- the saturated hydrocarbon group represented by R 3 has 1 to 15 carbon atoms, preferably 5 to 15 carbon atoms, and more preferably 8 to 15 carbon atoms.
- saturated hydrocarbon groups represented by R 3 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, s-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, etc. is mentioned.
- the alkoxy group-substituted alkyl group represented by R 3 has 2 to 15 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 3 to 10 carbon atoms.
- the alkoxy-substituted alkyl group represented by R 3 includes methoxymethyl group, ethoxymethyl group, 2-methoxyethoxymethyl group, benzyloxymethyl group and the like.
- curable compound (C') having a glycoluril skeleton examples include compounds represented by the following formula (3).
- R 7 to R 10 each independently represent a hydrocarbon group having 1 to 15 carbon atoms, at least two of which are hydrocarbon groups having double bonds at their ends.
- R 11 and R 12 each represent a hydrogen atom or a saturated hydrocarbon group having 1 to 15 carbon atoms.
- a compound having an isocyanurate skeleton is preferable as the curable compound (C′), since a cured product having an appropriate crosslink density and excellent low dielectric properties can be easily obtained.
- a compound represented by is more preferable, and a compound represented by the following formula is even more preferable.
- R represents a saturated hydrocarbon group having 5 to 15 carbon atoms, preferably a saturated hydrocarbon group having 8 to 15 carbon atoms.
- the content of the curable compound (C) (when two or more curable compounds (C) are included, the total amount of these) is It is preferably 5% by mass or more, more preferably 7% by mass or more, still more preferably 8.5% by mass or more, and preferably 25% by mass or less with respect to the total amount (100% by mass) of the active ingredient. , more preferably 20% by mass or less, and still more preferably 15% by mass or less.
- the content of the curable compound (C) is 5% by mass or more based on the total amount of active ingredients in the raw material composition, a curable adhesive layer that provides a cured product with excellent adhesive strength is easily formed.
- the content of the curable compound (C) is 25% by mass or less based on the total amount of active ingredients in the raw material composition, a curable adhesive layer that provides a cured product with excellent low dielectric properties can be easily formed.
- the content of the curable compound (C) (two or more curable compounds (C ) is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, still more preferably 7 parts by mass or more, still more preferably 10 parts by mass or more, and preferably It is 30 parts by mass or less, more preferably 25 parts by mass or less, still more preferably 20 parts by mass or less, and even more preferably 16 parts by mass or less.
- Component (D) is a polyphenylene ether resin having a reactive functional group (hereinafter sometimes referred to as "polyphenylene ether resin (D)").
- a polyphenylene ether resin is a resin having a polyphenylene skeleton in its main chain.
- a polyphenylene skeleton refers to a skeleton having a repeating unit represented by the following formula or a repeating unit in which hydrogen atoms in the above formula are substituted.
- Polyphenylene ether resin (D) is a compound having a polyphenylene ether skeleton and a reactive functional group. Since the polyphenylene ether resin (D) has a polyphenylene ether skeleton, the curable adhesive layer containing the polyphenylene ether resin (D) is excellent in low dielectric properties. Moreover, since the polyphenylene ether resin (D) has a reactive functional group, the cured product of the curable adhesive layer containing the polyphenylene ether resin (D) has excellent heat resistance. Polyphenylene ether resin (D) can be used individually by 1 type or in combination of 2 or more types.
- Examples of the polyphenylene ether skeleton in the polyphenylene ether resin (D) include those represented by the following formula (4).
- X is a divalent group represented by the following formula (5) or formula (6)
- each Y is independently a divalent group represented by the following formula (7) is a group
- a and b are integers of 0 to 100, and at least one of a and b is 1 or more.
- * represents a bond (same below).
- R 13 to R 20 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, preferably a hydrogen atom or a methyl group.
- R 21 to R 28 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, preferably a hydrogen atom or a methyl group.
- A represents a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.
- R 29 to R 32 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, preferably a hydrogen atom or a methyl group.
- Examples of the polyphenylene ether skeleton in the polyphenylene ether resin (D) include those represented by the following formula (8).
- Examples of reactive functional groups in the polyphenylene ether resin (D) include groups having an ethylenically unsaturated bond such as vinyl, allyl, acryloyl, methacryloyl, cyclopentenyl, vinylbenzyl, and vinylnaphthyl; group; hydroxyl group; and the like.
- the reactive functional group is preferably a group having an ethylenically unsaturated bond, more preferably a vinylbenzyl group, since a cured product having excellent low dielectric properties can be easily obtained.
- the polyphenylene ether resin (D) a resin having a reactive functional group at both ends of the polyphenylene ether skeleton is preferable because a cured product having excellent low dielectric properties can be easily obtained.
- the raw material composition is a resin having a reactive functional group at both ends of the polyphenylene ether skeleton
- the raw material composition contains, as another component, reactive functional groups at both ends of the polyphenylene ether skeleton.
- a polyphenylene ether resin other than the resin having a group may be contained.
- the content of the other polyphenylene ether resin is preferably 0 to 50 parts by mass, more preferably 100 parts by mass of the total amount of the resin having reactive functional groups at both ends of the polyphenylene ether skeleton. is 0 to 30 parts by mass, more preferably 0 to 10 parts by mass, and even more preferably 0 to 5 parts by mass.
- the polyphenylene ether resin (D) can be obtained by forming a polyphenylene ether skeleton and then introducing a reactive functional group to the terminal.
- a polyphenylene ether resin (D) having vinylbenzyl groups at both ends as reactive functional groups was reacted with a bifunctional phenol compound and a monofunctional phenol compound to obtain a polymer having phenolic hydroxyl groups at both ends. Then, it can be obtained by vinylbenzyl etherifying the terminal phenolic hydroxyl group using 4-(chloromethyl)styrene.
- Examples of the polyphenylene ether resin (D) include compounds represented by the following formula (9).
- a and b are integers of 0 to 100, and at least one of a and b is 1 or more.
- the raw material composition contains, as another component, a polyphenylene other than the compound represented by the above formula (9) It may contain an ether resin.
- the content of the other polyphenylene ether resin is preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, with respect to 100 parts by mass of the total amount of the compound represented by the above formula (9). parts, more preferably 0 to 10 parts by weight, and even more preferably 0 to 5 parts by weight.
- the number average molecular weight (Mn) of the polyphenylene ether resin (D) is preferably 500 to 5,000, more preferably 500 to 3,000, still more preferably 700 to 2,500, still more preferably 1,000 to 2. , 000.
- the number average molecular weight (Mn) of the polyphenylene ether resin (D) is obtained by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and can be obtained as a standard polystyrene conversion value, and specific measurement conditions is as described above.
- the content of the polyphenylene ether resin (D) (when two or more (D) components are included, the total amount of these) is the active ingredient of the raw material composition
- the total amount (100% by mass) of preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 30% by mass % by mass or less, more preferably 25% by mass or less.
- the content of the polyphenylene ether resin (D) is 1% by mass or more based on the total amount of active ingredients in the raw material composition, a curable adhesive layer that provides a cured product with excellent low dielectric properties is easily formed.
- the content of the polyphenylene ether resin (D) is 30% by mass or less in the total amount of active ingredients in the raw material composition, a curable adhesive layer with excellent sticking properties is easily formed.
- the total amount of these when included) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, still more preferably 20 parts by mass or more, and preferably 50 parts by mass parts or less, more preferably 40 parts by mass or less, even more preferably 35 parts by mass or less, still more preferably 30 parts by mass or less.
- the raw material composition may contain a silane coupling agent (F) as a curable component (X).
- the silane coupling agents (F) can be used singly or in combination of two or more.
- silane coupling agent (F) organosilicon compounds having at least one alkoxysilyl group in the molecule are preferred.
- Silane coupling agents (F) include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyl Silane coupling agents having a (meth)acryloyl group such as roxypropyltrimethoxysilane; Silane coupling agents having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinyltris(2-methoxyethoxy)silane; 2-(3,4-epoxycyclohexyl
- the content of the silane coupling agent (F) (when two or more silane coupling agents (F) are included, the total amount of these) is the raw material It is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.08% by mass or more, and preferably is 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, and even more preferably 0.5% by mass or less.
- the content of the silane coupling agent (F) is 0.01% by mass or more in the total amount of active ingredients in the raw material composition, so that the curable adhesive layer gives a cured product having excellent adhesion after a high temperature and high humidity test. becomes easier to form.
- the content of the silane coupling agent (F) is 5% by mass or less in the total amount of active ingredients in the raw material composition, a curable adhesive layer that gives a cured product with excellent adhesion after a high-temperature and high-humidity test is formed. easier to be
- the total amount of these when the agent (F) is included is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.1 parts by mass or more, and even more preferably 0.1 part by mass or more. It is 15 parts by mass or more, preferably 3 parts by mass or less, more preferably 1 part by mass or less, still more preferably 0.7 parts by mass or less, and even more preferably 0.5 parts by mass or less.
- the raw material composition may contain a cationic polymerization initiator as the (E) component.
- a cationic polymerization initiator can be used individually by 1 type or in combination of 2 or more types.
- the cationic polymerization initiator (E) include thermal cationic polymerization initiators and photocationic polymerization initiators, and preferred are thermal cationic polymerization initiators that can be polymerized by a simple process.
- Thermal cationic polymerization initiators are compounds that can generate cationic species that initiate polymerization upon heating.
- Thermal cationic polymerization initiators include sulfonium salts, quaternary ammonium salts, phosphonium salts, diazonium salts, iodonium salts and the like.
- Sulfonium salts include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroalcinate, tris(4-methoxyphenyl)sulfonium hexafluoroalcinate, and diphenyl(4-phenylthiophenyl)sulfonium. hexafluoroalcinate and the like.
- the quaternary ammonium salts include tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogensulfate, tetraethylammonium tetrafluoroborate, tetraethylammonium p-toluenesulfonate, N,N-dimethyl-N- benzylanilinium hexafluoroantimonate, N,N-dimethyl-N-benzylanilinium tetrafluoroborate, N,N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N,N-diethyl-N-benzyltrifluoromethanesulfonate , N,N-dimethyl-N-(4-methoxybenzyl)pyridinium hexafluoroantimonate,
- Phosphonium salts include ethyltriphenylphosphonium hexafluoroantimonate, tetrabutylphosphonium hexafluoroantimonate, and the like.
- iodonium salts include diphenyliodonium hexafluoroarsinate, bis(4-chlorophenyl)iodonium hexafluoroarsinate, bis(4-bromophenyl)iodonium hexafluoroarsinate, phenyl(4-methoxyphenyl)iodonium hexafluoroarsinate, and the like. are mentioned.
- the content of the cationic polymerization initiator (E) (when two or more (E) components are included, the total amount of these) is the cationic polymerizable compound is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.1 parts by mass or more, and more More preferably 0.2 parts by mass or more, preferably 6 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 4 parts by mass or less.
- the content of the cationic polymerization initiator is 0.01 parts by mass or more, it becomes easier to prevent a decrease in reactivity.
- the content of the cationic polymerization initiator is 6 parts by mass or less, it becomes easy to suppress corrosion of the adherend.
- the raw material composition may contain a solvent and be in the form of a solution.
- solvents include aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as heptane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, and methylcyclohexane; and the like. These solvents can be used singly or in combination of two or more. When the raw material composition contains a solvent, the content of the solvent can be appropriately determined in consideration of coatability and the like.
- the raw material composition may contain components (other components) other than those described above as long as the effects of the present invention are not impaired.
- Other components include additives such as UV absorbers, antistatic agents, light stabilizers, antioxidants, resin stabilizers, fillers, pigments, extenders and softeners. These can be used individually by 1 type or in combination of 2 or more types. When the raw material composition contains these additives, the content thereof can be appropriately determined according to the purpose.
- the raw material composition can be prepared by appropriately mixing and stirring the binder resin (A), the cross-linking agent (B), and other optional components according to a conventional method.
- the curable adhesive layer constituting the adhesive sheet of the present invention is a layer formed using the raw material composition.
- a curable adhesive layer can be formed by applying the raw material composition onto a process sheet or a protective sheet, drying the resulting coating film, and allowing the curing reaction (I) to proceed. .
- Examples of methods for applying the raw material composition include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.
- Methods for drying the coating film include conventionally known drying methods such as hot air drying, hot roll drying, and infrared irradiation.
- the conditions for drying the coating film are, for example, 80 to 150° C. for 30 seconds to 5 minutes.
- the drying treatment of the coating film and the curing reaction (I) can be combined.
- the reactive functional group in the binder resin (A) is a carboxy group or a carboxylic anhydride group
- the cross-linking agent (B) is an isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, a metal chelate-based cross-linking agent, or the like.
- the drying treatment and the curing reaction (I) can be performed simultaneously, and the curable adhesive layer can be efficiently formed.
- the thickness of the curable adhesive layer is usually 1 ⁇ m or more, preferably 5 ⁇ m or more.
- the thickness of the curable adhesive layer is usually 50 ⁇ m or less, preferably 25 ⁇ m or less.
- the thickness of the curable adhesive layer is 1 ⁇ m or more, it is easy to follow a step, and it is easy to obtain adhesiveness.
- the thickness of the curable adhesive layer is 50 ⁇ m or less, the rigidity is not excessively increased, and flexibility is easily obtained.
- the gel fraction of the curable adhesive layer is 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, and particularly preferably 25% by mass or more.
- the gel fraction of the curable adhesive layer is usually 70% by mass or less, preferably 60% by mass or less, and more preferably less than 50% by mass.
- a curable adhesive layer having a gel fraction of 10% by mass or more has a sufficiently formed crosslinked structure as a curable adhesive layer. Therefore, even if such a curable adhesive layer is subjected to heat treatment such as hot press treatment, a large amount of the adhesive component does not ooze out, and contamination of the surroundings is suppressed.
- the gel fraction of the curable adhesive layer is 70% by mass or less, a curable adhesive layer having excellent curability and adhesion to an adherend can be easily formed.
- the gel fraction of the curable adhesive layer can be calculated by performing an experiment in which the curable adhesive layer is immersed in toluene at 23° C. for 168 hours, as described in Examples.
- the curable adhesive layer preferably has low dielectric properties.
- a curable adhesive layer having low dielectric properties is preferably used as a material for forming adhesive members, protective members, insulating members, and the like in electronic devices.
- the dielectric loss tangent of the curable adhesive layer at 23° C. and a frequency of 1 GHz is preferably less than 0.0050, more preferably 0.0030 or less, more preferably 0.0020 or less, still more preferably 0.0015 or less. , more preferably 0.0012 or less, still more preferably 0.0010 or less, and particularly preferably 0.0008 or less. Although there is no particular lower limit for the dielectric loss tangent under these conditions, it is usually 0.0001 or more.
- the dielectric constant of the curable adhesive layer at 23°C and a frequency of 1 GHz is preferably 3.00 or less, more preferably 2.75 or less, and still more preferably 2.50 or less. Although there is no particular lower limit for the dielectric constant under these conditions, it is usually 2.00 or more.
- the curable adhesive layer is a curable layer.
- the raw material composition of the curable adhesive layer includes, as the curing reaction, one having only the curing reaction (I) [raw material composition ( ⁇ )], and as the curing reaction, the curing reaction (I ) and curing reaction (II) [raw material composition ( ⁇ )].
- the "curability" of the curable adhesive layer formed using the raw material composition ( ⁇ ) is determined by the reaction between the unreacted binder resin (A) and the cross-linking agent (B) in the curable adhesive layer (i.e. , curing reaction (I)).
- the "curability" of the curable adhesive layer formed using the raw material composition ( ⁇ ) is usually due to both curing reaction (I) and curing reaction (II), or curing It is due only to reaction (II).
- the curing conditions for the curable adhesive layer can be appropriately determined according to the curable component contained in the curable adhesive layer.
- the curable adhesive layer is a thermosetting adhesive layer containing the components (C) and (D) as curable components
- heating the curable adhesive layer causes the curable
- the curing reaction of the adhesive layer can proceed efficiently.
- the heating temperature for this curable adhesive layer is usually 140°C or higher, preferably 150 to 180°C.
- the heating time for this curable adhesive layer is usually 0.5 to 3 hours, preferably 1 to 2 hours.
- the gel fraction of the cured product is usually larger than the gel fraction of the curable adhesive layer.
- the cured product of the curable adhesive layer functions as an adhesive member, a protective member, an insulating member, or the like, the cured product preferably undergoes a sufficient curing reaction.
- the gel fraction of the cured product in such a state is preferably 50% by mass or more, more preferably 55% by mass or more.
- the gel fraction of the cured product can be determined by a method similar to the method for calculating the gel fraction of the curable adhesive layer.
- the adhesive sheet of the present invention has the curable adhesive layer.
- the adhesive sheet of the present invention may have a protective sheet or the like on one side or both sides for protection during storage or transportation.
- the adhesive sheet of the present invention is suitably used as an adhesive sheet for electronic devices.
- electronic devices include communication devices such as smartphones and tablet terminals.
- the curable adhesive layer that constitutes the adhesive sheet of the present invention can be used to adhere various parts in an electronic device, or to form a protective material or insulating material for circuits in an electronic device.
- the adhesive sheet of the present invention is suitably used as an adhesive sheet for coverlay films.
- a coverlay film is, for example, a laminated film used to protect the surface of a flexible printed wiring board, and usually has an insulating resin layer and an adhesive layer.
- a coverlay film can be produced by thermocompression bonding a curable adhesive layer constituting the adhesive sheet of the present invention with an insulating resin film.
- Binder resin (A1) maleic anhydride-modified ⁇ -olefin polymer [manufactured by Mitsui Chemicals, trade name: UNISTOL H-200, number average molecular weight: 47,000]
- Isocyanate-based cross-linking agent (B1) 1,3,5-tris(5-isocyanatopentyl)-1,3,5-triazine-2,4,6-trione [manufactured by Mitsui Chemicals, Inc., trade name: Stabio D-370N, molecular weight: 462]
- Binder resin (A1) 100 parts by mass, isocyanate cross-linking agent (B1) 0.5 parts by mass, curable compound (C1) 12.5 parts by mass, polyphenylene ether resin (D1) 25 parts by mass, cationic polymerization initiator (E1) 0.12 parts by mass and 0.2 parts by mass of the silane coupling agent (F1) were dissolved in toluene to prepare a raw material composition.
- the obtained raw material composition is applied on the release-treated surface of a release sheet (first release sheet, product name: SP-PET752150, manufactured by Lintec Corporation) to form a coating film, and the resulting coating film is C. for 2 minutes to form a curable adhesive layer with a thickness of 15 .mu.m.
- second release sheet product name: SP-PET381130, manufactured by Lintec Corporation
- Examples 2 to 5 Comparative Example 1
- a raw material composition was prepared and an adhesive sheet was obtained in the same manner as in Example 1, except that the amounts or types of the components were changed to those shown in Table 1.
- the test sample was taken out, dried in an oven at 100°C for 2 hours, and then allowed to stand for 24 hours in an environment with a temperature of 23°C and a relative humidity of 50%.
- FIG. 1 is a schematic plan view of the laminated body used for evaluating the exudation of the adhesive component in the examples after being subjected to a heat press treatment. As shown in FIG.
- the maximum value X of the distance between the oozing adhesive component 2 and the polyimide film 3 when viewed from the top is defined as "the oozing length of the adhesive component", and is shown in Table 1. described.
- the curable adhesive layers of the adhesive sheets obtained in Examples 1 to 5 all have high gel fraction values. Therefore, even if these curable adhesive layers are subjected to heat press treatment under the conditions of 171° C., 1.38 MPa, and 20 minutes, the amount of the adhesive components oozing out is small. On the other hand, the curable adhesive layer of the adhesive sheet of Comparative Example 1 has a low gel fraction value. For this reason, if the heat press treatment is performed on this curable adhesive layer under the same conditions, the amount of the adhesive component oozing out is large. Moreover, the curable adhesive layers of the adhesive sheets obtained in Examples 1 to 5 are excellent in low dielectric properties.
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Abstract
Description
〔1〕硬化性接着剤層を有する接着シートであって、
前記硬化性接着剤層の原料組成物が、下記(A)成分、及び(B)成分を含有し、かつ、(B)成分を前記原料組成物の有効成分の全量に対して0.1質量%以上含有するものであり、
前記硬化性接着剤層のゲル分率が10質量%以上である、接着シート。
(A)成分:反応性官能基を有するバインダー樹脂
(B)成分:前記(A)成分と反応し得る架橋剤
〔2〕前記(A)成分が、ポリオレフィン系樹脂である、〔1〕に記載の接着シート。
〔3〕前記(A)成分が、酸変性樹脂である、〔1〕又は〔2〕に記載の接着シート。
〔4〕前記(B)成分が、イソシアヌレート骨格を有する化合物である、〔1〕~〔3〕のいずれかに記載の接着シート。
〔5〕前記(B)成分が、イソシアネート基を2以上有する化合物である、〔1〕~〔4〕のいずれかに記載の接着シート。
〔6〕前記硬化性接着剤層が、さらに下記(C)成分を含有する原料組成物から形成された層である、〔1〕~〔5〕のいずれかに記載の接着シート。
(C)成分:25℃で液体である非芳香族の硬化性化合物
〔7〕前記(C)成分が、末端に二重結合を有する炭化水素基を2以上有する化合物である、〔6〕に記載の接着シート。
〔8〕前記硬化性接着剤層が、さらに下記(D)成分を含有する原料組成物から形成された層である、〔1〕~〔7〕のいずれかに記載の接着シート。
(D)成分:反応性官能基を有するポリフェニレンエーテル樹脂
〔9〕前記硬化性接着剤層が、さらに下記(E)成分を含有する原料組成物から形成された層である、〔1〕~〔8〕のいずれかに記載の接着シート。
(E)成分:カチオン重合開始剤
〔10〕前記硬化性接着剤層の23℃、周波数1GHzにおける誘電正接が0.005未満である、〔1〕~〔9〕のいずれかに記載の接着シート。
〔11〕前記硬化性接着剤層の23℃、周波数1GHzにおける誘電率が3.00以下である、〔1〕~〔10〕のいずれかに記載の接着シート。
〔12〕前記硬化性接着剤層が、160℃、1時間の条件で硬化させた後にゲル分率が50質量%以上の硬化物を与えるものである、〔1〕~〔11〕のいずれかに記載の接着シート。
〔13〕電子デバイスに用いられる、〔1〕~〔12〕のいずれかに記載の接着シート。
〔14〕カバーレイフィルムに用いられる、〔1〕~〔12〕のいずれかに記載の接着シート。 Thus, according to the present invention, the following adhesive sheets [1] to [14] are provided.
[1] An adhesive sheet having a curable adhesive layer,
The raw material composition of the curable adhesive layer contains the following components (A) and (B), and the amount of component (B) is 0.1 mass based on the total amount of active ingredients in the raw material composition. % or more,
The adhesive sheet, wherein the curable adhesive layer has a gel fraction of 10% by mass or more.
(A) component: binder resin having a reactive functional group (B) component: cross-linking agent capable of reacting with component (A) [2] described in [1], wherein component (A) is a polyolefin resin adhesive sheet.
[3] The adhesive sheet of [1] or [2], wherein the component (A) is an acid-modified resin.
[4] The adhesive sheet according to any one of [1] to [3], wherein the component (B) is a compound having an isocyanurate skeleton.
[5] The adhesive sheet according to any one of [1] to [4], wherein the component (B) is a compound having two or more isocyanate groups.
[6] The adhesive sheet according to any one of [1] to [5], wherein the curable adhesive layer is a layer formed from a raw material composition further containing component (C) below.
Component (C): A non-aromatic curable compound that is liquid at 25° C. [7] Component (C) is a compound having two or more hydrocarbon groups with double bonds at their terminals [6] Adhesive sheet as described.
[8] The adhesive sheet according to any one of [1] to [7], wherein the curable adhesive layer is a layer formed from a raw material composition further containing component (D) below.
(D) component: polyphenylene ether resin having a reactive functional group [9] The curable adhesive layer is a layer formed from a raw material composition further containing the following component (E) [1] to [ 8] The adhesive sheet according to any one of the above items.
(E) component: cationic polymerization initiator [10] The adhesive sheet according to any one of [1] to [9], wherein the curable adhesive layer has a dielectric loss tangent at 23° C. and a frequency of 1 GHz of less than 0.005. .
[11] The adhesive sheet according to any one of [1] to [10], wherein the curable adhesive layer has a dielectric constant of 3.00 or less at 23° C. and a frequency of 1 GHz.
[12] Any one of [1] to [11], wherein the curable adhesive layer gives a cured product having a gel fraction of 50% by mass or more after curing at 160° C. for 1 hour. Adhesive sheet described in .
[13] The adhesive sheet according to any one of [1] to [12], which is used for electronic devices.
[14] The adhesive sheet according to any one of [1] to [12], which is used for a coverlay film.
また、本明細書に記載された数値範囲として、例えば「60~100」との記載は、「60以上、100以下」という範囲であることを意味する。
さらに、本明細書に記載された上限値及び下限値の規定において、それぞれの選択肢の中から適宜選択して、任意に組み合わせて、下限値~上限値の数値範囲を規定することができる。
加えて、本明細書に記載された好ましい態様として記載の各種要件は複数組み合わせることができる。 For the numerical ranges described herein, the upper and lower limits can be combined arbitrarily. For example, when the numerical range is described as "preferably 30 to 100, more preferably 40 to 80", the range of "30 to 80" and the range of "40 to 100" are also described in this specification. included in the specified numerical range. Further, for example, when the numerical range is described as "preferably 30 or more, more preferably 40 or more, and preferably 100 or less, more preferably 80 or less", "30 to 80" Ranges and ranges from "40 to 100" are also included in the numerical ranges described herein.
Also, as a numerical range described in this specification, for example, the description of "60 to 100" means a range of "60 or more and 100 or less".
Furthermore, in the definition of the upper limit value and the lower limit value described in this specification, it is possible to define the numerical range from the lower limit value to the upper limit value by appropriately selecting from each option and combining them arbitrarily.
In addition, various requirements described as preferred embodiments described herein can be combined.
(測定条件の例)
・ゲル浸透クロマトグラフ装置:東ソー株式会社製、製品名「HLC-8020」
・カラム:「TSK guard column HXL-L」、「TSK gel G2500HXL」、「TSK gel G2000HXL」及び「TSK gel G1000HXL」を順次連結したもの(いずれも東ソー株式会社製)
・カラム温度:40℃
・展開溶媒:テトラヒドロフラン
・流速:1.0mL/min In the present specification, the number average molecular weight (Mn) can be obtained as a standard polystyrene conversion value by performing gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent. can be measured by
(Example of measurement conditions)
・ Gel permeation chromatograph device: manufactured by Tosoh Corporation, product name “HLC-8020”
・ Column: "TSK guard column HXL-L", "TSK gel G2500HXL", "TSK gel G2000HXL" and "TSK gel G1000HXL" sequentially connected (all manufactured by Tosoh Corporation)
・Column temperature: 40°C
・Developing solvent: tetrahydrofuran ・Flow rate: 1.0 mL/min
(A)成分:反応性官能基を有するバインダー樹脂
(B)成分:前記(A)成分と反応し得る架橋剤
本明細書において、「有効成分」とは、組成物中の成分であって、溶媒以外の成分をいう。 The adhesive sheet of the present invention is an adhesive sheet having a curable adhesive layer, wherein the raw material composition of the curable adhesive layer contains the following components (A) and (B), and ( The adhesive sheet contains component B) in an amount of 0.1% by mass or more relative to the total amount of active ingredients in the raw material composition, and the curable adhesive layer has a gel fraction of 10% by mass or more. .
(A) component: a binder resin having a reactive functional group (B) component: a cross-linking agent capable of reacting with the (A) component A component other than a solvent.
本発明の接着シートを構成する硬化性接着剤層の原料組成物は、上記(A)成分、及び(B)成分を含有し、(B)成分の含有量が原料組成物の有効成分の全量に対して0.1質量%以上に調整している。 <<Raw material composition of curable adhesive layer>>
The raw material composition for the curable adhesive layer constituting the adhesive sheet of the present invention contains the above components (A) and (B), and the content of component (B) is the total amount of active ingredients in the raw material composition. is adjusted to 0.1% by mass or more.
後述するように、この反応を利用することで、ゲル分率が10質量%以上の硬化性接着剤層を効率よく形成することができる。
なお、本明細書において、バインダー樹脂(A)と架橋剤(B)が関与する架橋反応を「硬化反応(I)」と記載することがある。 Since the cross-linking agent (B) is a compound that can react with the binder resin (A), the binder resin (A) and the cross-linking agent are formed in the coating film (curable adhesive layer) obtained by applying the raw material composition. (B) can be reacted to build a crosslinked structure within the curable adhesive layer.
As will be described later, by utilizing this reaction, a curable adhesive layer having a gel fraction of 10% by mass or more can be efficiently formed.
In this specification, the cross-linking reaction involving the binder resin (A) and the cross-linking agent (B) may be referred to as "curing reaction (I)".
複数回の硬化反応を確実に行うことができ、硬化性接着剤層内の接着剤成分の染み出しをより確実に抑制し得ることから、硬化性成分(X)は、硬化反応(I)に関与しない化合物が好ましい。
すなわち、硬化性成分(X)が硬化反応(I)に関与する化合物である場合、硬化性接着剤層内に架橋構造を構築し、本発明の接着シートを製造する工程と、本発明の接着シートを使用して2つの被着体をより強固に接着する工程の両工程において硬化反応(I)が必要になるため、硬化性接着剤層内に架橋構造を構築するために開始させた硬化反応(I)を途中で一旦停止させる必要があり、硬化反応(I)を高度に制御する必要がある。
一方、硬化性成分(X)が硬化反応(I)に関与しない化合物である場合、硬化反応(I)がほぼ完結したとしても、その接着剤層は硬化性成分(X)に由来する硬化性を有しているため、この硬化性を利用して2つの被着体をより強固に接着する工程を行うことができる。このように、硬化反応(I)に関与しない硬化性成分(X)を含有する原料組成物を用いることで、硬化反応(I)を高度に制御しなくても、本発明の接着シートを効率よく製造することができる。 The curable component (X) may be a compound that participates in the curing reaction (I) or a compound that does not participate in the curing reaction (I).
The curable component (X) can be used for the curing reaction (I) because the curing reaction can be reliably performed a plurality of times and the oozing of the adhesive component in the curable adhesive layer can be suppressed more reliably. Non-participating compounds are preferred.
That is, when the curable component (X) is a compound that participates in the curing reaction (I), a step of constructing a crosslinked structure in the curable adhesive layer to produce the adhesive sheet of the present invention, and Since the curing reaction (I) is required in both steps of the process of more firmly bonding two adherends using a sheet, curing initiated to build a crosslinked structure within the curable adhesive layer It is necessary to temporarily stop the reaction (I) in the middle, and it is necessary to control the curing reaction (I) to a high degree.
On the other hand, when the curable component (X) is a compound that does not participate in the curing reaction (I), even if the curing reaction (I) is substantially completed, the adhesive layer will still have the curability derived from the curable component (X). Therefore, it is possible to carry out a step of bonding two adherends more strongly by utilizing this curability. Thus, by using the raw material composition containing the curable component (X) that does not participate in the curing reaction (I), the adhesive sheet of the present invention can be efficiently produced without highly controlling the curing reaction (I). can be manufactured well.
(C)成分:25℃で液体である非芳香族の硬化性化合物
(D)成分:反応性官能基を有するポリフェニレンエーテル樹脂
(F)成分:シランカップリング剤 The curable component (X) includes the following components (C), (D) and (F).
Component (C): Non-aromatic curable compound that is liquid at 25° C. Component (D): Polyphenylene ether resin having a reactive functional group Component (F): Silane coupling agent
成分(E):カチオン重合開始剤
また、本発明の一態様で用いる原料組成物は、本発明の効果を損なわない範囲で、さらに、上記の(A)成分~(F)成分以外の成分を含有してもよい。 When the curing reaction (I) or curing reaction (II) is a cationic polymerization reaction, the raw material composition used in one aspect of the present invention may further contain the following component (E).
Component (E): Cationic polymerization initiator Further, the raw material composition used in one embodiment of the present invention further contains components other than the above components (A) to (F) within a range that does not impair the effects of the present invention. may contain.
硬化性接着剤層の形成材料である原料組成物(以下、単に「原料組成物」と記載することがある。)は、(A)成分として、反応性官能基を有するバインダー樹脂(以下、「バインダー樹脂(A)」と記載することがある。)を含有する。
バインダー樹脂(A)を含有する原料組成物を用いることで、熱プレス処理等の加熱処理を受けたときに周囲を汚染し難い硬化性接着剤層が形成され易くなる。
バインダー樹脂(A)は、1種単独で、あるいは2種以上を組み合わせて用いることができる。 [(A) component: binder resin having a reactive functional group]
A raw material composition (hereinafter, sometimes simply referred to as "raw material composition"), which is a material for forming a curable adhesive layer, contains, as component (A), a binder resin having a reactive functional group (hereinafter, " It may be described as "binder resin (A)").
By using the raw material composition containing the binder resin (A), it becomes easier to form a curable adhesive layer that does not easily stain the surroundings when subjected to heat treatment such as hot press treatment.
Binder resin (A) can be used individually by 1 type or in combination of 2 or more types.
バインダー樹脂(A)の数平均分子量(Mn)は、テトラヒドロフラン(THF)を溶媒として用いてゲル・パーミエーション・クロマトグラフィー(GPC)を行い、標準ポリスチレン換算値として求めることができ、具体的な測定条件としては上述のとおりである。 The number average molecular weight (Mn) of the binder resin (A) is not particularly limited. 000 or more, preferably 10,000 to 150,000, more preferably 10,000 to 100,000.
The number average molecular weight (Mn) of the binder resin (A) can be obtained as a standard polystyrene conversion value by performing gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and specific measurement The conditions are as described above.
バインダー樹脂(A)の含有量が50質量%以上であると、熱プレス処理等の加熱処理を受けたときに周囲を汚染し難い硬化性接着剤層が形成され易くなる。
バインダー樹脂(A)の含有量が95質量%以下であると、低誘電特性(本明細書において、「低誘電特性」とは、「低誘電率及び低誘電正接」をいう。)に優れる硬化性接着剤層が形成され易くなる。 The content of the binder resin (A) contained in the raw material composition (the total amount of these when containing two or more binder resins (A)) is based on the total amount (100% by mass) of the active ingredients in the raw material composition. is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 65% by mass or more, and is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass. 80% by mass or less, and more preferably 80% by mass or less.
When the content of the binder resin (A) is 50% by mass or more, it becomes easier to form a curable adhesive layer that does not easily stain the surroundings when subjected to heat treatment such as hot press treatment.
When the content of the binder resin (A) is 95% by mass or less, excellent curing with low dielectric properties (in this specification, "low dielectric properties" means "low dielectric constant and low dielectric loss tangent") This facilitates the formation of a flexible adhesive layer.
これらの中でも、バインダー樹脂(A)としては、ポリオレフィン系樹脂が好ましい。バインダー樹脂(A)がポリオレフィン系樹脂であることで、低誘電特性に優れる硬化性接着剤層が形成され易くなる。 Examples of the binder resin (A) include polyolefin-based resins, phenoxy-based resins, polyimide-based resins, polyamideimide-based resins, polyvinyl butyral-based resins, and polycarbonate-based resins.
Among these, polyolefin-based resins are preferable as the binder resin (A). When the binder resin (A) is a polyolefin resin, a curable adhesive layer with excellent low dielectric properties can be easily formed.
前記原料組成物において、他のバインダー樹脂の含有量は、ポリオレフィン系樹脂の全量100質量部に対して、好ましくは0~50質量部、より好ましくは0~30質量部、更に好ましくは0~10質量部、より更に好ましくは0~5質量部である。 In the case of a raw material composition in which the component (A) is a polyolefin resin, the raw material composition may contain other binder resins than the polyolefin resin as other components.
In the raw material composition, the content of the other binder resin is preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, and still more preferably 0 to 10 parts by mass with respect to 100 parts by mass of the total polyolefin resin. parts by weight, more preferably 0 to 5 parts by weight.
オレフィン系単量体と共重合可能な単量体としては、酢酸ビニル、(メタ)アクリル酸エステル、スチレン等が挙げられる。ここで、「(メタ)アクリル酸」は、アクリル酸又はメタクリル酸の意味である(以下にて同じ。)。
これらの「オレフィン系単量体と共重合可能な単量体」は、1種を単独で、あるいは2種以上を組み合わせて用いることができる。 The olefinic monomer is preferably an α-olefin having 2 to 8 carbon atoms, more preferably ethylene, propylene, 1-butene, isobutylene, or 1-hexene, and still more preferably ethylene or propylene. These olefinic monomers can be used singly or in combination of two or more.
Examples of monomers copolymerizable with olefinic monomers include vinyl acetate, (meth)acrylic acid esters, and styrene. Here, "(meth)acrylic acid" means acrylic acid or methacrylic acid (same below).
These "monomers copolymerizable with olefinic monomers" can be used singly or in combination of two or more.
バインダー樹脂の変性処理に用いる変性剤は、分子内に反応性官能基を有する化合物である。反応性官能基としては、先に説明したものが挙げられる。 Binder resin (A) is preferably a modified resin. The modified resin is a resin into which a reactive functional group is introduced, which is obtained by modifying a resin as a precursor using a modifying agent.
A modifier used for modifying the binder resin is a compound having a reactive functional group in the molecule. Reactive functional groups include those previously described.
(A)成分として酸変性樹脂を用いることで、低誘電特性に優れる硬化性接着剤層が形成され易くなる。さらに、酸変性樹脂として酸無水物構造が導入された樹脂を用いることで、原料組成物の可使時間を長く保ち易くなる傾向がある。 Examples of modified resins include resins into which acid groups have been introduced (acid-modified resins) and resins into which hydroxyl groups have been introduced, and acid-modified resins are preferred. Among the acid-modified resins, resins into which an acid anhydride structure is introduced are preferable.
By using an acid-modified resin as the component (A), a curable adhesive layer with excellent low dielectric properties can be easily formed. Furthermore, by using a resin into which an acid anhydride structure is introduced as the acid-modified resin, there is a tendency that the pot life of the raw material composition can be easily maintained for a long time.
前記原料組成物において、他のバインダー樹脂の含有量は、酸変性樹脂の全量100質量部に対して、好ましくは0~50質量部、より好ましくは0~30質量部、更に好ましくは0~10質量部、より更に好ましくは0~5質量部である。 In the case of a raw material composition in which the component (A) is an acid-modified resin, the raw material composition may contain, as other components, a binder resin other than the acid-modified resin.
In the raw material composition, the content of the other binder resin is preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, and still more preferably 0 to 10 parts by mass with respect to 100 parts by mass of the total amount of the acid-modified resin. parts by weight, more preferably 0 to 5 parts by weight.
これらは、1種を単独で、あるいは2種以上を組み合わせて用いることができる。これらの中でも、接着強度がより高い硬化物を与える硬化性接着剤層が形成され易いことから、無水マレイン酸が好ましい。 Unsaturated carboxylic acids to be reacted with the resin include unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, and aconitic acid; maleic anhydride, itaconic anhydride, and glutaconic anhydride. acids, unsaturated carboxylic anhydrides such as citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, and tetrahydrophthalic anhydride;
These can be used individually by 1 type or in combination of 2 or more types. Among these, maleic anhydride is preferable because it facilitates the formation of a curable adhesive layer that gives a cured product with higher adhesive strength.
前記原料組成物において、他のバインダー樹脂の含有量は、酸変性ポリオレフィン系樹脂の全量100質量部に対して、好ましくは0~50質量部、より好ましくは0~30質量部、更に好ましくは0~10質量部、より更に好ましくは0~5質量部である。 In the case of a raw material composition in which the component (A) is an acid-modified polyolefin-based resin, the raw material composition may contain other binder resins other than the acid-modified polyolefin-based resin as other components.
In the raw material composition, the content of the other binder resin is preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, and still more preferably 0 parts by mass with respect to 100 parts by mass of the total amount of the acid-modified polyolefin resin. to 10 parts by weight, more preferably 0 to 5 parts by weight.
原料組成物は、(B)成分として、(A)成分と反応し得る架橋剤(以下、「架橋剤(B)」と記載することがある。)を含有する。
架橋剤(B)を含有する原料組成物を用いることで、熱プレス処理等の加熱処理を受けたときに周囲を汚染し難い硬化性接着剤層が形成され易くなる。
なお、架橋剤(B)は、1種単独で、あるいは2種以上を組み合わせて用いることができる。 [Component (B): Crosslinking agent capable of reacting with component (A)]
The raw material composition contains, as the component (B), a cross-linking agent capable of reacting with the component (A) (hereinafter sometimes referred to as "cross-linking agent (B)").
By using the raw material composition containing the cross-linking agent (B), it becomes easier to form a curable adhesive layer that does not easily stain the surroundings when subjected to heat treatment such as hot press treatment.
In addition, a crosslinking agent (B) can be used individually by 1 type or in combination of 2 or more types.
架橋剤(B)の分子量が1000以下であることで、(A)成分との反応の衝突確率が高まり、架橋構造を形成し易くなり、熱プレス処理等の加熱処理を受けたときに周囲を汚染し難い硬化性接着剤層が形成され易い原料組成物とすることができる。
架橋剤(B)の分子量の下限値は特にないが、通常100以上、好ましくは200以上である。
なお、架橋剤(B)の分子量は、架橋剤(B)として用いられる化合物の構造式から定まる式量である。 The molecular weight of the cross-linking agent (B) is preferably 1000 or less, more preferably 800 or less, even more preferably 700 or less, even more preferably 600 or less, and particularly preferably 500 or less.
When the molecular weight of the cross-linking agent (B) is 1000 or less, the collision probability of the reaction with the component (A) increases, making it easier to form a cross-linked structure, and when subjected to heat treatment such as hot press treatment, the surroundings The raw material composition can easily form a curable adhesive layer that is difficult to stain.
Although there is no particular lower limit for the molecular weight of the cross-linking agent (B), it is usually 100 or more, preferably 200 or more.
The molecular weight of the cross-linking agent (B) is a formula weight determined from the structural formula of the compound used as the cross-linking agent (B).
架橋剤(B)の含有量が、原料組成物の有効成分全量に対して0.1質量%以上であることで、熱プレス処理等の加熱処理を受けたときに周囲を汚染し難い硬化性接着剤層が形成され易くなる。
また、架橋剤(B)の含有量が、原料組成物の有効成分全量に対して5質量%以下であることで、低誘電特性に優れる硬化性接着剤層が形成され易くなる。 The content of the cross-linking agent (B) (the total amount of these when two or more cross-linking agents (B) are included) is 0.1 mass with respect to the total amount (100 mass%) of the active ingredients in the raw material composition % or more, preferably 0.2 mass % or more, more preferably 0.3 mass % or more, still more preferably 0.5 mass % or more, even more preferably 0.7 mass % or more, particularly preferably 0.7 mass % or more. It is 9% by mass or more, preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less, and even more preferably 2% by mass or less.
The content of the cross-linking agent (B) is 0.1% by mass or more with respect to the total amount of active ingredients in the raw material composition, so that it has curability that does not easily stain the surroundings when subjected to heat treatment such as hot press treatment. An adhesive layer is easily formed.
Further, when the content of the cross-linking agent (B) is 5% by mass or less with respect to the total amount of active ingredients in the raw material composition, a curable adhesive layer having excellent low dielectric properties can be easily formed.
例えば、架橋剤(B)としては、イソシアネート系架橋剤、エポキシ系架橋剤、金属キレート系架橋剤、アジリジン系架橋剤等を用いることができる。これらの中でも、貯蔵安定性の観点から、イソシアネート系架橋剤、エポキシ系架橋剤、及び金属キレート系架橋剤から選ばれる1種以上が好ましい。
また、本発明の一態様において、例えば、バインダー樹脂(A)が酸変性樹脂であり、バインダー樹脂(A)中の反応性官能基がカルボキシ基やカルボン酸無水物基である場合、架橋剤(B)としては、イソシアネート系架橋剤、エポキシ系架橋剤、及び金属キレート系架橋剤から選ばれる1種以上が好ましい。 Cross-linking agent (B) is a compound capable of reacting with component (A). Therefore, as the cross-linking agent (B), it is necessary to appropriately select one having a reactive group or a reactive site that is reactive with the reactive functional group in the binder resin (A).
For example, as the cross-linking agent (B), an isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, a metal chelate-based cross-linking agent, an aziridine-based cross-linking agent, or the like can be used. Among these, one or more selected from isocyanate-based cross-linking agents, epoxy-based cross-linking agents, and metal chelate-based cross-linking agents are preferable from the viewpoint of storage stability.
Further, in one aspect of the present invention, for example, when the binder resin (A) is an acid-modified resin and the reactive functional group in the binder resin (A) is a carboxy group or a carboxylic anhydride group, a cross-linking agent ( B) is preferably one or more selected from isocyanate-based cross-linking agents, epoxy-based cross-linking agents, and metal chelate-based cross-linking agents.
イソシアネート系架橋剤としては、例えば、2,4-トリレンジイソシアネート、2,6-トリレンジイソシアネート、水添トリレンジイソシアネート、水添キシレンジイソシアネート、1,5-ペンタメチレンジイソシアネート、1,6-ヘキサメチレンジイソシアネート、ジフェニルメタン-4,4-ジイソシアネート、イソホロンジイソシアネート、1,3-ビス(イソシアナトメチル)シクロヘキサン、テトラメチルキシリレンジイソシアネート、1,5-ナフタレンジイソシアネート、トリフェニルメタントリイソシアネート、およびこれらのポリイソシアネート化合物とトリメチロールプロパン等のポリオール化合物とのアダクト体、これらポリイソシアネート化合物のビュレット体やイソシアヌレート体等が挙げられる。 An isocyanate-based cross-linking agent is a compound having two or more isocyanate groups in the molecule.
Examples of isocyanate cross-linking agents include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, 1,5-pentamethylene diisocyanate, and 1,6-hexamethylene. Diisocyanate, diphenylmethane-4,4-diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, tetramethylxylylene diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, and polyisocyanate compounds thereof and adducts of polyol compounds such as trimethylolpropane, burettes and isocyanurates of these polyisocyanate compounds, and the like.
エポキシ系架橋剤としては、1,3-ビス(N,N-ジグリシジルアミノメチル)シクロヘキサン、N,N,N’,N’-テトラグリシジル-m-キシリレンジアミン、エチレングリコールジグリシジルエーテル、1,6-ヘキサンジオールジグリシジルエーテル、トリメチロールプロパンジグリシジルエーテル、ジグリシジルアニリン、ジグリシジルアミン等が挙げられる。 An epoxy-based cross-linking agent is a compound having two or more epoxy groups in its molecule.
Epoxy crosslinking agents include 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-m-xylylenediamine, ethylene glycol diglycidyl ether, 1 ,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidylaniline, diglycidylamine and the like.
金属キレート系架橋剤としては、例えば、金属イオンがアルミニウムイオン、ジルコニウムイオン、チタニウムイオン、亜鉛イオン、鉄イオン、スズイオン等である金属キレート化合物を使用することができる。これらの中でも、アルミニウムキレート化合物が好ましい。 A metal chelate-based cross-linking agent is a chelate compound having metal ions functioning as cross-linking points.
As metal chelate-based cross-linking agents, for example, metal chelate compounds whose metal ions are aluminum ions, zirconium ions, titanium ions, zinc ions, iron ions, tin ions, and the like can be used. Among these, aluminum chelate compounds are preferred.
架橋剤(B)がイソシアヌレート骨格を有する化合物であることで、低誘電特性に優れる硬化性接着剤層が形成され易くなる。
なお、(B)成分がイソシアヌレート骨格を有する化合物である原料組成物とした場合、当該原料組成物は、他の成分として、イソシアヌレート骨格を有する化合物以外の他の架橋剤を含有してもよい。
前記原料組成物において、他の架橋剤の含有量は、イソシアヌレート骨格を有する化合物の全量100質量部に対して、好ましくは0~100質量部、より好ましくは0~50質量部、更に好ましくは0~30質量部、より更に好ましくは0~10質量部、特に好ましくは0~5質量部である。 In one aspect of the present invention, the cross-linking agent (B) is preferably a compound having an isocyanurate skeleton, more preferably a compound having an isocyanurate skeleton and two or more isocyanate groups.
When the cross-linking agent (B) is a compound having an isocyanurate skeleton, a curable adhesive layer with excellent low dielectric properties can be easily formed.
In the case of a raw material composition in which the component (B) is a compound having an isocyanurate skeleton, the raw material composition may contain, as another component, a cross-linking agent other than the compound having an isocyanurate skeleton. good.
In the raw material composition, the content of the other cross-linking agent is preferably 0 to 100 parts by mass, more preferably 0 to 50 parts by mass, and still more preferably 100 parts by mass of the total amount of the compound having an isocyanurate skeleton. 0 to 30 parts by weight, more preferably 0 to 10 parts by weight, particularly preferably 0 to 5 parts by weight.
なお、(B)成分がイソシアネート系架橋剤である原料組成物とした場合、当該原料組成物は、他の成分として、当該イソシアネート系架橋剤以外の他の架橋剤を含有してもよい。
前記原料組成物において、他の架橋剤の含有量は、前記イソシアネート系架橋剤の全量100質量部に対して、好ましくは0~100質量部、より好ましくは0~50質量部、更に好ましくは0~30質量部、より更に好ましくは0~10質量部、特に好ましくは0~5質量部である。 In one aspect of the present invention, the cross-linking agent (B) is preferably an isocyanate-based cross-linking agent, which is a compound having two or more isocyanate groups, since a curable adhesive layer having excellent low dielectric properties is easily formed. The isocyanurate of the compound is more preferable, and the isocyanurate of 1,5-pentamethylene diisocyanate [1,3,5-tris(5-isocyanatopentyl)-1,3,5-triazine-2,4,6-trione ] or an isocyanurate of 1,6-hexamethylene diisocyanate [1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazine-2,4,6-trione] is more preferable.
In the case of a raw material composition in which the component (B) is an isocyanate-based cross-linking agent, the raw material composition may contain other cross-linking agents other than the isocyanate-based cross-linking agent as other components.
In the raw material composition, the content of the other cross-linking agent is preferably 0 to 100 parts by mass, more preferably 0 to 50 parts by mass, and still more preferably 0 parts by mass with respect to 100 parts by mass of the total amount of the isocyanate-based cross-linking agent. to 30 parts by mass, more preferably 0 to 10 parts by mass, and particularly preferably 0 to 5 parts by mass.
(B)成分がエポキシ系架橋剤である原料組成物とした場合、当該原料組成物は、他の成分として、エポキシ系架橋剤以外の他の架橋剤を含有してもよい。
前記原料組成物において、他の架橋剤の含有量は、エポキシ系架橋剤の全量100質量部に対して、好ましくは0~100質量部、より好ましくは0~50質量部、更に好ましくは0~30質量部、より更に好ましくは0~10質量部、特に好ましくは0~5質量部である。 In one aspect of the present invention, the cross-linking agent (B) is preferably an epoxy-based cross-linking agent, since a curable adhesive layer that does not easily contaminate the surroundings is easily formed when subjected to heat treatment such as hot press treatment. .
In the case of a raw material composition in which the component (B) is an epoxy-based cross-linking agent, the raw material composition may contain other cross-linking agents other than the epoxy-based cross-linking agent as other components.
In the raw material composition, the content of the other cross-linking agent is preferably 0 to 100 parts by mass, more preferably 0 to 50 parts by mass, and still more preferably 0 to 100 parts by mass, with respect to 100 parts by mass of the total epoxy cross-linking agent. 30 parts by weight, more preferably 0 to 10 parts by weight, particularly preferably 0 to 5 parts by weight.
後述するように、この反応を利用することで、ゲル分率が10質量%以上の硬化性接着剤層を効率よく形成することができ、熱プレス処理等の加熱処理を受けたときに周囲を汚染し難い硬化性接着剤層が形成され易くなる。 Since the cross-linking agent (B) is a compound that can react with the binder resin (A), the binder resin (A) and the cross-linking agent are formed in the coating film (curable adhesive layer) obtained by applying the raw material composition. (B) can be reacted to build a crosslinked structure within the curable adhesive layer.
As will be described later, by utilizing this reaction, a curable adhesive layer having a gel fraction of 10% by mass or more can be efficiently formed, and when subjected to heat treatment such as heat press treatment, the surrounding area can be A curable adhesive layer that is difficult to stain is easily formed.
(C)成分は、25℃で液体である非芳香族の硬化性化合物(以下、「硬化性化合物(C)」と記載することがある。)である。
硬化性化合物(C)は、1種を単独で、あるいは2種以上を組み合わせて用いることができる。 [Component (C): non-aromatic curable compound that is liquid at 25°C]
Component (C) is a non-aromatic curable compound that is liquid at 25° C. (hereinafter sometimes referred to as “curable compound (C)”).
Curable compound (C) can be used individually by 1 type or in combination of 2 or more types.
「25℃で液体」とは、25℃において流動性を有することを意味する。例えば、25℃で液体の化合物とは、E型粘度計を用いて、25℃、1.0rpmにて測定した粘度が、2~10000mPa・sの化合物である。 The curable compound (C) is a compound that is liquid at 25°C. Therefore, when the curable compound (C) is the curable component (X) that does not participate in the curing reaction (I), the curable adhesive layer containing this curable compound (C) exhibits good wettability during lamination. It has spreadability and is excellent in lamination aptitude.
"Liquid at 25°C" means having fluidity at 25°C. For example, a compound that is liquid at 25° C. is a compound with a viscosity of 2 to 10000 mPa·s measured at 25° C. and 1.0 rpm using an E-type viscometer.
(C)成分が複素環骨格を有する化合物である原料組成物とした場合、当該原料組成物は、他の成分として、当該複素環骨格を有する化合物以外の他の硬化性化合物を含有してもよい。
前記原料組成物において、他の硬化性化合物の含有量は、前記複素環骨格を有する化合物の全量100質量部に対して、好ましくは0~50質量部、より好ましくは0~30質量部、更に好ましくは0~10質量部、より更に好ましくは0~5質量部である。
複素環骨格としては、イソシアヌレート骨格やグリコールウリル骨格が挙げられる。
複素環骨格は、n回回転軸を対称要素として有することが好ましい。そのような複素環骨格を有する硬化性化合物(C)を含有する硬化性接着剤層は、より低誘電特性に優れる傾向がある。 The curable compound (C) is preferably a compound having a heterocyclic skeleton. When the curable compound (C) is a compound having a heterocyclic skeleton, it becomes easier to form a curable adhesive layer that gives a cured product with excellent adhesive strength and low dielectric properties.
(C) When the raw material composition is a compound having a heterocyclic skeleton, the raw material composition may contain, as other components, a curable compound other than the compound having the heterocyclic skeleton. good.
In the raw material composition, the content of the other curable compound is preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, and more preferably 0 to 30 parts by mass, relative to 100 parts by mass of the total amount of the compound having a heterocyclic skeleton. It is preferably 0 to 10 parts by weight, and more preferably 0 to 5 parts by weight.
The heterocyclic skeleton includes an isocyanurate skeleton and a glycoluril skeleton.
The heterocyclic skeleton preferably has an n-fold rotation axis as a symmetry element. A curable adhesive layer containing such a curable compound (C) having a heterocyclic skeleton tends to have excellent low dielectric properties.
分子量が1,000以下の硬化性化合物は、25℃で液体という要件を満たす傾向がある。
また、硬化性化合物(C)の分子量は、100以上が好ましく、200以上がより好ましく、275以上がさらに好ましい。
分子量が100以上の硬化性化合物(C)は、硬化性接着剤層を形成する際や、硬化性接着剤層を使用する際に加熱処理が行われても揮発し難いため、硬化性接着剤層に分子量が高い硬化性化合物(C)を添加することで、目的の物性を有する硬化物が得られ易くなる。 The molecular weight of the curable compound (C) is preferably 1,000 or less, more preferably 800 or less, still more preferably 650 or less, and even more preferably 500 or less.
Curable compounds with a molecular weight of 1,000 or less tend to meet the requirement of being liquid at 25°C.
Moreover, the molecular weight of the curable compound (C) is preferably 100 or more, more preferably 200 or more, and even more preferably 275 or more.
The curable compound (C) having a molecular weight of 100 or more is difficult to volatilize even when heat treatment is performed when forming the curable adhesive layer or when using the curable adhesive layer. By adding a curable compound (C) having a high molecular weight to the layer, it becomes easier to obtain a cured product having the desired physical properties.
硬化性化合物(C)として、硬化性化合物(C’)を用いることで、より低誘電特性に優れる硬化物を与える硬化性接着剤層が形成され易くなる。
(C)成分が上記硬化性化合物(C’)である原料組成物とした場合、当該原料組成物は、他の成分として、当該硬化性化合物(C’)以外の他の硬化性化合物を含有してもよい。
前記原料組成物において、他の硬化性化合物の含有量は、前記硬化性化合物(C’)の全量100質量部に対して、好ましくは0~50質量部、より好ましくは0~30質量部、更に好ましくは0~10質量部、より更に好ましくは0~5質量部である。 As the curable compound (C), for example, a compound having two or more hydrocarbon groups having double bonds at the terminals (hereinafter, this compound may be referred to as "curable compound (C')"). mentioned.
By using the curable compound (C′) as the curable compound (C), it becomes easier to form a curable adhesive layer that gives a cured product with excellent low dielectric properties.
When the raw material composition in which the component (C) is the curable compound (C'), the raw material composition contains, as another component, a curable compound other than the curable compound (C'). You may
In the raw material composition, the content of the other curable compound is preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, with respect to 100 parts by mass of the total amount of the curable compound (C'), More preferably 0 to 10 parts by mass, and even more preferably 0 to 5 parts by mass.
末端に二重結合を有する炭化水素基としては、ビニル基、アリル基、3-ブテニル基、4-ペンテニル基、5-ヘキセニル基、イソプロペニル基、1-メチル-2-プロペニル基、ビニルベンジル基、ビニルナフチル基等が挙げられる。これらの中でも、アリル基が好ましい。 The number of carbon atoms in the hydrocarbon group having a double bond at the end contained in the curable compound (C') is preferably 2-10, more preferably 2-5.
Hydrocarbon groups having a double bond at the end include vinyl group, allyl group, 3-butenyl group, 4-pentenyl group, 5-hexenyl group, isopropenyl group, 1-methyl-2-propenyl group and vinylbenzyl group. , a vinyl naphthyl group, and the like. Among these, an allyl group is preferred.
また、硬化物中に形成される架橋構造が適度に疎らであることで、硬化物中のクラックの発生が抑制される傾向がある。このため、末端に二重結合を有する炭化水素基の数は、好ましくは2~4、より好ましくは2である。 The number of hydrocarbon groups having a double bond at the terminal contained in the curable compound (C') is two or more. When the number of hydrocarbon groups having a double bond at the terminal is 2 or more, it becomes easier to form a curable adhesive layer that gives a cured product with excellent adhesive strength and heat resistance.
In addition, when the crosslinked structure formed in the cured product is moderately sparse, the occurrence of cracks in the cured product tends to be suppressed. Therefore, the number of hydrocarbon groups having a double bond at the end is preferably 2-4, more preferably 2.
イソシアヌレート骨格を有する硬化性化合物(C’)としては、下記式(1)又は(2)で表される化合物が挙げられる。 Examples of the curable compound (C') include a curable compound (C') having an isocyanurate skeleton and a curable compound (C') having a glycoluril skeleton.
Examples of the curable compound (C') having an isocyanurate skeleton include compounds represented by the following formula (1) or (2).
式(2)中、R4~R6は、それぞれ独立に、末端に二重結合を有する炭化水素基を表す。 In formula (1), R 1 and R 2 each independently represent a hydrocarbon group having a double bond at the end; R 3 is a saturated hydrocarbon group having 1 to 15 carbon atoms; represents an alkoxy group-substituted alkyl group.
In formula (2), R 4 to R 6 each independently represent a hydrocarbon group having a double bond at its end.
硬化性化合物(C)の含有量が、原料組成物の有効成分全量中5質量%以上であることで、接着強度に優れる硬化物を与える硬化性接着剤層が形成され易くなる。
硬化性化合物(C)の含有量が、原料組成物の有効成分全量中25質量%以下であることで、低誘電特性に優れる硬化物を与える硬化性接着剤層が形成され易くなる。 When the raw material composition contains a curable compound (C), the content of the curable compound (C) (when two or more curable compounds (C) are included, the total amount of these) is It is preferably 5% by mass or more, more preferably 7% by mass or more, still more preferably 8.5% by mass or more, and preferably 25% by mass or less with respect to the total amount (100% by mass) of the active ingredient. , more preferably 20% by mass or less, and still more preferably 15% by mass or less.
When the content of the curable compound (C) is 5% by mass or more based on the total amount of active ingredients in the raw material composition, a curable adhesive layer that provides a cured product with excellent adhesive strength is easily formed.
When the content of the curable compound (C) is 25% by mass or less based on the total amount of active ingredients in the raw material composition, a curable adhesive layer that provides a cured product with excellent low dielectric properties can be easily formed.
(D)成分は、反応性官能基を有するポリフェニレンエーテル樹脂(以下において、「ポリフェニレンエーテル樹脂(D)」と記載することがある。)である。
ポリフェニレンエーテル樹脂とは、主鎖にポリフェニレン骨格を有する樹脂をいう。
ポリフェニレン骨格とは、下記式で表される繰り返し単位、又は、上記式中の水素原子が置換されてなる繰り返し単位を有する骨格をいう。 [(D) component: polyphenylene ether resin having a reactive functional group]
Component (D) is a polyphenylene ether resin having a reactive functional group (hereinafter sometimes referred to as "polyphenylene ether resin (D)").
A polyphenylene ether resin is a resin having a polyphenylene skeleton in its main chain.
A polyphenylene skeleton refers to a skeleton having a repeating unit represented by the following formula or a repeating unit in which hydrogen atoms in the above formula are substituted.
ポリフェニレンエーテル樹脂(D)はポリフェニレンエーテル骨格を有することから、ポリフェニレンエーテル樹脂(D)を含有する硬化性接着剤層は低誘電特性に優れる。
また、ポリフェニレンエーテル樹脂(D)は反応性官能基を有することから、ポリフェニレンエーテル樹脂(D)を含有する硬化性接着剤層の硬化物は耐熱性に優れる。
ポリフェニレンエーテル樹脂(D)は、1種を単独で、あるいは2種以上を組み合わせて用いることができる。 Polyphenylene ether resin (D) is a compound having a polyphenylene ether skeleton and a reactive functional group.
Since the polyphenylene ether resin (D) has a polyphenylene ether skeleton, the curable adhesive layer containing the polyphenylene ether resin (D) is excellent in low dielectric properties.
Moreover, since the polyphenylene ether resin (D) has a reactive functional group, the cured product of the curable adhesive layer containing the polyphenylene ether resin (D) has excellent heat resistance.
Polyphenylene ether resin (D) can be used individually by 1 type or in combination of 2 or more types.
これらの中でも、低誘電特性に優れる硬化物が得られ易いことから、反応性官能基は、エチレン性不飽和結合を有する基が好ましく、ビニルベンジル基がより好ましい。 Examples of reactive functional groups in the polyphenylene ether resin (D) include groups having an ethylenically unsaturated bond such as vinyl, allyl, acryloyl, methacryloyl, cyclopentenyl, vinylbenzyl, and vinylnaphthyl; group; hydroxyl group; and the like.
Among these, the reactive functional group is preferably a group having an ethylenically unsaturated bond, more preferably a vinylbenzyl group, since a cured product having excellent low dielectric properties can be easily obtained.
(D)成分がポリフェニレンエーテル骨格の両末端に反応性官能基を有する樹脂である原料組成物とした場合、当該原料組成物は、他の成分として、当該ポリフェニレンエーテル骨格の両末端に反応性官能基を有する樹脂以外の他のポリフェニレンエーテル樹脂を含有してもよい。
前記原料組成物において、他のポリフェニレンエーテル樹脂の含有量は、前記ポリフェニレンエーテル骨格の両末端に反応性官能基を有する樹脂の全量100質量部に対して、好ましくは0~50質量部、より好ましくは0~30質量部、更に好ましくは0~10質量部、より更に好ましくは0~5質量部である。 As the polyphenylene ether resin (D), a resin having a reactive functional group at both ends of the polyphenylene ether skeleton is preferable because a cured product having excellent low dielectric properties can be easily obtained.
(D) When the raw material composition is a resin having a reactive functional group at both ends of the polyphenylene ether skeleton, the raw material composition contains, as another component, reactive functional groups at both ends of the polyphenylene ether skeleton. A polyphenylene ether resin other than the resin having a group may be contained.
In the raw material composition, the content of the other polyphenylene ether resin is preferably 0 to 50 parts by mass, more preferably 100 parts by mass of the total amount of the resin having reactive functional groups at both ends of the polyphenylene ether skeleton. is 0 to 30 parts by mass, more preferably 0 to 10 parts by mass, and even more preferably 0 to 5 parts by mass.
例えば、反応性官能基として両末端にビニルベンジル基を有するポリフェニレンエーテル樹脂(D)は、2官能フェノール化合物と1官能フェノール化合物を反応させて、両末端にフェノール性水酸基を有する重合体を得た後、4-(クロロメチル)スチレンを用いて末端フェノール性水酸基をビニルベンジルエーテル化することで得ることができる。 The polyphenylene ether resin (D) can be obtained by forming a polyphenylene ether skeleton and then introducing a reactive functional group to the terminal.
For example, a polyphenylene ether resin (D) having vinylbenzyl groups at both ends as reactive functional groups was reacted with a bifunctional phenol compound and a monofunctional phenol compound to obtain a polymer having phenolic hydroxyl groups at both ends. Then, it can be obtained by vinylbenzyl etherifying the terminal phenolic hydroxyl group using 4-(chloromethyl)styrene.
前記原料組成物において、他のポリフェニレンエーテル樹脂の含有量は、上記式(9)で表される化合物の全量100質量部に対して、好ましくは0~50質量部、より好ましくは0~30質量部、更に好ましくは0~10質量部、より更に好ましくは0~5質量部である。 (D) When the raw material composition is a compound represented by the above formula (9), the raw material composition contains, as another component, a polyphenylene other than the compound represented by the above formula (9) It may contain an ether resin.
In the raw material composition, the content of the other polyphenylene ether resin is preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, with respect to 100 parts by mass of the total amount of the compound represented by the above formula (9). parts, more preferably 0 to 10 parts by weight, and even more preferably 0 to 5 parts by weight.
ポリフェニレンエーテル樹脂(D)の数平均分子量(Mn)は、テトラヒドロフラン(THF)を溶媒として用いてゲルパーミエーションクロマトグラフィー(GPC)を行い、標準ポリスチレン換算値として求めることができ、具体的な測定条件としては上述のとおりである。 The number average molecular weight (Mn) of the polyphenylene ether resin (D) is preferably 500 to 5,000, more preferably 500 to 3,000, still more preferably 700 to 2,500, still more preferably 1,000 to 2. , 000.
The number average molecular weight (Mn) of the polyphenylene ether resin (D) is obtained by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and can be obtained as a standard polystyrene conversion value, and specific measurement conditions is as described above.
ポリフェニレンエーテル樹脂(D)の含有量が、原料組成物の有効成分全量中1質量%以上であることで、低誘電特性に優れる硬化物を与える硬化性接着剤層が形成され易くなる。
ポリフェニレンエーテル樹脂(D)の含有量が、原料組成物の有効成分全量中30質量%以下であることで、貼付性に優れる硬化性接着剤層が形成され易くなる。 When the raw material composition contains a polyphenylene ether resin (D), the content of the polyphenylene ether resin (D) (when two or more (D) components are included, the total amount of these) is the active ingredient of the raw material composition The total amount (100% by mass) of preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 30% by mass % by mass or less, more preferably 25% by mass or less.
When the content of the polyphenylene ether resin (D) is 1% by mass or more based on the total amount of active ingredients in the raw material composition, a curable adhesive layer that provides a cured product with excellent low dielectric properties is easily formed.
When the content of the polyphenylene ether resin (D) is 30% by mass or less in the total amount of active ingredients in the raw material composition, a curable adhesive layer with excellent sticking properties is easily formed.
原料組成物は、硬化性成分(X)として、シランカップリング剤(F)を含有してもよい。
シランカップリング剤(F)は、1種を単独で、あるいは2種以上を組み合わせて用いることができる。 [(F) component: silane coupling agent]
The raw material composition may contain a silane coupling agent (F) as a curable component (X).
The silane coupling agents (F) can be used singly or in combination of two or more.
シランカップリング剤(F)としては、3-メタクリロキシプロピルメチルジメトキシシラン、3-メタクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルメチルジエトキシシラン、3-メタクリロキシプロピルトリエトキシシラン、3-アクリロキシプロピルトリメトキシシラン等の(メタ)アクリロイル基を有するシランカップリング剤;
ビニルトリメトキシシラン、ビニルトリエトキシシラン、ジメトキシメチルビニルシラン、ジエトキシメチルビニルシラン、トリクロロビニルシラン、ビニルトリス(2-メトキシエトキシ)シラン等のビニル基を有するシランカップリング剤;
2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、3-グリシドキシプロピルトリエトキシシラン、8-グリシドキシオクチルトリメトキシシラン等のエポキシ基を有するシランカップリング剤;
p-スチリルトリメトキシシラン、p-スチリルトリエトキシシラン等のスチリル基を有するシランカップリング剤;
N-(2-アミノエチル)-3-アミノプロピルメチルジメトキシシラン、N-(2-アミノエチル)-3-アミノプロピルトリメトキシシラン、N-(2-アミノエチル)-3-アミノプロピルトリエトキシシラン、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、3-トリエトキシシリル-N-(1,3-ジメチル・ブチリデン)プロピルアミン、N-フェニル-3-アミノプロピルトリメトキシシラン、N-(ビニルベンジル)-2-アミノエチル-3-アミノプロピルトリメトキシシランの塩酸塩等のアミノ基を有するシランカップリング剤;
3-ウレイドプロピルトリメトキシシラン、3-ウレイドプロピルトリエトキシシラン等のウレイド基を有するシランカップリング剤;
3-クロロプロピルトリメトキシシラン、3-クロロプロピルトリエトキシシラン等のハロゲン原子を有するシランカップリング剤;
3-メルカプトプロピルメチルジメトキシシラン、3-メルカプトプロピルトリメトキシシラン等のメルカプト基を有するシランカップリング剤;
ビス(トリメトキシシリルプロピル)テトラスルフィド、ビス(トリエトキシシリルプロピル)テトラスルフィド等のスルフィド基を有するシランカップリング剤;
3-イソシアネートプロピルトリメトキシシラン、3-イソシアネートプロピルトリエトキシシラン等のイソシアネート基を有するシランカップリング剤;
アリルトリクロロシラン、アリルトリエトキシシラン、アリルトリメトキシシラン等のアリル基を有するシランカップリング剤;
3-ヒドロキシプロピルトリメトキシシラン、3-ヒドロキシプロピルトリエトキシシラン等の水酸基を有するシランカップリング剤;等が挙げられる。 A known silane coupling agent can be used as the silane coupling agent (F). Among them, organosilicon compounds having at least one alkoxysilyl group in the molecule are preferred.
Silane coupling agents (F) include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyl Silane coupling agents having a (meth)acryloyl group such as roxypropyltrimethoxysilane;
Silane coupling agents having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinyltris(2-methoxyethoxy)silane;
2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 8-glycid Silane coupling agents having an epoxy group such as xyoctyltrimethoxysilane;
Silane coupling agents having a styryl group such as p-styryltrimethoxysilane and p-styryltriethoxysilane;
N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane , 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N - Silane coupling agents having an amino group such as hydrochloride of (vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane;
Silane coupling agents having a ureido group such as 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane;
Silane coupling agents having halogen atoms such as 3-chloropropyltrimethoxysilane and 3-chloropropyltriethoxysilane;
Silane coupling agents having a mercapto group such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane;
Silane coupling agents having a sulfide group such as bis(trimethoxysilylpropyl)tetrasulfide and bis(triethoxysilylpropyl)tetrasulfide;
Silane coupling agents having an isocyanate group such as 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane;
Silane coupling agents having an allyl group such as allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilane;
silane coupling agents having a hydroxyl group such as 3-hydroxypropyltrimethoxysilane and 3-hydroxypropyltriethoxysilane;
シランカップリング剤(F)の含有量が、原料組成物の有効成分全量中0.01質量%以上であることで、高温高湿試験後の接着性に優れる硬化物を与える硬化性接着剤層が形成され易くなる。
シランカップリング剤(F)の含有量が、原料組成物の有効成分全量中5質量%以下であることで、高温高湿試験後の接着性に優れる硬化物を与える硬化性接着剤層が形成され易くなる。 When the raw material composition contains a silane coupling agent (F), the content of the silane coupling agent (F) (when two or more silane coupling agents (F) are included, the total amount of these) is the raw material It is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.08% by mass or more, and preferably is 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, and even more preferably 0.5% by mass or less.
The content of the silane coupling agent (F) is 0.01% by mass or more in the total amount of active ingredients in the raw material composition, so that the curable adhesive layer gives a cured product having excellent adhesion after a high temperature and high humidity test. becomes easier to form.
When the content of the silane coupling agent (F) is 5% by mass or less in the total amount of active ingredients in the raw material composition, a curable adhesive layer that gives a cured product with excellent adhesion after a high-temperature and high-humidity test is formed. easier to be
原料組成物は、(E)成分として、カチオン重合開始剤を含有してもよい。
硬化反応(I)や硬化反応(II)がカチオン重合反応である場合、原料組成物にカチオン重合開始剤を添加することで、これらの硬化反応を効率よく進行させることができる。
カチオン重合開始剤は、1種を単独で、あるいは2種以上を組み合わせて用いることができる。
カチオン重合開始剤(E)としては、熱カチオン重合開始剤や、光カチオン重合開始剤が挙げられ、簡便な工程により重合が可能な熱カチオン重合開始剤が好ましい。 [(E) component: cationic polymerization initiator]
The raw material composition may contain a cationic polymerization initiator as the (E) component.
When the curing reaction (I) or the curing reaction (II) is a cationic polymerization reaction, adding a cationic polymerization initiator to the raw material composition allows these curing reactions to proceed efficiently.
A cationic polymerization initiator can be used individually by 1 type or in combination of 2 or more types.
Examples of the cationic polymerization initiator (E) include thermal cationic polymerization initiators and photocationic polymerization initiators, and preferred are thermal cationic polymerization initiators that can be polymerized by a simple process.
熱カチオン重合開始剤としては、スルホニウム塩、第四級アンモニウム塩、ホスホニウム塩、ジアゾニウム塩、ヨードニウム塩等が挙げられる。 Thermal cationic polymerization initiators are compounds that can generate cationic species that initiate polymerization upon heating.
Thermal cationic polymerization initiators include sulfonium salts, quaternary ammonium salts, phosphonium salts, diazonium salts, iodonium salts and the like.
カチオン重合開始剤の含有量が0.01質量部以上であることで、反応性が低下することを防ぎ易くなる。
カチオン重合開始剤の含有量が6質量部以下であることで、被着体の腐食を抑制し易くなる。 When the raw material composition contains the cationic polymerization initiator (E), the content of the cationic polymerization initiator (E) (when two or more (E) components are included, the total amount of these) is the cationic polymerizable compound is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.1 parts by mass or more, and more More preferably 0.2 parts by mass or more, preferably 6 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 4 parts by mass or less.
When the content of the cationic polymerization initiator is 0.01 parts by mass or more, it becomes easier to prevent a decrease in reactivity.
When the content of the cationic polymerization initiator is 6 parts by mass or less, it becomes easy to suppress corrosion of the adherend.
原料組成物は、溶媒を含有して、溶液の形態としてもよい。
溶媒としては、ベンゼン、トルエンなどの芳香族炭化水素系溶媒;酢酸エチル、酢酸ブチルなどのエステル系溶媒;アセトン、メチルエチルケトン、メチルイソブチルケトンなどのケトン系溶媒;n-ペンタン、n-ヘキサン、n-ヘプタンなどの脂肪族炭化水素系溶媒;シクロペンタン、シクロヘキサン、メチルシクロヘキサンなどの脂環式炭化水素系溶媒;等が挙げられる。
これらの溶媒は、1種を単独で、あるいは2種以上を組み合わせて用いることができる。
原料組成物が溶媒を含有するとき、溶媒の含有量は、塗布性等を考慮して適宜決定することができる。 〔solvent〕
The raw material composition may contain a solvent and be in the form of a solution.
Examples of solvents include aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as heptane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane, and methylcyclohexane; and the like.
These solvents can be used singly or in combination of two or more.
When the raw material composition contains a solvent, the content of the solvent can be appropriately determined in consideration of coatability and the like.
原料組成物は、本発明の効果を妨げない範囲で、これまでに説明してきたもの以外の成分(その他の成分)を含有してもよい。
その他の成分としては、紫外線吸収剤、帯電防止剤、光安定剤、酸化防止剤、樹脂安定剤、充填剤、顔料、増量剤、軟化剤等の添加剤が挙げられる。
これらは1種を単独で、あるいは2種以上を組み合わせて用いることができる。
原料組成物がこれらの添加剤を含有するとき、その含有量は、目的に合わせて適宜決定することができる。 [Other ingredients]
The raw material composition may contain components (other components) other than those described above as long as the effects of the present invention are not impaired.
Other components include additives such as UV absorbers, antistatic agents, light stabilizers, antioxidants, resin stabilizers, fillers, pigments, extenders and softeners.
These can be used individually by 1 type or in combination of 2 or more types.
When the raw material composition contains these additives, the content thereof can be appropriately determined according to the purpose.
原料組成物は、バインダー樹脂(A)及び架橋剤(B)と、その他の任意成分を、常法に従って適宜混合・攪拌することにより調製することができる。 [Method for producing raw material composition]
The raw material composition can be prepared by appropriately mixing and stirring the binder resin (A), the cross-linking agent (B), and other optional components according to a conventional method.
本発明の接着シートを構成する硬化性接着剤層は、前記原料組成物を用いて形成された層である。 <<Curable adhesive layer>>
The curable adhesive layer constituting the adhesive sheet of the present invention is a layer formed using the raw material composition.
塗膜を乾燥するときの条件としては、例えば、80~150℃で30秒から5分間である。 Methods for drying the coating film include conventionally known drying methods such as hot air drying, hot roll drying, and infrared irradiation.
The conditions for drying the coating film are, for example, 80 to 150° C. for 30 seconds to 5 minutes.
例えば、バインダー樹脂(A)中の反応性官能基がカルボキシ基やカルボン酸無水物基であり、架橋剤(B)が、イソシアネート系架橋剤、エポキシ系架橋剤、金属キレート系架橋剤等である場合、塗膜を約100℃に加熱することで、乾燥処理と硬化反応(I)とを同時に行うことができ、硬化性接着剤層を効率よく形成することができる。 When the curing reaction (I) is a reaction initiated by heat, the drying treatment of the coating film and the curing reaction (I) can be combined.
For example, the reactive functional group in the binder resin (A) is a carboxy group or a carboxylic anhydride group, and the cross-linking agent (B) is an isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, a metal chelate-based cross-linking agent, or the like. In this case, by heating the coating film to about 100° C., the drying treatment and the curing reaction (I) can be performed simultaneously, and the curable adhesive layer can be efficiently formed.
また、硬化性接着層の厚さは通常50μm以下であり、好ましくは25μm以下である。
硬化性接着剤層の厚さが1μm以上であると、段差に追従しやすくなり接着性を得やすい。
硬化性接着剤層の厚さが50μm以下であると、剛性が高くなり過ぎずフレキシブル性が得やすい。 The thickness of the curable adhesive layer is usually 1 μm or more, preferably 5 μm or more.
The thickness of the curable adhesive layer is usually 50 µm or less, preferably 25 µm or less.
When the thickness of the curable adhesive layer is 1 μm or more, it is easy to follow a step, and it is easy to obtain adhesiveness.
When the thickness of the curable adhesive layer is 50 μm or less, the rigidity is not excessively increased, and flexibility is easily obtained.
硬化性接着剤層のゲル分率は、通常70質量%以下であり、好ましくは60質量%以下であり、さらに好ましくは50質量%未満である。
ゲル分率が10質量%以上の硬化性接着剤層は、硬化性接着剤層としては架橋構造が十分に形成されたものである。したがって、そのような硬化性接着剤層に対して熱プレス処理等の加熱処理を行っても、接着剤成分が大量に染み出すことはなく、周囲の汚染が抑制される。
硬化性接着剤層のゲル分率が70質量%以下であることで、硬化性や、被着体との密着性に優れる硬化性接着剤層が形成され易くなる。
硬化性接着剤層のゲル分率は、実施例に記載するように、硬化性接着剤層を、23℃で168時間、トルエンに浸漬させる実験を行うことにより算出することができる。 The gel fraction of the curable adhesive layer is 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, and particularly preferably 25% by mass or more.
The gel fraction of the curable adhesive layer is usually 70% by mass or less, preferably 60% by mass or less, and more preferably less than 50% by mass.
A curable adhesive layer having a gel fraction of 10% by mass or more has a sufficiently formed crosslinked structure as a curable adhesive layer. Therefore, even if such a curable adhesive layer is subjected to heat treatment such as hot press treatment, a large amount of the adhesive component does not ooze out, and contamination of the surroundings is suppressed.
When the gel fraction of the curable adhesive layer is 70% by mass or less, a curable adhesive layer having excellent curability and adhesion to an adherend can be easily formed.
The gel fraction of the curable adhesive layer can be calculated by performing an experiment in which the curable adhesive layer is immersed in toluene at 23° C. for 168 hours, as described in Examples.
先に説明したように、硬化性接着剤層の原料組成物としては、硬化反応として、硬化反応(I)のみを有するもの〔原料組成物(α)〕や、硬化反応として、硬化反応(I)と硬化反応(II)とを有するもの〔原料組成物(β)〕がある。
原料組成物(α)を用いて形成された硬化性接着剤層の「硬化性」は、硬化性接着剤層中の未反応のバインダー樹脂(A)と架橋剤(B)との反応(すなわち、硬化反応(I))に起因するものである。
一方、原料組成物(β)を用いて形成された硬化性接着剤層の「硬化性」は、通常、硬化反応(I)と硬化反応(II)の両方に起因するものか、又は、硬化反応(II)のみに起因するものである。 The curable adhesive layer is a curable layer.
As described above, the raw material composition of the curable adhesive layer includes, as the curing reaction, one having only the curing reaction (I) [raw material composition (α)], and as the curing reaction, the curing reaction (I ) and curing reaction (II) [raw material composition (β)].
The "curability" of the curable adhesive layer formed using the raw material composition (α) is determined by the reaction between the unreacted binder resin (A) and the cross-linking agent (B) in the curable adhesive layer (i.e. , curing reaction (I)).
On the other hand, the "curability" of the curable adhesive layer formed using the raw material composition (β) is usually due to both curing reaction (I) and curing reaction (II), or curing It is due only to reaction (II).
例えば、硬化性接着剤層が、硬化性成分として前記(C)成分及び(D)成分を含有する熱硬化性の接着剤層である場合、硬化性接着剤層を加熱することで、硬化性接着剤層の硬化反応を効率よく進行させることができる。
この硬化性接着剤層の加熱温度は、通常140℃以上、好ましくは150~180℃である。
この硬化性接着剤層の加熱時間は、通常0.5~3時間、好ましくは1~2時間である。 The curing conditions for the curable adhesive layer can be appropriately determined according to the curable component contained in the curable adhesive layer.
For example, when the curable adhesive layer is a thermosetting adhesive layer containing the components (C) and (D) as curable components, heating the curable adhesive layer causes the curable The curing reaction of the adhesive layer can proceed efficiently.
The heating temperature for this curable adhesive layer is usually 140°C or higher, preferably 150 to 180°C.
The heating time for this curable adhesive layer is usually 0.5 to 3 hours, preferably 1 to 2 hours.
硬化性接着剤層の硬化物が、接着部材、保護部材、絶縁部材等として機能するとき、その硬化物は、硬化反応が十分に進行したものであることが好ましい。
そのような状態の硬化物のゲル分率は、好ましくは50質量%以上であり、より好ましくは55質量%以上である。
また、硬化反応が十分に進行した状態の硬化物のゲル分率の上限値は特にないが、通常95質量%以下、好ましくは90質量%以下である。
硬化物のゲル分率は、硬化性接着剤層のゲル分率の算出方法と同様の方法により求めることができる。 In the cured product formed by curing the curable adhesive layer, more crosslinked structures are usually formed than in the curable adhesive layer. Therefore, the gel fraction of the cured product is usually larger than the gel fraction of the curable adhesive layer.
When the cured product of the curable adhesive layer functions as an adhesive member, a protective member, an insulating member, or the like, the cured product preferably undergoes a sufficient curing reaction.
The gel fraction of the cured product in such a state is preferably 50% by mass or more, more preferably 55% by mass or more.
Although there is no particular upper limit for the gel fraction of the cured product in which the curing reaction has sufficiently progressed, it is usually 95% by mass or less, preferably 90% by mass or less.
The gel fraction of the cured product can be determined by a method similar to the method for calculating the gel fraction of the curable adhesive layer.
本発明の接着シートは、前記硬化性接着剤層を有するものである。
本発明の接着シートは、保管時や運搬時の保護のため、片側又は両側に保護シート等を有していてもよい。 《Adhesive sheet》
The adhesive sheet of the present invention has the curable adhesive layer.
The adhesive sheet of the present invention may have a protective sheet or the like on one side or both sides for protection during storage or transportation.
電子デバイスとしては、スマートフォン、タブレット端末等の通信機器が挙げられる。
例えば、本発明の接着シートを構成する硬化性接着剤層を用いて、電子デバイス中の各種部品を接着したり、電子デバイス中の回路の保護材や絶縁材を形成したりすることができる。 The adhesive sheet of the present invention is suitably used as an adhesive sheet for electronic devices.
Examples of electronic devices include communication devices such as smartphones and tablet terminals.
For example, the curable adhesive layer that constitutes the adhesive sheet of the present invention can be used to adhere various parts in an electronic device, or to form a protective material or insulating material for circuits in an electronic device.
例えば、本発明の接着シートを構成する硬化性接着剤層を、絶縁性樹脂フィルムと熱圧着させることで、カバーレイフィルムを製造することができる。 The adhesive sheet of the present invention is suitably used as an adhesive sheet for coverlay films. A coverlay film is, for example, a laminated film used to protect the surface of a flexible printed wiring board, and usually has an insulating resin layer and an adhesive layer.
For example, a coverlay film can be produced by thermocompression bonding a curable adhesive layer constituting the adhesive sheet of the present invention with an insulating resin film.
・バインダー樹脂(A1):無水マレイン酸変性α-オレフィン重合体〔三井化学株式会社製、商品名:ユニストールH-200、数平均分子量:47,000〕
・イソシアネート系架橋剤(B1):1,3,5-トリス(5-イソシアネートペンチル)-1,3,5-トリアジン-2,4,6-トリオン、〔三井化学株式会社製、商品名:スタビオD-370N、分子量:462〕
・エポキシ系架橋剤(B2):1,3-ビス(N,N-ジグリシジルアミノメチル)シクロヘキサン、〔三菱ガス化学株式会社製、商品名:TETRAD-C、分子量:362〕
・金属キレート系架橋剤(B3):アルミニウムトリス(アセチルアセトナート)、〔綜研化学株式会社製,商品名:M-5A、分子量:324〕
・硬化性化合物(C1):イソシアヌレート骨格と2つのアリル基を有する化合物〔四国化成工業株式会社製、商品名:L-DAIC〕
・ポリフェニレンエーテル樹脂(D1):ビニルベンジル変性ポリフェニレンエーテル〔三菱ガス化学株式会社製、商品名:OPE-2St 1200、数平均分子量:1200〕
・カチオン重合開始剤(E1):熱カチオン重合開始剤〔三新化学工業株式会社製、商品名:サンエイドSI-B3〕
・シランカップリング剤(F1):8-グリシドキシオクチルトリメトキシシラン〔信越化学工業株式会社製、商品名:KBM4803〕 [Compounds used in Examples or Comparative Examples]
- Binder resin (A1): maleic anhydride-modified α-olefin polymer [manufactured by Mitsui Chemicals, trade name: UNISTOL H-200, number average molecular weight: 47,000]
Isocyanate-based cross-linking agent (B1): 1,3,5-tris(5-isocyanatopentyl)-1,3,5-triazine-2,4,6-trione [manufactured by Mitsui Chemicals, Inc., trade name: Stabio D-370N, molecular weight: 462]
Epoxy-based cross-linking agent (B2): 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, [manufactured by Mitsubishi Gas Chemical Company, Inc., trade name: TETRAD-C, molecular weight: 362]
- Metal chelate-based cross-linking agent (B3): aluminum tris (acetylacetonate) [manufactured by Soken Chemical Co., Ltd., trade name: M-5A, molecular weight: 324]
Curable compound (C1): a compound having an isocyanurate skeleton and two allyl groups [manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: L-DAIC]
- Polyphenylene ether resin (D1): vinylbenzyl-modified polyphenylene ether [manufactured by Mitsubishi Gas Chemical Company, trade name: OPE-2St 1200, number average molecular weight: 1200]
- Cationic polymerization initiator (E1): Thermal cationic polymerization initiator [manufactured by Sanshin Chemical Industry Co., Ltd., product name: San-Aid SI-B3]
- Silane coupling agent (F1): 8-glycidoxyoctyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM4803]
バインダー樹脂(A1)100質量部、イソシアネート架橋剤(B1)0.5質量部、硬化性化合物(C1)12.5質量部、ポリフェニレンエーテル樹脂(D1)25質量部、カチオン重合開始剤(E1)0.12質量部、シランカップリング剤(F1)0.2質量部をトルエンに溶解し、原料組成物を調製した。
剥離シート(第1剥離シート、リンテック株式会社製、商品名:SP-PET752150)の剥離処理面上に、得られた原料組成物を塗布して塗膜を形成し、得られた塗膜を100℃で2分間乾燥し、厚さが15μmの硬化性接着剤層を形成した。この硬化性接着剤層の表出した表面上に、もう1枚の剥離シート(第2剥離シート、リンテック株式会社製、商品名:SP-PET381130)の剥離処理面を貼り合わせて接着シートを得た。 [Example 1]
Binder resin (A1) 100 parts by mass, isocyanate cross-linking agent (B1) 0.5 parts by mass, curable compound (C1) 12.5 parts by mass, polyphenylene ether resin (D1) 25 parts by mass, cationic polymerization initiator (E1) 0.12 parts by mass and 0.2 parts by mass of the silane coupling agent (F1) were dissolved in toluene to prepare a raw material composition.
The obtained raw material composition is applied on the release-treated surface of a release sheet (first release sheet, product name: SP-PET752150, manufactured by Lintec Corporation) to form a coating film, and the resulting coating film is C. for 2 minutes to form a curable adhesive layer with a thickness of 15 .mu.m. On the exposed surface of this curable adhesive layer, another release sheet (second release sheet, product name: SP-PET381130, manufactured by Lintec Corporation) is laminated to obtain an adhesive sheet. rice field.
成分の配合量もしくは種類を第1表に記載のものに変更したこと以外は、実施例1と同様にして原料組成物を調製し、接着シートを得た。 [Examples 2 to 5, Comparative Example 1]
A raw material composition was prepared and an adhesive sheet was obtained in the same manner as in Example 1, except that the amounts or types of the components were changed to those shown in Table 1.
実施例又は比較例で得た接着シートを縦80mm×横80mmの大きさに切断した後、剥離シートを2枚とも剥がし、硬化性接着剤層を得た。次いで、得られた硬化性接着剤層を、予め質量を測定したポリエステル製メッシュ(メッシュサイズ200)に包み込み、試験サンプルを作製した。試験サンプルを温度23℃、相対湿度50%の環境下に24時間静置した後、試験サンプルの質量を精密天秤にて秤量した。得られた測定値に基づき、浸漬前の硬化性接着剤層の質量(M1)を算出した。
次に、試験サンプルを、室温下(23℃)でトルエン0.2Lに168時間浸漬させた。浸漬後、試験サンプルを取り出し、当該試験サンプルを、100℃のオーブン中にて2時間乾燥させた後、温度23℃、相対湿度50%の環境下で、24時間静置した。乾燥後の試験サンプルの質量を精密天秤にて秤量した。得られた測定値に基づき、浸漬及び乾燥後の硬化性接着剤層の質量(M2)を算出した。
M1の値、及び、M2の値から、下記式により硬化性接着剤層のゲル分率を算出した。
・ゲル分率(質量%)=(M2/M1)×100 [Gel Fraction of Curable Adhesive Layer]
After cutting the adhesive sheet obtained in Examples or Comparative Examples into a size of 80 mm long×80 mm wide, both release sheets were peeled off to obtain a curable adhesive layer. Next, the resulting curable adhesive layer was wrapped in a pre-weighed polyester mesh (mesh size 200) to prepare a test sample. After the test sample was allowed to stand in an environment with a temperature of 23° C. and a relative humidity of 50% for 24 hours, the mass of the test sample was weighed with a precision balance. Based on the obtained measured value, the mass (M1) of the curable adhesive layer before immersion was calculated.
Next, the test sample was immersed in 0.2 L of toluene at room temperature (23° C.) for 168 hours. After the immersion, the test sample was taken out, dried in an oven at 100°C for 2 hours, and then allowed to stand for 24 hours in an environment with a temperature of 23°C and a relative humidity of 50%. The mass of the test sample after drying was weighed with a precision balance. Based on the measured values obtained, the mass (M2) of the curable adhesive layer after immersion and drying was calculated.
From the value of M1 and the value of M2, the gel fraction of the curable adhesive layer was calculated by the following formula.
・Gel fraction (% by mass) = (M2/M1) x 100
実施例又は比較例で得た接着シートを縦80mm×横80mmの大きさに切断した後、オーブンにて160℃で1時間加熱した。剥離シートを剥がして得られた硬化物を用いて、上記と同様にして硬化物のゲル分率を算出した。 [Gel fraction of cured product]
The adhesive sheets obtained in Examples or Comparative Examples were cut into a size of 80 mm long×80 mm wide, and then heated in an oven at 160° C. for 1 hour. Using the cured product obtained by peeling off the release sheet, the gel fraction of the cured product was calculated in the same manner as described above.
実施例又は比較例で得た接着シートの剥離シートを1枚剥がし、露出した硬化性接着剤層を、熱ラミネーターを用いて100℃でポリイミドフィルム(東レ・デュポン社製、カプトン、厚さ25μm)と圧着させ、剥離シート/硬化性接着剤層/ポリイミドフィルム、の構造の積層体を得た。次いで、この積層体の剥離シートを剥がし、露出した硬化性接着剤層を、熱ラミネーターを用いて100℃で銅箔と圧着させ、銅箔/硬化性接着剤層/ポリイミドフィルム、の構造の積層体を得た。なお、銅箔が他の2つの層に比べて面積が広いため、硬化性接着剤層の接着剤成分が染み出た場合、銅箔上に付着することになる。
この積層体に対して、171℃、1.38MPaの条件で20分間熱プレス処理を行った。
冷却後、平面視で接着剤層(硬化物)から最も染み出た接着剤成分の長さ〔図1中のXで示される部分の長さ(μm)〕を、デジタル顕微鏡を用いて測定した。結果を第1表に示す。なお、図1は、実施例において、接着剤成分の染み出しを評価する際に用いた積層体を熱プレス処理した後を平面視した際の模式平面図である。図1に示すように、熱プレス処理により、前記積層体の銅箔1とポリイミドフィルム3と間に挟持された接着剤層(硬化物)の一部は、染み出して、銅箔1上に染み出した接着剤成分2が付着し得る。この際、図1のように、平面視した際に、染み出した接着剤成分2とポリイミドフィルム3までの距離の最大値Xを「接着剤成分の染み出し長さ」とし、第1表に記載している。 [Evaluation of component exudation]
One release sheet of the adhesive sheet obtained in Examples or Comparative Examples was peeled off, and the exposed curable adhesive layer was covered with a polyimide film (manufactured by DuPont-Toray, Kapton, thickness 25 μm) at 100° C. using a heat laminator. to obtain a laminate having a structure of release sheet/curable adhesive layer/polyimide film. Then, the release sheet of this laminate is peeled off, and the exposed curable adhesive layer is pressed against copper foil at 100° C. using a heat laminator to laminate a structure of copper foil/curable adhesive layer/polyimide film. got a body Since the copper foil has a larger area than the other two layers, when the adhesive component of the curable adhesive layer seeps out, it adheres to the copper foil.
This laminate was subjected to a heat press treatment under conditions of 171° C. and 1.38 MPa for 20 minutes.
After cooling, the length of the most exuded adhesive component from the adhesive layer (cured product) in plan view [the length (μm) of the portion indicated by X in FIG. 1] was measured using a digital microscope. . The results are shown in Table 1. In addition, FIG. 1 is a schematic plan view of the laminated body used for evaluating the exudation of the adhesive component in the examples after being subjected to a heat press treatment. As shown in FIG. 1, a part of the adhesive layer (cured material) sandwiched between the
実施例又は比較例で得た接着シートの硬化性接着剤層を約1mmの厚さになるように複数枚重ねた後、熱ラミネーターを用いて100℃で融着処理を行い、剥離シート/約1mmの厚さの硬化性接着剤層/剥離シート、の構造の積層体を得た。この積層体の両側の剥離シートを剥離して、測定用試料を得た。
得られた測定用試料について、RFインピーダンス・マテリアルアナライザ(キーサイト・テクノロジー社製、E4991A)を用いて、23℃、1GHzにおける比誘電率及び誘電正接を測定した。なお、本明細書では、高周波領域とは、300MHz~300GHzの領域を指すものであるが、本実施例では、高周波領域の一例として1GHzを採用した。結果を第1表に示す。 [Dielectric constant, dielectric loss tangent]
After stacking a plurality of curable adhesive layers of the adhesive sheets obtained in Examples or Comparative Examples so as to have a thickness of about 1 mm, a heat laminator is used to perform fusion bonding at 100 ° C., and a release sheet / about A laminate of the structure curable adhesive layer/release sheet with a thickness of 1 mm was obtained. The release sheets on both sides of this laminate were peeled off to obtain a sample for measurement.
The dielectric constant and dielectric loss tangent at 23° C. and 1 GHz were measured using an RF impedance material analyzer (manufactured by Keysight Technologies, E4991A) for the obtained measurement sample. In this specification, the high frequency region refers to the region of 300 MHz to 300 GHz, but in this embodiment, 1 GHz is used as an example of the high frequency region. The results are shown in Table 1.
一方、比較例1の接着シートの硬化性接着剤層は、ゲル分率の値が低い。このため、この硬化性接着剤層に対して同条件で熱プレス処理を行うと、接着剤成分の染み出し量が多い。
また、実施例1~5で得られた接着シートの硬化性接着剤層は、低誘電特性に優れている。 The curable adhesive layers of the adhesive sheets obtained in Examples 1 to 5 all have high gel fraction values. Therefore, even if these curable adhesive layers are subjected to heat press treatment under the conditions of 171° C., 1.38 MPa, and 20 minutes, the amount of the adhesive components oozing out is small.
On the other hand, the curable adhesive layer of the adhesive sheet of Comparative Example 1 has a low gel fraction value. For this reason, if the heat press treatment is performed on this curable adhesive layer under the same conditions, the amount of the adhesive component oozing out is large.
Moreover, the curable adhesive layers of the adhesive sheets obtained in Examples 1 to 5 are excellent in low dielectric properties.
2:染み出した接着剤成分
3:ポリイミドフィルム 1: Copper foil 2: Exuded adhesive component 3: Polyimide film
Claims (14)
- 硬化性接着剤層を有する接着シートであって、
前記硬化性接着剤層の原料組成物が、下記(A)成分、及び(B)成分を含有し、かつ、(B)成分を前記原料組成物の有効成分の全量に対して0.1質量%以上含有するものであり、
前記硬化性接着剤層のゲル分率が10質量%以上である、接着シート。
(A)成分:反応性官能基を有するバインダー樹脂
(B)成分:前記(A)成分と反応し得る架橋剤 An adhesive sheet having a curable adhesive layer,
The raw material composition of the curable adhesive layer contains the following components (A) and (B), and the amount of component (B) is 0.1 mass based on the total amount of active ingredients in the raw material composition. % or more,
The adhesive sheet, wherein the curable adhesive layer has a gel fraction of 10% by mass or more.
(A) component: binder resin having a reactive functional group (B) component: cross-linking agent capable of reacting with component (A) - 前記(A)成分が、ポリオレフィン系樹脂である、請求項1に記載の接着シート。 The adhesive sheet according to claim 1, wherein the component (A) is a polyolefin resin.
- 前記(A)成分が、酸変性樹脂である、請求項1又は2に記載の接着シート。 The adhesive sheet according to claim 1 or 2, wherein the component (A) is an acid-modified resin.
- 前記(B)成分が、イソシアヌレート骨格を有する化合物である、請求項1~3のいずれかに記載の接着シート。 The adhesive sheet according to any one of claims 1 to 3, wherein the component (B) is a compound having an isocyanurate skeleton.
- 前記(B)成分が、イソシアネート基を2以上有する化合物である、請求項1~4のいずれかに記載の接着シート。 The adhesive sheet according to any one of claims 1 to 4, wherein the component (B) is a compound having two or more isocyanate groups.
- 前記硬化性接着剤層が、さらに下記(C)成分を含有する原料組成物から形成された層である、請求項1~5のいずれかに記載の接着シート。
(C)成分:25℃で液体である非芳香族の硬化性化合物 The adhesive sheet according to any one of claims 1 to 5, wherein the curable adhesive layer is a layer formed from a raw material composition further containing component (C) below.
Component (C): A non-aromatic curable compound that is liquid at 25°C - 前記(C)成分が、末端に二重結合を有する炭化水素基を2以上有する化合物である、請求項6に記載の接着シート。 The adhesive sheet according to claim 6, wherein the component (C) is a compound having two or more hydrocarbon groups with double bonds at their ends.
- 前記硬化性接着剤層が、さらに下記(D)成分を含有する原料組成物から形成された層である、請求項1~7のいずれかに記載の接着シート。
(D)成分:反応性官能基を有するポリフェニレンエーテル樹脂 The adhesive sheet according to any one of claims 1 to 7, wherein the curable adhesive layer is a layer formed from a raw material composition further containing component (D) below.
(D) component: polyphenylene ether resin having a reactive functional group - 前記硬化性接着剤層が、さらに下記(E)成分を含有する原料組成物から形成された層である、請求項1~8のいずれかに記載の接着シート。
(E)成分:カチオン重合開始剤 The adhesive sheet according to any one of claims 1 to 8, wherein the curable adhesive layer is a layer formed from a raw material composition further containing component (E) below.
(E) component: cationic polymerization initiator - 前記硬化性接着剤層の23℃、周波数1GHzにおける誘電正接が0.005未満である、請求項1~9のいずれかに記載の接着シート。 The adhesive sheet according to any one of claims 1 to 9, wherein the curable adhesive layer has a dielectric loss tangent of less than 0.005 at 23°C and a frequency of 1 GHz.
- 前記硬化性接着剤層の23℃、周波数1GHzにおける誘電率が3.00以下である、請求項1~10のいずれかに記載の接着シート。 The adhesive sheet according to any one of claims 1 to 10, wherein the curable adhesive layer has a dielectric constant of 3.00 or less at 23°C and a frequency of 1 GHz.
- 前記硬化性接着剤層が、160℃、1時間の条件で硬化させた後にゲル分率が50質量%以上の硬化物を与えるものである、請求項1~11のいずれかに記載の接着シート。 The adhesive sheet according to any one of claims 1 to 11, wherein the curable adhesive layer gives a cured product having a gel fraction of 50% by mass or more after curing at 160°C for 1 hour. .
- 電子デバイスに用いられる、請求項1~12のいずれかに記載の接着シート。 The adhesive sheet according to any one of claims 1 to 12, which is used for electronic devices.
- カバーレイフィルムに用いられる、請求項1~12のいずれかに記載の接着シート。
The adhesive sheet according to any one of claims 1 to 12, which is used for a coverlay film.
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JP2018035226A (en) * | 2016-08-30 | 2018-03-08 | リンテック株式会社 | Adhesive composition, and adhesive sheet |
JP2018173549A (en) * | 2017-03-31 | 2018-11-08 | リンテック株式会社 | Adhesive composition, adhesive, adhesive sheet, and display body |
JP2020029557A (en) * | 2018-08-21 | 2020-02-27 | 東洋紡株式会社 | Adhesive composition, laminate, and packaging material for lithium ion battery |
WO2021045125A1 (en) * | 2019-09-06 | 2021-03-11 | 東洋紡株式会社 | Polyolefin-based adhesive composition |
JP2021161130A (en) * | 2020-03-30 | 2021-10-11 | 東洋紡株式会社 | Dimer diol-copolymerized polyimide urethane resin and adhesive composition containing the resin |
JP2022053533A (en) * | 2020-09-24 | 2022-04-05 | 三菱ケミカル株式会社 | Adhesive composition, adhesive, and adhesive layer |
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JPWO2022210672A1 (en) | 2022-10-06 |
CN117098822A (en) | 2023-11-21 |
TW202300607A (en) | 2023-01-01 |
KR20230161422A (en) | 2023-11-27 |
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