TWI859245B - Photocurable resin composition and a method of producing the display device - Google Patents
Photocurable resin composition and a method of producing the display device Download PDFInfo
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- TWI859245B TWI859245B TW109118316A TW109118316A TWI859245B TW I859245 B TWI859245 B TW I859245B TW 109118316 A TW109118316 A TW 109118316A TW 109118316 A TW109118316 A TW 109118316A TW I859245 B TWI859245 B TW I859245B
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- resin composition
- photocurable resin
- meth
- image display
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- 239000011342 resin composition Substances 0.000 title claims abstract description 157
- 238000000034 method Methods 0.000 title claims description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 109
- 239000011347 resin Substances 0.000 claims abstract description 76
- 229920005989 resin Polymers 0.000 claims abstract description 76
- 239000000178 monomer Substances 0.000 claims abstract description 53
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 claims abstract description 28
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 27
- 238000000576 coating method Methods 0.000 claims abstract description 25
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- 239000003999 initiator Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- -1 isostearyl Chemical group 0.000 claims description 19
- 239000000853 adhesive Substances 0.000 claims description 12
- 238000010030 laminating Methods 0.000 claims description 11
- 230000001678 irradiating effect Effects 0.000 claims description 10
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 5
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 4
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical group COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 9
- 238000001723 curing Methods 0.000 description 50
- 239000000463 material Substances 0.000 description 23
- 238000003860 storage Methods 0.000 description 18
- 230000003287 optical effect Effects 0.000 description 15
- 239000011521 glass Substances 0.000 description 14
- 238000005259 measurement Methods 0.000 description 14
- 238000010586 diagram Methods 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 238000000016 photochemical curing Methods 0.000 description 11
- 229920000515 polycarbonate Polymers 0.000 description 9
- 239000004417 polycarbonate Substances 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 150000003505 terpenes Chemical class 0.000 description 4
- 235000007586 terpenes Nutrition 0.000 description 4
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 3
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007607 die coating method Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000013191 viscoelastic testing Methods 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- PRBBFHSSJFGXJS-UHFFFAOYSA-N (2,2-dimethyl-3-prop-2-enoyloxypropyl) prop-2-enoate;3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)C(O)=O.C=CC(=O)OCC(C)(C)COC(=O)C=C PRBBFHSSJFGXJS-UHFFFAOYSA-N 0.000 description 1
- RHNJVKIVSXGYBD-UHFFFAOYSA-N 10-prop-2-enoyloxydecyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCCOC(=O)C=C RHNJVKIVSXGYBD-UHFFFAOYSA-N 0.000 description 1
- STFXXRRQKFUYEU-UHFFFAOYSA-N 16-methylheptadecyl prop-2-enoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)C=C STFXXRRQKFUYEU-UHFFFAOYSA-N 0.000 description 1
- PPVGIYDGIOTKTB-UHFFFAOYSA-N 2-butylheptan-1-ol Chemical compound CCCCCC(CO)CCCC PPVGIYDGIOTKTB-UHFFFAOYSA-N 0.000 description 1
- QRNFTMKPBPCPJO-UHFFFAOYSA-N 2-ethylhexyl hexanoate Chemical compound CCCCCC(=O)OCC(CC)CCCC QRNFTMKPBPCPJO-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- PGDIJTMOHORACQ-UHFFFAOYSA-N 9-prop-2-enoyloxynonyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCOC(=O)C=C PGDIJTMOHORACQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 1
- DTGKSKDOIYIVQL-MRTMQBJTSA-N Isoborneol Natural products C1C[C@@]2(C)[C@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-MRTMQBJTSA-N 0.000 description 1
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- NXQNMWHBACKBIG-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCCC(O)(O)O Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCCC(O)(O)O NXQNMWHBACKBIG-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 101100012902 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) FIG2 gene Proteins 0.000 description 1
- 101100233916 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) KAR5 gene Proteins 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- REJKHFKLPFJGAQ-UHFFFAOYSA-N oxiran-2-ylmethanethiol Chemical compound SCC1CO1 REJKHFKLPFJGAQ-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- FAQJJMHZNSSFSM-UHFFFAOYSA-N phenylglyoxylic acid Chemical class OC(=O)C(=O)C1=CC=CC=C1 FAQJJMHZNSSFSM-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Abstract
本發明提供不產生由使用具有(甲基)丙烯醯基之(甲基)丙烯酸酯低聚物而導致之界面密接強度降低或延伸性降低等問題之光硬化性樹脂組成物，作為於製造影像顯示構件與透光性覆蓋構件經由由光硬化性樹脂組成物形成之透光性之光硬化樹脂層進行積層而成之影像顯示裝置時，利用噴墨塗佈法而塗佈之光硬化性樹脂組成物。 光硬化性樹脂組成物之羥值為120 mgKOH/g以上，且含有：不具有(甲基)丙烯醯基之(甲基)丙烯酸酯聚合物、單官能(甲基)丙烯酸酯單體、奪氫型光聚合起始劑及黏著賦予劑。黏著賦予劑於光硬化性樹脂組成物中之含量為1〜9質量%。光硬化性樹脂組成物具有於25℃為10 mPa∙s以上且於60℃為30 mPa∙s以下之黏度。The present invention provides a photocurable resin composition that does not cause problems such as reduced interfacial adhesion strength or reduced elongation caused by using a (meth)acrylic (meth)acrylate oligomer, and is used as a photocurable resin composition applied by inkjet coating when manufacturing an image display device in which an image display component and a light-transmitting cover component are laminated via a light-transmitting photocurable resin layer formed by the photocurable resin composition. The photocurable resin composition has a hydroxyl value of 120 mgKOH/g or more and contains: a (meth)acrylate polymer without a (meth)acrylic (meth)acrylate group, a monofunctional (meth)acrylate monomer, a hydrogen-scavenging photopolymerization initiator, and an adhesion-imparting agent. The content of the tackifier in the photocurable resin composition is 1 to 9 mass %. The photocurable resin composition has a viscosity of 10 mPa∙s or more at 25°C and 30 mPa∙s or less at 60°C.
Description
本發明係關於一種光硬化性樹脂組成物，其可提供對玻璃、(甲基)丙烯酸樹脂、聚碳酸酯等透明光學材料之密接性優異，且表現出良好之延伸性之光硬化物，且可較佳地應用於噴墨塗佈法。The present invention relates to a photocurable resin composition which can provide a photocurable product having excellent adhesion to transparent optical materials such as glass, (meth) acrylic resin, polycarbonate, etc. and exhibiting good elongation, and can be preferably applied to an inkjet coating method.
且說，作為透明覆蓋材料等透光性覆蓋構件與液晶顯示面板等影像顯示構件經由光硬化樹脂層進行積層而成之影像顯示裝置，廣為人知有液晶顯示裝置或有機EL裝置等。於該等影像顯示裝置中，夾持著光硬化樹脂層之透光性覆蓋構件及影像顯示構件之至少對向面分別由透明光學材料構成。習知此種影像顯示裝置藉由如下方式而製造：利用模塗（die coat）法或網版塗佈法等將光硬化性樹脂組成物塗佈於平坦之影像顯示構件或透光性覆蓋構件之任一者之表面，形成光硬化性樹脂組成物膜，對該光硬化性樹脂組成物膜照射紫外線使其暫時硬化而形成暫時硬化樹脂層，並將另一構件積層於暫時硬化樹脂層，自透光性覆蓋構件側照射紫外線使暫時硬化樹脂層正式硬化。As an image display device formed by laminating a light-transmitting cover member such as a transparent cover material and an image display member such as a liquid crystal display panel via a photo-curing resin layer, a liquid crystal display device or an organic EL device is widely known. In such image display devices, at least the facing surfaces of the light-transmitting cover member and the image display member sandwiching the photo-curing resin layer are respectively formed of transparent optical materials. It is known that such an image display device is manufactured by coating a photocurable resin composition on the surface of either a flat image display component or a light-transmitting cover component by die coating or screen coating to form a photocurable resin composition film, irradiating the photocurable resin composition film with ultraviolet rays to temporarily cure it to form a temporarily curing resin layer, laminating another component on the temporarily curing resin layer, and irradiating the temporarily curing resin layer with ultraviolet rays from the light-transmitting cover component side to fully cure the temporarily curing resin layer.
近年來，隨著彎曲之影像顯示裝置之上市，開始塗佈於彎曲為橫槽狀、碗狀等形狀之影像顯示構件或透光性覆蓋構件。於該情形時，需要將光硬化性樹脂組成物於影像顯示構件或透光性覆蓋構件之中心部塗佈為相對較厚，且向周邊部逐漸塗佈為較薄，故揭示有利用可對每塊微細區域容易地設定油墨塗佈量之噴墨塗佈法代替習知之模塗法或網版塗佈法，將光硬化性樹脂組成物塗佈於影像顯示構件或透光性覆蓋構件之方法（專利文獻1）。In recent years, with the introduction of curved image display devices, the coating has begun to be applied to image display components or light-transmitting cover components that are curved in a transverse groove shape, a bowl shape, etc. In this case, it is necessary to apply the photocurable resin composition relatively thickly in the center of the image display component or the light-transmitting cover component and gradually apply it thinner toward the peripheral portion. Therefore, a method of applying the photocurable resin composition to the image display component or the light-transmitting cover component using an inkjet coating method that can easily set the ink coating amount for each fine area instead of the conventional die coating method or screen coating method is disclosed (Patent Document 1).
於專利文獻1中，為了於影像顯示裝置之製造中應用噴墨塗佈法，使用如下之丙烯酸系光硬化性樹脂組成物作為光硬化性樹脂組成物，該丙烯酸系光硬化性樹脂組成物係除單官能(甲基)丙烯酸酯單體以外亦含有具有(甲基)丙烯醯基之分子量為5000以上之(甲基)丙烯酸酯低聚物，進而含有光或熱自由基聚合起始劑者，且其黏度被調整為150 mPa∙s以下，具體而言為27〜141 mPa∙s（25℃）（參照實施例）。 [先前技術文獻] [專利文獻]In Patent Document 1, in order to apply the inkjet coating method in the manufacture of an image display device, the following acrylic photocurable resin composition is used as the photocurable resin composition. The acrylic photocurable resin composition contains, in addition to the monofunctional (meth)acrylate monomer, a (meth)acrylate oligomer having a molecular weight of 5000 or more and having a (meth)acryloyl group, and further contains a photo or thermal free radical polymerization initiator, and its viscosity is adjusted to 150 mPa∙s or less, specifically 27 to 141 mPa∙s (25°C) (see the embodiment). [Prior art document] [Patent document]
[專利文獻1]日本特開2017-210578號公報[Patent Document 1] Japanese Patent Application Publication No. 2017-210578
[發明所欲解決之課題][The problem that the invention wants to solve]
然而，專利文獻1中所使用之光硬化性樹脂組成物由於含有之(甲基)丙烯酸酯低聚物具有(甲基)丙烯醯基，故存在於光硬化時引起交聯反應而硬化收縮之問題。因此，於利用由此種光硬化性樹脂組成物構成之光硬化樹脂層將透光性覆蓋構件與影像顯示構件積層之情形時，存在如下之問題：於光硬化樹脂層與透光性覆蓋構件之界面及/或光硬化樹脂層與影像顯示構件之界面產生由光硬化樹脂層之硬化收縮所導致之應力，界面密接強度降低之問題；或用於緩和於影像顯示裝置變形之情形時於界面所產生之應力之延伸性降低之問題。於使用於高溫環境下易變形之聚碳酸酯作為影像顯示裝置中使用之透明光學材料之情形時，該等問題有顯著明顯化之傾向。However, the photocurable resin composition used in Patent Document 1 contains (meth)acrylate oligomers with (meth)acrylic groups, which causes a crosslinking reaction during photocuring and causes shrinkage during curing. Therefore, when a light-transmitting cover member and an image display member are laminated using a photocurable resin layer composed of such a photocurable resin composition, there are the following problems: stress caused by the curing shrinkage of the photocurable resin layer is generated at the interface between the photocurable resin layer and the light-transmitting cover member and/or the interface between the photocurable resin layer and the image display member, and the problem of reduced interface adhesion strength; or the problem of reduced elongation for alleviating stress generated at the interface when the image display device is deformed. These problems tend to become more pronounced when polycarbonate, which is easily deformed in a high temperature environment, is used as a transparent optical material used in an image display device.
本發明之目的在於為了解決此種習知之問題，提供不產生由使用具有(甲基)丙烯醯基之(甲基)丙烯酸酯低聚物導致之界面密接強度降低或延伸性降低等問題之光硬化性樹脂組成物，作為於製造影像顯示構件與透光性覆蓋構件經由由光硬化性樹脂組成物形成之透光性之光硬化樹脂層進行積層而成之影像顯示裝置時，利用噴墨塗佈法而塗佈之光硬化性樹脂組成物。 [解決課題之技術手段]The purpose of the present invention is to solve the known problems and provide a photocurable resin composition that does not cause problems such as reduced interface adhesion strength or reduced elongation caused by using a (meth)acrylate oligomer having a (meth)acryl group, as a photocurable resin composition applied by inkjet coating when manufacturing an image display device in which an image display component and a light-transmitting cover component are laminated via a light-transmitting photocurable resin layer formed by the photocurable resin composition. [Technical means for solving the problem]
本案發明人等發現，藉由如下方式可達成上述目的，從而完成本發明：使用「羥值為特定數值以上且不具有(甲基)丙烯醯基之(甲基)丙烯酸酯聚合物」代替「具有(甲基)丙烯醯基之(甲基)丙烯酸酯低聚物」作為「應與構成光硬化性樹脂組成物之(甲基)丙烯酸酯單體併用之高分子物質」，並且使用奪氫型光聚合起始劑作為光聚合起始劑，進而將光硬化性樹脂組成物之黏度調整為於25℃為10 mPa∙s以上、於60℃為30 mPa∙s以下，並且併用黏著賦予劑。The inventors of the present invention have found that the above-mentioned object can be achieved by the following method, thereby completing the present invention: using "a (meth)acrylate polymer having a hydroxyl value of a specific value or more and not having a (meth)acrylate group" instead of "a (meth)acrylate oligomer having a (meth)acrylate group" as "a polymer substance to be used together with a (meth)acrylate monomer constituting a photocurable resin composition", and using a hydrogen-scavenging photopolymerization initiator as a photopolymerization initiator, and further adjusting the viscosity of the photocurable resin composition to be 10 mPa∙s or more at 25°C and 30 mPa∙s or less at 60°C, and using a tackifier in combination.
即，本發明提供一種光硬化性樹脂組成物，其可應用於影像顯示裝置，且含有以下之成分（A）〜（D）： ＜成分（A）＞羥值為120 mgKOH/g以上且不具有(甲基)丙烯醯基之(甲基)丙烯酸酯聚合物； ＜成分（B）＞單官能(甲基)丙烯酸酯單體； ＜成分（C）＞奪氫型光聚合起始劑；及 ＜成分（D）＞黏著賦予劑； 該影像顯示裝置係影像顯示構件與透光性覆蓋構件經由由光硬化性樹脂組成物形成之透光性之光硬化樹脂層進行積層而成， 成分（D）黏著賦予劑於光硬化性樹脂組成物中之含量為1〜9質量%， 光硬化性樹脂組成物之黏度於25℃為10 mPa∙s以上且於60℃為30 mPa∙s以下。That is, the present invention provides a photocurable resin composition which can be used in an image display device and contains the following components (A) to (D): <Component (A)> Hydroxyl value is 120 mgKOH/g or more and having no (meth)acryloyl group; <Component (B)> Monofunctional (meth)acrylate monomer; <Component (C)> Hydrogen-absorptive photopolymerization initiator; and <Component (D)> Adhesive agent; The image display device is formed by laminating an image display component and a light-transmitting covering component via a light-transmitting photocurable resin layer formed by a photocurable resin composition, the content of the adhesive agent of component (D) in the photocurable resin composition is 1 to 9% by mass, the viscosity of the photocurable resin composition is 10 mPa∙s or more at 25°C and 30 mPa∙s or less at 60°C.
又，本發明提供一種影像顯示裝置之製造方法，該影像顯示裝置係影像顯示構件與透光性覆蓋構件經由由光硬化性樹脂組成物形成之透光性之光硬化樹脂層進行積層而成，該影像顯示裝置之製造方法具有以下之步驟（a）〜（c）： ＜步驟（a）＞ 使上述本發明之光硬化性樹脂組成物自噴墨塗佈裝置之噴嘴噴出而於影像顯示構件或透光性覆蓋構件之任一構件之表面形成光硬化性樹脂組成物膜； ＜步驟（b）＞ 於光硬化性樹脂組成物膜積層另一構件，使影像顯示構件與透光性覆蓋構件貼合；及 ＜步驟（c）＞ 藉由對夾持於兩面板之光硬化性樹脂組成物膜照射紫外線使其硬化，從而獲得藉由光硬化樹脂層將影像顯示構件與透光性覆蓋構件積層而成之影像顯示裝置。In addition, the present invention provides a method for manufacturing an image display device, wherein the image display device is formed by laminating an image display component and a light-transmitting covering component via a light-transmitting photocurable resin layer formed by a photocurable resin composition. The method for manufacturing the image display device comprises the following steps (a) to (c): <Step (a)> The light-curable resin composition of the present invention is ejected from the nozzle of an inkjet coating device and is applied to the image display component or the light-transmitting covering component. A photocurable resin composition film is formed on the surface of any one of the light-transmitting covering components; <Step (b)> Another component is laminated on the photocurable resin composition film so that the image display component and the light-transmitting covering component are bonded together; and <Step (c)> The photocurable resin composition film sandwiched between two panels is irradiated with ultraviolet rays to cure, thereby obtaining an image display device in which the image display component and the light-transmitting covering component are laminated by the photocurable resin layer.
又，本發明提供一種影像顯示裝置之製造方法，該影像顯示裝置係影像顯示構件與透光性覆蓋構件經由由光硬化性樹脂組成物形成之透光性之光硬化樹脂層進行積層而成，該影像顯示裝置之製造方法具有以下步驟（aa）〜（dd）： ＜步驟（aa）＞ 使上述本發明之光硬化性樹脂組成物自噴墨塗佈裝置之噴嘴噴出而於影像顯示構件或透光性覆蓋構件之任一構件之表面形成光硬化性樹脂組成物膜； ＜步驟（bb）＞ 對光硬化性樹脂組成物膜照射紫外線而形成暫時硬化樹脂層； ＜步驟（cc）＞ 於暫時硬化樹脂層積層另一構件，使影像顯示構件與透光性覆蓋構件貼合：及 ＜步驟（dd）＞ 藉由對夾持於兩面板之暫時硬化樹脂層照射紫外線使其正式硬化，從而獲得藉由光硬化樹脂層將影像顯示構件與透光性覆蓋構件積層而成之影像顯示裝置。 [發明之效果]In addition, the present invention provides a method for manufacturing an image display device, wherein the image display device is formed by laminating an image display component and a light-transmitting covering component via a light-transmitting photocuring resin layer formed by a photocuring resin composition. The method for manufacturing the image display device comprises the following steps (aa) to (dd): <Step (aa)> The photocuring resin composition of the present invention is ejected from the nozzle of an inkjet coating device to form a light-curing layer on the surface of either the image display component or the light-transmitting covering component. <Step (bb)> Irradiating the photocurable resin composition film with ultraviolet rays to form a temporary curing resin layer; <Step (cc)> Laminating another component on the temporary curing resin layer to bond the image display component to the light-transmitting covering component: and <Step (dd)> Irradiating the temporary curing resin layer sandwiched between two panels with ultraviolet rays to formally cure it, thereby obtaining an image display device formed by laminating the image display component and the light-transmitting covering component through the photocurable resin layer. [Effect of the invention]
本發明之光硬化性樹脂組成物可應用於影像顯示裝置，該影像顯示裝置係影像顯示構件與透光性覆蓋構件經由由光硬化性樹脂組成物形成之透光性之光硬化樹脂層進行積層而成，作為應與主要的聚合成分之單官能(甲基)丙烯酸酯單體併用之成分，不使用「可與該單體聚合之具有(甲基)丙烯醯基之低聚物」，而是使用「羥值為120 mgKOH/g以上且不具有(甲基)丙烯醯基之(甲基)丙烯酸酯聚合物」，並且使用奪氫型光聚合起始劑作為光聚合起始劑。此種(甲基)丙烯酸酯聚合物雖然無助於基於(甲基)丙烯醯基之光聚合，但被奪氫型光聚合起始劑奪氫而生成自由基，其結果，作為側鏈或聚合物交聯鏈而併入至由(甲基)丙烯酸酯單體形成之聚合鏈，可對光硬化性樹脂組成物賦予良好之塑化性、成膜性、接著性。The photocurable resin composition of the present invention can be applied to an image display device, wherein an image display component and a light-transmitting cover component are laminated via a light-transmitting photocurable resin layer formed by the photocurable resin composition, and as a component to be used together with a monofunctional (meth)acrylate monomer as a main polymerization component, instead of using "an oligomer having a (meth)acrylic group that can be polymerized with the monomer", a "(meth)acrylate polymer having a hydroxyl value of 120 mgKOH/g or more and not having a (meth)acrylic group" is used, and a hydrogen-abstracting photopolymerization initiator is used as the photopolymerization initiator. Although such (meth)acrylate polymers do not contribute to photopolymerization based on (meth)acryloyl groups, they are dehydrogenated by hydrogen-depleting photopolymerization initiators to generate free radicals, which are then incorporated into the polymer chain formed by (meth)acrylate monomers as side chains or polymer crosslinking chains, thereby imparting good plasticization, film-forming properties, and adhesion to the photocurable resin composition.
進而，本發明之光硬化性樹脂組成物含有黏著賦予劑。因此，關於本發明之光硬化性樹脂組成物之光硬化物，可使對玻璃或聚碳酸酯等透明光學材料之界面密接強度提昇，且亦可使延伸性提昇。Furthermore, the photocurable resin composition of the present invention contains a tackifier. Therefore, the photocured product of the photocurable resin composition of the present invention can improve the interfacial adhesion strength with transparent optical materials such as glass and polycarbonate, and can also improve the elongation.
並且，本發明之光硬化性樹脂組成物表現出於25℃為10 mPa∙s以上、於60℃為30 mPa∙s以下之黏度，故可於包含25℃、60℃等溫度的較廣之噴墨塗佈溫度條件下表現出良好之噴墨塗佈適合性。Furthermore, the photocurable resin composition of the present invention exhibits a viscosity of 10 mPa∙s or more at 25°C and 30 mPa∙s or less at 60°C, and thus exhibits good inkjet coating suitability under a wide range of inkjet coating temperature conditions including 25°C and 60°C.
以下，首先對本發明之光硬化性樹脂組成物進行說明，其後對利用該光硬化性樹脂組成物製造影像顯示裝置之方法進行說明。Hereinafter, the photocurable resin composition of the present invention will be described first, and then a method for manufacturing an image display device using the photocurable resin composition will be described.
＜光硬化性樹脂組成物＞ 本發明之光硬化性樹脂組成物可較佳地應用於影像顯示裝置，且含有以下之成分（A）、成分（B）、成分（C）及成分（D），黏度於25℃為10 mPa∙s以上且於60℃為30 mPa∙s以下，該影像顯示裝置係影像顯示構件與透光性覆蓋構件經由由光硬化性樹脂組成物形成之透光性之硬化樹脂層進行積層而成。<Photocurable resin composition> The photocurable resin composition of the present invention can be preferably applied to an image display device, and contains the following components (A), (B), (C) and (D), and has a viscosity of 10 mPa∙s or more at 25°C and 30 mPa∙s or less at 60°C. The image display device is formed by laminating an image display component and a light-transmitting covering component via a light-transmitting hardened resin layer formed by the photocurable resin composition.
再者，關於可較佳地應用本發明之光硬化性樹脂組成物之影像顯示裝置及構成該影像顯示裝置之影像顯示構件或透光性覆蓋構件，於本發明之影像顯示裝置之製造方法之說明中一併加以說明。Furthermore, an image display device to which the photocurable resin composition of the present invention can be preferably applied and an image display component or a light-transmitting covering component constituting the image display device are described together with the description of the manufacturing method of the image display device of the present invention.
＜成分（A）＞ 為了對硬化物賦予塑化性，並且確保良好之成膜性（維持膜性）及接著性，本發明之光硬化性樹脂組成物含有羥值為120 mgKOH/g以上、較佳為170 mgKOH/g以上且不具有(甲基)丙烯醯基之(甲基)丙烯酸酯聚合物。具有羥值係表示於分子內具有羥基，藉由具有羥基，可與後文所述之成分（D）奪氫型光聚合起始劑協同作用而鍵結於聚合鏈之側鏈。再者，於本說明書中，「(甲基)丙烯酸酯」係包含丙烯酸酯及甲基丙烯酸酯之用語。<Component (A)> In order to impart plasticity to the cured product and ensure good film-forming (film-maintaining) and adhesive properties, the photocurable resin composition of the present invention contains a (meth)acrylate polymer having a hydroxyl value of 120 mgKOH/g or more, preferably 170 mgKOH/g or more, and having no (meth)acryloyl group. Having a hydroxyl value means having a hydroxyl group in the molecule, and by having a hydroxyl group, it can synergistically act with the component (D) hydrogen-scavenging photopolymerization initiator described later to bond to the side chain of the polymer chain. Furthermore, in this specification, "(meth)acrylate" is a term that includes acrylate and methacrylate.
關於成分（A）(甲基)丙烯酸酯聚合物，羥值係指使1 g聚合物中之羥基乙醯化後，用以中和使乙醯基水解而生成之乙酸所需要之KOH之質量（mg）。因此，羥值越大則表示羥基越多。將成分（A）(甲基)丙烯酸酯聚合物之羥值設為120 mgKOH/g以上之原因在於：若未達120 mgKOH/g，則有光硬化性樹脂組成物之硬化物之交聯密度低，尤其是高溫下之彈性模數降低變得顯著之傾向。再者，若僅使該硬化物之交聯密度增大，則只要大量使用後文中所述之成分（E）多官能(甲基)丙烯酸酯單體即可，但擔心光硬化性樹脂組成物之硬化物變脆，故藉由利用分子量某種程度較高之聚合物使其交聯，可對硬化物賦予良好之柔軟性與凝聚力。因此，若羥值過高，則存在光硬化性樹脂組成物之硬化物之交聯密度變得過高，失去柔軟性之傾向，因此羥值為400 mgKOH/g以下，較佳為350 mgKOH/g以下。Regarding the component (A) (meth)acrylate polymer, the hydroxyl value refers to the mass (mg) of KOH required to neutralize the acetic acid generated by the hydrolysis of the acetyl group after the hydroxyl group in 1 g of the polymer is acetylated. Therefore, the larger the hydroxyl value, the more hydroxyl groups there are. The reason for setting the hydroxyl value of the component (A) (meth)acrylate polymer to 120 mgKOH/g or more is that if it does not reach 120 mgKOH/g, the crosslinking density of the cured product of the photocurable resin composition is low, and the elastic modulus decreases significantly, especially at high temperatures. Furthermore, if only the crosslinking density of the cured product is to be increased, a large amount of component (E) multifunctional (meth)acrylate monomer described later can be used, but there is a concern that the cured product of the photocurable resin composition will become brittle, so by crosslinking the polymer with a certain degree of molecular weight, the cured product can be given good flexibility and cohesion. Therefore, if the hydroxyl value is too high, the crosslinking density of the cured product of the photocurable resin composition becomes too high and tends to lose flexibility, so the hydroxyl value is 400 mgKOH/g or less, preferably 350 mgKOH/g or less.
又，若具有(甲基)丙烯醯基，則成分（B）及成分（C）過度併入至由(甲基)丙烯酸酯單體構成之聚合鏈之主鏈之可能性增大，因此為了防止該情況而使用不具有(甲基)丙烯醯基者作為成分（A）(甲基)丙烯酸酯聚合物。Furthermore, if a (meth)acryl group is present, there is a greater possibility that the components (B) and (C) are excessively incorporated into the main chain of the polymer chain composed of the (meth)acrylate monomer. Therefore, in order to prevent this, a (meth)acrylate polymer having no (meth)acryl group is used as the component (A).
成分（A）(甲基)丙烯酸酯聚合物之重量平均分子量Mn若過小，則有未導入羥基之分子增加，滲出等風險上升之傾向，故較佳為5000以上，更佳為100000以上；若過大，則有由黏度上升導致噴出不良之傾向，故較佳為500000以下，更佳為300000以下。再者，於本說明書中，聚合物之重量平均分子量Mw及數量平均分子量Mn可利用凝膠滲透層析法（GPC）進行測定（標準聚苯乙烯分子量換算）。If the weight average molecular weight Mn of the component (A) (meth)acrylate polymer is too small, the number of molecules without hydroxyl groups increases, and the risk of seepage tends to increase, so it is preferably 5000 or more, more preferably 100000 or more; if it is too large, the viscosity tends to increase, resulting in poor spraying, so it is preferably 500000 or less, more preferably 300000 or less. In addition, in this specification, the weight average molecular weight Mw and number average molecular weight Mn of the polymer can be measured by gel permeation chromatography (GPC) (converted to standard polystyrene molecular weight).
又，成分（A）(甲基)丙烯酸酯聚合物之分散度（Mw/Mn）若過低，則有聚合物與未反應之單體類易分離之傾向，故較佳為3以上；若過高，則會使不需要之分子量相對較低之聚合物成分混入，故較佳為10以下。If the dispersion degree (Mw/Mn) of the (meth)acrylate polymer of component (A) is too low, the polymer and the unreacted monomers tend to separate easily, so it is preferably 3 or more. If it is too high, unnecessary polymer components with relatively low molecular weight may be mixed in, so it is preferably 10 or less.
作為此種成分（A）(甲基)丙烯酸酯聚合物，可較佳地列舉含羥基之(甲基)丙烯酸酯單體與不含羥基之(甲基)丙烯酸酯單體之共聚物。較佳為於常溫為液狀。再者，亦可例示含羥基之(甲基)丙烯酸酯單體之均聚物，但若聚合物之極性過高，則有於常溫成為高黏度液體或固體之傾向，且擔心與其他成分之相容性降低。As such component (A) (meth)acrylate polymer, a copolymer of a hydroxyl-containing (meth)acrylate monomer and a hydroxyl-free (meth)acrylate monomer can be preferably cited. It is preferably liquid at room temperature. Furthermore, a homopolymer of a hydroxyl-containing (meth)acrylate monomer can also be cited, but if the polarity of the polymer is too high, it tends to become a high-viscosity liquid or solid at room temperature, and there is a concern that the compatibility with other components will be reduced.
所謂作為構成成分（A）(甲基)丙烯酸酯聚合物之單體單元的含羥基之(甲基)丙烯酸酯單體，其係於分子中具有1個以上羥基之(甲基)丙烯酸酯，具體而言，可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-羥基-3-氯丙酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、乙二醇(甲基)丙烯酸酯、聚乙二醇(甲基)丙烯酸酯、丙二醇(甲基)丙烯酸酯、聚丙二醇(甲基)丙烯酸酯、環己基二甲醇單(甲基)丙烯酸酯等。其中，就極性控制或價格之方面而言，可較佳地例示(甲基)丙烯酸2-羥基乙酯。The hydroxyl-containing (meth)acrylate monomer as a monomer unit constituting the (meth)acrylate polymer of component (A) is a (meth)acrylate having one or more hydroxyl groups in the molecule, and specifically includes 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, ethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate, propylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, cyclohexyl dimethanol mono(meth)acrylate, etc. Among them, 2-hydroxyethyl (meth)acrylate is preferably exemplified in terms of polarity control or price.
作為可構成成分（A）(甲基)丙烯酸酯聚合物之不含羥基之(甲基)丙烯酸酯單體，例如較佳為烷基之碳數為1〜18之直鏈或具有分支之單官能(甲基)丙烯酸烷基酯，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸十三烷基酯等。Examples of the (meth)acrylate monomer not containing a hydroxyl group that can constitute the (meth)acrylate polymer of component (A) include, for example, a linear or branched monofunctional (meth)acrylate alkyl ester having an alkyl group with a carbon number of 1 to 18, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, tridecyl (meth)acrylate, and the like.
作為成分（A）(甲基)丙烯酸酯聚合物之尤佳之例，就獲得容易性或發明效果之實現性等觀點而言，可列舉丙烯酸2-羥基乙酯與丙烯酸2-乙基己酯之共聚物。可進一步共聚丙烯酸異莰基酯。As a particularly preferred example of the (meth)acrylate polymer of component (A), a copolymer of 2-hydroxyethyl acrylate and 2-ethylhexyl acrylate can be cited from the viewpoint of ease of acquisition and realization of the inventive effect. Isoborneol acrylate can be further copolymerized.
成分（A）(甲基)丙烯酸酯聚合物於光硬化性樹脂組成物中之含量若過少，則有變脆之傾向，故較佳為1質量%以上，更佳為10質量%以上；若過多，則有由黏度上升導致噴出不良之傾向，故較佳為55質量%以下，更佳為45質量%以下。If the content of the (meth)acrylate polymer of component (A) in the photocurable resin composition is too low, the composition tends to become brittle, and is preferably 1% by mass or more, more preferably 10% by mass or more. If the content is too high, the viscosity tends to increase, resulting in poor ejection, and is preferably 55% by mass or less, more preferably 45% by mass or less.
＜成分（B）＞ 本發明之光硬化性樹脂組成物含有單官能(甲基)丙烯酸酯單體作為聚合成分。作為單官能(甲基)丙烯酸酯單體，可考慮光硬化性樹脂組成物之使用目的或需實現之物性等而自公知之單官能(甲基)丙烯酸酯單體之中適當選擇。成分（B）單官能(甲基)丙烯酸酯單體於光硬化性樹脂組成物中之含量雖取決於其種類，但擔心若過少則產生界面密接強度不足，且擔心若過多則延伸性降低，故較佳為30質量%以上，更佳為60質量%以上，較佳為90質量%以下，更佳為80質量%以下。<Component (B)> The photocurable resin composition of the present invention contains a monofunctional (meth)acrylate monomer as a polymerizable component. As the monofunctional (meth)acrylate monomer, it is possible to appropriately select from known monofunctional (meth)acrylate monomers in consideration of the purpose of use of the photocurable resin composition or the physical properties to be achieved. The content of the component (B) monofunctional (meth)acrylate monomer in the photocurable resin composition depends on its type, but if it is too little, there is a concern that the interface adhesion strength is insufficient, and if it is too much, there is a concern that the elongation is reduced. Therefore, it is preferably 30% by mass or more, more preferably 60% by mass or more, preferably 90% by mass or less, and more preferably 80% by mass or less.
再者，成分（B）單官能(甲基)丙烯酸酯單體根據種類而存在如下情形：於其硬化後與成分（A）之羥值為120 mgKOH/g以上且不具有(甲基)丙烯醯基之(甲基)丙烯酸酯聚合物之相容性降低，從而招致光硬化樹脂層之白濁化。因此，作為成分（B）單官能(甲基)丙烯酸酯單體，就與含有羥基之成分（A）(甲基)丙烯酸酯聚合物之親和性高，且可期待高溫高濕環境中之可靠性提昇之方面而言，較佳為使用含有1個以上羥基、較佳為含有1個羥基的含羥基之單官能(甲基)丙烯酸酯。於該情形時，為了將光硬化性樹脂組成物之硬化物之接著性或黏度分別設定為良好之範圍，較佳為併用不含羥基之(甲基)丙烯酸酯。即，較佳為由成分（B1）含羥基之單官能(甲基)丙烯酸酯單體與成分（B2）不含羥基之單官能(甲基)丙烯酸酯單體構成成分（B）單官能(甲基)丙烯酸酯單體。Furthermore, the monofunctional (meth)acrylate monomer of component (B) may have a reduced compatibility with the (meth)acrylate polymer of component (A) having a hydroxyl value of 120 mgKOH/g or more and having no (meth)acryloyl group, which may cause the photocured resin layer to become cloudy, depending on the type. Therefore, as the monofunctional (meth)acrylate monomer of component (B), a hydroxyl-containing monofunctional (meth)acrylate containing one or more hydroxyl groups, preferably one hydroxyl group, is preferably used, in terms of high affinity with the (meth)acrylate polymer of component (A) containing a hydroxyl group and improved reliability in a high temperature and high humidity environment. In this case, in order to set the adhesion and viscosity of the cured product of the photocurable resin composition to a good range, it is preferred to use a (meth)acrylate that does not contain a hydroxyl group. That is, it is preferred that the monofunctional (meth)acrylate monomer of component (B) is composed of a monofunctional (meth)acrylate monomer containing a hydroxyl group of component (B1) and a monofunctional (meth)acrylate monomer containing a hydroxyl group of component (B2).
作為成分（B1）含羥基之單官能(甲基)丙烯酸酯單體之具體例，可例示與可構成成分（A）(甲基)丙烯酸酯聚合物的含羥基之(甲基)丙烯酸酯單體相同之單體。其中較佳為選自(甲基)丙烯酸4-羥基丁酯及(甲基)丙烯酸2-羥基乙酯之至少一種，但尤佳為(甲基)丙烯酸4-羥基丁酯。Specific examples of the hydroxyl-containing monofunctional (meth)acrylate monomer of component (B1) include the same monomers as the hydroxyl-containing (meth)acrylate monomers that can constitute the (meth)acrylate polymer of component (A). Among them, at least one selected from 4-hydroxybutyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate is preferred, and 4-hydroxybutyl (meth)acrylate is particularly preferred.
成分（B1）含羥基之單官能(甲基)丙烯酸酯單體於光硬化性樹脂組成物中之含量若過少，則有高溫高濕環境中之光硬化性樹脂組成物之硬化物所要求之特性之可靠性不足之傾向，故較佳為1質量%以上，更佳為5質量%以上；若過多，則硬化前或硬化後之樹脂之極性之平衡被破壞，有變得不透明之傾向，故較佳為30質量%以下，更佳為25質量%以下。If the content of the hydroxyl-containing monofunctional (meth)acrylate monomer of component (B1) in the photocurable resin composition is too low, the reliability of the properties required of the cured product of the photocurable resin composition in a high temperature and high humidity environment tends to be insufficient. Therefore, it is preferably 1 mass % or more, and more preferably 5 mass % or more. If it is too high, the polarity balance of the resin before or after curing is destroyed, and there is a tendency to become opaque. Therefore, it is preferably 30 mass % or less, and more preferably 25 mass % or less.
再者，作為成分（B1）含羥基之單官能(甲基)丙烯酸酯單體於光硬化性樹脂組成物中之含量，就與成分（A）(甲基)丙烯酸酯聚合物之關係而言，相對於成分（A）(甲基)丙烯酸酯聚合物100質量份，較佳為1〜3000質量份。只要為該範圍內，則可獲得能夠於各種環境下維持高透明性之效果。Furthermore, the content of the hydroxyl-containing monofunctional (meth)acrylate monomer as component (B1) in the photocurable resin composition is preferably 1 to 3000 parts by mass relative to 100 parts by mass of the (meth)acrylate polymer as component (A). Within this range, the effect of maintaining high transparency in various environments can be obtained.
作為成分（B2）不含羥基之單官能(甲基)丙烯酸酯單體之具體例，可例示與可構成成分（A）(甲基)丙烯酸酯聚合物的不含羥基之(甲基)丙烯酸酯單體相同之單體。其中較佳為選自(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸異癸酯及(甲基)丙烯酸辛酯之至少一種。尤佳為(甲基)丙烯酸異硬脂酯、(甲基)丙烯酸異癸酯。Specific examples of the monofunctional (meth)acrylate monomer not containing a hydroxyl group as component (B2) include the same monomers as the (meth)acrylate monomer not containing a hydroxyl group that can constitute the (meth)acrylate polymer as component (A). Among them, at least one selected from isostearyl (meth)acrylate, isodecyl (meth)acrylate and octyl (meth)acrylate is preferred. Isostearyl (meth)acrylate and isodecyl (meth)acrylate are particularly preferred.
成分（B2）不含羥基之單官能(甲基)丙烯酸酯單體於光硬化性樹脂組成物中之含量若過少，則有變為高黏度之傾向，故較佳為30質量%以上，更佳為65質量%以上；若過多，則有變脆之傾向，故較佳為90質量%以下，更佳為75質量%以下。If the content of the monofunctional (meth)acrylate monomer not containing a hydroxyl group as component (B2) in the photocurable resin composition is too low, the viscosity tends to be high, so it is preferably 30 mass % or more, more preferably 65 mass % or more; if it is too high, the composition tends to be brittle, so it is preferably 90 mass % or less, more preferably 75 mass % or less.
再者，作為成分（B2）不含羥基之單官能(甲基)丙烯酸酯單體於光硬化性樹脂組成物中之含量，就與成分（A）(甲基)丙烯酸酯聚合物之關係而言，相對於成分（A）(甲基)丙烯酸酯聚合物100質量份，較佳為54〜9000質量份。只要為該範圍內，則可獲得能夠於各種環境下維持高透明性，並且作為接著劑而發揮高性能之效果。Furthermore, the content of the monofunctional (meth)acrylate monomer not containing a hydroxyl group as component (B2) in the photocurable resin composition is preferably 54 to 9000 parts by mass relative to 100 parts by mass of the (meth)acrylate polymer as component (A). Within this range, the photocurable resin composition can maintain high transparency in various environments and exhibit high performance as an adhesive.
＜成分（C）＞ 本發明之光硬化性樹脂組成物不含有如安息香衍生物之分子內裂解型光聚合起始劑，而是含有奪氫型光聚合起始劑、較佳為分子內奪氫型光聚合起始劑作為光聚合起始劑。其用以使成分（A）含有羥基之(甲基)丙烯酸酯聚合物與聚合鏈之側鏈鍵結。<Component (C)> The photocurable resin composition of the present invention does not contain an intramolecular cleavage type photopolymerization initiator such as benzoin derivatives, but contains a hydrogenation type photopolymerization initiator, preferably an intramolecular hydrogenation type photopolymerization initiator as a photopolymerization initiator. It is used to make the (meth)acrylate polymer containing a hydroxyl group in component (A) bond to the side chain of the polymer chain.
作為成分（C）奪氫型光聚合起始劑，可使用公知之奪氫型光聚合起始劑，例如可列舉：二苯甲酮等二芳基酮類、苯甲醯甲酸甲酯等苯甲醯甲酸酯（phenylglyoxylate）類。作為較佳例，就無黃變且奪氫能力高之方面而言，可列舉苯甲醯甲酸甲酯。As the component (C) hydrogenation type photopolymerization initiator, a known hydrogenation type photopolymerization initiator can be used, for example, diaryl ketones such as benzophenone, phenylglyoxylates such as methyl benzoylcarboxylate. As a preferred example, methyl benzoylcarboxylate can be mentioned in terms of no yellowing and high hydrogenation ability.
成分（C）奪氫型光聚合起始劑於光硬化性樹脂組成物中之含量若過少，則有變得交聯不足之傾向，故較佳為0.1質量%以上，更佳為1質量%以上；若過多，則有導致環境可靠性變差之傾向，故較佳為10質量%以下，更佳為5質量%以下。If the content of the component (C) hydrogen-absorbent photopolymerization initiator in the photocurable resin composition is too little, crosslinking tends to be insufficient, so it is preferably 0.1% by mass or more, more preferably 1% by mass or more; if it is too much, environmental reliability tends to deteriorate, so it is preferably 10% by mass or less, more preferably 5% by mass or less.
＜成分（D）＞ 本發明之光硬化性樹脂組成物為了提昇硬化物之界面密接強度或延伸性而含有黏著賦予劑。作為黏著賦予劑，可根據使用目的而自公知之黏著賦予劑，例如松香系黏著賦予劑、氫化松香酯系黏著賦予劑、萜烯樹脂系黏著賦予劑、芳香族改質萜烯樹脂系黏著賦予劑、氫化萜烯樹脂系黏著賦予劑、萜烯酚樹脂系黏著賦予劑、脂肪族石油樹脂系黏著賦予劑、芳香族石油樹脂系黏著賦予劑、脂環族（氫化）石油樹脂系黏著賦予劑等中適當選擇。作為較佳之黏著賦予劑，可較佳地列舉無色透明性、無味無臭性、耐熱性、耐候性及電特性（絕緣性）之任一特性均優異之脂環族（氫化）石油樹脂系黏著賦予劑。作為尤佳之具體的黏著賦予劑，可列舉以ARKON（註冊商標）P90、M100或M115（荒川化學工業（股））之商標進行銷售之黏著賦予劑。<Component (D)> The photocurable resin composition of the present invention contains an adhesion agent in order to enhance the interfacial adhesion strength or elongation of the cured product. The tackifier can be appropriately selected from known tackifiers, such as rosin-based tackifiers, hydrogenated rosin ester-based tackifiers, terpene resin-based tackifiers, aromatic modified terpene resin-based tackifiers, hydrogenated terpene resin-based tackifiers, terpene phenol resin-based tackifiers, aliphatic petroleum resin-based tackifiers, aromatic petroleum resin-based tackifiers, alicyclic (hydrogenated) petroleum resin-based tackifiers, etc., depending on the purpose of use. As a preferred adhesive agent, an alicyclic (hydrogenated) petroleum resin-based adhesive agent having excellent colorless transparency, tasteless and odorless properties, heat resistance, weather resistance, and electrical properties (insulation) can be preferably cited. As a particularly preferred specific adhesive agent, an adhesive agent sold under the trademarks of ARKON (registered trademark) P90, M100, or M115 (Arakawa Chemical Industries, Ltd.) can be cited.
成分（D）黏著賦予劑於光硬化性樹脂組成物中之含量若過少，則有光硬化性樹脂組成物之硬化物對玻璃或聚碳酸酯之界面密接強度變得不充分之傾向，故為1質量%以上，較佳為2質量%以上，更佳為3質量%以上；若過多，則有硬化物白濁之傾向，故為9質量%以下，較佳為8質量%以下，更佳為6質量%以下。If the content of the component (D) adhesion-imparting agent in the photocurable resin composition is too small, the interfacial adhesion strength of the cured photocurable resin composition to glass or polycarbonate tends to be insufficient, so it is 1 mass % or more, preferably 2 mass % or more, and more preferably 3 mass % or more. If it is too large, the cured product tends to be turbid, so it is 9 mass % or less, preferably 8 mass % or less, and more preferably 6 mass % or less.
＜成分（E）＞ 為了提昇反應速度或維持高溫彈性模數，本發明之光硬化性樹脂組成物可含有多官能(甲基)丙烯酸酯單體。作為多官能(甲基)丙烯酸酯單體之具體例，可列舉：1,6-己二醇二丙烯酸酯（HDDA）、1,9-壬二醇二丙烯酸酯、1,10-癸二醇二丙烯酸酯、新戊四醇三丙烯酸酯等2官能以上之(甲基)丙烯酸酯類等。該等化合物只要無損發明效果，則可具有羥基等其他官能基。其中，作為多官能(甲基)丙烯酸酯單體之較佳之具體例，可列舉選自三羥甲基丙烷三丙烯酸酯、新戊四醇三丙烯酸酯及羥基三甲基乙酸新戊二醇二丙烯酸酯之至少一種。<Component (E)> In order to increase the reaction rate or maintain the high temperature elastic modulus, the photocurable resin composition of the present invention may contain a multifunctional (meth)acrylate monomer. Specific examples of multifunctional (meth)acrylate monomers include: 1,6-hexanediol diacrylate (HDDA), 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, pentaerythritol triacrylate and other (meth)acrylates with two or more functions. These compounds may have other functional groups such as hydroxyl groups as long as they do not impair the effect of the invention. Among them, as a preferred specific example of a multifunctional (meth)acrylate monomer, at least one selected from trihydroxymethylpropane triacrylate, pentaerythritol triacrylate and hydroxytrimethylacetic acid neopentyl glycol diacrylate can be listed.
成分（E）多官能(甲基)丙烯酸酯單體於光硬化性樹脂組成物中之含量若過少，則有交聯密度變低之傾向，故較佳為0.1質量%以上，更佳為1質量%以上；若過多，則有變脆之傾向，故較佳為5質量%以下，更佳為3質量%以下。If the content of the component (E) multifunctional (meth)acrylate monomer in the photocurable resin composition is too little, the crosslinking density tends to be low, so it is preferably 0.1 mass % or more, more preferably 1 mass % or more; if it is too much, it tends to become brittle, so it is preferably 5 mass % or less, more preferably 3 mass % or less.
＜其他成分＞ 於本發明之光硬化性樹脂組成物中，除上述成分（A）〜（D）、進而視需要之（E）以外，亦可於不損及本發明之效果的範圍內摻合各種添加劑。例如，作為用於降低硬化收縮率之液狀塑化成分，可摻合聚丁二烯系塑化劑、聚異戊二烯系塑化劑、鄰苯二甲酸酯系塑化劑、己二酸酯系塑化劑等。又，為了調整硬化物之分子量，可摻合2-巰基乙醇、月桂硫醇、環氧丙基硫醇、巰基乙酸、巰乙酸2-乙基己酯、2,3-二巰基-1-丙醇、α-甲基苯乙烯二聚物等作為鏈轉移劑。可進而視需要含有矽烷偶合劑等接著改善劑、抗氧化劑等通常之添加劑。<Other components> In addition to the above-mentioned components (A) to (D) and (E) as needed, various additives may be blended into the photocurable resin composition of the present invention within the range that does not impair the effect of the present invention. For example, as a liquid plasticizing component for reducing the curing shrinkage rate, polybutadiene plasticizers, polyisoprene plasticizers, phthalate plasticizers, adipate plasticizers, etc. may be blended. In addition, in order to adjust the molecular weight of the cured product, 2-butylethanol, lauryl mercaptan, glycidyl mercaptan, butylacetic acid, 2-ethylhexyl butylacetate, 2,3-dibutyl-1-propanol, α-methylstyrene dimer, etc. may be blended as a chain transfer agent. It may further contain common additives such as silane coupling agents, bonding improvers, antioxidants, etc. as needed.
＜光硬化性樹脂組成物之硬化前之黏度特性＞ 本發明之光硬化性樹脂組成物雖然含有以上所說明之成分，但為了於通常之噴墨噴出條件下實現良好之噴墨適合性，將黏度調整為於25℃為10 mPa∙s以上、較佳為15 mPa∙s以上，且於60℃為30 mPa∙s以下、較佳為20 mPa‧s以下。此處，若黏度於25℃未達10 mPa‧s，則容易自噴墨噴嘴產生滴液；若於60℃超過30 mPa‧s，則容易變得無法噴出。再者，光硬化性樹脂組成物之黏度可利用通常之黏彈性測定裝置進行測定。作為具體例，可使用流變儀（Haake RheoStress600、Thermo Scientific公司；測定條件、錐形轉子、＝35 mm、轉子角度2°、剪切速度120/s）進行測定。<Viscosity characteristics of the photocurable resin composition before curing> Although the photocurable resin composition of the present invention contains the components described above, in order to achieve good inkjet compatibility under normal inkjet ejection conditions, the viscosity is adjusted to be 10 mPa·s or more at 25°C, preferably 15 mPa·s or more, and 30 mPa·s or less at 60°C, preferably 20 mPa·s or less. Here, if the viscosity is less than 10 mPa·s at 25°C, dripping is likely to occur from the inkjet nozzle; if it exceeds 30 mPa·s at 60°C, it is likely to become impossible to eject. In addition, the viscosity of the photocurable resin composition can be measured using a normal viscoelasticity measuring device. As a specific example, a rheometer (Haake RheoStress600, Thermo Scientific; measurement conditions, conical rotor, =35 mm, rotor angle 2°, shear speed 120/s).
本發明之光硬化性樹脂組成物之黏度之調整可藉由調整各構成成分之種類、含量等而進行。The viscosity of the photocurable resin composition of the present invention can be adjusted by adjusting the type and content of each component.
＜光硬化性樹脂組成物之硬化後之各種特性＞ 為了評價本發明之光硬化性樹脂組成物於硬化後，作為光學材料之基本光學特性、界面密接強度之降低或延伸性之降低等問題，若無特別聲明，則較佳為針對成形為100 μm厚之膜形狀者觀察、測定以下特性。<Various properties of photocurable resin composition after curing> In order to evaluate the basic optical properties of the photocurable resin composition of the present invention as an optical material after curing, the reduction in interface adhesion strength or the reduction in elongation, etc., unless otherwise stated, it is preferred to observe and measure the following properties for a film shape formed into a 100 μm thick film.
（a）「硬化物之外觀」 目視觀察作為光學材料之基本光學特性之硬化物之外觀。其原因在於：作為影像顯示裝置用之光學材料，要求透明。(a) "Appearance of the cured product" Visually observe the appearance of the cured product as a basic optical property of the optical material. The reason is that as an optical material for image display devices, transparency is required.
（b）「於25℃、85℃之拉伸儲存彈性模數[Pa]」 作為動態黏彈性特性之一方面之「拉伸儲存彈性模數」，其數值越大，則彈性體越強，成為判斷影像顯示構件與透光性覆蓋構件之貼合性時之指標之一。雖然需要與後文中所述之損耗正切tanδ進行權衡，但一般而言，若「拉伸儲存彈性模數」變低則變為低彈性體，並且儘管存在極限，但有伴隨於此而貼合性變良好之傾向。「拉伸儲存彈性模數」可利用市售之動態黏彈性測定裝置（例如流變儀（Haake Mars II、Thermo Scientific公司；測定條件、錐形轉子、＝8 mm、頻率1 Hz））進行測量。此處，於25℃測定係為了判斷貼合後於常溫環境下之凝聚力。於該情形時，數值越大越佳。又，於85℃測定係為了判斷假定高溫環境下時之樹脂之凝聚力。(b) "Stretched storage modulus at 25°C and 85°C [Pa]" As one aspect of dynamic viscoelastic properties, the larger the value of the "stretched storage modulus", the stronger the elastic body, and it becomes one of the indicators for judging the adhesion between the image display component and the light-transmitting cover component. Although it needs to be weighed against the loss tangent tanδ described later, in general, if the "stretched storage modulus" becomes lower, it becomes a low-elastic body, and although there is a limit, there is a tendency for the adhesion to become better. The tensile storage modulus can be measured using a commercially available dynamic viscoelasticity test device (e.g., a rheometer (Haake Mars II, Thermo Scientific; test conditions, conical rotor, =8 mm, frequency 1 Hz)). Here, the measurement at 25°C is to determine the cohesion in a normal temperature environment after bonding. In this case, the larger the value, the better. In addition, the measurement at 85°C is to determine the cohesion of the resin in a high temperature environment.
（c）「於25℃之損耗正切tanδ（＝損失彈性模數/儲存彈性模數）」 「損耗正切tanδ」之數值越大，則表示黏性體越強，顯示出更良好之衝擊吸收性，可使用上述市售之動態黏彈性測定裝置進行測量。此處，於25℃進行測定係為了判斷影像顯示構件與透光性覆蓋構件之貼合性。(c) "Loss tangent tanδ at 25°C (= loss modulus of elasticity/storage modulus of elasticity)" The larger the value of "Loss tangent tanδ", the stronger the viscosity and the better the impact absorption. It can be measured using the above-mentioned commercially available dynamic viscoelasticity measuring device. Here, the measurement at 25°C is to determine the adhesion between the image display component and the light-transmitting cover component.
（d）「玻璃轉移溫度[℃]」 「玻璃轉移溫度」為可利用上述市售之動態黏彈性測定裝置進行測定之拉伸損失彈性模數之測定曲線之峰溫度，若較硬化物之使用溫度範圍高則有硬化物變脆之傾向，若較低則有流動之傾向。(d) "Glass transition temperature [°C]" "Glass transition temperature" is the peak temperature of the tensile loss modulus measurement curve that can be measured using the above-mentioned commercially available dynamic viscoelasticity measuring device. If it is higher than the use temperature range of the hardened material, the hardened material tends to become brittle, and if it is lower, it tends to flow.
（e）「伸長係數[%]」 「伸長係數」為利用公知之拉伸試驗機以一定之速度對長度Lo之膜樣品進行拉伸，斷裂時之長度L1 相對於上述Lo之比率。只要上述（b）拉伸彈性模數為特定之範圍，該數值越大，則表示對變形之追隨性良好。(e) "Elongation coefficient [%]""Elongationcoefficient" is the ratio of the length L1 at the time of fracture to the above Lo when the film sample of length Lo is stretched at a certain speed using a known tensile testing machine. As long as the above (b) tensile modulus is within a specific range, the larger the value, the better the deformation tracking performance.
（f）「界面密接強度[N/cm2 ]」 關於界面密接強度，該數值越大，則表示密接性良好。該測定可於以下條件下進行。即，於2片載玻片之一者之中央，例如以直徑5 mm、平均100 μm之厚度塗佈光硬化性樹脂組成物，形成光硬化性樹脂組成物膜之後，以正交之方式載置另一載玻片，藉由對夾持於2片載玻片之光硬化性樹脂組成物膜照射紫外線而使光硬化性樹脂組成物膜硬化，藉此獲得透光性之光暫時硬化樹脂層作為界面密接強度試驗用樣品，可使用市售之拉伸試驗機（例如Autograph AGS-X、島津製作所（股）製造）測定所獲得之該樣品之界面密接強度。(f) "Interface Adhesion Strength [N/cm 2 ]" Regarding the interface adhesion strength, the larger the value, the better the adhesion. This measurement can be performed under the following conditions. That is, a photocurable resin composition is coated on the center of one of two glass slides, for example, with a diameter of 5 mm and an average thickness of 100 μm to form a photocurable resin composition film, and then another glass slide is placed in an orthogonal manner. The photocurable resin composition film sandwiched between the two glass slides is irradiated with ultraviolet rays to cure the photocurable resin composition film, thereby obtaining a light-transmitting light-temporarily cured resin layer as a sample for an interface adhesion strength test. The interface adhesion strength of the obtained sample can be measured using a commercially available tensile tester (for example, Autograph AGS-X, manufactured by Shimadzu Corporation).
＜光硬化性樹脂組成物之製備＞ 本發明之光硬化性樹脂組成物可藉由依照慣例將成分（A）〜（D）及視需要摻合之其他成分均勻地混合而製備。<Preparation of photocurable resin composition> The photocurable resin composition of the present invention can be prepared by uniformly mixing components (A) to (D) and other components as required according to conventional practice.
＜影像顯示裝置之製造方法＞ 其次，以下參照圖式對具有步驟（a）〜（c）之本發明之影像顯示裝置之製造方法之毎個步驟加以詳細說明。再者，於圖式中，相同之圖號表示相同或類似之構成元件。<Manufacturing method of image display device> Next, each step of the manufacturing method of the image display device of the present invention having steps (a) to (c) is described in detail below with reference to the drawings. Furthermore, in the drawings, the same figure numbers represent the same or similar components.
＜步驟（a）（塗佈步驟）＞ 首先，如圖1所示，準備透光性覆蓋構件1，如圖2所示，自噴墨噴嘴3將光硬化性樹脂組成物2塗佈於透光性覆蓋構件1之表面1a，形成光硬化性樹脂組成物膜4。該情形之塗佈厚度可根據透光性覆蓋構件1或影像顯示構件之表面狀態、所需之硬化樹脂層之膜物性等而適當設定。<Step (a) (Coating step)> First, as shown in FIG1, a light-transmitting covering member 1 is prepared, and as shown in FIG2, a photocurable resin composition 2 is coated on the surface 1a of the light-transmitting covering member 1 from an inkjet nozzle 3 to form a photocurable resin composition film 4. The coating thickness in this case can be appropriately set according to the surface state of the light-transmitting covering member 1 or the image display member, the film properties of the desired curing resin layer, etc.
再者，為了獲得所需之厚度，可進行複數次該光硬化性樹脂組成物2之塗佈。Furthermore, in order to obtain a desired thickness, the photocurable resin composition 2 may be applied multiple times.
作為透光性覆蓋構件1，只要具有如能夠目視辨認形成於影像顯示構件之影像之透光性即可，可列舉：玻璃、丙烯酸樹脂、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚碳酸酯等板狀材料或片狀材料。可對該等材料實施單面或雙面硬塗（hard coat）處理、抗反射處理等。透光性覆蓋構件1之厚度或彈性等物性可根據使用目的而適當決定。As the light-transmitting cover member 1, any material that has light-transmitting properties such that the image formed on the image display member can be visually recognized may be glass, acrylic resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, or other plate-like or sheet-like materials. Such materials may be subjected to single-sided or double-sided hard coating, anti-reflection treatment, etc. The physical properties of the light-transmitting cover member 1, such as thickness and elasticity, may be appropriately determined according to the intended use.
又，透光性覆蓋構件1亦包括使上述板狀材料或片狀材料與如觸控板等之位置輸入元件經由公知之接著劑或本發明之光硬化性樹脂組成物之暫時硬化樹脂層或硬化樹脂層而一體化而成者。Furthermore, the light-transmitting cover member 1 also includes a member obtained by integrating the plate-like material or sheet-like material with a position input element such as a touch panel via a known adhesive or a temporarily hardened resin layer or a hardened resin layer of the photocurable resin composition of the present invention.
本步驟中所使用之光硬化性樹脂組成物2之性狀為於噴墨條件下為液狀。由於使用液狀者，故透光性覆蓋構件1之表面形狀或影像顯示構件之表面形狀中即使存在變形亦可消除該變形。The photocurable resin composition 2 used in this step is in a liquid state under inkjet conditions. Since a liquid is used, even if there is deformation in the surface shape of the light-transmitting covering member 1 or the surface shape of the image display member, the deformation can be eliminated.
＜步驟（b）（貼合步驟）＞ 其次，如圖3所示，自透光性覆蓋構件1之光硬化性樹脂組成物膜4側貼合影像顯示構件5。貼合可藉由使用公知之壓接裝置於10℃〜80℃進行加壓而進行。<Step (b) (bonding step)> Next, as shown in FIG3 , the image display member 5 is bonded to the light-transmitting cover member 1 from the side of the photocurable resin composition film 4 . The bonding can be performed by applying pressure at 10°C to 80°C using a known press-bonding device.
作為影像顯示構件5，可列舉：液晶顯示面板、有機EL顯示面板、電漿顯示面板、觸控面板等。此處，觸控面板係指使如液晶顯示面板之顯示元件與如觸控板之位置輸入元件經由公知之接著劑或本發明之光硬化性樹脂組成物之暫時硬化樹脂層或硬化樹脂層而一體化而成者。再者，於觸控板與透光性覆蓋構件1已經一體化之情形時，可不採用觸控面板作為影像顯示構件5。The image display component 5 may include a liquid crystal display panel, an organic EL display panel, a plasma display panel, a touch panel, etc. Here, the touch panel refers to a display element such as a liquid crystal display panel and a position input element such as a touch panel integrated through a known adhesive or a temporary curing resin layer or a curing resin layer of the photocurable resin composition of the present invention. Furthermore, when the touch panel and the light-transmitting cover component 1 are already integrated, the touch panel may not be used as the image display component 5.
＜步驟（c）（硬化步驟）＞ 其次，如圖4所示，自透光性覆蓋構件1側向步驟（b）中形成之光硬化性樹脂組成物膜4照射紫外線UV使其硬化，如圖5所示般形成透光性之光硬化樹脂層6。藉此獲得影像顯示裝置100。再者，使光硬化性樹脂組成物膜4硬化係用以使光硬化性樹脂組成物2自液狀成為不流動之狀態，進而對光硬化樹脂層6賦予黏著性，且即使上下翻轉亦不流下而提昇操作性。此種硬化之程度係透光性之光硬化樹脂層6之硬化率（凝膠分率）較佳成為40%以上、更佳成為60%以上之程度。此處，硬化率（凝膠分率）係指定義為紫外線照射後之(甲基)丙烯醯基之存在量相對於紫外線照射前之光硬化性樹脂組成物2中之(甲基)丙烯醯基之存在量之比率（消耗量比率）之數值，該數值越大，越表示硬化進行較多。再者，關於光硬化樹脂層6之透光性之程度，只要具有如可目視辨認形成於影像顯示構件之影像之透光性即可。<Step (c) (hardening step)> Next, as shown in FIG. 4 , the light-curing resin composition film 4 formed in step (b) is irradiated with ultraviolet light UV from the side of the light-transmitting cover member 1 to harden it, and a light-transmitting light-curing resin layer 6 is formed as shown in FIG. 5 . Thus, an image display device 100 is obtained. Furthermore, the light-curing resin composition film 4 is hardened to make the light-curing resin composition 2 from a liquid state to a non-flowing state, thereby giving adhesion to the light-curing resin layer 6, and even if it is turned upside down, it does not flow down, thereby improving operability. The degree of such hardening is preferably such that the hardening rate (gel fraction) of the light-transmitting light-curing resin layer 6 is 40% or more, and more preferably 60% or more. Here, the curing rate (gel fraction) is defined as the ratio (consumption ratio) of the amount of (meth)acrylic groups present after ultraviolet irradiation to the amount of (meth)acrylic groups present in the photocurable resin composition 2 before ultraviolet irradiation. The larger the value, the more the curing progresses. In addition, the degree of light transmittance of the photocurable resin layer 6 is sufficient as long as the light transmittance is such that the image formed on the image display member can be visually recognized.
再者，硬化率（凝膠分率）可藉由將紫外線照射前之樹脂組成物層之「FT-IR測定圖中之1640〜1620 cm-1 之吸收峰距基準線之高度（X）」與「紫外線照射後之樹脂組成物層之FT-IR測定圖中之1640〜1620 cm-1 之吸收峰距基準線之高度（Y）」代入以下數式（1）而算出。Furthermore, the curing rate (gel fraction) can be calculated by substituting the "height of the absorption peak at 1640 to 1620 cm -1 from the baseline in the FT-IR measurement chart of the resin composition layer before ultraviolet irradiation (X)" and the "height of the absorption peak at 1640 to 1620 cm -1 from the baseline in the FT-IR measurement chart of the resin composition layer after ultraviolet irradiation (Y)" into the following formula (1).
硬化率（%）＝{（X－Y）/X}×100 （1）Hardening rate (%) = {(X-Y)/X}×100 (1)
關於紫外線之照射，只要可使其硬化直至硬化率（凝膠分率）較佳成為95%以上，則光源之種類、輸出、累積光量等並無特別限制，可採用利用公知之紫外線照射所進行之(甲基)丙烯酸酯之光自由基聚合之製程條件。Regarding the ultraviolet irradiation, as long as it can be cured until the curing rate (gel fraction) is preferably above 95%, there is no particular limitation on the type of light source, output, and accumulated light amount, and the process conditions of photo-radical polymerization of (meth)acrylate by ultraviolet irradiation known in the art can be adopted.
再者，透光性之光硬化樹脂層6之透光性程度只要為如可目視辨認形成於影像顯示構件5之影像之透光性即可。The light-transmitting photo-curing resin layer 6 may have a light-transmitting property such that the image formed on the image display member 5 can be visually recognized.
又，亦可不使光硬化性樹脂組成物一次性正式硬化，而是如以下步驟（aa）〜（dd）那樣，於暫時硬化之後將其貼合，進而進行正式硬化。Furthermore, instead of fully curing the photocurable resin composition all at once, it is also possible to temporarily cure the photocurable resin composition and then bond the photocurable resin composition together, and then fully cure the photocurable resin composition, as in the following steps (aa) to (dd).
＜步驟（aa）（塗佈步驟）＞ 首先，如圖6所示，準備透光性覆蓋構件10，如圖7所示，自噴墨噴嘴30將光硬化性樹脂組成物20塗佈於透光性覆蓋構件10之表面10a，形成光硬化性樹脂組成物膜40。該情形之塗佈厚可根據透光性覆蓋構件10或影像顯示構件之表面狀態、所需之硬化樹脂層之膜物性等而適當設定。<Step (aa) (Coating step)> First, as shown in FIG6, a light-transmitting covering member 10 is prepared, and as shown in FIG7, a photocurable resin composition 20 is coated on the surface 10a of the light-transmitting covering member 10 from an inkjet nozzle 30 to form a photocurable resin composition film 40. The coating thickness in this case can be appropriately set according to the surface state of the light-transmitting covering member 10 or the image display member, the film properties of the desired hardened resin layer, etc.
再者，為了獲得所需之厚度，該光硬化性樹脂組成物20之塗佈可進行複數次。Furthermore, in order to obtain a desired thickness, the photocurable resin composition 20 may be applied multiple times.
＜步驟（bb）（暫時硬化步驟）＞ 其次，如圖8所示，藉由對步驟（aa）中所塗佈之光硬化性樹脂組成物膜40照射紫外線UV使其暫時硬化，如圖9所示般形成暫時硬化樹脂層45。此處，使其暫時硬化係用以使光硬化性樹脂組成物20自液狀成為不顯著流動之狀態，且使其即使上下翻轉亦不流下以提昇操作性。此種暫時硬化之程度如下所示：暫時硬化樹脂層45之硬化率（凝膠分率）較佳為40%以上，更佳為60%以上。上限可為100%，但較佳為未達100%。更佳為未達95%。<Step (bb) (temporary curing step)> Next, as shown in FIG8, the photocurable resin composition film 40 applied in step (aa) is temporarily cured by irradiating it with ultraviolet rays UV, and a temporarily cured resin layer 45 is formed as shown in FIG9. Here, the temporary curing is used to make the photocurable resin composition 20 from a liquid state into a state where it does not flow significantly, and to prevent it from flowing down even if it is turned upside down to improve the operability. The degree of such temporary curing is as follows: The curing rate (gel fraction) of the temporarily cured resin layer 45 is preferably 40% or more, and more preferably 60% or more. The upper limit can be 100%, but it is preferably less than 100%. It is more preferably less than 95%.
＜步驟（cc）（貼合步驟）＞ 其次，如圖10所示，使透光性覆蓋構件10貼合於影像顯示構件50之暫時硬化樹脂層45側。貼合可藉由使用公知之壓接裝置於10℃〜80℃進行加壓而進行。<Step (cc) (bonding step)> Next, as shown in FIG10 , the light-transmissive cover member 10 is bonded to the temporarily hardened resin layer 45 side of the image display member 50 . The bonding can be performed by applying pressure at 10°C to 80°C using a known press-fitting device.
＜步驟（dd）（正式硬化步驟）＞ 其次，如圖11所示，對夾持於影像顯示構件50與透光性覆蓋構件10之間的暫時硬化樹脂層45照射紫外線UV使其正式硬化。藉此，使影像顯示構件50與透光性覆蓋構件10經由透光性之光硬化樹脂層60積層而獲得影像顯示裝置100（圖12）。再者，於暫時硬化樹脂層之硬化率為100%之情形時，可省略本步驟（dd），但較佳為始終實施以使其確實地正式硬化。<Step (dd) (Formal Curing Step)> Secondly, as shown in FIG11, the temporary curing resin layer 45 sandwiched between the image display component 50 and the light-transmitting cover component 10 is irradiated with ultraviolet light UV to formally cure it. In this way, the image display component 50 and the light-transmitting cover component 10 are laminated via the light-transmitting light-curing resin layer 60 to obtain the image display device 100 (FIG12). Furthermore, when the curing rate of the temporary curing resin layer is 100%, this step (dd) can be omitted, but it is better to always implement it to ensure that it is formally cured.
又，於本步驟中進行正式硬化係用以使暫時硬化樹脂層45充分地硬化，使影像顯示構件50與透光性覆蓋構件10接著並積層。此種正式硬化之程度設定為不低於暫時硬化樹脂層45之硬化率。通常情況下，將透光性之光硬化樹脂層60之硬化率（凝膠分率）較佳設定為95%以上，更佳設定為98%以上。In addition, the formal curing in this step is used to fully cure the temporary curing resin layer 45 so that the image display member 50 and the light-transmitting cover member 10 are laminated in contact. The degree of this formal curing is set to be not less than the curing rate of the temporary curing resin layer 45. Generally, the curing rate (gel fraction) of the light-transmitting light-curing resin layer 60 is preferably set to be 95% or more, and more preferably set to be 98% or more.
再者，透光性之光硬化樹脂層60之透光性之程度只要為如可目視辨認形成於影像顯示構件50之影像之透光性即可。再者，於以上之步驟（aa）〜（dd）中係將光硬化性樹脂組成物塗佈於透光性覆蓋構件，但亦可塗佈於影像顯示構件，其後積層透光性覆蓋構件。 [實施例]Furthermore, the light-transmitting photo-curable resin layer 60 only needs to have a light-transmitting degree such that the image formed on the image display component 50 can be visually recognized. Furthermore, in the above steps (aa) to (dd), the photo-curable resin composition is applied to the light-transmitting covering component, but it can also be applied to the image display component and then the light-transmitting covering component is layered. [Example]
以下，藉由實施例對本發明加以具體說明，但本發明並不限定於該等實施例。再者，實施例、比較例中使用之成分如下所示。Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In addition, the components used in the examples and comparative examples are as follows.
(甲基)丙烯酸酯聚合物 Hitaloid（註冊商標）7927（日立化成（股））；MW190,000、170 mgKOH/g(Meth)acrylate polymer Hitaloid (registered trademark) 7927 (Hitachi Chemical Co., Ltd.); MW 190,000, 170 mgKOH/g
含羥基之單官能(甲基)丙烯酸酯單體 4-HBA（丙烯酸4-羥基丁酯）Monofunctional (meth)acrylate monomer containing hydroxyl group 4-HBA (4-hydroxybutyl acrylate)
不含羥基之單官能(甲基)丙烯酸酯單體 ISTA（丙烯酸異硬脂酯） IDA（丙烯酸異癸酯）Hydroxyl-free monofunctional (meth)acrylate monomers ISTA (isostearyl acrylate) IDA (isodecyl acrylate)
多官能(甲基)丙烯酸酯單體 PETIA（新戊四醇(三/四)丙烯酸酯；Daicel-allnex（股））Multifunctional (meth)acrylate monomer PETIA (neopentaerythritol (tri/tetra)acrylate; Daicel-allnex (stock))
奪氫型光聚合起始劑 Omnirad（註冊商標）MBF（IGM Resins B.V.）、苯甲醯甲酸甲酯Hydrogen-absorbent photopolymerization initiator Omnirad (registered trademark) MBF (IGM Resins B.V.), methyl benzoate
實施例1〜4、比較例1〜2 藉由將表1所示之摻合成分均勻地混合而製備光硬化性樹脂組成物。針對所獲得之光硬化性樹脂組成物，以如下之方式對有助於噴墨塗佈性之光硬化前之液狀物性之「黏度[mPa∙s]」進行測定。又，以如下所說明之方式對光硬化後之「硬化物之外觀」、「於25℃、85℃之拉伸儲存彈性模數[Pa]」、「於25℃之損耗正切tanδ（＝損失彈性模數/儲存彈性模數）」、「玻璃轉移溫度[℃]」、「伸長係數[%]」及「界面密接強度[N/cm2 ]」進行測定。Examples 1 to 4, Comparative Examples 1 to 2 A photocurable resin composition was prepared by uniformly mixing the blending components shown in Table 1. The obtained photocurable resin composition was measured for the "viscosity [mPa∙s]" of the liquid property before photocuring, which contributes to the inkjet coating property, in the following manner. In addition, the "appearance of the cured product", "tensile storage modulus at 25°C and 85°C [Pa]", "loss tangent tanδ at 25°C (= loss modulus/storage modulus)", "glass transition temperature [°C]", "elongation coefficient [%]", and "interface adhesion strength [N/cm 2 ]" after photocuring were measured in the following manner.
＜光硬化前＞ （光硬化性樹脂組成物之黏度） 使用流變儀（Haake RheoStress600、Thermo Scientific公司；測定條件、錐形轉子、＝35 mm、轉子角度2°、剪切速度120/s）測定光硬化性樹脂組成物之於25℃與60℃之黏度。將測定結果示於表1。關於光硬化性樹脂組成物之噴墨塗佈性，期望於25℃之黏度為10 mPa∙s以上、且於60℃之黏度為30 mPa∙s以下。＜Before light curing＞ (Viscosity of the light curing resin composition) The rheometer (Haake RheoStress600, Thermo Scientific; measurement conditions, conical rotor, =35 mm, rotor angle 2°, shear rate 120/s) to measure the viscosity of the photocurable resin composition at 25°C and 60°C. The measurement results are shown in Table 1. Regarding the inkjet coating property of the photocurable resin composition, it is expected that the viscosity at 25°C is 10 mPa∙s or more and the viscosity at 60°C is 30 mPa∙s or less.
＜光硬化後＞ 以如下所說明之方式觀察或測定光硬化性樹脂組成物之光硬化後之「硬化物之外觀」、「於25℃、85℃之拉伸儲存彈性模數[Pa]」、「於25℃之損耗正切tanδ（＝損失彈性模數/儲存彈性模數）」、「玻璃轉移溫度[℃]」、「伸長係數[%]」、「界面密接強度[N/cm2 ]」。<After photocuring> After photocuring, the photocurable resin composition was observed or measured for "appearance of the cured product", "tensile storage modulus at 25°C and 85°C [Pa]", "loss tangent tanδ at 25°C (= loss modulus/storage modulus)", "glass transition temperature [°C]", "elongation coefficient [%]", and "interface adhesion strength [N/cm 2 ]" in the manner described below.
（硬化物之外觀） 使用紫外線照射裝置（LC-8、Hamamatsu Photonics（股）製造）以累計光量成為5000 mJ/cm2 之方式對光硬化性樹脂組成物照射強度為200 mW/cm2 之紫外線，藉此使光硬化性樹脂組成物硬化。目視觀察所獲得之硬化物為透明抑或為白濁。將觀察結果示於表1。作為影像顯示裝置用之光學材料，要求不白濁。(Appearance of Cured Material) The photocurable resin composition was irradiated with ultraviolet light at an intensity of 200 mW/ cm2 using an ultraviolet irradiation device (LC-8, manufactured by Hamamatsu Photonics Co., Ltd.) in such a manner that the accumulated light amount became 5000 mJ/ cm2 , thereby curing the photocurable resin composition. The obtained cured material was visually observed to determine whether it was transparent or turbid. The observation results are shown in Table 1. As an optical material for an image display device, it is required not to be turbid.
（於25℃、85℃之拉伸儲存彈性模數[Pa]） 以使光硬化性樹脂組成物成為2 mm厚之方式塗佈於實施了脫模處理之PET膜上，藉由使用紫外線照射裝置（LC-8、Hamamatsu Photonics（股）製造），以累計光量成為5000 mJ/cm2 之方式照射強度為200 mW/cm2 之紫外線而使光硬化性樹脂組成物膜硬化，並將其自PET膜剝離，藉此製成黏彈性試驗用樣品膜。針對所獲得之樣品膜，使用黏彈性測定裝置（DMS6100、Seiko Instruments公司製造；測定條件、長度＝20 mm、厚度＝2 mm、寬＝10 mm、頻率1 Hz）測定於25℃及85℃之拉伸儲存彈性模數。作為影像顯示裝置用之光學材料而言，期望拉伸儲存彈性模數之數值處於1.0E＋05〜7.0E＋05之範圍。(Tensile storage elastic modulus at 25°C and 85°C [Pa]) A photocurable resin composition was applied to a PET film subjected to a mold release treatment in such a manner that the thickness was 2 mm. The photocurable resin composition film was cured by irradiating it with ultraviolet light at an intensity of 200 mW/ cm2 using an ultraviolet irradiation device (LC-8, manufactured by Hamamatsu Photonics Co., Ltd.) in such a manner that the cumulative light amount became 5000 mJ/ cm2 . The film was then peeled off from the PET film to prepare a sample film for a viscoelasticity test. The obtained sample film was measured for tensile storage modulus at 25°C and 85°C using a viscoelasticity measuring device (DMS6100, manufactured by Seiko Instruments; measuring conditions, length = 20 mm, thickness = 2 mm, width = 10 mm, frequency 1 Hz). For optical materials used in image display devices, the tensile storage modulus is expected to be in the range of 1.0E+05 to 7.0E+05.
（於25℃之損耗正切tanδ（＝損失彈性模數/儲存彈性模數）） 以與拉伸儲存彈性模數之測定相同之方式製成黏彈性試驗用樣品膜，並使用相同之黏彈性測定裝置測定拉伸損失彈性模數，算出該數值相對於之前測定之拉伸儲存彈性模數之比率（%）作為損耗正切tanδ。作為影像顯示裝置用之光學材料，期望損耗正切tanδ之數值處於1〜2之範圍。(Loss tangent tanδ at 25°C (= loss modulus/storage modulus)) The sample film for viscoelastic test is prepared in the same way as the measurement of tensile storage modulus, and the tensile loss modulus is measured using the same viscoelastic measuring device. The ratio (%) of this value to the previously measured tensile storage modulus is calculated as the loss tangent tanδ. As an optical material for image display devices, the loss tangent tanδ value is expected to be in the range of 1 to 2.
（玻璃轉移溫度「℃」） 以與拉伸儲存彈性模數之測定相同之方式製成黏彈性試驗用樣品膜，並使用相同之黏彈性測定裝置測定其玻璃轉移溫度。作為影像顯示裝置用之光學材料，較佳為玻璃轉移溫度之範圍為-60〜0℃之範圍。(Glass transition temperature "℃") The sample film for viscoelastic test is made in the same way as the measurement of tensile storage elastic modulus, and its glass transition temperature is measured using the same viscoelastic measurement device. As an optical material for image display devices, the glass transition temperature range is preferably -60 to 0℃.
（伸長係數「%」） 以成為特定之厚度之方式於剝離膜上滴加光硬化性樹脂組成物，之後進行紫外線照射使其硬化，並切為特定之大小（例如1 mm、10 mm寬、30 mm長）而製成試樣，使用拉伸試驗機（Tensilon、Orientec公司）測定其伸長係數。測定條件為環境溫度25℃、拉伸速度10 mm/分鐘，將測定值代入「伸長係數（%）＝L/L0×100」之數學式，求出伸長係數。此處，L0為基準長度，L為直至斷裂為止之位移長度。作為影像顯示裝置用之光學材料，於上述於25℃之拉伸儲存彈性模數為上述範圍內之情形時，較佳為100〜200%之範圍。其原因在於：可使樹脂硬化物追隨影像顯示構件之翹曲，可較大程度地抑制自樹脂硬化物與貼合構件界面之剝離。(Elongation coefficient "%") A photocurable resin composition is dripped onto the peeling film to a specific thickness, then cured by ultraviolet irradiation, and cut into specific sizes (e.g. 1 mm, 10 mm wide, 30 mm long) to make a specimen, and its elongation coefficient is measured using a tensile testing machine (Tensilon, Orientec). The measurement conditions are an ambient temperature of 25°C and a tensile speed of 10 mm/min. The measured value is substituted into the mathematical formula "Elongation coefficient (%) = L/L0×100" to obtain the elongation coefficient. Here, L0 is the reference length, and L is the displacement length until fracture. When the elastic modulus of the optical material used in the image display device is within the above range at 25°C, it is preferably in the range of 100-200%. The reason is that the cured resin can follow the warping of the image display component, and the peeling of the cured resin and the bonding component interface can be suppressed to a large extent.
（界面密接強度（裂解強度）[N/cm2 ]） 準備2片松浪硝子工業公司製造之載玻片（40（W）×70（L）×0.4（t）mm、型號S1112），於一載玻片之中央以直徑5 mm、平均100 μm之厚度塗佈光硬化性樹脂組成物，首先，藉由使用紫外線照射裝置（LC-8、Hamamatsu Photonics（股）製造）以累計光量成為2000 mJ/cm2 之方式照射強度為200 mW/cm2 之紫外線而使光硬化性樹脂組成物膜半硬化，於所獲得之半硬化樹脂膜，以正交之方式載置另一載玻片，藉由以累計光量成為5000 mJ/cm2 之方式對夾持於2片載玻片之半硬化性樹脂膜照射強度為200 mW/cm2 之紫外線而使光半硬化樹脂層正式硬化，從而形成透光性之光硬化樹脂層。藉此獲得接著強度試驗用樣品。使用拉伸試驗機（Autograph AGS-X，島津製作所（股）；試驗速度5 mm/min、試驗溫度85℃）測定該樣品之接著強度。將獲得之結果示於表1及圖13、14。作為光學材料，期望對於玻璃之界面密接強度之數值處於85〜100 N/cm2 之範圍，對於聚碳酸酯之界面密接強度之數值處於35〜45 N/cm2 之範圍。(Interface adhesion strength (cracking strength) [N/cm 2 ]) Two slide glasses (40 (W) × 70 (L) × 0.4 (t) mm, model S1112) manufactured by Matsunami Glass Industries, Ltd. were prepared. A photocurable resin composition was applied to the center of one slide glass with a diameter of 5 mm and an average thickness of 100 μm. First, the photocurable resin composition film was semi-cured by irradiating it with ultraviolet light at an intensity of 200 mW/cm 2 using an ultraviolet irradiation device (LC-8, manufactured by Hamamatsu Photonics Co., Ltd.) in such a manner that the accumulated light intensity became 2000 mJ/cm 2. Another slide glass was placed orthogonally on the semi-cured resin film, and the photocurable resin composition film was semi-cured by irradiating it with ultraviolet light at an intensity of 200 mW/cm 2 using an ultraviolet irradiation device (LC-8, manufactured by Hamamatsu Photonics Co., Ltd.). 2, the semi-cured resin film sandwiched between two glass slides was irradiated with ultraviolet light at an intensity of 200 mW/ cm2 to formally cure the semi-cured resin layer, thereby forming a light-transmitting light-cured resin layer. In this way, a sample for bonding strength test was obtained. The bonding strength of the sample was measured using a tensile testing machine (Autograph AGS-X, Shimadzu Corporation; test speed 5 mm/min, test temperature 85°C). The obtained results are shown in Table 1 and Figures 13 and 14. As an optical material, the interface bonding strength with respect to glass is expected to be in the range of 85 to 100 N/ cm2 , and the interface bonding strength with respect to polycarbonate is expected to be in the range of 35 to 45 N/ cm2 .
[表1]
（評價結果之考察） 實施例1〜4之光硬化性樹脂組成物含有羥值為120 mgKOH/g以上之不具有(甲基)丙烯醯基之(甲基)丙烯酸酯聚合物、單官能(甲基)丙烯酸酯單體及奪氫型光聚合起始劑，進而於光硬化性樹脂組成物中含有2.9〜4.7質量%之黏著賦予劑，由於其黏度於25℃為10 mPa∙s以上且於60℃為30 mPa∙s以下，故根據表1或圖13、14可知：硬化前，噴墨塗佈性優異；硬化後，不僅界面密接強度優異，延伸性亦優異。(Evaluation results) The photocurable resin composition of Examples 1 to 4 contains a (meth)acrylate polymer without a (meth)acryloyl group having a hydroxyl value of 120 mgKOH/g or more, a monofunctional (meth)acrylate monomer, and a hydrogen-scavenging photopolymerization initiator. The photocurable resin composition further contains 2.9 to 4.7 mass % of an adhesive agent. Since the viscosity is 10 mPa∙s or more at 25°C and 30 mPa∙s or less at 60°C, it can be seen from Table 1 or Figures 13 and 14 that before curing, the inkjet coating property is excellent; after curing, not only the interface adhesion strength is excellent, but also the elongation is excellent.
另一方面，比較例1之光硬化性樹脂組成物之硬化物不含有黏著賦予劑，故與實施例1〜4之光硬化性樹脂組成物之硬化物相比而言，界面密接強度不充分。尤其是對於聚碳酸酯之界面密接強度大幅降低，並且伸長係數亦降低。由此可知，藉由以特定量範圍含有黏著賦予劑，可改善界面密接強度及延伸性。On the other hand, the cured product of the photocurable resin composition of Comparative Example 1 does not contain an adhesion-imparting agent, so the interface adhesion strength is insufficient compared with the cured products of the photocurable resin compositions of Examples 1 to 4. In particular, the interface adhesion strength to polycarbonate is greatly reduced, and the elongation coefficient is also reduced. It can be seen that the interface adhesion strength and elongation can be improved by containing an adhesion-imparting agent in a specific amount range.
再者，於比較例2之情形時，由於過度含有黏著賦予劑，故硬化物白濁。 [產業上之可利用性]Furthermore, in the case of Comparative Example 2, the cured product was cloudy due to excessive inclusion of the adhesive. [Industrial Applicability]
本發明之光硬化性樹脂組成物係作為利用噴墨塗佈法而塗佈之光硬化性樹脂組成物而言，不產生由使用具有(甲基)丙烯醯基之(甲基)丙烯酸酯低聚物而導致之界面密接強度降低或延伸性降低等問題者，因此於製造影像顯示構件與透光性覆蓋構件經由透光性之光硬化樹脂層進行積層而成之影像顯示裝置時，可用於形成光硬化樹脂層。The photocurable resin composition of the present invention is a photocurable resin composition applied by inkjet coating, and does not cause problems such as reduced interface adhesion strength or reduced elongation caused by using a (meth)acrylate oligomer having a (meth)acryl group. Therefore, it can be used to form a photocurable resin layer when manufacturing an image display device in which an image display component and a light-transmitting cover component are laminated via a light-transmitting photocurable resin layer.
1、10:透光性覆蓋構件 1a、10a:透光性覆蓋構件之表面 2、20:光硬化性樹脂組成物 3、30:噴墨噴嘴 4、40:光硬化性樹脂組成物膜 45:暫時硬化樹脂層 5、50:影像顯示構件 6、60:光硬化樹脂層 100:影像顯示裝置1, 10: Translucent covering member 1a, 10a: Surface of translucent covering member 2, 20: Photocurable resin composition 3, 30: Inkjet nozzle 4, 40: Photocurable resin composition film 45: Temporarily cured resin layer 5, 50: Image display member 6, 60: Photocurable resin layer 100: Image display device
[圖1]係本發明之影像顯示裝置之製造方法之步驟（a）之說明圖。 [圖2]係本發明之影像顯示裝置之製造方法之步驟（a）之說明圖。 [圖3]係本發明之影像顯示裝置之製造方法之步驟（b）之說明圖。 [圖4]係本發明之影像顯示裝置之製造方法之步驟（b）之說明圖。 [圖5]係本發明之影像顯示裝置之製造方法之步驟（c）之說明圖。 [圖6]係本發明之影像顯示裝置之製造方法之步驟（aa）之說明圖。 [圖7]係本發明之影像顯示裝置之製造方法之步驟（aa）之說明圖。 [圖8]係本發明之影像顯示裝置之製造方法之步驟（bb）之說明圖。 [圖9]係本發明之影像顯示裝置之製造方法之步驟（bb）之說明圖。 [圖10]係本發明之影像顯示裝置之製造方法之步驟（cc）之說明圖。 [圖11]係本發明之影像顯示裝置之製造方法之步驟（dd）之說明圖。 [圖12]係本發明之影像顯示裝置之製造方法之步驟（dd）之說明圖。 [圖13]係實施例1〜4及比較例1之光硬化性樹脂組成物之硬化物對聚碳酸酯之界面密接強度之比較條形圖。 [圖14]係實施例1、4及比較例1之光硬化性樹脂組成物之硬化物對玻璃之界面密接強度之比較條形圖。[Figure 1] is an explanatory diagram of step (a) of the method for manufacturing the image display device of the present invention. [Figure 2] is an explanatory diagram of step (a) of the method for manufacturing the image display device of the present invention. [Figure 3] is an explanatory diagram of step (b) of the method for manufacturing the image display device of the present invention. [Figure 4] is an explanatory diagram of step (b) of the method for manufacturing the image display device of the present invention. [Figure 5] is an explanatory diagram of step (c) of the method for manufacturing the image display device of the present invention. [Figure 6] is an explanatory diagram of step (aa) of the method for manufacturing the image display device of the present invention. [Figure 7] is an explanatory diagram of step (aa) of the method for manufacturing the image display device of the present invention. [Figure 8] is an explanatory diagram of step (bb) of the method for manufacturing the image display device of the present invention. [Figure 9] is an explanatory diagram of step (bb) of the method for manufacturing the image display device of the present invention. [Figure 10] is an explanatory diagram of step (cc) of the method for manufacturing the image display device of the present invention. [Figure 11] is an explanatory diagram of step (dd) of the method for manufacturing the image display device of the present invention. [Figure 12] is an explanatory diagram of step (dd) of the method for manufacturing the image display device of the present invention. [Figure 13] is a bar graph comparing the interfacial adhesion strength of the cured product of the photocurable resin composition of Examples 1 to 4 and Comparative Example 1 to polycarbonate. FIG. 14 is a bar graph comparing the interfacial adhesion strength of the cured products of the photocurable resin compositions of Examples 1 and 4 and Comparative Example 1 to glass.
1:透光性覆蓋構件 1: Translucent covering components
5:影像顯示構件 5: Image display component
6:光硬化樹脂層 6: Light-hardened resin layer
100:影像顯示裝置 100: Image display device
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