JP6353306B2 - RESIN COMPOSITION FOR OPTICAL SHEET-TYPE ADHESIVE CONTAINING POLYMER EPOXY RESIN, ADHESIVE FOR OPTICAL SHEET COMPRISING THE COMPOSITION, AND CURED PRODUCT THEREOF, AND METHOD FOR PRODUCING POLYMER EPOXY RESIN USED FOR THE COMPOSITION - Google Patents
RESIN COMPOSITION FOR OPTICAL SHEET-TYPE ADHESIVE CONTAINING POLYMER EPOXY RESIN, ADHESIVE FOR OPTICAL SHEET COMPRISING THE COMPOSITION, AND CURED PRODUCT THEREOF, AND METHOD FOR PRODUCING POLYMER EPOXY RESIN USED FOR THE COMPOSITION Download PDFInfo
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- JP6353306B2 JP6353306B2 JP2014147867A JP2014147867A JP6353306B2 JP 6353306 B2 JP6353306 B2 JP 6353306B2 JP 2014147867 A JP2014147867 A JP 2014147867A JP 2014147867 A JP2014147867 A JP 2014147867A JP 6353306 B2 JP6353306 B2 JP 6353306B2
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- Prior art keywords
- epoxy resin
- bisphenol
- resin
- sheet
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003822 epoxy resin Substances 0.000 title claims description 158
- 229920000647 polyepoxide Polymers 0.000 title claims description 158
- 239000000853 adhesive Substances 0.000 title claims description 62
- 230000001070 adhesive effect Effects 0.000 title claims description 61
- 239000011342 resin composition Substances 0.000 title claims description 61
- 229920000642 polymer Polymers 0.000 title claims description 47
- 230000003287 optical effect Effects 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000000203 mixture Substances 0.000 title description 22
- -1 phenol compound Chemical class 0.000 claims description 82
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 75
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 71
- 238000006243 chemical reaction Methods 0.000 claims description 62
- 239000007810 chemical reaction solvent Substances 0.000 claims description 52
- 229920005989 resin Polymers 0.000 claims description 47
- 239000011347 resin Substances 0.000 claims description 47
- 239000002966 varnish Substances 0.000 claims description 40
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 35
- 239000003054 catalyst Substances 0.000 claims description 26
- 239000004593 Epoxy Substances 0.000 claims description 23
- 230000001588 bifunctional effect Effects 0.000 claims description 21
- 238000009835 boiling Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000005227 gel permeation chromatography Methods 0.000 claims description 11
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 11
- 238000002834 transmittance Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 6
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000007870 radical polymerization initiator Substances 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 50
- 239000007787 solid Substances 0.000 description 29
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 23
- 230000015572 biosynthetic process Effects 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 21
- 238000001723 curing Methods 0.000 description 18
- 125000003700 epoxy group Chemical group 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- 229920003986 novolac Polymers 0.000 description 13
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 6
- 238000004040 coloring Methods 0.000 description 6
- SLAFUPJSGFVWPP-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 SLAFUPJSGFVWPP-UHFFFAOYSA-M 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- XFZJGFIKQCCLGK-UHFFFAOYSA-M 1,1-dimethyl-4-phenylpiperazinium iodide Chemical compound [I-].C1C[N+](C)(C)CCN1C1=CC=CC=C1 XFZJGFIKQCCLGK-UHFFFAOYSA-M 0.000 description 5
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 150000002460 imidazoles Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000006839 xylylene group Chemical group 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical class CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical class CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical class CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- IKWKJIWDLVYZIY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 IKWKJIWDLVYZIY-UHFFFAOYSA-M 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 150000001896 cresols Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- 235000010292 orthophenyl phenol Nutrition 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000013008 thixotropic agent Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical class C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- OLQWMCSSZKNOLQ-ZXZARUISSA-N (3s)-3-[(3r)-2,5-dioxooxolan-3-yl]oxolane-2,5-dione Chemical compound O=C1OC(=O)C[C@H]1[C@@H]1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-ZXZARUISSA-N 0.000 description 1
- RUEBPOOTFCZRBC-UHFFFAOYSA-N (5-methyl-2-phenyl-1h-imidazol-4-yl)methanol Chemical compound OCC1=C(C)NC(C=2C=CC=CC=2)=N1 RUEBPOOTFCZRBC-UHFFFAOYSA-N 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- FWHUTKPMCKSUCV-UHFFFAOYSA-N 1,3-dioxo-3a,4,5,6,7,7a-hexahydro-2-benzofuran-5-carboxylic acid Chemical compound C1C(C(=O)O)CCC2C(=O)OC(=O)C12 FWHUTKPMCKSUCV-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- RUFZNDNBXKOZQV-UHFFFAOYSA-N 2,3-dihydro-1h-pyrrolo[1,2-a]benzimidazole Chemical compound C1=CC=C2N(CCC3)C3=NC2=C1 RUFZNDNBXKOZQV-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- QXSNXUCNBZLVFM-UHFFFAOYSA-N 2-methyl-1h-imidazole;1,3,5-triazinane-2,4,6-trione Chemical compound CC1=NC=CN1.O=C1NC(=O)NC(=O)N1 QXSNXUCNBZLVFM-UHFFFAOYSA-N 0.000 description 1
- VWSLLSXLURJCDF-UHFFFAOYSA-N 2-methyl-4,5-dihydro-1h-imidazole Chemical compound CC1=NCCN1 VWSLLSXLURJCDF-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- RJIQELZAIWFNTQ-UHFFFAOYSA-N 2-phenyl-1h-imidazole;1,3,5-triazinane-2,4,6-trione Chemical compound O=C1NC(=O)NC(=O)N1.C1=CNC(C=2C=CC=CC=2)=N1 RJIQELZAIWFNTQ-UHFFFAOYSA-N 0.000 description 1
- BKCCAYLNRIRKDJ-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1h-imidazole Chemical compound N1CCN=C1C1=CC=CC=C1 BKCCAYLNRIRKDJ-UHFFFAOYSA-N 0.000 description 1
- ZDZYGYFHTPFREM-UHFFFAOYSA-N 3-[3-aminopropyl(dimethoxy)silyl]oxypropan-1-amine Chemical compound NCCC[Si](OC)(OC)OCCCN ZDZYGYFHTPFREM-UHFFFAOYSA-N 0.000 description 1
- ZLAOXGYWRBSWOY-UHFFFAOYSA-N 3-chloropropyl(methoxy)silane Chemical compound CO[SiH2]CCCCl ZLAOXGYWRBSWOY-UHFFFAOYSA-N 0.000 description 1
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- 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
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Landscapes
- Adhesive Tapes (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、タッチパネルの貼り合せに等に使用する、光学シート状接着剤用高分子エポキシ樹脂組成物、該組成物よりなる光学シート用接着剤、及びその硬化物、並びに、前記組成物に使用する高分子エポキシ樹脂の製造方法に関する。 The present invention is used for bonding a touch panel, etc., a polymer epoxy resin composition for an optical sheet adhesive, an optical sheet adhesive comprising the composition, and a cured product thereof, and used for the composition The present invention relates to a method for producing a polymer epoxy resin.
タッチパネルの貼り合せに使用する接着剤には、従来、液状硬化性樹脂（特許文献１）や光学用両面テープ（ＯＣＡ）（特許文献２）が使用されている。しかし、液状硬化性樹脂では気泡の混入や接着剤のはみ出しが起こり、その問題を解決するためにダム材を形成する方法も試されているが工程が増えてしまうため、生産性が落ちてしまい、好ましくない（特許文献３）。またＯＣＡは作業が容易で生産性は高いものの、貼り合せ面の段差に追従できない、接着力が弱く信頼性が得られないといった問題があった。そこで、これらの問題を解決するため、液状硬化性樹脂や光学用両面テープの特性を併せ持つ、硬化性シート状接着剤が近年考えられている。 Conventionally, liquid curable resin (patent document 1) and optical double-sided tape (OCA) (patent document 2) are used for the adhesive used for bonding of a touch panel. However, in liquid curable resins, air bubbles are mixed in and the adhesive sticks out, and a method of forming a dam material has been tried to solve the problem, but the number of steps increases, so productivity decreases. This is not preferable (Patent Document 3). In addition, although OCA is easy to work and has high productivity, there are problems that it cannot follow the steps on the bonding surface, has poor adhesive strength, and cannot provide reliability. Therefore, in order to solve these problems, a curable sheet-like adhesive having characteristics of a liquid curable resin and an optical double-sided tape has been recently considered.
硬化性シート状接着剤は、硬化性の接着剤であるが、常温では固体シート状であり、加熱溶融することで流動し、硬化に至る接着剤である。この硬化性シート状接着剤はエポキシ樹脂やアクリル酸エステル樹脂等の硬化性樹脂成分と自己造膜性のあるポリマー成分から構成されている。 The curable sheet adhesive is a curable adhesive, but is a solid sheet at room temperature, and is an adhesive that flows when heated and melted to reach curing. This curable sheet adhesive is composed of a curable resin component such as an epoxy resin or an acrylate resin and a polymer component having a self-forming property.
一方、高分子エポキシ樹脂は自己造膜性、他樹脂との相溶性の点からシート状樹脂組成物に多く使用されている。また高分子エポキシ樹脂は、分子鎖中に極性基の水酸基を含有しており基板との密着性に優れることから、種々の接着剤に使用されている。しかし、これまでは、高分子エポキシ樹脂は、その高い絶縁性等から層間絶縁膜等の電子材料分野（特許文献４）や塗料（特許文献５）に使用されるのみであり、これまで透明性は重視されていなかった。 On the other hand, polymeric epoxy resins are often used in sheet-like resin compositions from the viewpoint of self-forming properties and compatibility with other resins. In addition, the polymer epoxy resin contains a polar hydroxyl group in the molecular chain and is excellent in adhesion to the substrate, and is therefore used in various adhesives. However, until now, polymer epoxy resins have only been used in the field of electronic materials (Patent Document 4) and paints (Patent Document 5) such as an interlayer insulating film because of their high insulating properties and the like. Was not valued.
高分子エポキシ樹脂を光学シート状接着剤に使用する場合、一般的にビスフェノールＡ型高分子エポキシ樹脂は、透明性が高く光学材料に適しているが、樹脂粘度が高く、エポキシ樹脂組成物を得る際に、ハンドリング性が悪いという問題があった。また粘度を下げるために、ビスフェノールＦ型高分子エポキシ樹脂を使用することもできるが、ビスフェノールＦ型高分子エポキシ樹脂は着色しており、透過率が低いという問題があった。 When a polymer epoxy resin is used for an optical sheet adhesive, generally a bisphenol A type polymer epoxy resin is highly transparent and suitable for an optical material, but has a high resin viscosity and an epoxy resin composition is obtained. However, there was a problem of poor handling. In order to lower the viscosity, a bisphenol F type polymer epoxy resin can be used, but the bisphenol F type polymer epoxy resin is colored and has a problem of low transmittance.
配合割合を増しても成形時のハンドリング性が良好で、かつフィルム性やシート成形能が良い、光学特性に優れた光学シート状接着剤に好適な高分子エポキシ樹脂を含む比較的粘度の低い樹脂組成物を提供することを目的とする。 Resin having a relatively low viscosity, including a polymer epoxy resin suitable for optical sheet adhesives with excellent optical properties and excellent handling properties during molding, good film properties and sheet molding ability even when the blending ratio is increased An object is to provide a composition.
本発明者らは、鋭意検討の結果、特定の条件下、特定の触媒を用いて合成したビスフェノールＡ骨格とビスフェノールＦ骨格とを特定の割合で含む高分子エポキシ樹脂を含む樹脂組成物が前記課題を解決することを見出し、本発明を完成させた。
即ち、本発明の要旨は２官能エポキシ樹脂（ａ）と２価フェノール化合物（ｂ）とを反応して得られる高分子エポキシ樹脂と硬化性樹脂成分とを含む透明なシート状接着剤用樹脂組成物であって、
該２官能エポキシ樹脂（ａ）はエポキシ当量が１７０〜２００ｇ／ｅｑ．のビスフェノールＡ型エポキシ樹脂及び／又はエポキシ当量が１５０〜１８０ｇ／ｅｑ．のビスフェノールＦ型エポキシ樹脂であり、
該２価フェノール化合物（ｂ）はビスフェノールＡ及び／又はビスフェノールＦであり、
該高分子エポキシ樹脂は下記一般式（１）で表され、
As a result of intensive studies, the present inventors have developed a resin composition containing a polymer epoxy resin containing a bisphenol A skeleton and a bisphenol F skeleton synthesized using a specific catalyst at a specific ratio under specific conditions. The present invention has been completed.
That is, the gist of the present invention is a transparent resin composition for a sheet-like adhesive comprising a polymer epoxy resin obtained by reacting a bifunctional epoxy resin (a) and a divalent phenol compound (b) and a curable resin component. A thing,
The bifunctional epoxy resin (a) has an epoxy equivalent of 170 to 200 g / eq. Bisphenol A type epoxy resin and / or epoxy equivalent of 150 to 180 g / eq. Bisphenol F type epoxy resin,
The dihydric phenol compound (b) is bisphenol A and / or bisphenol F,
The polymer epoxy resin is represented by the following general formula (1):
高分子エポキシ樹脂中の（Ｅ）及び（Ｐ）の合計モルに対して、ビスフェノールＦ型エポキシ樹脂の骨格残基及びビスフェノールＦの骨格残基の合計モルが３５〜５５モル％の範囲であり、メチルエチルケトンの５０質量％ワニスのハーゼン単位色相が５０以下であることを特徴とする透明なシート状接着剤用樹脂組成物である。
The total mole of the skeletal residue of the bisphenol F type epoxy resin and the skeletal residue of bisphenol F is in the range of 35 to 55 mol% with respect to the total mole of (E) and (P) in the polymer epoxy resin, A transparent resin composition for sheet-like adhesives, wherein the Hazen unit hue of 50% by mass of varnish of methyl ethyl ketone is 50 or less.
本発明に係る高分子エポキシ樹脂を含む光学シート状接着剤用樹脂組成物は比較的粘度の低い樹脂組成物なので、成形時のハンドリング性が良好でフィルムやシートの成形能が良好で、光学特性に優れた光学シート状接着剤に好適な高分子エポキシ樹脂を含有する透明なシート状接着剤用樹脂組成物である。 Since the resin composition for an optical sheet adhesive containing the polymer epoxy resin according to the present invention is a resin composition having a relatively low viscosity, the handling property at the time of molding is good, the molding ability of the film or sheet is good, and the optical characteristics It is a transparent resin composition for sheet-like adhesives containing a polymer epoxy resin suitable for an optical sheet-like adhesive excellent in.
以下、本発明を詳述する。 The present invention is described in detail below.
すなわち、本発明は、
２官能エポキシ樹脂（ａ）と２価フェノール化合物（ｂ）とを反応して得られる高分子エポキシ樹脂を含む透明なシート状接着剤用樹脂組成物であって、その高分子エポキシ樹脂が
エポキシ当量１７０〜２００ｇ／ｅｑ．のビスフェノールＡ型エキシ樹脂及び／又はエポキシ当量１５０〜１８０ｇ／ｅｑ．のビスフェノールＦ型エポキシ樹脂である２官能エポキシ樹脂（ａ）と
ビスフェノールＡ及び／又はビスフェノールＦである２価フェノール化合物（ｂ）とを、（ａ）／（ｂ）＝１．００１／１〜１．１／１のモル比で用い、
反応触媒として４級ホスホニウム塩類化合物、及び／又はホスフィン類化合物を用い、
反応溶媒として沸点が１００℃以上であり、かつ２０℃での蒸気圧が０．６ｋＰａ以上である有機溶剤を
総仕込み量に対して３〜７０質量％用いて、
１２０〜１６５℃の反応温度で反応させて得られ、
かつ、高分子エポキシ樹脂中のビスフェノールＦの骨格が全骨格に対して３５〜５５モル％であり、
メチルエチルケトンの５０質量％ワニスのハーゼン単位色相が５０以下
であることを特徴とする透明なシート状接着剤用樹脂組成物である。
That is, the present invention
A transparent resin composition for a sheet-like adhesive containing a polymer epoxy resin obtained by reacting a bifunctional epoxy resin (a) with a divalent phenol compound (b), the polymer epoxy resin having an epoxy equivalent 170-200 g / eq. Bisphenol A type exci resin and / or epoxy equivalent of 150 to 180 g / eq. A bifunctional epoxy resin (a) which is a bisphenol F type epoxy resin and a dihydric phenol compound (b) which is bisphenol A and / or bisphenol F, (a) / (b) = 1.0001 / 1 Used in a 1/1 molar ratio,
Quaternary phosphonium salts compound as a reaction catalyst, and / or phosphines compound employed,
An organic solvent having a boiling point of 100 ° C. or higher as a reaction solvent and a vapor pressure at 20 ° C. of 0.6 kPa or higher is used in an amount of 3 to 70% by mass with respect to the total charged amount,
Obtained by reacting at a reaction temperature of 120-165 ° C.,
And the skeleton of bisphenol F in the polymer epoxy resin is 35 to 55 mol% with respect to the total skeleton,
A transparent resin composition for sheet-like adhesives, wherein the Hazen unit hue of 50% by mass of varnish of methyl ethyl ketone is 50 or less.
前記２官能エポキシ樹脂（ａ）が、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）によるｎ＝０成分が９６面積％以上あるビスフェノールＡ型エポキシ樹脂を５０〜１００質量％含有している２官能エポキシ樹脂が好ましい。
前記２価フェノール化合物（ｂ）が、ＧＰＣによる二核体純度が９６面積％以上のビスフェノールＦを５０〜１００質量％含有している２価フェノール化合物が好ましい。
The bifunctional epoxy resin (a) is preferably a bifunctional epoxy resin containing 50 to 100% by mass of a bisphenol A type epoxy resin in which n = 0 component by gel permeation chromatography (GPC) is 96 area% or more. .
The divalent phenol compound (b) is preferably a divalent phenol compound containing 50 to 100% by mass of bisphenol F having a dinuclear purity of 96 area% or more by GPC.
また本発明は、前記透明なシート状接着剤用樹脂組成物から得られる硬化物である。
前記硬化物は、厚み１ｍｍの硬化物の波長４００ｎｍにおける透過率が８０％以上であり、黄色度（ＹＩ）が５以下であることは好ましい。
Moreover, this invention is the hardened | cured material obtained from the said resin composition for sheet-like adhesive agents.
The cured product preferably has a transmittance of 80% or more at a wavelength of 400 nm of a cured product having a thickness of 1 mm and a yellowness (YI) of 5 or less.
また本発明は、前記の透明なシート状接着剤用樹脂組成物から得られるシート状硬化性樹脂組成物であり、シート状接着剤である。 Moreover, this invention is a sheet-like curable resin composition obtained from the said transparent resin composition for sheet-like adhesives, and is a sheet-like adhesive.
また本発明は、前記透明なシート状接着剤用樹脂組成物に適する高分子エポキシ樹脂の製造方法である。 Moreover, this invention is a manufacturing method of the polymeric epoxy resin suitable for the said resin composition for sheet-like adhesives.
本発明の透明なシート状接着剤用樹脂組成物に適する前記高分子量エポキシ樹脂は、前記２官能エポキシ樹脂（ａ）と前記２価フェノール化合物（ｂ）とで反応を行う場合のモル比は、（ａ）／（ｂ）＝１．００１／１〜１．１／１であり、好ましくは１．００５〜１．０８であり、さらに好ましくは１．０１〜１．０６である。前記２官能エポキシ樹脂（ａ）と前記２価フェノール化合物（ｂ）のモル比を１．００１／１より小さく、又は１．１／１より大きくすると、フェノール基又はエポキシ基が過剰となり高分子量エポキシ樹脂が得られない。 The high molecular weight epoxy resin suitable for the transparent sheet-like adhesive resin composition of the present invention has a molar ratio when the bifunctional epoxy resin (a) and the dihydric phenol compound (b) are reacted. (A) / (b) = 1.001 / 1 to 1.1 / 1, preferably 1.005 to 1.08, and more preferably 1.01 to 1.06. When the molar ratio of the bifunctional epoxy resin (a) and the dihydric phenol compound (b) is smaller than 1.001 / 1 or larger than 1.1 / 1, the phenol group or epoxy group becomes excessive and the high molecular weight epoxy. Resin is not obtained.
前記２官能エポキシ樹脂（ａ）として、エポキシ当量が１７０〜２００ｇ／ｅｑ．のビスフェノールＡ型エポキシ樹脂及び／又はエポキシ当量が１５０〜１８０ｇ／ｅｑ．のビスフェノールＦ型エポキシ樹脂を使用することができる。ここでエポキシ当量とは１グラム当量のエポキシ基を含む樹脂のグラム数（ｇ／ｅｑ．）であり、ＪＩＳ Ｋ ７２３６に規定された方法に従って測定されるものである。これらのエポキシ当量は、前記のエポキシ当量範囲以下では不純物を多く含むため好ましくなく、この範囲以上では前記高分子量エポキシ樹脂が得られないため好ましくない。 As said bifunctional epoxy resin (a), epoxy equivalent is 170-200 g / eq. Bisphenol A type epoxy resin and / or epoxy equivalent of 150 to 180 g / eq. Bisphenol F type epoxy resin can be used. Here, the epoxy equivalent is the number of grams (g / eq.) Of a resin containing 1 gram equivalent of an epoxy group, and is measured according to the method defined in JIS K 7236. These epoxy equivalents are not preferred because they contain a large amount of impurities below the epoxy equivalent range, and are not preferred above the range because the high molecular weight epoxy resin cannot be obtained.
また前記２官能エポキシ樹脂（ａ）は、ビスフェノールＡとエピクロルヒドリンを反応させることで得られ、ＧＰＣによるｎ＝０成分が９６面積％以上であり、エポキシ当量１７０〜２００ｇ／ｅｑ．であるビスフェノールＡ型エポキシ樹脂を５０〜１００質量％含んでいることが好ましい。ｎ＝０成分を９６面積％以下含むビスフェノールＡを５０質量％以上含むと、前記高分子エポキシ樹脂中のビスフェノールＡ骨格の占める割合が増え、樹脂粘度が大きくなりすぎる恐れがある。り、またｎ＝０成分を９６面積％以下含むビスフェノールＡを５０質量％未満、即ちビスフェノールＦ型エポキシ樹脂を５０質量％以上含むと、着色が激しくなる恐れがある。 Moreover, the said bifunctional epoxy resin (a) is obtained by making bisphenol A and epichlorohydrin react, n = 0 component by GPC is 96 area% or more, and epoxy equivalent 170-200 g / eq. It is preferable that 50-100 mass% of bisphenol A type epoxy resins which are these are included. When 50 mass% or more of bisphenol A containing n = 0 component of 96 area% or less is contained, the proportion of the bisphenol A skeleton in the polymer epoxy resin increases, and the resin viscosity may be too high. Further, when the content of bisphenol A containing n = 0 component is less than 50% by mass, that is, when the content of bisphenol F-type epoxy resin is 50% by mass or more, coloring may be intense.
前記２価フェノール化合物（ｂ）として、ビスフェノールＡ又はビスフェノールＦを使用することもできるが、得られた前記高分子エポキシ樹脂のビスフェノールＦの骨格が全骨格に対して３５〜５５モル％である必要がある。これは、３５モル％より小さいと、フィルム性を持つ分子量まで高分子量化した際、ビスフェノールＡ骨格の増加により粘度が高くなってしまい、工業生産が可能な範囲にワニス化した場合、ろ過に時間がかかる、シートを得る際には膜厚の制御が難しい、溶剤の除去が難しい等、生産性や利便性に欠けるものになる。具体的には、不揮発分が５０質量％の２５℃でのワニス粘度は、１５０００ｍＰａ・ｓ以下が好ましく、１００００ｍＰａ・ｓ以下がより好ましい。また５５モル％以上までビスフェノールＦ骨格を増やしてしまうと、ビスフェノールＦ骨格由来の着色が起こる恐れがある。 Bisphenol A or bisphenol F may be used as the divalent phenol compound (b), but the bisphenol F skeleton of the obtained polymer epoxy resin should be 35 to 55 mol% based on the total skeleton. There is. If the molecular weight is less than 35 mol%, when the molecular weight is increased to a molecular weight having film properties, the viscosity increases due to an increase in the bisphenol A skeleton, and when the varnish is converted into a range that allows industrial production, it takes time for filtration. However, when obtaining a sheet, it is difficult to control the film thickness, it is difficult to remove the solvent, and the productivity and convenience are lacking. Specifically, the varnish viscosity at 25 ° C. with a nonvolatile content of 50% by mass is preferably 15000 mPa · s or less, and more preferably 10000 mPa · s or less. Further, when the bisphenol F skeleton is increased to 55 mol% or more, there is a possibility that coloring derived from the bisphenol F skeleton occurs.
本発明の透明なシート状接着剤用樹脂組成物に含まれる前記高分子エポキシ樹脂は、典型的には下記一般式（１）で表わされる。この時、（Ｅ）は原料エポキシ樹脂由来の骨格残基であり、（Ｐ）は原料フェノール化合物由来の骨格残基である。前記高分子エポキシ樹脂中の（Ｅ）及び（Ｐ）の合計モルに対し、ビスフェノールＦ型エポキシ樹脂の骨格残基及びビスフェノールＦの骨格残基の合計モルが３５〜５５モル％の範囲である必要がある。 The polymer epoxy resin contained in the transparent resin composition for sheet adhesive of the present invention is typically represented by the following general formula (1). At this time, (E) is a skeleton residue derived from the raw material epoxy resin, and (P) is a skeleton residue derived from the raw material phenol compound. The total mole of the skeletal residue of bisphenol F type epoxy resin and the skeletal residue of bisphenol F needs to be in the range of 35 to 55 mol% with respect to the total mole of (E) and (P) in the polymer epoxy resin. There is.
また前記２価フェノール化合物（ｂ）は、ＧＰＣによる二核体純度が９６面積％以上のビスフェノールＦを５０〜１００質量％含有している。二核体純度が９６面積％以下のビスフェノールＦを５０質量％以上含有した場合、ゲル化を引き起こし、前記高分子量エポキシ樹脂が得られない恐れがある。 Moreover, the said bivalent phenol compound (b) contains 50-100 mass% of bisphenol F whose binuclear purity by GPC is 96 area% or more. When the bisphenol F having a binuclear purity of 96 area% or less is contained in an amount of 50% by mass or more, gelation is caused and the high molecular weight epoxy resin may not be obtained.
本発明の透明なシート状接着剤用樹脂組成物に適した前記高分子エポキシ樹脂の製造時の反応温度は、１２０〜１６５℃であり、好ましくは１３０〜１６０℃であり、より好ましくは１３５〜１５５℃である。高分子エポキシ樹脂の製造に使用可能な反応溶媒は、反応温度を維持できる必要がある。 The reaction temperature during the production of the polymer epoxy resin suitable for the transparent resin composition for sheet-like adhesive of the present invention is 120 to 165 ° C, preferably 130 to 160 ° C, more preferably 135 to 135 ° C. 155 ° C. The reaction solvent that can be used for the production of the polymer epoxy resin must be able to maintain the reaction temperature.
そのため、前記反応溶媒の沸点は、１００℃以上であり、好ましくは１００〜１６５℃であり、より好ましくは１１０〜１６０℃であり、さらに好ましくは１２０〜１５５℃であり、反応時の還流温度を１３５℃以上で維持できる有機溶剤が特に好ましい。沸点が１００℃未満の反応溶媒は、反応系中を撹拌可能な粘度まで下げるために十分な量を加えた場合に、還流が低温で起こり、有用な触媒の活性温度まで反応系中の温度を上げる事ができない恐れがあり好ましくない。なお、反応温度を維持できればよいので沸点の上限は特に決める必要はない。 Therefore, the boiling point of the reaction solvent is 100 ° C. or more, preferably 100 to 165 ° C., more preferably 110 to 160 ° C., further preferably 120 to 155 ° C., and the reflux temperature during the reaction is An organic solvent that can be maintained at 135 ° C. or higher is particularly preferable. A reaction solvent having a boiling point of less than 100 ° C., when added in an amount sufficient to lower the viscosity of the reaction system to a stirrable viscosity, reflux occurs at a low temperature, and the temperature in the reaction system is increased to the activation temperature of a useful catalyst. There is a possibility that it cannot be raised. Note that the upper limit of the boiling point need not be determined as long as the reaction temperature can be maintained.
また前記反応溶媒の２０℃での蒸気圧は０．６ｋＰａ以上であり、好ましくは０．６〜５ｋＰａであり、より好ましくは１〜４ｋＰａであり、さらに好ましくは１．５〜３ｋＰａである。２０℃での蒸気圧が０．６ｋＰａ未満の反応溶媒は、シート状の樹脂組成物を得る際に反応溶媒が残ってしまいボイドの発生や異臭の原因になる恐れがあり好ましくない。なお、２０℃での蒸気圧が大きくなると沸点で下がり、沸点の下限値よって自動的に値が定まるため２０℃での蒸気圧の上限値は特に決める必要はない。 The vapor pressure of the reaction solvent at 20 ° C. is 0.6 kPa or more, preferably 0.6 to 5 kPa, more preferably 1 to 4 kPa, and further preferably 1.5 to 3 kPa. A reaction solvent having a vapor pressure of less than 0.6 kPa at 20 ° C. is not preferable because the reaction solvent remains when a sheet-shaped resin composition is obtained, which may cause generation of voids or a strange odor. Note that when the vapor pressure at 20 ° C. increases, the boiling point decreases, and the value is automatically determined by the lower limit value of the boiling point. Therefore, the upper limit value of the vapor pressure at 20 ° C. need not be determined.
前記反応溶媒を具体的に例示すれば、プロピレングリコールモノメチルエーテルアセテート、シクロペンタノン、ジブチルエーテル、ジイソプロピルケトン、メチルイソブチルケトン、キシレン、トルエン等が挙げられるが、特にこれらに限定されるものではない。またこれらの反応溶媒を単独又は混合して用いることができる。 Specific examples of the reaction solvent include propylene glycol monomethyl ether acetate, cyclopentanone, dibutyl ether, diisopropyl ketone, methyl isobutyl ketone, xylene, and toluene, but are not particularly limited thereto. These reaction solvents can be used alone or in combination.
また前記反応溶媒の使用量は、総仕込み量に対して３〜７０質量％、好ましくは４〜６０質量％、さらに好ましくは５〜５０質量％である。前記反応溶媒が３質量％以下では反応時の粘度が高くなり、均一な撹拌ができなくなる恐れや反応発熱の制御ができなくなる恐れがある。また前記反応溶媒が７０質量％以上ではモノマー濃度が薄くなり、反応速度が極端に低下し反応時間が増大する恐れや目的の分子量まで反応が進まず前記高分子量エポキシ樹脂が得られない恐れがある。 Moreover, the usage-amount of the said reaction solvent is 3-70 mass% with respect to the total preparation amount, Preferably it is 4-60 mass%, More preferably, it is 5-50 mass%. If the reaction solvent is 3% by mass or less, the viscosity at the time of reaction becomes high, and there is a fear that uniform stirring cannot be performed and the reaction exotherm cannot be controlled. On the other hand, if the reaction solvent is 70% by mass or more, the monomer concentration becomes thin, the reaction rate may be extremely lowered and the reaction time may be increased, or the reaction may not proceed to the target molecular weight and the high molecular weight epoxy resin may not be obtained. .
また前記高分子エポキシ樹脂の製造で使用可能な反応触媒は、前記４級ホスホニウム塩類化合物、又は前記ホスフィン類化合物である。一般的に高分子エポキシ樹脂を得るための反応触媒としては、前記４級アンモニウム塩類化合物、前記４級ホスホニウム塩類化合物、又は前記ホスフィン類化合物以外にも、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物類；トリエチルアミン、ベンジルジメチルアミン、１，８−ジアザビシクロ（５．４．０）ウンデセン−１（ＤＢＵ）等の第３級アミン類化合物；２−メチルイミダゾール、２−エチル−４−メチルイミダゾール等のイミダゾール類化合物等も知られている。しかしながら、アルカリ金属水酸化物類や第３級アミン類化合物を使用した場合、着色が起こりやすく、イミダゾール類化合物を使用した場合は反応が速く制御が難しいため好ましくない。光学特性に優れる高分子エポキシ樹脂を得るためには、着色が起こり難く、触媒活性も高い４級アンモニウム塩類化合物、４級ホスホニウム塩類化合物又はホスフィン類化合物が好ましく、４級ホスホニウム塩類化合物又はホスフィン類化合物がさらに好ましい。 The reaction catalyst that can be used in the production of the polymer epoxy resin is the quaternary phosphonium salt compound or the phosphine compound. In general, as a reaction catalyst for obtaining a polymer epoxy resin, an alkali metal such as sodium hydroxide or potassium hydroxide is used in addition to the quaternary ammonium salt compound, the quaternary phosphonium salt compound, or the phosphine compound. Hydroxides; tertiary amine compounds such as triethylamine, benzyldimethylamine, 1,8-diazabicyclo (5.4.0) undecene-1 (DBU); 2-methylimidazole, 2-ethyl-4-methyl Imidazole compounds such as imidazole are also known. However, when alkali metal hydroxides or tertiary amine compounds are used, coloring is likely to occur, and when imidazole compounds are used, the reaction is fast and difficult to control, which is not preferable. In order to obtain a polymer epoxy resin having excellent optical properties, a quaternary ammonium salt compound, a quaternary phosphonium salt compound or a phosphine compound, which is hardly colored and has high catalytic activity, is preferred, and a quaternary phosphonium salt compound or a phosphine compound. Is more preferable.
前記反応触媒を具体的に例示すれば、前記４級ホスホニウム塩類化合物としては、ベンジルトリフェニルホスホニウムクロライド、ｎ−ブチルトリフェニルホスホニウムブロマイド、エチルトリフェニルホスホニウムアイオダイド、エチルトリフェニルホスホニウムブロマイド等が、前記ホスフィン類化合物としてはトリフェニルホスフィン、トリブチルホスフィン等が挙げられるが、これらに限定されるものではない。またこれらの触媒を単独又は組み合わせて用いることができる。
If specific examples of the reaction catalyst, the pre-Symbol quaternary phosphonium salts compounds, benzyl triphenyl phosphonium chloride, n- butyl triphenyl phosphonium bromide, ethyl triphenyl phosphonium iodide, and the like ethyl triphenyl phosphonium bromide, Examples of the phosphine compound include, but are not limited to, triphenylphosphine and tributylphosphine. These catalysts can be used alone or in combination.
本発明の透明なシート状接着剤用樹脂組成物に含まれる前記高分子エポキシ樹脂はメチルエチルケトン５０質量％の樹脂ワニスを作成した際に、ハーゼン単位色相が５０以下が好ましい。ハーゼン単位色相が５０より大きいと、シート状接着剤を得る際に着色が起こり、視認性を低下させる恐れがある。 The polymer epoxy resin contained in the transparent resin composition for sheet-like adhesive of the present invention preferably has a Hazen unit hue of 50 or less when a resin varnish of 50% by mass of methyl ethyl ketone is prepared. If the Hazen unit hue is greater than 50, coloring may occur when the sheet-like adhesive is obtained, and visibility may be reduced.
本発明の透明なシート状接着剤用樹脂組成物に含まれる前記高分子量エポキシ樹脂の分子量は、特に規定していないが、ＧＰＣによるポリスチレン換算の重量平均分子量が、２００００〜２０００００が好ましく、２５０００〜１８００００がより好ましく、３００００〜１６００００がさらに好ましく、３５０００〜１０００００が特に好ましい。重量平均分子量が２００００以下ではフィルム性能が発現しない恐れがあり、２０００００以上では高粘度になりやすく、ハンドリング性に欠ける恐れがある。 The molecular weight of the high molecular weight epoxy resin contained in the transparent resin composition for sheet-like adhesive of the present invention is not particularly specified, but the weight average molecular weight in terms of polystyrene by GPC is preferably 20000 to 200000, and 25000. 180000 are more preferable, 30000-16000 are more preferable, and 35000-100,000 are especially preferable. If the weight average molecular weight is 20000 or less, the film performance may not be exhibited, and if it is 200,000 or more, the viscosity tends to be high and the handling property may be lacking.
本発明の透明なシート状接着剤用樹脂組成物において、前記製造方法で得られる前記高分子エポキシ樹脂以外の成分には、硬化性樹脂成分を含む必要がある。また光学用途に使用するため、樹脂組成物をワニス化した際に、無色透明である必要がある。具体的には、ワニス化した際にハーゼン単位色相が５０以下である。ハーゼン単位色相が５０より大きいと、シートにした際に着色が起こり、タッチパネルの接着に使用した際に視認性を低下させる原因となる恐れがある。硬化性樹脂成分は、例えば、エポキシ樹脂を硬化剤で硬化させる樹脂組成、エポキシ樹脂をイミダゾール触媒で硬化させる樹脂組成、アクリル酸エステル樹脂をラジカル重合開始剤で硬化させる樹脂組成等が挙げられる。 In the transparent resin composition for sheet-like adhesive of the present invention, the components other than the polymer epoxy resin obtained by the production method need to contain a curable resin component. Moreover, since it uses for an optical use, when a resin composition is varnished, it needs to be colorless and transparent. Specifically, the Hazen unit hue is 50 or less when varnished. If the Hazen unit hue is larger than 50, coloring occurs when the sheet is formed, and this may cause a decrease in visibility when used for bonding the touch panel. Examples of the curable resin component include a resin composition for curing an epoxy resin with a curing agent, a resin composition for curing an epoxy resin with an imidazole catalyst, and a resin composition for curing an acrylate resin with a radical polymerization initiator.
透明なシート状接着剤用樹脂組成物中の前記高分子エポキシ樹脂の含有量は、前記高分子エポキシ樹脂と硬化性樹脂成分の合計量に対して、１０〜９０質量％が好ましく、２０〜７０質量％がより好ましく、３０〜５０質量％がさらに好ましい。１０質量％未満ではフィルム性能が発現しない恐れがある。また本発明の樹脂組成物を接着剤シートにする場合は、被着体の接着力を保つためには、硬化反応が起こらない温度（６０℃以下）で段差に追従するような流動性が必要だが、９０質量％以上では、十分な流動性が得られない恐れがある。 10-90 mass% is preferable with respect to the total amount of the said polymer epoxy resin and curable resin component, and, as for content of the said polymer epoxy resin in the transparent resin composition for sheet-like adhesives, 20-70. The mass% is more preferable, and 30 to 50 mass% is more preferable. If it is less than 10% by mass, the film performance may not be exhibited. In addition, when the resin composition of the present invention is used as an adhesive sheet, fluidity is required to follow a step at a temperature at which a curing reaction does not occur (60 ° C. or less) in order to maintain the adhesion of the adherend. However, if it is 90% by mass or more, sufficient fluidity may not be obtained.
前記硬化性樹脂成分としてのエポキシ樹脂を硬化剤で硬化させる組成物としては、エポキシ樹脂とアミン類化合物、エポキシ樹脂とフェノール類化合物、エポキシ樹脂と酸無水物、エポキシ樹脂とイミダゾール類化合物、又はこれらをさらに組み合わせた組成物が挙げられる。ここで使用されるエポキシ樹脂は低分子量品が好ましく、具体的にはエポキシ当量で２０００ｇ／ｅｑ．以下が好ましい。エポキシ当量が２０００ｇ／ｅｑ．より大きいと、十分な架橋密度が得られず、耐熱性に劣る恐れがある。また高粘度になりやすく樹脂ワニスにした際に十分な流動性を得る事ができず、ハンドリング性に劣る恐れがある。 Examples of the composition for curing the epoxy resin as the curable resin component with a curing agent include an epoxy resin and an amine compound, an epoxy resin and a phenol compound, an epoxy resin and an acid anhydride, an epoxy resin and an imidazole compound, or these The composition which combined these further is mentioned. The epoxy resin used here is preferably a low molecular weight product, specifically, an epoxy equivalent of 2000 g / eq. The following is preferred. Epoxy equivalent is 2000 g / eq. If it is larger, a sufficient crosslinking density cannot be obtained and the heat resistance may be inferior. Moreover, when it is easy to become a high viscosity and it is set as a resin varnish, sufficient fluidity | liquidity cannot be obtained and there exists a possibility that it may be inferior to handling property.
前記エポキシ樹脂を具体的に例示すれば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールフルオレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、ジフェニルエーテル型エポキシ樹脂等の２官能エポキシ樹脂や、ノボラック型エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、トリフェノールエタン型エポキシ樹脂、トリスフェノール型エポキシ樹脂等の多官能エポキシ樹脂や、ジシクロペンタジエン型エポキシ樹脂、シクロアルキレングリコールエポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂等を挙げることが可能であるが、これらに制限されるものではない。また本発明の透明なシート状接着剤用樹脂組成物は、１種類のエポキシ樹脂又は２種類以上のエポキシ樹脂を含有してもよい。 Specific examples of the epoxy resin include bifunctional epoxy resins such as bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, bisphenol fluorene type epoxy resin, biphenyl type epoxy resin, and diphenyl ether type epoxy resin. And polyfunctional epoxy resins such as novolac type epoxy resin, triphenolmethane type epoxy resin, triphenolethane type epoxy resin, trisphenol type epoxy resin, dicyclopentadiene type epoxy resin, cycloalkylene glycol epoxy resin, hydrogenated bisphenol A-type epoxy resin and the like can be mentioned, but are not limited thereto. Moreover, the resin composition for transparent sheet adhesives of this invention may contain 1 type of epoxy resins or 2 or more types of epoxy resins.
エポキシ樹脂の硬化剤としての前記アミン類化合物を具体的に例示すれば、１，４−ジアザビシクロ［２，２，２］オクタン、１，８−ジアザビシクロ［５，４，０］ウンデセン−７、１，５−ジアザビシクロ［４，３，０］ノネン−５ジエチリデントリアミン（ＤＥＴＡ）、トリエチリデンテトラアミン（ＴＥＴＡ）、テトラエチリデンペンタアミン（ＴＥＰＡ）、ジエチルアミノプロピルアミン（ＤＥＡＰＡ）、メチレンジアミン、Ｎ−アミノエチルアミン（ＡＥＰ）、ｍ−キシリレンジアミン（ＭＸＤＡ）とメチレンジ（アミノシクロヘキサン）、ｍ−フェニルジアミン（ＭＰＤＡ）、ジアミノジフェニルメタン（ＭＤＡ）、ジアミノジフェニルスルホン（ＤＡＤＰＳ）、ジアミノジフェニルエーテル、トルエンジアミン、ビフェニルアミンとメチレンジ（クロロアニリン）等のアミン類化合物が挙げられるが、これらに制限されるものではない。 Specific examples of the amine compounds as curing agents for epoxy resins include 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] undecene-7, 1 , 5-diazabicyclo [4,3,0] nonene-5 diethylidenetriamine (DETA), triethylidenetetraamine (TETA), tetraethylidenepentamine (TEPA), diethylaminopropylamine (DEAPA), methylenediamine, N-amino Ethylamine (AEP), m-xylylenediamine (MXDA) and methylenedi (aminocyclohexane), m-phenyldiamine (MPDA), diaminodiphenylmethane (MDA), diaminodiphenylsulfone (DADPS), diaminodiphenyl ether, toluenediamine, biphenyl Min and methylenedi but amine compound of (chloroaniline) and the like, but is not limited thereto.
エポキシ樹脂の硬化剤としての前記フェノール類化合物を具体的に例示すれば、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、４，４’−ビフェノール、２，２’，６，６’−テトラメチル−４，４’−ビフェノール、２，２’−メチレン−ビス（４−メチル−６−ｔｅｒｔ−ブチルフェノール）、トリスヒドロキシフェニルメタン、１，１−ジ−４−ヒドロキシフェニルフルオレン等のフルオレン骨格を有するフェノール類、フェノール化ポリブタジエン等のポリフェノール化合物、フェノール、クレゾール類、エチルフェノール類、ブチルフェノール類、オクチルフェノール類、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、ナフトール類等の各種フェノールを原料とするノボラック樹脂、キシリレン骨格含有フェノールノボラック樹脂、ジシクロペンタジエン骨格含有フェノールノボラック樹脂、フルオレン骨格含有フェノールノボラック樹脂等のフェノール系ノボラック樹脂が挙げられ、好ましくはフェノール、クレゾール類、エチルフェノール類、ブチルフェノール類、オクチルフェノール類、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、ナフトール類等の各種フェノールを原料とするノボラック樹脂、キシリレン骨格含有フェノールノボラック樹脂、ジシクロペンタジエン骨格含有フェノールノボラック樹脂、フルオレン骨格含有フェノールノボラック樹脂等の各種ノボラック樹脂であり、さらに好ましくはフェノール、クレゾール類、オクチルフェノール、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、ナフトール類等の各種フェノール類を原料とするノボラック樹脂等の各種ノボラック樹脂であり、特に好ましくはキシリレン骨格含有フェノールノボラック樹脂等が挙げられるがこれらに制限されるわけではない。 Specific examples of the phenolic compounds as curing agents for epoxy resins include bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenol, 2,2 ′, 6,6′-tetramethyl-4, Phenols having a fluorene skeleton such as 4′-biphenol, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), trishydroxyphenylmethane, 1,1-di-4-hydroxyphenylfluorene, Polyphenolic compounds such as phenolized polybutadiene, novolak resins made from various phenols such as phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols, containing xylylene skeleton Phenolic novolak resins such as enol novolak resin, phenolic novolak resin containing dicyclopentadiene skeleton, phenol novolak resin containing fluorene skeleton, etc., preferably phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, naphthols and other novolak resins, xylylene skeleton-containing phenol novolac resins, dicyclopentadiene skeleton-containing phenol novolac resins, fluorene skeleton-containing phenol novolac resins, and the like, and more preferably Is phenol, cresol, octylphenol, bisphenol A, bisphenol F, bisphenol S, naphtho And various phenols Le, etc. in various novolak resins of the novolak resin as a raw material, not particularly but preferably include xylylene skeleton-containing phenol novolak resin and the like is limited thereto.
エポキシ樹脂の硬化剤としての前記酸無水物を具体的に例示すれば、脂肪族構造又は脂環構造を持つ酸無水物が好ましく、芳香族酸無水物は着色が起こるので好ましくない。例えば、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、水素化メチルナジック酸無水物、シクロヘキサン−１，３，４−トリカルボン酸−３，４−無水物、脂肪族二塩基酸ポリ無水物、１，２，３，４−ブタンテトラカルボン酸二無水物、メチルビシクロ［２．２．１］ヘプタン−２，３−ジカルボン酸無水物、ビシクロ［２．２．１］ヘプタン−２，３−ジカルボン酸無水物等が挙げられるが、これらに制限されるものではない。 Specifically, the acid anhydride as the epoxy resin curing agent is preferably an acid anhydride having an aliphatic structure or an alicyclic structure, and an aromatic acid anhydride is not preferable because coloring occurs. For example, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, hydrogenated methylnadic anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, aliphatic dibasic acid polyanhydride, 1 , 2,3,4-butanetetracarboxylic dianhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, bicyclo [2.2.1] heptane-2,3-dicarboxylic An acid anhydride etc. are mentioned, However, It is not restrict | limited to these.
また、エポキシ樹脂の硬化剤としての前記イミダゾール類化合物を具体的に例示すれば、２−メチルイミダゾール、２−ヘプタデシルイミダゾール、２−フェニルイミダゾール、２−フェニルー４−メチルイミダゾール、１−シアノエチル−２−フェニルイミダゾール、１−シアノエチル−２−ウンデシルイミダゾリウムトリメリテイト、１−シアノエチル−２−フェニルイミダゾリウムトリメリテイト、２，４−ジアミノー６−［２’−メチルイミダゾリル−（１’）］−エチル−ｓ−トリアジン、２，４−ジアミノ−６−［２’−ウンデシルイミダゾリル−（１’）］−エチル−ｓ−トリアジン、２，４−ジアミノ−６−［２’−エチル−４’−メチルイミダゾリル−（１’）］−エチル−ｓ−トリアジン、２，４−ジアミノ−６−［２’−メチルイミダゾリル−（１’）］−エチル−ｓ−トリアジンイソシアヌル酸付加物、２−フェニルイミダゾールイソシアヌル酸付加物、２−メチルイミダゾールイソシアヌル酸付加物、２−フェニル−４，５−ジヒドロキシメチルイミダゾール、２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール、２−メチルイミダゾリン、２−フェニルイミダゾリン、２，３−ジヒドロ−１Ｈ−ピロロ［１，２−ａ］ベンズイミダゾール等がある。これらのイミダゾール類化合物を単独又は組み合わせて用いることができる。 Specific examples of the imidazole compounds as curing agents for epoxy resins include 2-methylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 1-cyanoethyl-2. -Phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] -Ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4 '-Methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6- [2 -Methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, Examples include 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole. These imidazole compounds can be used alone or in combination.
本発明の透明なシート状接着剤用樹脂組成物に用いるこれらの硬化剤は、アミン類化合物、フェノール類化合物、酸無水物、イミダゾール類化合物等の硬化剤を単独又は組み合わせて使用することができる。 These curing agents used in the transparent resin composition for sheet-like adhesives of the present invention can be used alone or in combination with curing agents such as amine compounds, phenolic compounds, acid anhydrides, and imidazole compounds. .
前記硬化性樹脂組成分としてのアクリル酸エステル樹脂をラジカル重合開始剤で硬化させる樹脂組成には、（メタ）アクリレート系化合物の熱硬化性樹脂組成物や光硬化性樹脂組成物が挙げられる。（メタ）アクリレート系化合物は、粘度調整や硬化成分として用いられる分子中に少なくとも１個以上の（メタ）アクリロイル基を有するアクリレートである。この場合の樹脂組成物は、（メタ）アクリレート系化合物と、熱重合開始剤、光重合開始剤、又はその両方を必須成分とする。本発明の透明なシート状接着剤用樹脂組成物も同様に（メタ）アクリレート系化合物の熱硬化性樹脂組成物や光硬化性樹脂組成物にすることができる。 Examples of the resin composition for curing the acrylic ester resin as the curable resin composition with a radical polymerization initiator include a thermosetting resin composition of a (meth) acrylate compound and a photocurable resin composition. The (meth) acrylate compound is an acrylate having at least one (meth) acryloyl group in a molecule used as a viscosity adjusting or curing component. The resin composition in this case contains a (meth) acrylate compound and a thermal polymerization initiator, a photopolymerization initiator, or both as essential components. The transparent resin composition for sheet-like adhesives of the present invention can also be made into a thermosetting resin composition or a photocurable resin composition of a (meth) acrylate compound.
これらの使用できる（メタ）アクリレート系化合物を具体的に例示すれば、イソボルニル（メタ）アクリレート、シクロへキシル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、アクリロイルモルホリン、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、シクロへキサン−１，４−ジメタノールモノ（メタ）アクリレート、テトラヒドロフロフリル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェニルポリエトキシ（メタ）アクリレート、２−ヒドロキシ−３−フェニルオキシプロピル（メタ）アクリレート、ｏ−フェニルフェノールモノエトキシ（メタ）アクリレート、ｏ−フェニルフェノールポリエトキシ（メタ）アクリレート、ｐ−クミルフェノキシエチル（メタ）アクリレート、イソボニル（メタ）アクリレート、トリブロモフェニルオキシエチル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート等の単官能（メタ）アクリル酸エステル、１，４−ブタンジオールジ（メタ）アクリレート、１，６−へキサンジオールジ（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート、ビスフェノールＡポリエトキシジ（メタ）アクリレート、ビスフエノールＡポリプロポキシジ（メタ）アクリレート、ビスフエノールＦポリエトキシジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリオキシエチル（メタ）アクリレート、トリス（２ーヒドロキシエチル）イソシアヌレートトリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、トリス（アクリロキシエチル）イソシアヌレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、トリペンタエリスリトールヘキサ（メタ）アクリレート、トリペンタエリスリトールペンタ（メタ）アクリレート、ヒドロキシビバリン酸ネオペンチルグリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンポリエトキシトリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、シクロヘキサンジメタノールジ（メタ）アクリレート及びジメチロールトリシクロデカンジ（メタ）アクリレート等の多官能（メタ）アクリレート、ポリオール化合物にポリイソシアネート化合物を反応させ、（メタ）アクリレートと反応することで得られるウレタン（メタ）アクリレート、エポキシ化合物と（メタ）アクリレートの反応で得られるエポキシアクリレート等が挙げられるが、これらに制限されるわけではない。これらの（メタ）アクリレート系化合物を単独又は組み合わせて用いることができる。 Specific examples of these (meth) acrylate compounds that can be used include isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (Meth) acrylate, cyclohexane-1,4-dimethanol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, Nyl polyethoxy (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, o-phenylphenol monoethoxy (meth) acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-cumylphenoxyethyl (Meth) acrylate, isobornyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, etc. Functional (meth) acrylic acid ester, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polypropoxydi (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris (2 -Hydroxyethyl) isocyanurate tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (acryloxyethyl) ) Isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentae Lithritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, hydroxypentaglycolic acid neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, Multifunctional (meth) acrylates such as ditrimethylolpropane tetra (meth) acrylate, cyclohexanedimethanol di (meth) acrylate and dimethyloltricyclodecane di (meth) acrylate, and a polyisocyanate compound are reacted with a polyol compound (meth) Examples include urethane (meth) acrylate obtained by reacting with acrylate, epoxy acrylate obtained by reaction of epoxy compound and (meth) acrylate, and the like. , But it is not limited to these. These (meth) acrylate compounds can be used alone or in combination.
また、（メタ）アクリレート系化合物の重合開始剤として使用できる化合物としては、加熱や活性エネルギー線光の照射等の手段により、ラジカルを発生させるものであれば特に限定せずに使用することができる。重合開始剤として使用できるこれらの化合物を具体的に例示すれば、加熱により硬化させる場合には、アゾビスイソブチロニトリル、過酸化ベンゾイル等のアゾ系、過酸化物系開始剤等の通常のラジカル熱重合に使用できるものはいずれも使用することができる。またラジカル重合を光ラジカル重合によって行う場合、ベンゾイン類、アセトフェノン類、アントラキノン類、チオキサントン類、ケタール類、ベンゾフェノン類、ホスフィンオキサイド類等の通常の光ラジカル重合に使用できるものはいずれも使用することができる。これらの重合光開始剤は、単独又は２種以上の混合物として使用でき、さらには、光ラジカル重合開始剤に対しては、第３級アミン類化合物、Ｎ，Ｎ−ジメチルアミノ安息香酸エチルエステル等の促進剤等と組み合わせて使用することができる。 Moreover, as a compound which can be used as a polymerization initiator of a (meth) acrylate type compound, it can be used without particular limitation as long as it generates radicals by means such as heating or irradiation with active energy rays. . Specific examples of these compounds that can be used as a polymerization initiator include those such as azobisisobutyronitrile, azo-type peroxides such as benzoyl peroxide, and peroxide-type initiators that are cured by heating. Any of those that can be used for radical thermal polymerization can be used. When radical polymerization is carried out by photoradical polymerization, any of those that can be used for normal photoradical polymerization such as benzoins, acetophenones, anthraquinones, thioxanthones, ketals, benzophenones, and phosphine oxides can be used it can. These polymerization photoinitiators can be used alone or as a mixture of two or more. Furthermore, for photoradical polymerization initiators, tertiary amine compounds, N, N-dimethylaminobenzoic acid ethyl ester, etc. It can be used in combination with an accelerator.
本発明の透明なシート状接着剤用樹脂組成物には必要に応じてフィラーを用いることができる。具体的には水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、タルク、焼成タルク、マイカ、クレー、カオリン、水酸化チタン、酸化チタンシリカ粉、ガラス粉末、シリカバルーン、雲母等の無機フィラーが挙げられるが、有機系又は無機系の耐湿顔料、鱗片状顔料等顔料等を配合してもよい。一般的無機充填剤を用いる理由として、耐衝撃性の向上が挙げられる。またガラス繊維、パルプ繊維、合成繊維、セラミック繊維等の繊維質充填剤や、微粒子ゴム、熱可塑性エラストマー等の有機充填剤等を配合することができる。 A filler can be used as needed for the transparent resin composition for sheet-like adhesives of this invention. Specific examples include inorganic fillers such as aluminum hydroxide, magnesium hydroxide, calcium carbonate, talc, calcined talc, mica, clay, kaolin, titanium hydroxide, titanium oxide silica powder, glass powder, silica balloon, and mica. Organic or inorganic moisture-resistant pigments, pigments such as scaly pigments, and the like may be blended. The reason for using a general inorganic filler is an improvement in impact resistance. Moreover, fiber fillers, such as glass fiber, pulp fiber, synthetic fiber, and ceramic fiber, organic fillers, such as fine particle rubber and a thermoplastic elastomer, etc. can be mix | blended.
また本発明の透明なシート状接着剤用樹脂組成物中には、必要に応じて、難燃剤、揺変性付与材、流動性向上剤、レベリング剤、消泡剤、帯電防止剤、分散剤、表面調整剤、カップリング剤等の添加剤を配合してもよい。揺変性付与材としては、シリコン系、ヒマシ油系、脂肪族アマイドワックス、酸化ポリエチレンワックス、有機ベントナイト系等を挙げ類ことができる。さらに必要に応じて、本発明の光学素子用硬化性樹脂組成物には、カルナバワックス、ＯＰワックス等の離型剤、カーボンブラック等の着色剤、三酸化アンチモン等の難燃剤、シリコンオイル等の低応力化剤、ステアリン酸カルシウム等の潤滑剤を配合できる。カップリング剤としては、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、γ−メタクリロキシプロピルトリメトキシシラン、ビニルトリアセトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、β−（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、γ−クロロプロピルメトキシシラン、ビニルトリクロロシラン、γ−メルカプトプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−β（アミノエチル）−γ−アミノプロピルトリメトキシシラン等が挙げられる。 Further, in the transparent resin composition for sheet-like adhesive of the present invention, if necessary, flame retardant, thixotropic agent, fluidity improver, leveling agent, antifoaming agent, antistatic agent, dispersant, You may mix | blend additives, such as a surface modifier and a coupling agent. Examples of the thixotropic agent include silicon, castor oil, aliphatic amide wax, oxidized polyethylene wax, and organic bentonite. Further, if necessary, the curable resin composition for an optical element of the present invention includes a release agent such as carnauba wax and OP wax, a colorant such as carbon black, a flame retardant such as antimony trioxide, and a silicone oil. A lubricant such as a low stress agent and calcium stearate can be blended. As coupling agents, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl Triethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-chloropropylmethoxysilane, vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β ( Aminoethyl) -γ-aminopropyltrimethoxysilane and the like.
本発明の透明なシート状接着剤用樹脂組成物は、公知のエポキシ樹脂組成物と同様な方法により成型、硬化して硬化物とすることができる。成型方法、硬化方法は公知のエポキシ樹脂組成物と同様の方法をとることができ、本発明の透明なシート状接着剤用樹脂組成物固有の方法は不要である。例えば、樹脂ワニスを作成した後、離形フィルムの上にキャストすることで、シート状樹脂組成物を作成することができる。これを熱又は光で硬化させることで、硬化物とすることができる。 The transparent resin composition for sheet-like adhesive of the present invention can be molded and cured by the same method as known epoxy resin compositions to obtain a cured product. The molding method and the curing method can be the same as the known epoxy resin composition, and the method unique to the transparent resin composition for sheet-like adhesive of the present invention is unnecessary. For example, after creating a resin varnish, the sheet-like resin composition can be created by casting on a release film. It can be set as a hardened | cured material by hardening this with a heat | fever or light.
また本発明の硬化物は、厚み１ｍｍの硬化物を作成した場合、波長４００ｎｍにおける透過率が８０％以上であり、黄色度（ＹＩ）が５以下である必要がある。波長４００ｎｍにおける透過率が８０％以下、又はＹＩが５以上である場合、タッチパネルを液晶ディスプレイに貼り合せた場合に、視認性を低下させるので好ましくない。高分子エポキシ樹脂中のビスフェノールＦの骨格が全骨格に対して３５〜５５モル％の範囲内であり、かつ、その高分子エポキシ樹脂のメチルエチルケトンの５０質量％ワニスのハーゼン単位色相が５０以下である高分子エポキシ樹脂を本発明の透明なシート状接着剤用樹脂組成物に用いれば、厚み１ｍｍの硬化物を作成した場合、波長４００ｎｍにおける透過率が８０％以上であり、黄色度（ＹＩ）が５以下の硬化物が得られる。 Moreover, when the cured product of the present invention is a cured product having a thickness of 1 mm, it is necessary that the transmittance at a wavelength of 400 nm is 80% or more and the yellowness (YI) is 5 or less. When the transmittance at a wavelength of 400 nm is 80% or less, or YI is 5 or more, visibility is lowered when the touch panel is bonded to a liquid crystal display, which is not preferable. The skeleton of bisphenol F in the polymer epoxy resin is in the range of 35 to 55 mol% with respect to the total skeleton, and the Hazen unit hue of 50% by mass varnish of methyl ethyl ketone of the polymer epoxy resin is 50 or less. When a polymer epoxy resin is used in the transparent resin composition for sheet-like adhesive of the present invention, when a cured product having a thickness of 1 mm is prepared, the transmittance at a wavelength of 400 nm is 80% or more, and the yellowness (YI) is A cured product of 5 or less is obtained.
本発明の透明なシート状接着剤用樹脂組成物は光学特性、粘度特性に優れ、光学シート状接着剤に好適であることが判った。 The transparent resin composition for sheet-like adhesives of the present invention was found to be excellent in optical properties and viscosity properties and suitable for optical sheet-like adhesives.
以下、実施例及び比較例に基づき本発明を具体的に説明するが本発明の範囲がこれらの実施例に限定されるものではない。以下の合成例、実施例、及び比較例に於いて、「部」は質量部を、「％」は質量％をそれぞれ示す。また本発明では以下の試験方法を使用した。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example and a comparative example, the scope of the present invention is not limited to these Examples. In the following synthesis examples, examples, and comparative examples, “part” represents part by mass, and “%” represents mass%. In the present invention, the following test method was used.
（１）重量平均分子量
東ソー株式会社製 ＴＳＫｇｅｌＧ４０００ＨＸＬ、ＴＳＫｇｅｌＧ３０００ＨＸＬ、ＴＳＫｇｅｌＧ２０００ＨＸＬを直列に備えたものを使用し、カラム温度は４０℃にした。また溶離液にはテトラヒドロフランを用い、１ｍＬ／ｍｉｎの流速とし、検出器はＲＩ（示差屈折計）検出器を用いた。試料濃度は１％テトラヒドロフラン溶液で、１００μＬ注入した。標準ポリスチレンによる検量線により重量平均分子量を求めた。
(1) Weight average molecular weight Tosoh Corporation TSKgelG4000HXL, TSKgelG3000HXL, TSKgelG2000HXL were used in series, and the column temperature was 40 ° C. Tetrahydrofuran was used as the eluent, the flow rate was 1 mL / min, and a RI (differential refractometer) detector was used as the detector. The sample concentration was 1% tetrahydrofuran solution, and 100 μL was injected. The weight average molecular weight was determined by a standard polystyrene calibration curve.
（２）粘度
ＪＩＳ Ｋ ７２３３規格、単一円筒回転粘度計法に準拠して測定した。すなわち、５００ｍＬの円筒缶に樹脂４００ｇをはかりとり、２５±０．２℃の恒温水槽で５時間放置して恒温にする。回転粘度計のローターを樹脂に浸漬して測定を行う。
(2) Viscosity Viscosity was measured in accordance with JIS K 7233 standard and single cylinder rotational viscometer method. That is, 400 g of resin is weighed into a 500 mL cylindrical can and left in a constant temperature water bath at 25 ± 0.2 ° C. for 5 hours to make the temperature constant. Measurement is performed by immersing the rotor of the rotational viscometer in resin.
（３）色数
ＪＩＳ Ｋ ００７１規格、ハーゼン単位色数に準拠して測定した。
(3) Number of colors Measured in accordance with JIS K 0071 standard and Hazen unit number of colors.
（４）固形分濃度
ＪＩＳ Ｋ ７２３５規格に準拠して、２００℃、１時間の加熱条件で測定した。
(4) Solid content concentration Based on JIS K 7235 standard, it measured on 200 degreeC and the heating conditions of 1 hour.
（５）フィルム性
試験フィルムを目視及び指触にて確認した。フィルム状に形成されたものを○、フィルム状に形成されなかったものを×とした。
(5) Film property test The film was confirmed by visual observation and finger touch. What was formed in the film form was set as (circle), and what was not formed in the film form was set as x.
（６）流動性
樹脂組成物をガラス上に塗布し、６０℃、１０分間に加熱した後、目視及び指触にて流動するかを確認した。流動したものを○、流動しなかったものを×とした。
(6) The flowable resin composition was applied on glass, heated at 60 ° C. for 10 minutes, and then confirmed to flow visually or by touch. The one that flowed was marked with ◯ and the one that did not flow was marked with ×.
（７）透過率
分光光度計（日本分光株式会社製、Ｖ−６５０）を使用し、波長４００ｎｍでの透過率を測定した。
(7) A transmittance spectrophotometer (manufactured by JASCO Corporation, V-650) was used to measure the transmittance at a wavelength of 400 nm.
（８）ＹＩ値
測色色差計（有限会社東京電色製、ＴＣ−１５００ＭＣ−８８）を使用して測定した。
(8) YI value Measured using a colorimetric color difference meter (TC-1500MC-88, manufactured by Tokyo Denshoku Co., Ltd.).
合成例、実施例、及び比較例で使用した略号は以下の通りである。 Abbreviations used in Synthesis Examples, Examples, and Comparative Examples are as follows.
（エポキシ樹脂）
ＹＤ−１２８：新日鉄住金化学株式会社製、ビスフェノールＡ型液状エポキシ樹脂、エポキシ当量：１８７ｇ／ｅｑ．
ＹＤ−８１２５：新日鉄住金化学株式会社製、ビスフェノールＡ型液状エポキシ樹脂、エポキシ当量：１７２ｇ／ｅｑ．
ＹＤＦ−１７０：新日鉄住金化学株式会社製、ビスフェノールＦ型液状エポキシ樹脂、エポキシ当量：１６７ｇ／ｅｑ．
ＹＤＦ−８１７０：新日鉄住金化学株式会社製、ビスフェノールＦ型液状エポキシ樹脂、エポキシ当量：１５８ｇ／ｅｑ．
ＹＤ−０１４：新日鉄住金化学株式会社製、ビスフェノールＡ型固形エポキシ樹脂、エポキシ当量：９４８ｇ／ｅｑ．、軟化点９８℃
(Epoxy resin)
YD-128: manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol A type liquid epoxy resin, epoxy equivalent: 187 g / eq.
YD-8125: manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol A type liquid epoxy resin, epoxy equivalent: 172 g / eq.
YDF-170: manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol F type liquid epoxy resin, epoxy equivalent: 167 g / eq.
YDF-8170: manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol F type liquid epoxy resin, epoxy equivalent: 158 g / eq.
YD-014: manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol A type solid epoxy resin, epoxy equivalent: 948 g / eq. , Softening point 98 ℃
（フェノール化合物）
ＢＰＡ：新日鉄住金化学株式会社製、ビスフェノールＡ
ＢＰＦＤ：群栄化学工業株式会社製、ビスフェノールＦ、蒸留タイプ、純度９８％以上
(Phenol compound)
BPA: Nippon Steel & Sumikin Chemical Co., Ltd., bisphenol A
BPFD: manufactured by Gunei Chemical Industry Co., Ltd., bisphenol F, distillation type, purity of 98% or more
（反応溶媒）
ＰＭＡ：プロピレングリコールモノメチルエーテルアセテート、沸点＝１４５℃、蒸気圧（２０℃）＝３．８ｋＰａ
ＣＰＡ：シクロペンタノン、沸点＝１３０℃、蒸気圧（２０℃）＝１．６ｋＰａ
ＮＢＡ：１−ブタノール、沸点＝１１７℃、蒸気圧（２０℃）＝０．７ｋＰａ
ＴＯＬ：トルエン、沸点＝１１０℃、蒸気圧（２０℃）＝２．９ｋＰａ
ＣＨＡ：シクロヘキサノン、沸点＝１５５℃、蒸気圧（２０℃）＝０．４５ｋＰａ
ＭＥＫ：メチルエチルケトン、沸点＝８０℃、蒸気圧（２０℃）＝９．５ｋＰａ
(Reaction solvent)
PMA: propylene glycol monomethyl ether acetate, boiling point = 145 ° C., vapor pressure (20 ° C.) = 3.8 kPa
CPA: cyclopentanone, boiling point = 130 ° C., vapor pressure (20 ° C.) = 1.6 kPa
NBA: 1-butanol, boiling point = 117 ° C, vapor pressure (20 ° C) = 0.7 kPa
TOL: toluene, boiling point = 110 ° C, vapor pressure (20 ° C) = 2.9 kPa
CHA: cyclohexanone, boiling point = 155 ° C., vapor pressure (20 ° C.) = 0.45 kPa
MEK: methyl ethyl ketone, boiling point = 80 ° C., vapor pressure (20 ° C.) = 9.5 kPa
（触媒）
ＴＰＰ−ＢＢ：北興化学株式会社製、ｎ−ブチルトリフェニルホスホニウムブロマイド
ＥＴＰＰＩ：日本化学工業株式会社製、エチルトリフェニルホスホニウムアイオダイド
ＤＭＰＰ：ケイ・アイ化成株式会社製、トリス（２，６−ジメトキシフェニル）ホスフィン
(catalyst)
TPP-BB: manufactured by Hokuko Chemical Co., Ltd., n-butyltriphenylphosphonium bromide ETPPI: manufactured by Nippon Chemical Industry Co., Ltd., ethyltriphenylphosphonium iodide DMPP: manufactured by K. Kasei Chemical Co., Ltd., tris (2,6-dimethoxyphenyl ) Phosphine
（酸無水物）
ＭＨ−７００：新日本理化株式会社製、メチルヘキサヒドロ無水フタル酸とヘキサヒドロ無水フタル酸の混合物
(Acid anhydride)
MH-700: New Nippon Rika Co., Ltd., a mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride
（硬化促進剤）
２ＰＺＣＮＳ−ＰＷ：四国化成工業株式会社製、１−シアノエチル−２−フェニルイミダゾリウムトリメリテイト
２Ｅ４ＭＺ：四国化成工業株式会社製、２−エチル−４−メチルイミダゾール
(Curing accelerator)
2PZCNS-PW: manufactured by Shikoku Chemicals Co., Ltd., 1-cyanoethyl-2-phenylimidazolium trimellitate 2E4MZ: manufactured by Shikoku Chemicals Co., Ltd., 2-ethyl-4-methylimidazole
（アクリレート系化合物）
ＤＣＰＡ：共栄社化学株式会社製、ジメチロールトリシクロデカンジアクリレート
ＴＭＰＡ：共栄社化学株式会社製、ジトリメチロールプロパントリアクリレート
ＤＰＨＡ：共栄社化学株式会社製、ジペンタエリスリトールヘキサアクリレート
(Acrylate compounds)
DCPA: Kyoeisha Chemical Co., Ltd., dimethylol tricyclodecane diacrylate TMPA: Kyoeisha Chemical Co., Ltd., ditrimethylolpropane triacrylate DPHA: Kyoeisha Chemical Co., Ltd., dipentaerythritol hexaacrylate
（ラジカル重合開始剤）
ＨＣＰＫ：１−ヒドロキシ−シクロへキシル−フェニル−ケトン
ＢＰＥＨ：日油株式会社製、ｔ−ブチルパーオキシ−２−エチル−ヘキサノエート（製品名：パーブチルＯ）
(Radical polymerization initiator)
HCPK: 1-hydroxy-cyclohexyl-phenyl-ketone BPEH: manufactured by NOF Corporation, t-butyl peroxy-2-ethyl-hexanoate (product name: perbutyl O)
合成例１
撹拌機、温度計、窒素吹き込み管、及び冷却管を備えた反応装置にエポキシ樹脂としてＹＤ−１２８を５００部とＹＤＦ−１７０を４０部、フェノール化合物としてＢＰＦＤを３４０部、及び反応溶媒としてＰＭＡを１４５部（固形分濃度８５％）仕込み、１３０℃で溶融混合させた。このときのフェノール性水酸基とエポキシ基のモル比は１：１．０６９であった。その後、触媒としてＴＰＰ−ＢＢを０．３４部添加し、１６０℃まで昇温し、反応を開始した。反応開始後５時間目に反応溶媒としてＰＭＡを１２９部追加し固形分濃度を７５％にして、さらに触媒としてＴＰＰ−ＢＢを０．３４部追加して、さらに７時間撹拌を続けて反応を行った。反応終了後、反応溶媒としてＭＥＫを５４７部加えて高分子量エポキシ樹脂のＰＭＡ／ＭＥＫ混合ワニスを得た。得られた混合ワニスを１３０℃に保持されている真空オーブン中に入れ、オーブンの内部圧力が０．４ｋＰａに到達してから３０分間保持して溶剤を除去した後、直ちにＭＥＫで不揮発分を５０％希釈して樹脂ワニス１を得た。
Synthesis example 1
In a reactor equipped with a stirrer, thermometer, nitrogen blowing tube, and cooling tube, 500 parts of YD-128 and 40 parts of YDF-170 as epoxy resin, 340 parts of BPFD as a phenol compound, and PMA as a reaction solvent 145 parts (solid content concentration: 85%) were charged and melt-mixed at 130 ° C. At this time, the molar ratio of the phenolic hydroxyl group to the epoxy group was 1: 1.068. Thereafter, 0.34 parts of TPP-BB was added as a catalyst, the temperature was raised to 160 ° C., and the reaction was started. Five hours after the start of the reaction, 129 parts of PMA was added as a reaction solvent to a solid concentration of 75%, and 0.34 parts of TPP-BB was further added as a catalyst, and the reaction was further continued for 7 hours. It was. After the completion of the reaction, 547 parts of MEK was added as a reaction solvent to obtain a PMA / MEK mixed varnish of a high molecular weight epoxy resin. The obtained mixed varnish was put in a vacuum oven maintained at 130 ° C., and after the internal pressure of the oven reached 0.4 kPa, the solvent was removed for 30 minutes. % Resin dilution 1 was obtained.
合成例２
実施例１で使用した装置を用い、エポキシ樹脂としてＹＤ−１２８を５００部、フェノール化合物としてＢＰＦＤを１９２部とＢＰＡを８０部、及び反応溶媒としてＣＰＡを８６部（固形分濃度９０％）仕込み、１３０℃で溶融混合させた。このときのフェノール性水酸基とエポキシ基のモル比は１：１．０２０であった。その後、触媒としてＴＰＰ−ＢＢを０．２７部添加し、１５５℃まで昇温し、反応を開始した。反応開始後４時間目に反応溶媒としてＣＰＡを１０７部追加し固形分濃度を８０％にして、さらに触媒としてＴＰＰ−ＢＢを０．２７部追加して、さらに５時間撹拌を続けて反応を行った後、反応溶媒としてＣＰＡを２２４部追加し固形分濃度を７０％にして、さらに５時間撹拌を続けて反応を行った。反応終了後、反応溶媒としてＣＰＡを３５５部加えて高分子量エポキシ樹脂のＣＰＡワニスを得た。得られたＣＰＡワニスを実施例１と同様の操作を行い樹脂ワニス２を得た。
Synthesis example 2
Using the apparatus used in Example 1, 500 parts of YD-128 as an epoxy resin, 192 parts of BPFD and 80 parts of BPA as a phenol compound, and 86 parts of CPA as a reaction solvent (solid content concentration 90%) were charged. It was melt-mixed at 130 ° C. At this time, the molar ratio of the phenolic hydroxyl group to the epoxy group was 1: 1.020. Thereafter, 0.27 parts of TPP-BB was added as a catalyst, the temperature was raised to 155 ° C., and the reaction was started. At 4 hours after the start of the reaction, 107 parts of CPA was added as a reaction solvent to a solid content concentration of 80%, and 0.27 parts of TPP-BB was added as a catalyst, and the reaction was further continued for 5 hours. Thereafter, 224 parts of CPA was added as a reaction solvent to make the solid content concentration 70%, and the reaction was further continued for 5 hours with stirring. After completion of the reaction, 355 parts of CPA was added as a reaction solvent to obtain a high molecular weight epoxy resin CPA varnish. The obtained CPA varnish was subjected to the same operation as in Example 1 to obtain a resin varnish 2.
合成例３
実施例１で使用した装置を用い、エポキシ樹脂としてＹＤ−１２８を５００部、フェノール化合物としてＢＰＦＤを２６２部、及び反応溶媒としてＰＭＡを４０部（固形分濃度９５％）仕込み、１３０℃で溶融混合させた。このときのフェノール性水酸基とエポキシ基のモル比は１：１．０２１であった。その後、触媒としてＴＰＰ−ＢＢを０．２６部添加し、１５５℃まで昇温し、反応を開始した。反応開始後５時間目に反応溶媒としてＰＭＡを９４部追加し固形分濃度を８５％にして、さらに触媒としてＴＰＰ−ＢＢを０．２６部追加して、さらに７時間撹拌を続けて反応を行った。反応終了後、反応溶媒としてＭＥＫを６２８部加えて高分子量エポキシ樹脂のＰＭＡ／ＭＥＫ混合ワニスを得た。得られた混合ワニスを実施例１と同様の操作を行い樹脂ワニス３を得た。
Synthesis example 3
Using the apparatus used in Example 1, 500 parts of YD-128 as an epoxy resin, 262 parts of BPFD as a phenol compound, and 40 parts of PMA as a reaction solvent (solid content concentration 95%) were charged and melt mixed at 130 ° C. I let you. At this time, the molar ratio of the phenolic hydroxyl group to the epoxy group was 1: 1.021. Thereafter, 0.26 parts of TPP-BB was added as a catalyst, the temperature was raised to 155 ° C., and the reaction was started. At 5 hours after the start of the reaction, 94 parts of PMA was added as a reaction solvent to a solid content concentration of 85%, and 0.26 parts of TPP-BB was added as a catalyst, and stirring was continued for further 7 hours to carry out the reaction. It was. After the reaction was completed, 628 parts of MEK was added as a reaction solvent to obtain a PMA / MEK mixed varnish of a high molecular weight epoxy resin. The obtained mixed varnish was subjected to the same operation as in Example 1 to obtain a resin varnish 3.
合成例４
実施例１で使用した装置を用い、エポキシ樹脂としてＹＤ−８１２５を５００部、フェノール化合物としてＢＰＦＤを２９０部、及び反応溶媒としてＣＰＡを８８部（固形分濃度９０％）仕込み、１３０℃で溶融混合させた。このときのフェノール性水酸基とエポキシ基のモル比は１：１．００２であった。その後、触媒としてＤＭＰＰを０．２９部添加し、１５５℃まで昇温し、反応を開始した。反応開始後３時間目に反応溶媒としてＣＰＡを１１０部追加し固形分濃度を８０％にして、さらに４時間撹拌を続けて反応を行った後、さらに反応溶媒としてＣＰＡを２２９部追加し固形分濃度を７０％にして、触媒としてＤＭＰＰを０．２９部追加して、さらに７時間撹拌を続けて反応を行った。反応終了後、反応溶媒としてＭＥＫを３５５部加えて高分子量エポキシ樹脂のＣＰＡ／ＭＥＫ混合ワニスを得た。得られた混合ワニスを実施例１と同様の操作を行い樹脂ワニス４を得た。
Synthesis example 4
Using the apparatus used in Example 1, 500 parts of YD-8125 as an epoxy resin, 290 parts of BPFD as a phenol compound, and 88 parts of CPA as a reaction solvent (solid content concentration 90%) were charged and melt mixed at 130 ° C. I let you. At this time, the molar ratio of the phenolic hydroxyl group to the epoxy group was 1: 1.002. Thereafter, 0.29 parts of DMPP was added as a catalyst, the temperature was raised to 155 ° C., and the reaction was started. 3 hours after the start of the reaction, 110 parts of CPA was added as a reaction solvent to a solid content concentration of 80%, and the reaction was continued for another 4 hours, followed by further addition of 229 parts of CPA as a reaction solvent. The concentration was adjusted to 70%, 0.29 parts of DMPP was added as a catalyst, and the reaction was further continued for 7 hours with stirring. After completion of the reaction, 355 parts of MEK was added as a reaction solvent to obtain a CPA / MEK mixed varnish of a high molecular weight epoxy resin. The obtained mixed varnish was subjected to the same operation as in Example 1 to obtain a resin varnish 4.
合成例５
実施例１で使用した装置を用い、エポキシ樹脂としてＹＤ−１２８を８０部とＹＤ−８１２５を５００部、フェノール化合物としてＢＰＡを３７０部、及び反応溶媒としてＣＰＡを１０６部（固形分濃度９０％）仕込み、１３０℃で溶融混合させた。このときのフェノール性水酸基とエポキシ基のモル比は１：１．０５４であった。その後、触媒としてＴＰＰ−ＢＢを０．３７部添加し、１５５℃まで昇温し、反応を開始した。反応開始後５時間目に反応溶媒としてＣＰＡを１３２部追加し固形分濃度を８０％にして、さらに触媒としてＴＰＰ−ＢＢを０．３７部追加して、さらに５時間撹拌を続けて反応を行った後、反応溶媒としてＣＰＡを２７５部追加し固形分濃度を７０％にして、さらに５時間撹拌を続けて反応を行った。反応終了後、反応溶媒としてＭＥＫを４３７部加えて高分子量エポキシ樹脂のＣＰＡ／ＭＥＫ混合ワニスを得た。得られた混合ワニスを実施例１と同様の操作を行い樹脂ワニス５を得た。
Synthesis example 5
Using the apparatus used in Example 1, 80 parts of YD-128 and 500 parts of YD-8125 as an epoxy resin, 370 parts of BPA as a phenol compound, and 106 parts of CPA as a reaction solvent (solid content concentration 90%) The mixture was melted and mixed at 130 ° C. At this time, the molar ratio of the phenolic hydroxyl group and the epoxy group was 1: 1.54. Thereafter, 0.37 parts of TPP-BB was added as a catalyst, the temperature was raised to 155 ° C., and the reaction was started. Five hours after the start of the reaction, 132 parts of CPA was added as a reaction solvent to a solid content concentration of 80%, and 0.37 parts of TPP-BB was added as a catalyst, and the reaction was further continued for 5 hours. Thereafter, 275 parts of CPA was added as a reaction solvent to make the solid content concentration 70%, and the reaction was further continued for 5 hours with stirring. After completion of the reaction, 437 parts of MEK was added as a reaction solvent to obtain a CPA / MEK mixed varnish of a high molecular weight epoxy resin. The obtained mixed varnish was subjected to the same operation as in Example 1 to obtain a resin varnish 5.
合成例６
実施例１で使用した装置を用い、エポキシ樹脂としてＹＤＦ−８１７０を５００部、フェノール化合物としてＢＰＡを３５０部、及び反応溶媒としてＴＯＬを４５部（固形分濃度９５％）仕込み、１１０℃で溶融混合させた。このときのフェノール性水酸基とエポキシ基のモル比は１：１．０３１であった。その後、触媒としてＥＴＰＰＩを０．３５部添加し、１４０℃まで昇温し、反応を開始した。反応開始後５時間目に反応溶媒としてＴＯＬを１０５部追加し固形分濃度を８５％にして、さらに触媒としてＥＴＰＰＩを０．３５部追加して、さらに７時間撹拌を続けて反応を行った。反応終了後、反応溶媒としてＭＥＫを７００部加えて高分子量エポキシ樹脂のＴＯＬ／ＭＥＫ混合ワニスを得た。得られた混合ワニスを実施例１と同様の操作を行い樹脂ワニス６を得た。
Synthesis Example 6
Using the apparatus used in Example 1, 500 parts of YDF-8170 as an epoxy resin, 350 parts of BPA as a phenol compound, and 45 parts of TOL (solid content concentration 95%) as a reaction solvent were melt-mixed at 110 ° C. I let you. At this time, the molar ratio of the phenolic hydroxyl group to the epoxy group was 1: 1.031. Thereafter, 0.35 part of ETPPI was added as a catalyst, the temperature was raised to 140 ° C., and the reaction was started. 5 hours after the start of the reaction, 105 parts of TOL was added as a reaction solvent to a solid content concentration of 85%, and 0.35 parts of ETPPI was further added as a catalyst, and the reaction was further continued for 7 hours. After completion of the reaction, 700 parts of MEK was added as a reaction solvent to obtain a TOL / MEK mixed varnish of a high molecular weight epoxy resin. The obtained mixed varnish was subjected to the same operation as in Example 1 to obtain a resin varnish 6.
合成例７
実施例１で使用した装置を用い、エポキシ樹脂としてＹＤＦ−８１７０を５００部、フェノール化合物としてＢＰＦＤを３１０部、及び反応溶媒としてＣＰＡを９０部（固形分濃度９０％）仕込み、１３０℃で溶融混合させた。このときのフェノール性水酸基とエポキシ基のモル比は１：１．０２１であった。その後、触媒としてＤＭＰＰを０．３１部添加し、１５５℃まで昇温し、反応を開始した。反応開始後１０時間撹拌を続けて反応を行った。反応終了後、反応溶媒としてＭＥＫを７２０部加えて高分子量エポキシ樹脂のＣＰＡ／ＭＥＫ混合ワニスを得た。得られた混合ワニスを実施例１と同様の操作を行い樹脂ワニス７を得た。
Synthesis example 7
Using the apparatus used in Example 1, 500 parts of YDF-8170 as an epoxy resin, 310 parts of BPFD as a phenol compound, and 90 parts of CPA as a reaction solvent (solid content concentration 90%) were charged and melt mixed at 130 ° C. I let you. At this time, the molar ratio of the phenolic hydroxyl group to the epoxy group was 1: 1.021. Thereafter, 0.31 part of DMPP was added as a catalyst, the temperature was raised to 155 ° C., and the reaction was started. The reaction was continued by stirring for 10 hours after the start of the reaction. After completion of the reaction, 720 parts of MEK was added as a reaction solvent to obtain a CPA / MEK mixed varnish of a high molecular weight epoxy resin. The obtained mixed varnish was subjected to the same operation as in Example 1 to obtain a resin varnish 7.
合成例８
実施例１で使用した装置を用い、エポキシ樹脂としてＹＤ−１２８を５００部、フェノール化合物としてＢＰＡを３００部、及び反応溶媒としてＰＭＡを３４３部（固形分濃度７０％）仕込み、１３０℃で溶融混合させた。このときのフェノール性水酸基とエポキシ基のモル比は１：１．０１６であった。その後、触媒としてＤＭＰＰを０．３０部添加し、１６０℃まで昇温し、反応を開始した。反応開始後５時間目に反応溶媒としてＰＭＡを１９０部追加し固形分濃度を６０％にして、触媒としてＴＰＰ−ＢＢを０．３０部追加して、さらに５時間撹拌を続けて反応を行った後、反応溶媒としてＰＭＡを２６７部追加し固形分濃度を５０％にして、さらに５時間撹拌を続けて反応を行い、高分子量エポキシ樹脂のＰＭＡワニスを得た。得られたＰＭＡワニスを実施例１と同様の操作を行い樹脂ワニス８を得た。
Synthesis Example 8
Using the apparatus used in Example 1, 500 parts of YD-128 as an epoxy resin, 300 parts of BPA as a phenol compound, and 343 parts of PMA as a reaction solvent (solid content concentration 70%) were charged and melt mixed at 130 ° C. I let you. At this time, the molar ratio of the phenolic hydroxyl group to the epoxy group was 1: 1.016. Thereafter, 0.30 parts of DMPP was added as a catalyst, the temperature was raised to 160 ° C., and the reaction was started. Five hours after the start of the reaction, 190 parts of PMA was added as a reaction solvent to a solid concentration of 60%, and 0.30 part of TPP-BB was added as a catalyst, followed by further stirring for 5 hours to carry out the reaction. Thereafter, 267 parts of PMA was added as a reaction solvent to adjust the solid content concentration to 50%, and the reaction was continued for further 5 hours to obtain a PMA varnish of a high molecular weight epoxy resin. The obtained PMA varnish was subjected to the same operation as in Example 1 to obtain a resin varnish 8.
合成例９
実施例１で使用した装置を用い、ＹＤ−１２８を５００部、ＢＰＦを２６５部、及び反応溶媒としてＴＯＬとＮＢＡとの混合反応溶媒（ＴＯＬ／ＮＢＡ＝６５／３５（質量比））を１９１部を仕込み、８０℃で溶融混合させた。このときのフェノール性水酸基とエポキシ基のモル比は１：１．０２１であった。その後、触媒として４８．７％ＮａＯＨ水溶液を３．８部添加して反応を開始した。粘度の上昇に合わせて順次、前記ＴＯＬ／ＮＢＡ混合反応溶媒で希釈して最終的には固形分濃度を５０％にして合計１２時間反応を行った。その後、前記ＴＯＬ／ＮＢＡ混合反応溶媒で希釈して固形分濃度を４０％にした後、純水２００部、シュウ酸２．９部を加えて中和・分液を行い、さらに２０００部の純水を加え、水洗・分液を行い、脱水、濾過して高分子量エポキシ樹脂のＴＯＬ／ＮＢＡ混合ワニスを得た。得られた混合ワニスを実施例１と同様の操作を行い樹脂ワニス９を得た。
Synthesis Example 9
Using the apparatus used in Example 1, 500 parts of YD-128, 265 parts of BPF, and 191 parts of a mixed reaction solvent of TOL and NBA (TOL / NBA = 65/35 (mass ratio)) as a reaction solvent. Was melted and mixed at 80 ° C. At this time, the molar ratio of the phenolic hydroxyl group to the epoxy group was 1: 1.021. Then, 3.8 parts of 48.7% NaOH aqueous solution was added as a catalyst, and reaction was started. As the viscosity increased, the reaction mixture was diluted with the TOL / NBA mixed reaction solvent in order and finally the reaction was carried out for a total of 12 hours with a solid content concentration of 50%. Then, after diluting with the TOL / NBA mixed reaction solvent to a solid content concentration of 40%, 200 parts of pure water and 2.9 parts of oxalic acid were added for neutralization and liquid separation, and 2000 parts of pure water were added. Water was added, washed and separated, dehydrated and filtered to obtain a TOL / NBA mixed varnish of high molecular weight epoxy resin. The obtained mixed varnish was subjected to the same operation as in Example 1 to obtain a resin varnish 9.
合成例１０
合成例６の条件で、反応溶媒のみＴＯＬからＭＥＫに変更し、それ以外は同じ条件で合成を行った。すなわち、実施例１で使用した装置を用い、エポキシ樹脂としてＹＤＦ−８１７０を５００部、フェノール化合物としてＢＰＡを３５０部、及び反応溶媒としてＴＯＬを４５部（固形分濃度９５％）仕込み、１１０℃で溶融混合させた。このときのフェノール性水酸基とエポキシ基のモル比は１：１．０３１であった。その後、触媒としてＥＴＰＰＩを０．３５部添加し、還流温度まで昇温し、反応を開始した。しかし、系中の温度が１１０℃までしか上がらず、還流温度で２０時間撹拌を続けたが、高分子量エポキシ樹脂を得る事ができなかった。最終重量平均分子量は５５００だった。
Synthesis Example 10
Only the reaction solvent was changed from TOL to MEK under the conditions of Synthesis Example 6, and synthesis was performed under the same conditions except that. That is, using the apparatus used in Example 1, 500 parts of YDF-8170 as an epoxy resin, 350 parts of BPA as a phenol compound, and 45 parts of TOL (solid content concentration 95%) as a reaction solvent were charged at 110 ° C. Melt mixed. At this time, the molar ratio of the phenolic hydroxyl group to the epoxy group was 1: 1.031. Thereafter, 0.35 part of ETPPI was added as a catalyst, the temperature was raised to the reflux temperature, and the reaction was started. However, the temperature in the system increased only to 110 ° C., and stirring was continued for 20 hours at the reflux temperature, but a high molecular weight epoxy resin could not be obtained. The final weight average molecular weight was 5500.
合成例１１
合成例６の条件で、反応時の固形分濃度のみを９５％から２５％に変更し、それ以外は同じ条件で合成を行った。すなわち、実施例１で使用した装置を用い、エポキシ樹脂としてＹＤ−１２８を５００部、フェノール化合物としてＢＰＦＤを２６２部、及び反応溶媒としてＰＭＡを２２８６部（固形分濃度２５％）仕込み、１３０℃で溶融混合させた。このときのフェノール性水酸基とエポキシ基のモル比は１：１．０２１であった。その後、触媒としてＴＰＰ−ＢＢを０．２６部添加し、還流温度の１４５℃まで昇温し、反応を開始した。そのまま還流温度で２０時間撹拌を続けたが、高分子量エポキシ樹脂を得る事ができなかった。最終重量平均分子量は１５８００だった。
Synthesis Example 11
The synthesis was performed under the same conditions as in Synthesis Example 6 except that only the solid content concentration during the reaction was changed from 95% to 25%. That is, using the apparatus used in Example 1, 500 parts of YD-128 as an epoxy resin, 262 parts of BPFD as a phenol compound, and 2286 parts of PMA as a reaction solvent (solid content concentration 25%) were charged at 130 ° C. Melt mixed. At this time, the molar ratio of the phenolic hydroxyl group to the epoxy group was 1: 1.021. Thereafter, 0.26 parts of TPP-BB was added as a catalyst, and the temperature was raised to the reflux temperature of 145 ° C. to initiate the reaction. Stirring was continued for 20 hours at the reflux temperature, but a high molecular weight epoxy resin could not be obtained. The final weight average molecular weight was 15800.
合成例１２
合成例２の条件で、反応溶媒のみＣＰＡからＣＨＡに変更し、それ以外は同じ条件で合成を行った。すなわち、実施例１で使用した装置を用い、エポキシ樹脂としてＹＤ−１２８を５００部、フェノール化合物としてＢＰＦＤを１９２部とＢＰＡを８０部、及び反応溶媒としてＣＨＡを８６部（固形分濃度９０％）仕込み、１３０℃で溶融混合させた。このときのフェノール性水酸基とエポキシ基のモル比は１：１．０２０であった。その後、触媒としてＴＰＰ−ＢＢを０．２７部添加し、１５５℃まで昇温し、反応を開始した。反応液の粘度は上がったため、反応開始後２時間目に反応溶媒としてＣＨＡを１０７部追加し固形分濃度を８０％にした。さらに５時間撹拌を続けて反応を行った後、反応溶媒としてＣＨＡを２２４部追加し固形分濃度を７０％にして、さらに触媒としてＴＰＰ−ＢＢを０．２７部追加して、さらに５時間撹拌を続けて反応を行った。反応終了後、反応溶媒としてＣＨＡを３５５部加えて高分子量エポキシ樹脂のＣＨＡワニスを得た。得られたＣＨＡワニスを実施例１と同様の操作を行い樹脂ワニス１２を得た。
Synthesis Example 12
The synthesis was performed under the same conditions as in Synthesis Example 2 except that only the reaction solvent was changed from CPA to CHA. That is, using the apparatus used in Example 1, 500 parts of YD-128 as an epoxy resin, 192 parts of BPFD and 80 parts of BPA as a phenol compound, and 86 parts of CHA as a reaction solvent (solid content concentration 90%) The mixture was melted and mixed at 130 ° C. At this time, the molar ratio of the phenolic hydroxyl group to the epoxy group was 1: 1.020. Thereafter, 0.27 parts of TPP-BB was added as a catalyst, the temperature was raised to 155 ° C., and the reaction was started. Since the viscosity of the reaction solution increased, 107 parts of CHA was added as a reaction solvent at 2 hours after the start of the reaction to make the solid content concentration 80%. The reaction was continued for further 5 hours, and then 224 parts of CHA was added as a reaction solvent to a solid concentration of 70%, and 0.27 parts of TPP-BB was added as a catalyst, and the mixture was further stirred for 5 hours. The reaction was continued. After completion of the reaction, 355 parts of CHA was added as a reaction solvent to obtain a high molecular weight epoxy resin CHA varnish. The obtained CHA varnish was subjected to the same operation as in Example 1 to obtain a resin varnish 12.
合成例１〜９及び１２で得られた樹脂ワニス１〜９及び１２の性状を表１に示す。項目「ＢＰＦ骨格含有量（モル％）」は、原料エポキシ樹脂及びフェノール化合物の総モル量に対するビスフェノールＦ骨格を有するエポキシ樹脂及びフェノール化合物の合計モル量よりその含有量を計算した。 Table 1 shows the properties of the resin varnishes 1 to 9 and 12 obtained in Synthesis Examples 1 to 9 and 12. The item “BPF skeleton content (mol%)” was calculated from the total molar amount of the epoxy resin having a bisphenol F skeleton and the phenol compound relative to the total molar amount of the raw material epoxy resin and the phenol compound.
実施例１〜８、比較例１〜４
表２に示す配合で高分子エポキシ樹脂を含む樹脂組成物を得た。なお、表中の値は全て質量部である。同樹脂組成物を離型フィルム（ＰＥＴ製）へ溶剤乾燥後の樹脂厚みが６０μｍになるようにバーコーターにて塗布し、オーブン内で５０℃で６０分間乾燥させて、シート状接着剤を得た。得られたシート状接着剤でフィルム性を確認した。また得られたシート状接着剤を複数枚重ね合わせ、１ｍｍ厚のフッ素樹脂のスペーサーを介して鉄板に挟み、真空プレス装置にて成形を行い、厚み１ｍｍの平板試験片を得た。得られた平板試験片で、透過率とＹＩ値を測定した。なお、比較例４で得たシート状接着剤には溶剤臭が残り、べたつきもあって、フィルム性がなかったため、透過率とＹＩ値測定用の厚み１ｍｍの平板試験片が得られなかった。得られた樹脂組成物、及び硬化物の性状を表３に示す。
Examples 1-8, Comparative Examples 1-4
A resin composition containing a polymer epoxy resin was obtained with the formulation shown in Table 2. In addition, all the values in a table | surface are a mass part. The resin composition was applied to a release film (PET) with a bar coater so that the resin thickness after solvent drying was 60 μm, and dried in an oven at 50 ° C. for 60 minutes to obtain a sheet-like adhesive. It was. The film property was confirmed with the obtained sheet-like adhesive. A plurality of the obtained sheet-like adhesives were superposed on each other and sandwiched between iron plates via a 1 mm-thick fluororesin spacer, and molded with a vacuum press device to obtain a flat-plate test piece with a thickness of 1 mm. With the obtained flat plate test piece, the transmittance and YI value were measured. In addition, since the solvent-like odor remained in the sheet-like adhesive obtained in Comparative Example 4 and there was no film property, a flat test piece having a thickness of 1 mm for measuring transmittance and YI value could not be obtained. Table 3 shows properties of the obtained resin composition and cured product.
実施例９〜１６
表４に示す配合で高分子エポキシ樹脂を含む樹脂組成物を得た。なお、表中の値は全て質量部である。実施例１と同様の操作でシート状接着剤を得た。また得られたシート状接着剤を複数枚重ね合わせ、１ｍｍ厚のフッ素樹脂製のスペーサーを介して鉄板に挟み、真空プレス装置にて成形を行い、１ｍｍに厚みを調整した後、積算光量３０ｋＪ／ｍ２となるように紫外線を照射して、厚み１ｍｍの平板試験片を得た。実施例１と同様の評価を行った。得られた樹脂組成物、及び硬化物の性状を表５に示す。
Examples 9-16
A resin composition containing a polymer epoxy resin with the formulation shown in Table 4 was obtained. In addition, all the values in a table | surface are a mass part. A sheet-like adhesive was obtained by the same operation as in Example 1. In addition, a plurality of the obtained sheet-like adhesives are overlapped, sandwiched between iron plates via a 1 mm-thick fluororesin spacer, molded with a vacuum press device, adjusted to a thickness of 1 mm, and then integrated light quantity 30 kJ / Ultraviolet rays were irradiated so as to be m 2 to obtain a flat plate test piece having a thickness of 1 mm. Evaluation similar to Example 1 was performed. Table 5 shows properties of the obtained resin composition and cured product.
表３、表５から明らかなように、本発明の樹脂組成物は透明なシート状接着剤に好適である。 As is clear from Tables 3 and 5, the resin composition of the present invention is suitable for a transparent sheet adhesive.
Claims (13)
該２官能エポキシ樹脂（ａ）はエポキシ当量が１７０〜２００ｇ／ｅｑ．のビスフェノールＡ型エポキシ樹脂及び／又はエポキシ当量が１５０〜１８０ｇ／ｅｑ．のビスフェノールＦ型エポキシ樹脂であり、
該２価フェノール化合物（ｂ）はビスフェノールＡ及び／又はビスフェノールＦであり、
該高分子エポキシ樹脂は下記一般式（１）で表され、
高分子エポキシ樹脂中の（Ｅ）及び（Ｐ）の合計モルに対して、ビスフェノールＦ型エポキシ樹脂の骨格残基及びビスフェノールＦの骨格残基の合計モルが３５〜５５モル％の範囲であり、メチルエチルケトンの５０質量％ワニスのハーゼン単位色相が５０以下であることを特徴とする透明なシート状接着剤用樹脂組成物。 A transparent resin composition for a sheet-like adhesive comprising a polymer epoxy resin obtained by reacting a bifunctional epoxy resin (a) and a divalent phenol compound (b) and a curable resin component,
The bifunctional epoxy resin (a) has an epoxy equivalent of 170 to 200 g / eq. Bisphenol A type epoxy resin and / or epoxy equivalent of 150 to 180 g / eq. Bisphenol F type epoxy resin,
The dihydric phenol compound (b) is bisphenol A and / or bisphenol F,
The polymer epoxy resin is represented by the following general formula (1):
The total mole of the skeletal residue of the bisphenol F type epoxy resin and the skeletal residue of bisphenol F is in the range of 35 to 55 mol% with respect to the total mole of (E) and (P) in the polymer epoxy resin, A transparent resin composition for a sheet-like adhesive, characterized in that the Hazen unit hue of 50% by mass varnish of methyl ethyl ketone is 50 or less.
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