WO2012124475A1 - 液状硬化性樹脂組成物、これを用いた画像表示用装置の製造方法、及び画像表示用装置 - Google Patents
液状硬化性樹脂組成物、これを用いた画像表示用装置の製造方法、及び画像表示用装置 Download PDFInfo
- Publication number
- WO2012124475A1 WO2012124475A1 PCT/JP2012/054989 JP2012054989W WO2012124475A1 WO 2012124475 A1 WO2012124475 A1 WO 2012124475A1 JP 2012054989 W JP2012054989 W JP 2012054989W WO 2012124475 A1 WO2012124475 A1 WO 2012124475A1
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- WO
- WIPO (PCT)
- Prior art keywords
- resin composition
- image display
- meth
- curable resin
- acrylate
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 72
- 239000007788 liquid Substances 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 15
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 13
- 230000001681 protective effect Effects 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 25
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 19
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 9
- 230000001678 irradiating effect Effects 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 72
- -1 acryl Chemical group 0.000 description 48
- 239000004973 liquid crystal related substance Substances 0.000 description 47
- 238000006243 chemical reaction Methods 0.000 description 40
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 28
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 15
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 14
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
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- 230000015572 biosynthetic process Effects 0.000 description 12
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- 150000001252 acrylic acid derivatives Chemical class 0.000 description 11
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 7
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- 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 4
- WJIOHMVWGVGWJW-UHFFFAOYSA-N 3-methyl-n-[4-[(3-methylpyrazole-1-carbonyl)amino]butyl]pyrazole-1-carboxamide Chemical compound N1=C(C)C=CN1C(=O)NCCCCNC(=O)N1N=C(C)C=C1 WJIOHMVWGVGWJW-UHFFFAOYSA-N 0.000 description 4
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
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- 235000021122 unsaturated fatty acids Nutrition 0.000 description 4
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- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 3
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
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- 230000000052 comparative effect Effects 0.000 description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
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- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
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- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical class CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
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- 125000004066 1-hydroxyethyl group Chemical group [H]OC([H])([*])C([H])([H])[H] 0.000 description 1
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- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
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- MDKSQNHUHMMKPP-UHFFFAOYSA-N 2,5-bis(4-methoxyphenyl)-4-phenyl-1h-imidazole Chemical class C1=CC(OC)=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC(OC)=CC=2)N1 MDKSQNHUHMMKPP-UHFFFAOYSA-N 0.000 description 1
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- NSWNXQGJAPQOID-UHFFFAOYSA-N 2-(2-chlorophenyl)-4,5-diphenyl-1h-imidazole Chemical class ClC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 NSWNXQGJAPQOID-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- UIHRWPYOTGCOJP-UHFFFAOYSA-N 2-(2-fluorophenyl)-4,5-diphenyl-1h-imidazole Chemical class FC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 UIHRWPYOTGCOJP-UHFFFAOYSA-N 0.000 description 1
- XIOGJAPOAUEYJO-UHFFFAOYSA-N 2-(2-methoxyphenyl)-4,5-diphenyl-1h-imidazole Chemical class COC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 XIOGJAPOAUEYJO-UHFFFAOYSA-N 0.000 description 1
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- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- VZMLJEYQUZKERO-UHFFFAOYSA-N 2-hydroxy-1-(2-methylphenyl)-2-phenylethanone Chemical compound CC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 VZMLJEYQUZKERO-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical class OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- RTEZVHMDMFEURJ-UHFFFAOYSA-N 2-methylpentan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCCC(C)(C)OOC(=O)C(C)(C)C RTEZVHMDMFEURJ-UHFFFAOYSA-N 0.000 description 1
- AXYQEGMSGMXGGK-UHFFFAOYSA-N 2-phenoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)C(C=1C=CC=CC=1)OC1=CC=CC=C1 AXYQEGMSGMXGGK-UHFFFAOYSA-N 0.000 description 1
- NTZCFGZBDDCNHI-UHFFFAOYSA-N 2-phenylanthracene-9,10-dione Chemical compound C=1C=C2C(=O)C3=CC=CC=C3C(=O)C2=CC=1C1=CC=CC=C1 NTZCFGZBDDCNHI-UHFFFAOYSA-N 0.000 description 1
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- YFKMFQHIZCWXJD-UHFFFAOYSA-N 3-acridin-9-ylprop-2-enoic acid Chemical compound C1=CC=C2C(C=CC(=O)O)=C(C=CC=C3)C3=NC2=C1 YFKMFQHIZCWXJD-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 description 1
- MTRFEWTWIPAXLG-UHFFFAOYSA-N 9-phenylacridine Chemical compound C1=CC=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 MTRFEWTWIPAXLG-UHFFFAOYSA-N 0.000 description 1
- JQPNFFYPPWWWCH-UHFFFAOYSA-N 9-pyridin-2-ylacridine Chemical compound N1=CC=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 JQPNFFYPPWWWCH-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- QWPHERACDWWKSJ-UHFFFAOYSA-N CCCC(C=C1)=CC=C1OC1=CC=CC=C1.N=C=O.N=C=O Chemical compound CCCC(C=C1)=CC=C1OC1=CC=CC=C1.N=C=O.N=C=O QWPHERACDWWKSJ-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
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- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- LFOXEOLGJPJZAA-UHFFFAOYSA-N [(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphoryl]-(2,6-dimethoxyphenyl)methanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=O)(CC(C)CC(C)(C)C)C(=O)C1=C(OC)C=CC=C1OC LFOXEOLGJPJZAA-UHFFFAOYSA-N 0.000 description 1
- ARNIZPSLPHFDED-UHFFFAOYSA-N [4-(dimethylamino)phenyl]-(4-methoxyphenyl)methanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 ARNIZPSLPHFDED-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
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- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 150000001251 acridines Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- LHMRXAIRPKSGDE-UHFFFAOYSA-N benzo[a]anthracene-7,12-dione Chemical compound C1=CC2=CC=CC=C2C2=C1C(=O)C1=CC=CC=C1C2=O LHMRXAIRPKSGDE-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
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- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- LWMFAFLIWMPZSX-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene Chemical compound N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LWMFAFLIWMPZSX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000005670 ethenylalkyl group Chemical group 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000005286 illumination 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
- 125000005641 methacryl group Chemical group 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 229940086559 methyl benzoin Drugs 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 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
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 150000002894 organic compounds Chemical group 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- KOPQZJAYZFAPBC-UHFFFAOYSA-N propanoyl propaneperoxoate Chemical compound CCC(=O)OOC(=O)CC KOPQZJAYZFAPBC-UHFFFAOYSA-N 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 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
- 150000003839 salts Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 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
- 150000003440 styrenes Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 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
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
Definitions
- the present invention relates to a liquid curable resin composition, a method for producing an image display device using the same, and an image display device.
- a liquid crystal display device is exemplified as a typical image display device.
- a liquid crystal display device includes a liquid crystal cell in which liquid crystal is filled and sealed through a gap of about several microns between a glass substrate having a thickness of about 1 mm on which transparent electrodes and pixel patterns are formed, and both outer surfaces of the liquid crystal cell.
- the liquid crystal panel which consists of light sources, such as a polarizing plate affixed on and a backlight system, is included.
- a transparent front plate with a certain space in front of the liquid crystal panel, especially for mobile phones, game machines, digital cameras, and in-vehicle applications.
- a liquid crystal display device having a structure provided with a) is used.
- touch panels have been mounted on mobile phones, game machines, digital cameras, in-vehicle parts, notebook computers, desktop computers, personal computer monitors, and the like.
- a protective panel, a touch panel, and a liquid crystal panel are stacked in this order, and a constant structure is provided between the protective panel and the touch panel, and between the touch panel and the liquid crystal panel.
- Cited Document 1 a method of filling an oily material in the space between the protective panel and the liquid crystal panel is disclosed, and in Cited Document 2, a sheet obtained by copolymerizing an acrylic monomer is interposed between the protective panel and the liquid crystal panel. Each method has been proposed.
- a plasma display panel which is one of flat panel displays (FPD)
- FPD flat panel displays
- a protective panel made of glass or the like having a thickness of about 3 mm. Is provided on the front surface (viewing surface side).
- Patent Document 1 the oil used in Patent Document 1 is difficult to seal to prevent leakage, and there is a possibility that the material used in the liquid crystal panel may be eroded, so that the oil leaks when the protective panel is cracked. There's a problem.
- the optical film made of the resin described in Patent Document 3 has a problem that it becomes cloudy when a short-time wet heat resistance test is performed after application to a display.
- the optical films (sheets) of Patent Documents 2 and 4 have room for improvement when applied to image display devices such as larger liquid crystal display devices. That is, it is difficult to uniformly produce a large area optical film corresponding to a large image display device, and even if such an optical film can be produced, the large area optical film can be uniformly displayed as a large image. It is difficult to stack on the equipment. If the optical film cannot be laminated uniformly, it may cause problems such as color unevenness.
- the present invention can be suitably applied to fill a space between a protective panel and an image display unit in a large-sized image display device, and has excellent moisture heat resistance, and an image using the material. It is an object of the present invention to provide a method for manufacturing a display device and an image display device.
- the present invention provides (A) an acrylic polymer (hereinafter, sometimes referred to as “component (A)”), (B) a polymer having an ethylenically unsaturated bond in the molecule (hereinafter, occasionally). (Referred to as “component (B)”), (C) a monomer having one ethylenically unsaturated group in the molecule (hereinafter sometimes referred to as “component (C)”), and (D) a polymerization initiator. (Hereinafter referred to as “component (D)” in some cases), and the content of component (C) is 5 to 25 with respect to the total amount of components (A), (B) and (C).
- a liquid curable resin composition (hereinafter, also simply referred to as “curable resin composition”) having a mass% is provided.
- Such a curable resin composition is excellent in transparency when cured, has a small curing shrinkage rate, and is further excellent in wet heat resistance. Since the curable resin composition of the present invention is excellent in transparency when cured, it can be suitably used as a material used in the production of an image display device. Further, since the curable resin composition of the present invention exists in a liquid state, the space between the protective panel and the image display unit can be uniformly filled. Furthermore, since the curable resin composition of the present invention has a low curing shrinkage rate, it is possible to suppress warping of the substrate that may occur when cured with light or heat. Therefore, the curable resin composition of the present invention can be suitably used for filling the space between the protective panel and the image display unit in the large image display device.
- the component (B) is preferably a urethane polymer having a (meth) acryloyl group from the viewpoints of adhesiveness and toughness.
- the above curable resin composition is substantially free of organic solvent and has a viscosity at 25 ° C. of 500 to 5000 mPa ⁇ s from the viewpoint of workability and suppression of voids (bubbles in the curable resin composition). Preferably there is.
- substantially free of organic solvent means that the organic solvent may be present in a trace amount as long as the characteristics of the present invention are not significantly reduced.
- the content of the organic solvent may be 1000 ppm or less, preferably 500 ppm or less, and more preferably 100 ppm or less, based on the total amount of the curable resin composition. Further, it is particularly preferable that no organic solvent is contained.
- the organic solvent is an organic compound that does not have an ethylenically unsaturated group in the molecule, is liquid at 25 ° C., and has a boiling point of 250 ° C. or less at atmospheric pressure.
- the present invention is a method for manufacturing an image display device comprising an image display unit and a protection panel, the step of interposing the curable resin composition between the image display unit and the protection panel, and the protection And a process for curing the curable resin composition by irradiating light from the panel surface side.
- the present invention is also a method for manufacturing an image display device including an image display unit, a touch panel, and a protection panel, and between the image display unit and the touch panel and / or between the touch panel and the protection panel.
- a method for producing an image display device comprising the step of interposing the curable resin composition and the step of curing the liquid curable resin composition by irradiating light from the protective panel surface side.
- the present invention further provides an image display device manufactured by the above-described manufacturing method.
- the present invention in the manufacturing process of an image display device that is cured after filling the space between the protective panel and the image display unit with the resin composition, it is transparent, excellent in heat and humidity resistance, and cure shrinkage. It is possible to provide a curable resin composition having a low rate and a small stress applied to the image display unit.
- an image display device which has impact resistance, can produce a clear and high contrast image without double reflection.
- (meth) acrylate means “acrylate” and “methacrylate” corresponding thereto.
- (meth) acryl means “acryl” and “methacryl” corresponding thereto, and “(meth) acryloyl” means “acryloyl” and corresponding “methacryloyl”.
- the curable resin composition of the present invention has (A) an acrylic polymer, (B) a polymer having an ethylenically unsaturated bond in the molecule, and (C) one ethylenically unsaturated group in the molecule. It contains a monomer and (D) a polymerization initiator.
- A an acrylic polymer
- B a polymer having an ethylenically unsaturated bond in the molecule
- C one ethylenically unsaturated group in the molecule. It contains a monomer and (D) a polymerization initiator.
- the acrylic polymer as component (A) can be produced, for example, by radical polymerization of a polymerizable compound having a (meth) acryl group (hereinafter sometimes referred to as “monomer”).
- the acrylic polymer includes styrene; a polymerizable styrene derivative substituted at the ⁇ -position or aromatic ring such as vinyltoluene and ⁇ -methylstyrene, It may be copolymerized with one or more polymerizable monomers such as vinyl alkyl ether and esters of vinyl alcohol.
- Examples of the polymerizable compound having the (meth) acryl group include alkyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl ( (Meth) acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, Examples thereof include a (meth) acryl group and a compound having a hydroxyl group or an ether bond. These can be used individually by 1 type or in combination of 2 or more types.
- alkyl (meth) acrylate examples include a component (C1) described later.
- Examples of the compound having a (meth) acryl group and a hydroxyl group or an ether bond in the molecule include the component (C2) described later.
- acrylic polymer examples include (meth) acrylates having a structural unit derived from an alkyl (meth) acrylate having 4 to 18 carbon atoms and a hydroxyl group or an ether bond from the viewpoint of wet heat resistance and transparency (high haze). It is preferable to include a structural unit derived from an alkyl (meth) acrylate having 6 to 12 carbon atoms and a structural unit derived from a hydroxyalkyl (meth) acrylate having 1 to 5 carbon atoms. preferable.
- the component (A) contains a structural unit derived from an alkyl (meth) acrylate having 4 to 18 carbon atoms, alkyl (meth) having 4 to 18 carbon atoms from the viewpoint of wet heat resistance and transparency (high haze).
- the content of the structural unit derived from the acrylate is preferably 50 to 90% by mass, more preferably 55 to 85% by mass, based on the total mass (solid content) of the component (A). It is more preferably 60 to 80% by mass, and particularly preferably 65 to 75% by mass.
- the component (A) contains a structural unit derived from a (meth) acrylate having a hydroxyl group or an ether bond, it has a hydroxyl group or an ether bond from the viewpoint of wet heat resistance and transparency (high haze).
- the content of the structural unit derived from the acrylate is preferably 10 to 45% by mass, more preferably 15 to 40% by mass, and more preferably 20 to 35% based on the total mass (solid content) of the component (A). More preferably, it is more preferably 25% to 30% by weight.
- the weight average molecular weight of the component (A) is preferably 4,000 to 40,000, more preferably 5,000 to 30,000, from the viewpoints of curability, wet heat resistance and workability. 7,000 to 20,000 is particularly preferable.
- the weight average molecular weight is a value measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve. Further, the number average molecular weight, the weight average molecular weight, and the degree of dispersion are defined as follows.
- the content of the component (A) in the curable resin composition is 15 to from the total amount of the component (A), the component (B), and the component (C) from the viewpoints of curability, adhesion, and cure shrinkage.
- 60% by mass is preferable, 20 to 50% by mass is more preferable, and 25 to 45% by mass is particularly preferable.
- the (A) acrylic polymer is produced by a conventionally known method using the above-described components, for example, a method in which the above-described components are reacted in the presence of a radical polymerization initiator such as an organic peroxide or an azo compound. can do.
- a radical polymerization initiator such as an organic peroxide or an azo compound.
- ⁇ (B) component a polymer having an ethylenically unsaturated bond in the molecule>
- the polymer having an ethylenically unsaturated bond in the molecule as component (B) include a polyester oligomer having a (meth) acryloyl group, a urethane polymer having a (meth) acryloyl group, and polyethylene glycol mono (meth).
- examples include acrylate, polyethylene glycol di (meth) acrylate, polyprolene glycol mono (meth) acrylate, and polyprolene glycol di (meth) acrylate.
- a urethane polymer having a (meth) acryloyl group is preferable from the viewpoint of the toughness of the cured product and the balance of various properties.
- the urethane polymer having the (meth) acryloyl group is, for example, a compound obtained by reacting (b1) a diol compound and (b2) a compound having an isocyanate group (hereinafter referred to as “urethane polymer”). And (b3) monohydroxy (meth) acrylate, (b4) monocarboxylic acid having (meth) acryloyl group, or monoisocyanate compound having (meth) acryloyl group. it can.
- diol compound examples include polyether diols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; polyolefin diols such as polybutadiene diol, polyisoprene diol, hydrogenated polybutadiene diol, and hydrogenated polyisoprene diol; polyester diol , Polycaprolactone diol, and silicone diol.
- polyether diol is preferable from the viewpoint of relaxation of stress / impact, transparency, adhesiveness, and compatibility with the component (A).
- Examples of the divalent organic group represented by X in the general formula (2) include an aliphatic group having 1 to 20 carbon atoms, an alicyclic group having 5 to 20 carbon atoms, an unsubstituted group, and a methyl group. And arylene groups such as a phenylene group and a naphthylene group substituted with a lower alkyl group having 1 to 5 carbon atoms.
- the aliphatic group having 1 to 20 carbon atoms is more preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
- diisocyanates represented by the general formula (2) include diphenylmethane-2,4′-diisocyanate; 3,2′-, 3,3′-, 4,2′-, 4,3′-, 5,2'-, 5,3'-, 6,2'- or 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate; 3,2'-, 3,3'-, 4,2'- 4,3'-, 5,2'-, 5,3'-, 6,2'- or 6,3'-diethyldiphenylmethane-2,4'-diisocyanate; 3,2'-, 3,3 ' -, 4,2'-, 4,3'-, 5,2'-, 5,3'-, 6,2'- or 6,3'-dimethoxydiphenylmethane-2,4'-diisocyanate; diphenylmethane-4 , 4′-diisocyanate; diphenylmethane-3,3′-diisocyan
- X in the general formula (2) is a group having an aliphatic group having 1 to 20 carbon atoms or an alicyclic group having 5 to 20 carbon atoms. It is preferred to use certain aliphatic or alicyclic diisocyanate compounds. These can be used alone or in combination of two or more. In addition, as a compound which has an isocyanate group, you may use trifunctional or more polyisocyanate with the diisocyanate represented by General formula (2).
- the diisocyanates represented by the general formula (2) may be those stabilized with a blocking agent necessary to avoid changes over time.
- the blocking agent include hydroxy acrylate, alcohols typified by butanol, phenol, oxime, and the like, but are not particularly limited.
- the blending ratio when the (b1) diol compound and the diisocyanate represented by the general formula (2) are reacted is the number average molecular weight of the urethane polymer to be produced, and the terminal of the urethane polymer to be produced is a hydroxyl group. It is appropriately adjusted depending on whether it is an isocyanate group.
- the ratio of the number of isocyanate groups to the number of hydroxyl groups is preferably adjusted to be 1.01 or more, and the viewpoint of increasing the number average molecular weight Is preferably adjusted to less than 2.
- (b3) a compound capable of reacting with an isocyanate group such as a monohydroxy (meth) acrylate compound is used as a compound for introducing the (meth) acryloyl skeleton. Can do.
- Examples of (b3) monohydroxy (meth) acrylate compounds include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 1,4-cyclohexanedimethanol mono (Meth) acrylate, caprolactone or alkylene oxide adduct of each of the above (meth) acrylates, glycerin di (meth) acrylate, trimethylol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate , Ditrimethylolpropane tri (meth) acrylate and 2-acryloxyethanol. These compounds can be used individually by 1 type or in combination of 2 or more types.
- the blending ratio is preferably adjusted so that the ratio of the number of hydroxyl groups to the number of isocyanate groups (number of hydroxyl groups / isocyanate groups) is 1.01 or more. It is preferable to adjust to less than 2 from the viewpoint of increasing.
- a monocarboxylic acid having a (meth) acryloyl group or a monoisocyanate having a (meth) acryloyl group as a compound for introducing a (meth) acryloyl skeleton A compound capable of reacting with a hydroxyl group such as a compound can be used.
- Examples of the monocarboxylic acid having a (meth) acryloyl group include (meth) acrylic acid, and examples of the monoisocyanate compound having a (meth) acryloyl group include 2-isocyanatoethyl (meth) acrylate. .
- the urethane polymer which has a (meth) acryloyl group can also be manufactured by methods other than the above.
- methods for producing a urethane polymer having a (meth) acryloyl group for example, (b1) a diol compound and (b3) monohydroxy (meth) acrylate are mixed in a predetermined amount, and the temperature is raised to a predetermined temperature.
- (b2) a predetermined amount of the compound having an isocyanate group is added to the mixture of the component (b1) and the component (b3) over a predetermined time and allowed to react.
- (B) a polymer having an ethylenically unsaturated bond in the molecule is obtained by a conventionally known method using the above components, for example, the presence of a polymerization inhibitor such as p-methoxyphenol and a catalyst such as dibutyltin dilaurate. It can manufacture by the method of making the above-mentioned component react under.
- the average number of functional groups in the component (B) is preferably 0.5 to 2 and more preferably 0.5 to 1.5 from the viewpoint of further reducing the viscosity and curing shrinkage of the curable resin composition. More preferably, it is particularly preferably 0.5 to 1.
- the “functional group number” indicates the number of functional groups ((meth) acryloyl group) in one molecule of the component (B), and the “average functional group number” indicates the number of functional groups per molecule in the entire component (B). The average value is shown.
- the average number of functional groups can be calculated from the number of moles of each component when the component (B) is synthesized.
- the average number of functional groups can also be calculated from the 1 H-NMR integral value of component (B).
- the weight average molecular weight of the component (B) is preferably 1,000 to 40,000, more preferably 3,000 to 30,000, from the viewpoints of curability, wet heat resistance and workability. 5,000 to 20,000 is particularly preferable, and 6,000 to 10,000 is more preferable.
- the content of the component (B) in the curable resin composition is from 30 to the total amount of the component (A), the component (B), and the component (C) from the viewpoints of curability, adhesion, and cure shrinkage. It is preferably 80% by mass, more preferably 40 to 70% by mass, and particularly preferably 45 to 65% by mass.
- ⁇ (C) component a monomer having one ethylenically unsaturated group in the molecule>
- the monomer having one ethylenically unsaturated group in the molecule as component (C) is preferably liquid at room temperature (25 ° C.), particularly from the viewpoint of imparting adhesiveness and flexibility.
- an alkyl (meth) acrylate hereinafter, also referred to as “(C1) component”
- (C2) component a compound having a (meth) acryl group and a hydroxyl group or an ether bond in the molecule.
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents an alkyl group having 4 to 20 carbon atoms. From the viewpoint of imparting more adhesiveness and flexibility, R 2 is preferably an alkyl group having 6 to 18 carbon atoms, more preferably an alkyl group having 8 to 16 carbon atoms.
- alkyl (meth) acrylate represented by the general formula (3)
- alkyl (meth) acrylate represented by the general formula (3)
- examples of the alkyl (meth) acrylate represented by the general formula (3) include n-butyl (meth) acrylate, tert-butyl (meth) acrylate, isobutyl (meth) acrylate, and n-pentyl (meth) acrylate.
- N-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-hexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (Meth) acrylate etc. are mentioned. These can be used alone or in combination of two or more.
- the content ratio of the component (C1) in the component (C) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.
- Examples of the compound having a (meth) acryl group and a hydroxyl group or an ether bond in the molecule include 2-hydroxyethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3 -Hydroxypropyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 1-hydroxybutyl (meth) ) Hydroxyl-containing (meth) acrylates such as acrylate; Hydroxyl-containing (meth) acrylamides such as hydroxyethyl (meth) acrylamide; Polyethylene glycol mono (meth) such as diethylene glycol and triethylene glycol Crylate; Polypropylene glycol mono (meth) acrylates such as dipropylene glycol and
- a monomer having one ethylenically unsaturated group in the molecule other than the components (C1) and (C2) can be used.
- the monomer having one ethylenically unsaturated group in the molecule other than the component (C1) and the component (C2) include isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, Examples include (meth) acrylates having a cycloaliphatic structure such as cyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, benzyl (meth) acrylate, phenoxy (meth) acrylate, and styrene.
- the content of the component (C) in the curable resin composition is 5 to 25% by mass with respect to the total amount of the components (A), (B) and (C), but 8 to 25% by mass is included. It is preferably 10 to 25% by mass, more preferably 10 to 20% by mass.
- the content of the component (C) is 5% by mass or more, workability is improved because the viscosity of the curable resin composition does not increase excessively. Further, when the content of the component (C) is within 25% by mass, the curing shrinkage rate is lowered, and the reliability when used in an image display device can be improved.
- the content ratio of the component (C1) when the component (C1) and the component (C2) are used in combination is from the viewpoint of reducing the transparency of the cured product (high haze) and deformation of the cured product.
- the total amount of component (C) is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, and particularly preferably 70 to 85% by mass.
- the content ratio of the component (C2) is preferably 5 to 50% by mass in the total amount of the component (C) from the viewpoint of reducing the transparency (high haze) of the cured product and reducing the deformation of the cured product. It is more preferably 40% by mass, and particularly preferably 15 to 30% by mass.
- (D) component Polymerization initiator>
- (D) polymerization initiator either (D1) photopolymerization initiator or (D2) thermal polymerization initiator can be used, and these may be used in combination.
- (D1) As the photopolymerization initiator, for example, known materials such as benzophenone, anthraquinone, benzoin, sulfonium salt, diazonium salt, onium salt and the like can be used. These are particularly sensitive to ultraviolet light.
- photopolymerization initiator examples include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N-tetraethyl-4,4′-diaminobenzophenone, 4- Methoxy-4'-dimethylaminobenzophenone, ⁇ -hydroxyisobutylphenone, 2-ethylanthraquinone, t-butylanthraquinone, 1,4-dimethylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2- Methyl anthraquinone, 1,2-benzoanthraquinone, 2-phenylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, thioxanthone, 2-chlorothioxanthone, 2-ch
- ⁇ -hydroxyalkylphenone compounds such as 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, bis (2,4,6-trimethyl) Acylphosphine oxide such as benzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide
- oligo 2-hydroxy-2-methyl-1- (4- (1-methyl Vinyl) phenyl) propanone
- Photopolymerization initiators for producing thick films include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl.
- Acylphosphine oxide compounds such as -pentylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide are preferred.
- photopolymerization initiators may be used in combination.
- the thermal polymerization initiator is an initiator that generates radicals by heat.
- Specific examples thereof include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, t-butylperoxyneodecanoate, t-butylperoxybivalate, t-hexylperoxypivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, lauroyl peroxide, diacetylper Organic peroxides such as oxides; 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonyl), 2,2'-azobis (2,4-dimethylvaleronit
- the content of the (D) polymerization initiator in the curable resin composition is preferably 0.01 to 5% by mass with respect to the total amount of the component (A), the component (B) and the component (C). Is more preferably 3 to 3% by mass, particularly preferably 0.03 to 2% by mass.
- (D) When (D1) photopolymerization initiator is used as the polymerization initiator, the content thereof is 0.1 to 5 with respect to the total amount of component (A), component (B) and component (C).
- (D2) When a thermal polymerization initiator is used, its content is 0.01 to 1% by mass with respect to the total amount of component (A), component (B) and component (C). Is preferred.
- (D1) photoinitiator and (D2) thermal polymerization initiator it is preferable to use in these ranges, respectively.
- the curing reaction can be performed by a curing reaction by irradiation with active energy rays, a curing reaction by heat, or a combination thereof.
- Active energy rays refer to ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, ⁇ rays and the like. These methods can also be used for the synthesis of (A) an acrylic polymer.
- a photopolymerization initiator (D1) that can be polymerized by light.
- the curable resin composition of the present embodiment does not substantially contain an organic solvent.
- the viscosity (25 ° C.) of the curable resin composition of the present embodiment that does not substantially contain an organic solvent is preferably 500 to 5000 mPa ⁇ s, and more preferably 1000 to 4000 mPa ⁇ s.
- the viscosity is a value measured with an E-type viscometer (RE-80L, manufactured by Toki Sangyo Co., Ltd.) using a 3 ° cone rotor at 0.5 rpm.
- the curing shrinkage when the curable resin composition of the present embodiment is cured is preferably less than 3.0% from the viewpoint of further suppressing the warpage of the substrate such as the protective panel and the image display unit. More preferably, it is less than 1.5%. When the image display unit is warped, it may cause problems such as color unevenness.
- FIG. 1 is a side sectional view schematically showing an embodiment of the liquid crystal display device of the present invention.
- the liquid crystal display device shown in FIG. 1 includes an image display unit 1 in which a backlight system 50, a polarizing plate 22, a liquid crystal display cell 10, and a polarizing plate 20 are laminated in this order, and a polarizing plate on the viewing side of the liquid crystal display device.
- the transparent resin layer 32 is composed of a cured body of the curable resin composition of the present embodiment.
- FIG. 2 is a side sectional view schematically showing a liquid crystal display device equipped with a touch panel, which is an embodiment of the liquid crystal display device of the present invention.
- the liquid crystal display device shown in FIG. 2 includes an image display unit 1 in which a backlight system 50, a polarizing plate 22, a liquid crystal display cell 10, and a polarizing plate 20 are laminated in this order, and a polarizing plate on the viewing side of the liquid crystal display device. 20, a transparent resin layer 32 provided on the top surface, a touch panel 30 provided on the top surface of the transparent resin layer 32, a transparent resin layer 31 provided on the top surface of the touch panel 30, and a transparent protective substrate provided on the surface thereof 40.
- a transparent resin layer is interposed between the image display unit 1 and the touch panel 30 and between the touch panel 30 and the transparent protective substrate 40. It suffices to intervene in at least one of these.
- the touch panel is on-cell, the touch panel and the liquid crystal display cell are integrated.
- the liquid crystal display cell 10 of the liquid crystal display device of FIG. 1 may be replaced with an on-cell.
- the cured body of the curable resin composition of the present embodiment is provided as the transparent resin layer 31 or 32, it has impact resistance, is clear and has no double reflection. An image with high contrast is obtained.
- the liquid crystal display cell 10 can be made of a liquid crystal material well known in the art. Also, depending on the control method of the liquid crystal material, it is classified into TN (Twisted Nematic) method, STN (Super-twisted nematic) method, VA (Virtual Alignment) method, IPS (In-Place-Switching) method, etc. In the form, a liquid crystal display cell using any control method may be used.
- TN Transmission Nematic
- STN Super-twisted nematic
- VA Virtual Alignment
- IPS Intelligent Alignment
- polarizing plates 20 and 22 a polarizing plate common in this technical field can be used.
- the surfaces of these polarizing plates may be subjected to treatments such as antireflection, antifouling, and hard coat. Such surface treatment may be performed on one side of the polarizing plate or on both sides thereof.
- touch panel 30 those commonly used in this technical field can be used.
- the transparent resin layer 31 or 32 can be formed with a thickness of 0.02 mm to 3 mm, for example.
- the curable resin composition of the present embodiment is effective for thick films, and can be suitably used when the transparent resin layer 31 or 32 having a thickness of 0.1 mm or more is formed.
- a general optical transparent substrate can be used as the transparent protective substrate 40.
- a general optical transparent substrate include inorganic plates such as glass plates and quartz plates, resin plates such as acrylic plates and polycarbonate plates, and resin sheets such as thick polyester sheets.
- resin plates such as acrylic plates and polycarbonate plates
- resin sheets such as thick polyester sheets.
- a plate such as glass or acrylic is preferable, and a glass plate is more preferable.
- the surface of these transparent protective substrates may be subjected to treatments such as antireflection, antifouling, and hard coating. Such surface treatment may be performed on one side of the transparent protective substrate or on both sides.
- a plurality of transparent protective substrates can be used in combination.
- the backlight system 50 is typically composed of reflecting means such as a reflector and illumination means such as a lamp.
- the liquid crystal display device of FIG. 1 described above includes the step of interposing the curable resin composition of the present embodiment between the image display unit and the protective panel, and the curable resin by irradiating light from the protective panel surface side. And a step of curing the composition to form a transparent resin layer.
- the curable resin composition is applied on the image display unit or the protective panel, and then vacuum (reduced pressure) is applied.
- vacuum reduced pressure
- a method of pasting at atmospheric pressure, or a method of casting a curable resin composition between an image display unit and a protective panel arranged at a certain interval may be mentioned.
- you may form a dam around an image display unit and a protection panel.
- the liquid crystal display device of FIG. 2 described above includes a step of interposing the curable resin composition of the present embodiment between the image display unit and the touch panel and / or between the touch panel and the protective panel, And irradiating light from the protective panel surface side to cure the curable resin composition and forming a transparent resin layer.
- a method of interposing the curable resin composition the same method as in the liquid crystal display device of FIG.
- the light irradiation for example, using an ultraviolet irradiation device can be carried out under the conditions of exposure 500mJ / cm 2 ⁇ 5000mJ / cm 2.
- the exposure amount refers to a value obtained by multiplying the illuminance that can be measured with an ultraviolet illuminance meter UV-M02 (receiver: UV-36) manufactured by Oak Co., Ltd., by the irradiation time (seconds).
- the light source for ultraviolet irradiation may be a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, an LED lamp or the like, but it is preferable to use a high pressure mercury lamp or a metal halide lamp.
- irradiation from the protective panel surface side and irradiation from the side surface may be used in combination.
- hardening can also be accelerated
- the curable resin composition is cured by light irradiation, that is, the case where the curable resin composition contains a photopolymerization initiator (D1) has been described.
- the curable resin composition contains (D2) a thermal polymerization initiator
- the curable resin composition may be cured by heat.
- the liquid crystal display device that can be manufactured by using the curable resin composition of the present embodiment has been described above, but the image display that can be manufactured by using the curable resin composition of the present embodiment.
- the application apparatus is not limited to this, and can be applied to a plasma display (PDP), a cathode ray tube (CRT), a field emission display (FED), an organic EL display, a 3D display, electronic paper, and the like.
- PDP plasma display
- CRT cathode ray tube
- FED field emission display
- organic EL display organic EL display
- 3D display electronic paper, and the like.
- the image display device is 10 inches or larger, it is more preferable to produce a transparent resin layer using the curable resin composition of the present embodiment.
- TMDI mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate, mixing ratio: 4: 6 (mass ratio)
- Diisocyanate 209.8 g (1 mol) was uniformly added dropwise over 2 hours to carry out the reaction. After the completion of the dropwise addition, the reaction was terminated after confirming that the isocyanate had disappeared by IR measurement when the reaction was completed for 5 hours.
- TMDI mixture of 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate, mixing ratio: 4: 6 (mass ratio)
- Diisocyanate 209.8 g (1 mol) was uniformly added dropwise over 2 hours to carry out the reaction.
- Examples 1 to 13 and Comparative Examples 1 to 7 The components (A) to (D) were blended at the blending ratios shown in Table 1 and Table 2, and stirred and mixed to prepare curable resin compositions of Examples 1 to 13 and Comparative Examples 1 to 7.
- the unit of numerical values for the components (A) to (D) is parts by mass. “The amount of component (C) in the table” in the table indicates the amount of component (C) relative to the total amount of component (A), component (B) and component (C).
- the viscosity of the curable resin composition was measured at 25 ° C. using an E-type viscometer (RE-80L manufactured by Toki Sangyo).
- a curable resin composition is dropped on a 2-inch glass substrate, another glass substrate is bonded through a 175 ⁇ m spacer, and ultraviolet rays are irradiated at 2,000 mJ / cm 2 using an ultraviolet irradiation device. I got a piece. This test piece was placed in a test bath of 85 ° C./85% RH for 50 hours, peeled off, and visually evaluated for the presence or absence of bubbles, and evaluated according to the following criteria. A: No visual change B: Peeled off visually, bubbles were confirmed
- a curable resin composition is dropped onto a polyethylene terephthalate film (hereinafter referred to as a PET film) whose surface has a thickness of 50 ⁇ m manufactured by Fujimori Kogyo Co., Ltd., and another PET is formed so that the film thickness is 175 ⁇ m.
- the films were bonded together, and a transparent film in which the curable resin composition was cured by irradiating ultraviolet rays at 2,000 mJ / cm 2 using an ultraviolet irradiation device was produced.
- the PET film was peeled off, and the transmittance of the transparent film at a wavelength of 400 nm was measured using a spectrophotometer (UV-2400PC manufactured by Shimadzu Corporation). Further, the haze of the transparent film was measured using a haze meter (Suga Test Instruments Co., Ltd. HGM-2).
- a curable resin composition is dropped onto a PET film, and another PET film is bonded so as to have a film thickness of 175 ⁇ m, and an ultraviolet ray is radiated at 2,000 mJ / cm 2 using an ultraviolet ray irradiation device.
- a transparent film in which the product was cured was produced.
- the specific gravity of this transparent film and the resin composition before curing was measured using an electronic hydrometer (Alfa Mirage SD-200L), and the curing shrinkage was calculated from the following formula and evaluated according to the following criteria. .
- Curing shrinkage rate (%) ⁇ (specific gravity of resin composition after curing ⁇ specific gravity of resin composition before curing) / specific gravity of resin composition after curing ⁇ ⁇ 100
- SYMBOLS 1 Image display unit, 10 ... Liquid crystal display cell, 20, 22 ... Polarizing plate, 30 ... Touch panel, 31, 32 ... Transparent resin layer, 40 ... Transparent protective substrate, 50 ... Backlight system.
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Abstract
Description
(A)成分であるアクリル系重合体は、例えば、(メタ)アクリル基を有する重合性化合物(以下、場合により「モノマー」という)をラジカル重合させることにより製造することができる。なお、アクリル重合体は、(メタ)アクリル基を有する重合性化合物の他に、スチレン;ビニルトルエン及びα-メチルスチレン等のα-位若しくは芳香族環において置換されている重合可能なスチレン誘導体、ビニルアルキルエーテル、ビニルアルコールのエステル類等の1種又は2種以上の重合性単量体と共重合されたものであってもよい。
(a)数平均分子量(Mn)
Mn=Σ(NiMi)/ΣNi=ΣXiMi
(Xi=分子量Miの分子のモル分率=Ni/ΣNi)
(b)重量平均分子量(Mw)
Mw=Σ(NiMi2)/ΣNiMi=ΣWiMi
(Wi=分子量Miの分子の重量分率=NiMi/ΣNiMi)
(c)分子量分布(分散度)
分散度=Mw/Mn
(B)成分である分子内にエチレン性不飽和結合を有する重合体としては、例えば、(メタ)アクリロイル基を有するポリエステルオリゴマー、(メタ)アクリロイル基を有するウレタン重合体、ポリエチレングリコールモノ(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、ポリプロレングリコールモノ(メタ)アクリレート、ポリプロレングリコールジ(メタ)アクリレートが挙げられる。
また、(メタ)アクリロイル基を有するウレタン重合体は、上記以外の方法で製造することもできる。
(メタ)アクリロイル基を有するウレタン重合体の上記以外の製造方法としては、例えば、(b1)ジオール化合物と、(b3)モノヒドロキシ(メタ)アクリレートを各々所定量混合し、所定の温度に昇温した後、(b2)イソシアネート基を有する化合物の所定量を所定の時間かけて、(b1)成分と(b3)成分の混合物中に加えて反応させることでも得ることができる。
なお、(B)分子内にエチレン性不飽和結合を有する重合体は、上述の成分を用いて従来公知の方法、例えば、p-メトキシフェノール等の重合禁止剤及びジブチル錫ジラウレート等の触媒の存在下で上述の成分を反応させる方法で製造することができる。
(C)成分である分子内に1個のエチレン性不飽和基を有する単量体は、常温(25℃)で液状であることが好ましく、特に、接着性、及び柔軟性を付与させる観点から、下記一般式(3)で表されるアルキル(メタ)アクリレート(以下、「(C1)成分」ともいう。)を主に含むことが好ましい。また、耐湿熱信頼性及び塗工時の作業性の観点から、分子内に(メタ)アクリル基及び、水酸基若しくはエーテル結合を有する化合物(以下、「(C2)成分」ともいう。)を含むことがより好ましい。
上記一般式(3)で表されるアルキル(メタ)アクリレートしては、例えば、n-ブチル(メタ)アクリレート、tert-ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、n-ペンチル(メタ)アクリレート、n-オクチル(メタ)アクリレート、イソオクチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、イソデシル(メタ)アクリレート、n-ヘキシル(メタ)アクリレート、ステアリル(メタ)アクリレート、ラウリル(メタ)アクリレート、トリデシル(メタ)アクリレート等が挙げられる。これらは、単独で又は2種類以上組み合わせて用いることができる。
(C)成分中の(C1)成分の含有割合は、50質量%以上であることが好ましく、60質量%以上であることがより好ましく、70質量%以上であることが特に好ましい。
分子内に(メタ)アクリル基及び、水酸基若しくはエーテル結合を有する化合物としては、例えば、2-ヒドロキシエチル(メタ)アクリレート、1-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、3-ヒドロキシプロピル(メタ)アクリレート、1-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、3-ヒドロキシブチル(メタ)アクリレート、2-ヒドロキシブチル(メタ)アクリレート、1-ヒドロキシブチル(メタ)アクリレート等の水酸基含有(メタ)アクリレート;ヒドロキシエチル(メタ)アクリルアミド等の水酸基含有(メタ)アクリルアミド;ジエチレングリコールやトリエチレングリコール等のポリエチレングリコールモノ(メタ)アクリレート;ジプロピレングリコールやトリプロピレングリコール等のポリプロピレングリコールモノ(メタ)アクリレート;ジブチレングリコールやトリブチレングリコール等のポリブチレングリコールモノ(メタ)アクリレート;アクリロイルモルホリン等のモルホリン基含有(メタ)アクリレートが挙げられる。これらの中でも特に、耐湿熱信頼性及び塗工時の作業性をより向上できる観点から、4-ヒドロキシブチルアクリレート、アクリロイルモルホリンが好ましい。これらのアクリレートは2種類以上を組み合わせて使用してもよい。
(D)重合開始剤としては、(D1)光重合開始剤又は(D2)熱重合開始剤のいずれも使用することができ、これらを併用してもよい。
以下、本実施形態の硬化性樹脂組成物を用いることにより製造することが可能な画像表示用装置の一例である液晶表示装置について説明する。
特に、画像表示用装置が10インチサイズ以上において、本実施形態の硬化性樹脂組成物を用いて透明樹脂層を作製することがより好適である。
(GPC条件)
ポンプ:日立 L-6000型[(株)日立製作所製]
検出器:日立 L-3300 RI[(株)日立製作所製]
カラム:Gelpack GL-R420+Gelpack GL-R430+Gelpack GL-R440(計3本)(日立化成工業(株)製、商品名)
溶離液:THF
測定温度:25℃
冷却管、温度計、撹拌装置、滴下装置及び窒素注入管を備える反応容器にメチルエチルケトン575.0gをとり、150ml/分で窒素置換しながら、50分間で常温(25℃)から100℃まで加熱した。
その後、この温度に保ちながら、モノマーとして2-エチルヘキシルアクリレート805.0gと2-ヒドロキシエチルアクリレート345.0gを使用し、これらにt-ブチルパーオキシ-2-エチルヘキサノエート17.25gを溶解させた溶液を準備し、この溶液を150分間かけて滴下し、滴下終了後さらに1時間反応させた。
続いて、アゾビスイソブチロニトリル2.5gをメチルエチルケトン253.0gに溶解させた溶液を準備し、この溶液を30分間かけて滴下し、滴下終了後30分間で120℃まで昇温し、さらに2時間反応させた。
最後に、メチルエチルケトンを溜去することにより、2-エチルヘキシルアクリレート及び2-ヒドロキシエチルアクリレートのコポリマー(重量平均分子量20,000)を得た。
冷却管、温度計、撹拌装置、滴下装置及び窒素注入管を備える反応容器に、初期モノマーとして2-エチルヘキシルアクリレート84.0gと2-ヒドロキシエチルアクリレート36.0g及びメチルイソブチルケトン150.0gをとり、100ml/分で窒素置換しながら、15分間で常温(25℃)から70℃まで加熱した。
その後、この温度に保ちながら、追加モノマーとして2-エチルヘキシルアクリレート21.0gと2-ヒドロキシエチルアクリレート9.0gを使用し、これらにラウロイルパーオキシド0.6gを溶解させた溶液を準備し、この溶液を60分間かけて滴下し、滴下終了後さらに2時間反応させた。
続いて、メチルイソブチルケトンを溜去することにより、2-エチルヘキシルアクリレート及び2-ヒドロキシエチルアクリレートのコポリマー(重量平均分子量200,000)を得た。
冷却管、温度計、撹拌装置、滴下装置及び窒素注入管を備える反応容器にメチルエチルケトン575.0gをとり、150ml/分で窒素置換しながら、50分間で常温(25℃)から90℃まで加熱した。
その後、この温度に保ちながら、モノマーとして2-エチルヘキシルアクリレート805.0gと2-ヒドロキシエチルアクリレート345.0gを使用し、これらにt-ブチルパーオキシ-2-エチルヘキサノエート11.5gを溶解させた溶液を準備し、この溶液を150分間かけて滴下し、滴下終了後さらに1時間反応させた。
続いて、アゾビスイソブチロニトリル2.88gをメチルエチルケトン287.5gに溶解させた溶液を準備し、この溶液を30分間かけて滴下し、滴下終了後30分間で120℃まで昇温し、さらに2時間反応させた。
最後に、メチルエチルケトンを溜去することにより、2-エチルヘキシルアクリレート及び2-ヒドロキシエチルアクリレートのコポリマー(重量平均分子量40,000)を得た。
冷却管、温度計、撹拌装置、滴下装置及び窒素注入管を備える反応容器にメチルエチルケトン575.0gをとり、フラスコ内を2.5MPaに加圧した状態で、50分間で常温(25℃)から120℃まで加熱した。
その後、この温度に保ちながら、モノマーとして2-エチルヘキシルアクリレート805.0gと2-ヒドロキシエチルアクリレート345.0gを使用し、これらにt-ブチルパーオキシ-2-エチルヘキサノエート23.0gを溶解させた溶液を準備し、この溶液を150分間かけて滴下し、滴下終了後さらに1時間反応させた。
続いて、アゾビスイソブチロニトリル2.5gをメチルエチルケトン253.0gに溶解させた溶液を準備し、この溶液を30分間かけて滴下し、滴下終了後、さらに2時間保温し反応完了とした。
最後に、メチルエチルケトンを溜去することにより、2-エチルヘキシルアクリレート及び2-ヒドロキシエチルアクリレートのコポリマー(重量平均分子量9,000)を得た。
冷却管、温度計、撹拌装置、滴下装置及び窒素注入管を備える反応容器にメチルイソブチルケトン575.0gをとり、フラスコ内を2.5MPaに加圧した状態で、50分間で常温(25℃)から135℃まで加熱した。
その後、この温度に保ちながら、モノマーとして2-エチルヘキシルアクリレート805.0gと2-ヒドロキシエチルアクリレート345.0gを使用し、これらにt-ブチルパーオキシ-2-エチルヘキサノエート23.0gを溶解させた溶液を準備し、この溶液を150分間かけて滴下し、滴下終了後さらに1時間反応させた。
続いて、アゾビスイソブチロニトリル2.5gをメチルエチルケトン253.0gに溶解させた溶液を準備し、この溶液を30分間かけて滴下し、滴下終了後、30分間で142℃まで昇温し反応させた。
最後に、メチルイソブチルケトンを溜去することにより、2-エチルヘキシルアクリレート及び2-ヒドロキシエチルアクリレートのコポリマー(重量平均分子量7,000)を得た。
冷却管、温度計、攪拌装置、滴下漏斗及び空気注入管を備える反応容器にポリプロピレングリコール(分子量2,000)180g(0.09mol)、2-ヒドロキシエチルアクリレート2.33g(0.02mol)、重合禁止剤としてp-メトキシフェノール0.5g及び触媒としてジブチル錫ジラウレート0.05gをとった。空気を流しながら70℃に昇温後、70~75℃で攪拌しつつイソホロンジイソシアネート22.2g(0.1mol)を2時間かけて均一滴下し、反応を行った。
滴下終了後、5時間反応させたところで、IR測定によりイソシアネートが消失したことを確認して反応を終了し、ポリプロピレングリコールとイソホロンジイソシアネートを繰り返し単位として有し、エチレン性不飽和結合を有するポリウレタンアクリレート(重量平均分子量20,000、平均官能基数=2(計算値))を得た。
冷却管、温度計、攪拌装置、滴下漏斗及び空気注入管を備える反応容器にポリテトラメチレングリコール(分子量850)520.8g(0.613mol)、ジエチレングリコール1.06g(0.01mol)、不飽和脂肪酸ヒドロキシアルキルエステル修飾ε-カプロラクトン(プラクセルFA2D:ダイセル化学工業株式会社商品名)275.2g(0.8mol)、重合禁止剤としてp-メトキシフェノール0.5g、触媒としてジブチル錫ジラウレート0.3gをとった。空気を流しながら70℃に昇温後、70~75℃で攪拌しつつイソホロンジイソシアネート222g(1mol)を2時間かけて均一滴下し、反応を行った。
滴下終了後、5時間反応させたところで、IR測定によりイソシアネートが消失したことを確認して反応を終了し、ポリテトラメチレングリコールとイソホロンジイソシアネートを繰り返し単位として有し、エチレン性不飽和結合を有するポリウレタンアクリレート(重量平均分子量7,000、平均官能基数=2(計算値))を得た。
冷却管、温度計、攪拌装置、滴下漏斗及び空気注入管を備える反応容器にポリプロピレングリコール(分子量2,000)186.5g(0.093mol)、2-ヒドロキシエチルアクリレート1.60g(0.014mol)、重合禁止剤としてp-メトキシフェノール0.5g及び触媒としてジブチル錫ジラウレート0.05gをとった。空気を流しながら70℃に昇温後、70~75℃で攪拌しつつイソホロンジイソシアネート22.2g(0.1mol)を2時間かけて均一滴下し、反応を行った。
滴下終了後、5時間反応させたところで、IR測定によりイソシアネートが消失したことを確認して反応を終了し、ポリプロピレングリコールとイソホロンジイソシアネートを繰り返し単位として有し、エチレン性不飽和結合を有するポリウレタンアクリレート(重量平均分子量30,000、平均官能基数=2(計算値))を得た。
冷却管、温度計、攪拌装置、滴下漏斗及び空気注入管を備える反応容器にポリテトラメチレングリコール(分子量850)520.8g(0.613mol)、ジエチレングリコール1.06g(0.01mol)、不飽和脂肪酸ヒドロキシアルキルエステル修飾ε-カプロラクトン(プラクセルFA2D:ダイセル化学工業株式会社商品名)137.6g(0.4mol)、ブタノール34.9g(0.47mol)、重合禁止剤としてp-メトキシフェノール0.5g、触媒としてジブチル錫ジラウレート0.3gをとった。空気を流しながら70℃に昇温後、70~75℃で攪拌しつつイソホロンジイソシアネート222g(1mol)を2時間かけて均一滴下し、反応を行った。
滴下終了後、5時間反応させたところで、IR測定によりイソシアネートが消失したことを確認して反応を終了し、ポリテトラメチレングリコールとイソホロンジイソシアネートを繰り返し単位として有し、エチレン性不飽和結合を有するポリウレタンアクリレート(重量平均分子量7,000、平均官能基数=1(計算値))を得た。
冷却管、温度計、攪拌装置、滴下漏斗及び空気注入管を備える反応容器にポリテトラメチレングリコール(分子量850)520.8g(0.613mol)、ジエチレングリコール1.06g(0.01mol)、不飽和脂肪酸ヒドロキシアルキルエステル修飾ε-カプロラクトン(プラクセルFA2D:ダイセル化学工業株式会社商品名)137.6g(0.4mol)、ブタノール34.9g(0.47mol)、重合禁止剤としてp-メトキシフェノール0.5g、触媒としてジブチル錫ジラウレート0.3gをとった。空気を流しながら70℃に昇温後、70~75℃で攪拌しつつTMDI(2,2,4-トリメチルヘキサメチレンジイソシアネートと2,4,4-トリメチルヘキサメチレンジイソシアネートの混合物、混合比:4:6(質量比))ジイソシアネート209.8g(1mol)を2時間かけて均一滴下し、反応を行った。
滴下終了後、5時間反応させたところで、IR測定によりイソシアネートが消失したことを確認して反応を終了し、ポリテトラメチレングリコールとTMDIを繰り返し単位として有し、エチレン性不飽和結合を有するポリウレタンアクリレート(重量平均分子量7,000、平均官能基数=1(計算値))を得た。
冷却管、温度計、攪拌装置、滴下漏斗及び空気注入管を備える反応容器にポリテトラメチレングリコール(分子量850)520.8g(0.613mol)、ジエチレングリコール1.06g(0.01mol)、不飽和脂肪酸ヒドロキシアルキルエステル修飾ε-カプロラクトン(プラクセルFA2D:ダイセル化学工業株式会社商品名)68.8g(0.2mol)、ブタノール52.3g(0.71mol)、重合禁止剤としてp-メトキシフェノール0.5g、触媒としてジブチル錫ジラウレート0.3gをとった。空気を流しながら70℃に昇温後、70~75℃で攪拌しつつTMDI(2,2,4-トリメチルヘキサメチレンジイソシアネートと2,4,4-トリメチルヘキサメチレンジイソシアネートの混合物、混合比:4:6(質量比))ジイソシアネート209.8g(1mol)を2時間かけて均一滴下し、反応を行った。
表1及び表2に示す配合比で、(A)~(D)成分を配合し、攪拌混合して、実施例1~13及び比較例1~7の硬化性樹脂組成物を調製した。なお表中、(A)~(D)成分についての数値の単位は質量部である。表中の「(C)成分を配合量」とは、(A)成分、(B)成分及び(C)成分の総量に対する(C)成分の配合量を示す。
硬化性樹脂組成物の粘度は、25℃においてE型粘度計(東機産業製RE-80L)を用いて測定した。
硬化性樹脂組成物を2インチのガラス基板に滴下し、175μmのスペーサを介してもう一枚のガラス基板を貼合し、紫外線照射装置を用いて紫外線を2,000mJ/cm2照射して試験片を得た。この試験片を85℃/85%RHの試験槽に50時間投入し、剥がれ、気泡発生の有無を目視評価し、下記の基準で評価した。
A;目視で変化なし
B:目視で剥がれ、気泡が確認された
藤森工業社製の膜厚が50μmである表面が離型処理されたポリエチレンテレフタレートフィルム(以下、PETフィルムという)に硬化性樹脂組成物を滴下し、膜厚175μmとなるようにもう一枚のPETフィルムを貼り合わせ、紫外線照射装置を用いて紫外線を2,000mJ/cm2照射して硬化性樹脂組成物が硬化した透明膜を作製した。PETフィルムを剥がし、この透明膜の波長400nmにおける透過率を、分光光度計(島津製作所製UV-2400PC)を用いて測定した。また、この透明膜のヘイズを、ヘイズメータ(スガ試験機(株)HGM-2)を用いて測定した。
PETフィルムに硬化性樹脂組成物を滴下し、膜厚175μmとなるようにもう一枚のPETフィルムを貼り合わせ、紫外線照射装置を用いて紫外線を2,000mJ/cm2照射して硬化性樹脂組成物が硬化した透明膜を作製した。この透明膜と、硬化前の樹脂組成物の比重を、電子比重計(アルファーミラージュ(株)SD-200L)を用いて測定し、下式より硬化収縮率を算出し、下記の基準で評価した。
硬化収縮率(%)={(硬化後の樹脂組成物の比重-硬化前の樹脂組成物の比重)/硬化後の樹脂組成物の比重}×100
A:1.5%未満
B:1.5%以上3.0%未満
C:3.0%以上5.0%未満
D:5.0%以上
Claims (6)
- (A)アクリル系重合体、
(B)分子内にエチレン性不飽和結合を有する重合体、
(C)分子内に1個のエチレン性不飽和基を有する単量体、及び
(D)重合開始剤、
を含有し、
(C)成分の含有量が、(A)成分、(B)成分及び(C)成分の総量に対して5~25質量%である液状硬化性樹脂組成物。 - (B)成分が(メタ)アクリロイル基を有するウレタン重合体である、請求項1に記載の液状硬化性樹脂組成物。
- 実質的に有機溶媒を含有せず、25℃における粘度が500~5000mPa・sである、請求項1又は2に記載の液状硬化性樹脂組成物。
- 画像表示ユニットと、保護パネルと、を備える画像表示用装置の製造方法であって、
前記画像表示ユニットと前記保護パネルとの間に請求項1~3のいずれか一項に記載の液状硬化性樹脂組成物を介在させる工程と、
前記保護パネル面側から光照射して前記液状硬化性樹脂組成物を硬化させる工程と、を備える、画像表示用装置の製造方法。 - 画像表示ユニットと、タッチパネルと、保護パネルと、を備える画像表示用装置の製造方法であって、
前記画像表示ユニットと前記タッチパネルとの間、及び/又は、前記タッチパネルと前記保護パネルとの間に請求項1~3のいずれか一項に記載の液状硬化性樹脂組成物を介在させる工程と、
前記保護パネル面側から光照射して前記液状硬化性樹脂組成物を硬化させる工程と、を備える、画像表示用装置の製造方法。 - 請求項4又は5に記載の製造方法により製造される画像表示用装置。
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WO2016024626A1 (ja) * | 2014-08-14 | 2016-02-18 | 株式会社巴川製紙所 | 保護フィルム、フィルム積層体および偏光板 |
JP2020132783A (ja) * | 2019-02-21 | 2020-08-31 | ダイセル・オルネクス株式会社 | ウレタン(メタ)アクリレート、これを含む活性エネルギー線硬化性組成物、及びその硬化物 |
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JP2002214779A (ja) * | 2001-01-19 | 2002-07-31 | Asahi Kasei Corp | サンドブラスト用感光性樹脂積層体 |
JP2003215797A (ja) * | 2002-01-22 | 2003-07-30 | Asahi Kasei Corp | 光重合性樹脂組成物 |
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