WO2017073365A1 - Curable resin composition and display element - Google Patents
Curable resin composition and display element Download PDFInfo
- Publication number
- WO2017073365A1 WO2017073365A1 PCT/JP2016/080517 JP2016080517W WO2017073365A1 WO 2017073365 A1 WO2017073365 A1 WO 2017073365A1 JP 2016080517 W JP2016080517 W JP 2016080517W WO 2017073365 A1 WO2017073365 A1 WO 2017073365A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- water
- resin composition
- curable resin
- resin
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 76
- 239000011347 resin Substances 0.000 claims abstract description 176
- 229920005989 resin Polymers 0.000 claims abstract description 176
- 239000000178 monomer Substances 0.000 claims abstract description 52
- 229920001577 copolymer Polymers 0.000 claims abstract description 38
- 125000000524 functional group Chemical group 0.000 claims abstract description 26
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001768 cations Chemical class 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 238000004132 cross linking Methods 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 39
- 239000007864 aqueous solution Substances 0.000 description 35
- 238000000576 coating method Methods 0.000 description 23
- 229940048053 acrylate Drugs 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 19
- 239000002904 solvent Substances 0.000 description 16
- 239000007787 solid Substances 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000012528 membrane Substances 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- -1 ammonium ions Chemical class 0.000 description 9
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920001145 Poly(N-vinylacetamide) Polymers 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 230000003472 neutralizing effect Effects 0.000 description 5
- 230000002265 prevention Effects 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 2
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000012674 dispersion polymerization Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- KPQOXMCRYWDRSB-UHFFFAOYSA-N 1-(2-chlorophenyl)pyrrole-2,5-dione Chemical compound ClC1=CC=CC=C1N1C(=O)C=CC1=O KPQOXMCRYWDRSB-UHFFFAOYSA-N 0.000 description 1
- MKRBAPNEJMFMHU-UHFFFAOYSA-N 1-benzylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CC1=CC=CC=C1 MKRBAPNEJMFMHU-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- BAWHYOHVWHQWFQ-UHFFFAOYSA-N 1-naphthalen-1-ylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC2=CC=CC=C12 BAWHYOHVWHQWFQ-UHFFFAOYSA-N 0.000 description 1
- NQDOCLXQTQYUDH-UHFFFAOYSA-N 1-propan-2-ylpyrrole-2,5-dione Chemical compound CC(C)N1C(=O)C=CC1=O NQDOCLXQTQYUDH-UHFFFAOYSA-N 0.000 description 1
- DABFKTHTXOELJF-UHFFFAOYSA-N 1-propylpyrrole-2,5-dione Chemical compound CCCN1C(=O)C=CC1=O DABFKTHTXOELJF-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- PVFYDPMTPBPRQA-UHFFFAOYSA-N 2-methylprop-2-enenitrile;prop-2-enenitrile Chemical compound C=CC#N.CC(=C)C#N PVFYDPMTPBPRQA-UHFFFAOYSA-N 0.000 description 1
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 1
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical class CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 125000004069 aziridinyl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
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- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
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- PEOHLVWFSVQRLK-UHFFFAOYSA-N ethenylcarbamic acid Chemical compound OC(=O)NC=C PEOHLVWFSVQRLK-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 230000036541 health Effects 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 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
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 description 1
- HAZULKRCTMKQAS-UHFFFAOYSA-N n-ethenylbutanamide Chemical compound CCCC(=O)NC=C HAZULKRCTMKQAS-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- IUWVWLRMZQHYHL-UHFFFAOYSA-N n-ethenylpropanamide Chemical compound CCC(=O)NC=C IUWVWLRMZQHYHL-UHFFFAOYSA-N 0.000 description 1
- ISRXMEYARGEVIU-UHFFFAOYSA-N n-methyl-n-propan-2-ylpropan-2-amine Chemical compound CC(C)N(C)C(C)C ISRXMEYARGEVIU-UHFFFAOYSA-N 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 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
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- ZCIDKAKNWVZFKR-UHFFFAOYSA-M sodium N-ethenylcarbamate Chemical compound C(=C)NC([O-])=O.[Na+] ZCIDKAKNWVZFKR-UHFFFAOYSA-M 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
Definitions
- the present invention relates to a curable resin composition that can obtain a cured product that is excellent in transparency, adhesion, hardness, and heat-and-moisture resistance, and that can reduce the burden on the environment.
- the present invention also relates to a display element using the curable resin composition.
- Patent Document 1 discloses a coating composition containing a siloxane polymer and two or more types of organic solvents.
- Patent Document 2 discloses a resin, a polyfunctional monomer, a solvent, and photopolymerization initiation.
- a photosensitive transparent resin composition containing an agent and an organic compound-based ultraviolet absorber is disclosed. These compositions are excellent in transparency and are said to be suitably used for display device applications.
- Patent Document 1 and Patent Document 2 contain an organic solvent, an organic solvent is not used from the viewpoint of reducing the burden on the environment. Therefore, a resin composition having excellent transparency has been demanded.
- An object of the present invention is to provide a curable resin composition capable of obtaining a cured product excellent in transparency, adhesion, hardness, and heat-and-moisture resistance, and capable of reducing the burden on the environment. To do. Moreover, an object of this invention is to provide the display element which uses this curable resin composition.
- the present invention relates to a segment having a —C ( ⁇ O) OX group (X is hydrogen or a salt-forming cation) derived from a carboxyl group of a carboxyl group-containing ethylenically unsaturated monomer, and other ethylenically unsaturated monomers.
- a water-soluble resin that is a copolymer having a segment derived from a saturated monomer, a cross-linkable resin having a cross-linkable functional group capable of cross-linking the water-soluble resin, and a curable resin containing water It is a composition.
- the present invention is described in detail below.
- the present inventors use water as a solvent in place of the organic solvent used in conventional resin compositions, and use a water-soluble resin as a resin component, so that the resin composition is excellent in transparency without using an organic solvent.
- a water-soluble resin excellent in transparency a single amount of an ethylenically unsaturated monomer that is a carboxylic acid or a salt thereof and another ethylenically unsaturated monomer copolymerizable therewith The use of a copolymer as a body component was examined.
- the obtained cured product is excellent in transparency, there is a problem that it is inferior in adhesion, hardness, and heat-and-moisture resistance.
- the present inventors cross-linked the water-soluble resin with a cross-linkable resin that can cross-link the water-soluble resin, so that the cured product has transparency, adhesion, hardness. And it discovered that it was excellent in moist heat resistance, and could obtain the curable resin composition which can reduce the load to an environment, and came to complete this invention. Moreover, since the curable resin composition of the present invention can be cured by heating at a low temperature, damage to the device due to light irradiation or high-temperature heating can be prevented.
- the above-mentioned “transparent” means that the total light transmittance measured with a haze meter is 85% or more and the haze value (cloudiness value) is 1% or less. To do.
- the curable resin composition of the present invention contains a water-soluble resin.
- the water-soluble resin includes a segment having a —C ( ⁇ O) OX group (X is hydrogen or a salt-forming cation) derived from a carboxyl group of a carboxyl group-containing ethylenically unsaturated monomer, and other ethylene And a segment derived from a polymerizable unsaturated monomer (hereinafter also referred to as “water-soluble resin according to the present invention”).
- the water-soluble resin according to the present invention may be any of a random copolymer, a block copolymer, and a graft copolymer.
- the term “water-soluble” means that an aqueous solution can be obtained in a neutral range of pH 6 to pH 9.
- the water-soluble resin according to the present invention has excellent reactivity with water-soluble and crosslinkable resins.
- the —C ( ⁇ O) OX group is derived from the carboxyl group of the carboxyl group-containing ethylenically unsaturated monomer.
- the carboxyl group-containing ethylenically unsaturated monomer include acrylic acid, methacrylic acid, 3-acryloyloxypropionic acid, fumaric acid, itaconic acid, maleic acid, and crotonic acid. Of these, acrylic acid and methacrylic acid are preferable from the viewpoint of copolymerization.
- X is hydrogen or a salt-forming cation.
- examples of the salt-forming cation include ammonium ions and alkali metal ions.
- the “ammonium ion” means a cation derived from ammonia, a primary amine, a secondary amine, or a tertiary amine.
- the —C ( ⁇ O) OX group can be confirmed using an infrared spectrometer.
- the preferable lower limit of the content ratio of the segment having —C ( ⁇ O) OX group in the water-soluble resin according to the present invention is 5% by weight, and the preferable upper limit is 25% by weight.
- the content ratio of the segment having the —C ( ⁇ O) OX group is within this range, the obtained water-soluble resin is water-soluble and cross-linkable resin without deteriorating water resistance and storage stability. It becomes more excellent by the reactivity with.
- the more preferable lower limit of the content ratio of the segment having the —C ( ⁇ O) OX group is 10% by weight, and the more preferable upper limit is 15% by weight.
- the content ratio of the segment having the —C ( ⁇ O) OX group can be determined by 1 H-NMR and 13 C-NMR.
- Examples of the other ethylenically unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate.
- the preferable lower limit of the content ratio of the segment derived from the other ethylenically unsaturated monomer in the water-soluble resin according to the present invention is 75% by weight, and the preferable upper limit is 95% by weight.
- the content ratio of the segment derived from the other ethylenically unsaturated monomer is within this range, the cured product of the obtained curable resin composition is more excellent in moisture and heat resistance.
- the minimum with more preferable content rate of the segment originating in the said other ethylenically unsaturated monomer is 80 weight%, and a more preferable upper limit is 90 weight%.
- the water-soluble resin according to the present invention includes aromatic substituted maleimide monomers such as N-phenylmaleimide, N-benzylmaleimide, N- (1-naphthyl) maleimide, o-chlorophenylmaleimide, and N-methylmaleimide. , Segments derived from alkyl-substituted maleimide monomers such as N-ethylmaleimide, N-propylmaleimide and N-isopropylmaleimide.
- aromatic substituted maleimide monomers such as N-phenylmaleimide, N-benzylmaleimide, N- (1-naphthyl) maleimide, o-chlorophenylmaleimide, and N-methylmaleimide.
- the water-soluble resin according to the present invention is preferably a (meth) acrylic copolymer having the above-mentioned —C ( ⁇ O) OX group in the side chain.
- the water-soluble resin according to the present invention may be a copolymer having a segment derived from the carboxyl group-containing ethylenically unsaturated monomer and a segment derived from the other ethylenically unsaturated monomer.
- the copolymer may be neutralized with a base such as ammonia or amine to form a carboxylate.
- a method for producing a copolymer having a segment derived from the carboxyl group-containing ethylenically unsaturated monomer and a segment derived from the other ethylenically unsaturated monomer for example, a radical polymerization initiator and If necessary, using a molecular weight regulator, a monomer component constituting a copolymer such as the carboxyl group-containing ethylenically unsaturated monomer and the other ethylenically unsaturated monomer, bulk polymerization, Examples of the polymerization method include conventionally known methods such as solution polymerization, suspension polymerization, dispersion polymerization, and emulsion polymerization. Of these, solution polymerization is preferred.
- solvent used in the solution polymerization examples include aliphatic alcohols such as methanol, ethanol, isopropanol and glycol, cellosolves such as cellosolve and butylcellosolve, carbitols such as carbitol and butylcarbitol, and acetic acid.
- Esters such as cellosolve, carbitol acetate, propylene glycol monomethyl ether acetate, ethers such as diethylene glycol dimethyl ether, cyclic ethers such as tetrahydrofuran, ketones such as cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl sulfoxide, dimethylformamide, etc.
- organic solvents having the following polarity.
- Examples of the medium used for the suspension polymerization, the dispersion polymerization, the emulsion polymerization, and the like include liquid hydrocarbons such as benzene, toluene, hexane, and cyclohexane, and other nonpolar organic solvents. .
- radical polymerization initiator used when producing a copolymer having a segment derived from the carboxyl group-containing ethylenically unsaturated monomer and a segment derived from the other ethylenically unsaturated monomer
- Peroxides for example, Peroxides, azo initiators, and the like.
- the molecular weight modifier include ⁇ -methylstyrene dimer, mercaptan chain transfer agent, and the like.
- amine that can be used when neutralizing a copolymer having a segment derived from the carboxyl group-containing ethylenically unsaturated monomer and a segment derived from the other ethylenically unsaturated monomer
- primary amines such as methylamine, ethylamine, propylamine, isopropylamine
- secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, trimethylamine, triethylamine, N, N-dimethylpropylamine, N
- Tertiary amines such as N-dimethylisopropylamine, N, N-diisopropylmethylamine, N, N-diisopropylethylamine and the like can be mentioned.
- the minimum with a preferable weight average molecular weight of the water-soluble resin concerning this invention is 5000, and a preferable upper limit is 50,000.
- the weight average molecular weight of the water-soluble resin according to the present invention is within this range, the resulting curable resin composition has better adhesion.
- the minimum with a more preferable weight average molecular weight of the water-soluble resin concerning this invention is 10,000, and a more preferable upper limit is 20,000.
- the said weight average molecular weight is a value calculated
- Examples of the column for measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK). Moreover, tetrahydrofuran etc. are mentioned as a solvent used by GPC.
- the preferable lower limit of the —C ( ⁇ O) OX group equivalent of the water-soluble resin according to the present invention is 288, and the preferable upper limit is 4000.
- the —C ( ⁇ O) OX group equivalent of the water-soluble resin according to the present invention is within this range, the water-soluble resin and the reactivity with the cross-linkable resin are excellent.
- the more preferable lower limit of the —C ( ⁇ O) OX group equivalent of the water-soluble resin according to the present invention is 480, and the more preferable upper limit is 2000.
- the —C ( ⁇ O) OX group equivalent of the water-soluble resin according to the present invention is such that the weight (g) of the water-soluble resin according to the present invention is the —C ( ⁇ O) contained in the water-soluble resin according to the present invention. It is a value obtained by dividing by the number of moles (mol) of the OX group.
- water-soluble resin examples include (meth) acrylic acid / (meth) methyl acrylate copolymer, (meth) acrylic acid / (meth) ethyl acrylate copolymer, (meth ) Acrylic acid / (meth) propyl propyl copolymer, (meth) acrylic acid / (meth) isopropyl acrylate copolymer, (meth) acrylic acid / (meth) acrylic acid n-butyl copolymer, (meth ) Acrylic acid / (meth) acrylic acid isobutyl copolymer, (meth) acrylic acid / (meth) acrylic acid 2-ethylhexyl copolymer, (meth) acrylic acid / (meth) acrylic acid cyclohexyl copolymer, (meta ) Acrylic acid / (meth) acrylic acid 2-methylcyclohexyl copolymer, (meth) acrylic acid / (meth) acrylic acid / (meth)
- the water-soluble resin according to the present invention may be mixed with a cross-linkable resin after being previously in an aqueous solution state.
- aqueous solutions containing the water-soluble resin according to the present invention include Acryt 3SQ-424 and Acryt 3SQ-426 (both manufactured by Taisei Fine Chemical Co., Ltd.).
- the curable resin composition of the present invention contains a crosslinkable resin having a crosslinkable functional group capable of crosslinking the water-soluble resin according to the present invention.
- a crosslinkable resin having a crosslinkable functional group capable of crosslinking the water-soluble resin according to the present invention.
- the cured product of the curable resin composition of the present invention has adhesion to a glass substrate or an acrylic coating layer, hardness, and heat and humidity resistance. It will be excellent.
- the said crosslinkable resin also has the effect of improving the wettability at the time of application
- crosslinkable functional group possessed by the crosslinkable resin examples include an oxazoline group, an epoxy group, a hydroxy group, an amino group, an isocyanate group, a carbodiimide group, and an aziridine group. Of these, an oxazoline group is preferred because of good storage stability and curability upon heating.
- the crosslinkable resin preferably has two or more crosslinkable functional groups in one molecule.
- the preferable lower limit of the crosslinkable functional group equivalent of the crosslinkable resin is 100, and the preferable upper limit is 2000.
- the crosslinkable functional group equivalent of the crosslinkable resin is within this range, the cured product of the resulting curable resin composition is more excellent in adhesion, hardness, and moist heat resistance.
- the more preferable lower limit of the crosslinkable functional group equivalent of the crosslinkable resin is 120, and the more preferable upper limit is 600.
- the crosslinkable functional group equivalent of the crosslinkable resin is a value obtained by dividing the weight (g) of the crosslinkable resin by the number of moles (mol) of the crosslinkable functional group contained in the crosslinkable resin.
- the crosslinkable resin is preferably water-soluble.
- the resin skeleton of the crosslinkable resin include a polyacryl skeleton, a polyether skeleton, a polyester skeleton, a polyurethane skeleton, a polyamide skeleton, a polyimide skeleton, and a polystyrene skeleton. Of these, a polyacryl skeleton is preferable.
- the minimum with a preferable weight average molecular weight of the said crosslinkable resin is 500, and a preferable upper limit is 500,000.
- the weight average molecular weight of the crosslinkable resin is within this range, the water-soluble resin according to the present invention can be more uniformly crosslinked.
- the minimum with a more preferable weight average molecular weight of the said crosslinkable resin is 10,000, and a more preferable upper limit is 200,000.
- the crosslinkable resin may be mixed with the water-soluble resin according to the present invention after it is in an aqueous solution in advance.
- Epocross K series Epocross WS series (all are the Nippon Shokubai company make) etc. are mentioned, for example.
- the content ratio of the water-soluble resin according to the present invention and the crosslinkable resin is within this range, the cured product of the obtained curable resin composition is more excellent in adhesion, hardness, and moisture and heat resistance.
- the molar ratio of the —C ( ⁇ O) OX group of the water-soluble resin according to the present invention to the crosslinkable functional group of the crosslinkable resin is within this range, a cured product of the resulting curable resin composition is obtained. Is superior in adhesion, hardness, and heat-and-moisture resistance.
- the molar ratio of the —C ( ⁇ O) OX group of the water-soluble resin according to the present invention to the crosslinkable functional group of the crosslinkable resin is —C ( ⁇ O).
- the molar ratio of the —C ( ⁇ O) OX group of the water-soluble resin according to the present invention to the cross-linkable functional group of the cross-linkable resin is determined by the —C ( ⁇ O) of the water-soluble resin according to the present invention. It can be determined from the OX group equivalent, the crosslinkable functional group equivalent of the crosslinkable resin, and the content ratio of the water-soluble resin and the crosslinkable resin according to the present invention.
- the curable resin composition of the present invention is further provided with a —N (H) C ( ⁇ O) Y group (Y is an alkyl having 1 to 3 carbon atoms) for the purpose of improving the crack prevention property of the cured product.
- Y is an alkyl having 1 to 3 carbon atoms
- Examples of the ethylenically unsaturated monomer having a —N (H) C ( ⁇ O) Y group include N-vinylacetamide, N-vinylpropionamide, N-vinylbutyramide, N-vinylcarbamic acid, Examples include sodium N-vinylcarbamate and N-vinylformamide. Of these, N-vinylacetamide is preferable.
- the resin having the —N (H) C ( ⁇ O) Y group may be a homopolymer of an ethylenically unsaturated monomer having the —N (H) C ( ⁇ O) Y group.
- a copolymer of the ethylenically unsaturated monomer having the —N (H) C ( ⁇ O) Y group and other monomers may also be used.
- the thing similar to other ethylenically unsaturated monomers such as acrylamide, vinyl acetate, (meth) acrylic acid, sodium (meth) acrylate, methyl (meth) acrylate, acrylonitrile, etc. Or a salt thereof.
- the obtained copolymer is the above-mentioned copolymer having a segment derived from the carboxyl group-containing ethylenically unsaturated monomer and a segment derived from the other ethylenically unsaturated monomer. You may neutralize like the method of neutralizing.
- the preferable lower limit of the weight average molecular weight of the resin having the —N (H) C ( ⁇ O) Y group is 30,000, and the preferable upper limit is 5 million.
- the weight average molecular weight of the resin having the —N (H) C ( ⁇ O) Y group is in this range, the excellent coating property and adhesion property of the curable resin composition of the present invention are maintained.
- the cured product is more excellent in crack prevention.
- the more preferable lower limit of the weight average molecular weight of the resin having the —N (H) C ( ⁇ O) Y group is 300,000, and the more preferable upper limit is 4 million.
- the content of the resin having a —N (H) C ( ⁇ O) Y group is within this range, curing can be performed while maintaining excellent coating properties and adhesion of the curable resin composition of the present invention. Things are superior due to crack prevention.
- the curable resin composition of the present invention contains water as a solvent.
- water By using the above water as a solvent, the impact on the environment, such as the discharge of organic chemicals, the danger of fire, and the health of the handler when coating and drying the curable resin composition are adversely affected. Can be reduced.
- the water-soluble resin and the cross-linkable resin according to the present invention may be mixed after previously in the state of an aqueous solution.
- the content of water in the curable resin composition of the present invention is not particularly limited and is appropriately set so as to have a viscosity suitable for the coating method and the like, but in such an amount that the solid content concentration is 1 to 50% by weight. Preferably, the amount is 10 to 40% by weight.
- the curable resin composition of the present invention may contain other solvents such as organic solvents in addition to the above water, but does not contain other solvents for the purpose of the present invention to reduce the burden on the environment. It is preferable. When it contains the said other solvent, it is preferable that the content is 30 weight% or less of the whole solvent, and it is more preferable that it is 10 weight% or less. When the content of the other solvent is excessive, it is preferable to remove the other solvent by an appropriate method such as azeotropy. The removal of the other solvent may be performed before mixing with the water-soluble resin and the crosslinkable resin according to the present invention.
- organic solvents with low toxicity such as propylene glycols, such as propylene glycol monomethyl ether acetate, alcohols, such as ethyl alcohol and isopropyl alcohol, are mentioned, for example.
- the curable resin composition of the present invention is a pH adjuster such as ammonia water and sodium hydroxide, a viscosity adjuster, an ultraviolet absorber, an antioxidant, an antifoaming agent, and a leveling agent as long as the object of the present invention is not impaired. Further, various known additives such as coupling agents, pigments, and dyes may be contained. In the curable resin composition of the present invention, it is preferable to adjust the pH in order to suppress thickening and improve storage stability, and it is more preferable to adjust the pH appropriately to the high pH side.
- the curable resin composition of the present invention for example, a water-soluble resin according to the present invention, the crosslinkable resin, the water, an additive used as necessary, and the like are mixed with a stirrer. And the like. Moreover, it is preferable to filter using a filter after stirring so that it may become a uniform mixture.
- the coating method includes, for example, known methods such as spin coating, slit coating, screen printing, ink jet coating, electrostatic coating, bar coating, die coating, and roll coating.
- a coating method can be used, and it can be used by adjusting to a desired film thickness and a concentration and viscosity suitable for a predetermined coating method.
- the curable resin composition of the present invention can be cured by heating at a low temperature.
- the heating temperature for curing the curable resin composition of the present invention is not particularly limited, but is usually 80 ° C. to 250 ° C., and preferably 100 ° C. or more to reduce the heat treatment time, thereby suppressing yellowing due to heating. Therefore, the temperature is preferably 200 ° C. or lower.
- a display element having a cured product comprising the curable resin composition of the present invention is also one aspect of the present invention. Since the cured product made of the curable resin composition of the present invention is excellent in transparency, adhesion, hardness, and heat-and-moisture resistance, the display element of the present invention is particularly excellent in display performance.
- the present invention it is possible to provide a curable resin composition that can obtain a cured product that is excellent in transparency, adhesion, hardness, and heat-and-moisture resistance, and that can reduce the burden on the environment. it can. Moreover, according to this invention, the display element which uses this curable resin composition can be provided.
- Example 1 Preparation of water-soluble resin A A four-necked separable flask having a capacity of 1000 mL was equipped with a reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen gas inlet tube, and dropping funnel. 50 parts by weight of tetrahydrofuran was placed in the flask, and nitrogen gas was introduced and bubbled to remove dissolved oxygen.
- curable resin composition 100 parts by weight of an aqueous solution of water-soluble resin A obtained in the above-mentioned "(1) Preparation of water-soluble resin A” and an aqueous solution of a crosslinkable resin having an oxazoline group as a crosslinkable functional group (Nippon Shokubai Co., Ltd., “Epocross WS-300”, weight average molecular weight 120,000 of crosslinkable resin, oxazoline group equivalent 130 in crosslinkable resin, solid content 10 wt%) 69 parts by weight with a stirrer After mixing for a minute, the mixture was filtered through a membrane filter having a pore size of 5 ⁇ m to prepare a curable resin composition.
- a crosslinkable resin having an oxazoline group as a crosslinkable functional group Nippon Shokubai Co., Ltd., “Epocross WS-300”, weight average molecular weight 120,000 of crosslinkable resin, oxazoline group equivalent 130 in crosslinkable resin, solid content
- Example 2 As an aqueous solution containing a water-soluble resin, “Acryt 3SQ-424” (manufactured by Taisei Fine Chemical Co., Ltd., a water-soluble resin obtained by neutralizing a copolymer containing 15% by weight of methacrylic acid as a carboxyl group-containing ethylenically unsaturated monomer with ammonia) As an aqueous solution containing 100 parts by weight of a water-soluble resin, a weight average molecular weight of 16000, a —C ( ⁇ O) OX group equivalent weight of 590, a solid content of 25% by weight in the water-soluble resin, and “Epocross” 110 parts by weight of WS-300 was mixed with a stirrer for 30 minutes, and then filtered through a membrane filter having a pore size of 5 ⁇ m to prepare a curable resin composition.
- Example 6 A curable resin composition was obtained in the same manner as in Example 3 except that the blending amount of “Epocross WS-300” which is an aqueous solution of a crosslinkable resin having an oxazoline group as a crosslinkable functional group was changed as shown in Table 1. A product was prepared.
- Example 7 100 parts by weight of an aqueous solution of the water-soluble resin A obtained in “(1) Preparation of water-soluble resin A” in Example 1 and an aqueous solution containing a crosslinkable resin (“Epocross WS-700” manufactured by Nippon Shokubai Co., Ltd.) 70 weight parts of the weight average molecular weight of the functional resin, 40,000 oxazoline group in the crosslinkable resin, solid content rate 25 weight%) was mixed for 30 minutes with a stirrer, and then filtered through a membrane filter having a pore size of 5 ⁇ m. A curable resin composition was prepared.
- Example 8 100 parts by weight of “Acryt 3SQ-424” as an aqueous solution containing a water-soluble resin and 112 parts by weight of “Epocross WS-700” as an aqueous solution containing a crosslinkable resin were mixed for 30 minutes with a stirrer, and then the pore diameter was 5 ⁇ m.
- the curable resin composition was prepared by filtering through a membrane filter.
- Example 9 100 parts by weight of “Acryt 3SQ-426” as an aqueous solution containing a water-soluble resin and 112 parts by weight of “Epocross WS-700” as an aqueous solution containing a crosslinkable resin were mixed for 30 minutes with a stirrer, and then the pore diameter was 5 ⁇ m.
- the curable resin composition was prepared by filtering through a membrane filter.
- Example 10 100 parts by weight of “Acryt 3SQ-426” as an aqueous solution containing a water-soluble resin and 186 parts by weight of “Epocross WS-700” as an aqueous solution containing a crosslinkable resin were mixed for 30 minutes with a stirrer, and then the pore diameter was 5 ⁇ m.
- the curable resin composition was prepared by filtering through a membrane filter.
- Example 11 100 parts by weight of an aqueous solution of water-soluble resin A obtained in “(1) Preparation of water-soluble resin A” in Example 1, crosslinkable resin (manufactured by Nagase ChemteX Corporation, “Denacol EX-521”, A weight average molecular weight of 1294 and 10 parts by weight of an epoxy group equivalent of 183 in the crosslinkable resin were mixed with a stirrer for 30 minutes, and then filtered through a membrane filter having a pore size of 5 ⁇ m to prepare a curable resin composition.
- crosslinkable resin manufactured by Nagase ChemteX Corporation, “Denacol EX-521”
- a weight average molecular weight of 1294 and 10 parts by weight of an epoxy group equivalent of 183 in the crosslinkable resin were mixed with a stirrer for 30 minutes, and then filtered through a membrane filter having a pore size of 5 ⁇ m to prepare a curable resin composition.
- Example 12 As an aqueous solution containing a resin having a —N (H) C ( ⁇ O) Y group, “GE-191-053” (manufactured by Showa Denko KK, poly-N-vinylacetamide aqueous solution, poly-N-vinylacetamide A curable resin composition was prepared in the same manner as in Example 1 except that 49 parts by weight of a weight average molecular weight of about 1.5 million and a solid content of 5% by weight were blended.
- Example 13 A curable resin composition was prepared in the same manner as in Example 12 except that the amount of “GE-191-053” was changed to 21 parts by weight.
- Example 14 A curable resin composition was prepared in the same manner as in Example 12 except that the amount of “GE-191-053” was changed to 239 parts by weight.
- Example 15 As an aqueous solution containing a resin having a —N (H) C ( ⁇ O) Y group, “GE-191-103” (manufactured by Showa Denko KK, poly-N-vinylacetamide aqueous solution, poly-N-vinylacetamide A curable resin composition was prepared in the same manner as in Example 1 except that 24 parts by weight of a weight average molecular weight of about 900,000 and a solid content of 10% by weight were blended.
- Example 16 As an aqueous solution containing a resin having a —N (H) C ( ⁇ O) Y group, “GE-191-104” (manufactured by Showa Denko KK, poly-N-vinylacetamide aqueous solution, poly-N-vinylacetamide A curable resin composition was prepared in the same manner as in Example 1 except that 19 parts by weight of a weight average molecular weight of about 300,000 and a solid content of 13% by weight were blended.
- Example 17 As an aqueous solution containing a resin having a —N (H) C ( ⁇ O) Y group, “GE-167-000” (manufactured by Showa Denko KK, N-vinylacetamide / sodium acrylate copolymer, A curable resin composition was prepared in the same manner as in Example 1 except that 49 parts by weight of an aqueous solution having a solid content of 5% by weight obtained by dissolving a weight average molecular weight of about 2.6 million) in water was blended.
- Example 18 100 parts by weight of “Acryt 3SQ-426” as an aqueous solution containing a water-soluble resin and 20 parts by weight of “Epocross WS-300” as an aqueous solution containing a crosslinkable resin were mixed for 30 minutes with a stirrer, and then the pore diameter was 5 ⁇ m.
- the curable resin composition was prepared by filtering through a membrane filter.
- Example 19 100 parts by weight of “Acryt 3SQ-426” as an aqueous solution containing a water-soluble resin and 30 parts by weight of “Epocross WS-700” as an aqueous solution containing a crosslinkable resin were mixed for 30 minutes with a stirrer, and then the pore diameter was 5 ⁇ m.
- the curable resin composition was prepared by filtering through a membrane filter.
- Each curable resin composition obtained in Examples 12 to 17 was applied on a non-alkali glass substrate having a thickness of 0.7 mm, a width of 50 mm, and a length of 50 mm by spin coating, and then allowed to stand at room temperature for 10 minutes.
- a test piece having a thickness of about 10 ⁇ m was produced by drying at 120 ° C. for 10 minutes. The obtained test piece was visually observed, “ ⁇ ” when no cracks were confirmed, “ ⁇ ” when very slight cracks were confirmed, and “ ⁇ ” when cracks were clearly confirmed. The crack prevention property was evaluated.
- the present invention it is possible to provide a curable resin composition that can obtain a cured product that is excellent in transparency, adhesion, hardness, and heat-and-moisture resistance, and that can reduce the burden on the environment. it can. Moreover, according to this invention, the display element which uses this curable resin composition can be provided.
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Abstract
One purpose of the present invention is to provide a curable resin composition which enables the achievement of a cured product having excellent transparency, adhesion properties, hardness and wet heat resistance, while being capable of reducing the burden on the environment. Another purpose of the present invention is to provide a display element which is obtained using this curable resin composition.
The present invention is a curable resin composition that contains: a water-soluble resin which is a copolymer having a segment that has a -C(=O)OX group (wherein X represents a hydrogen atom or a salt-forming cation) derived from a carboxyl group of a carboxyl group-containing ethylenically unsaturated monomer and a segment that is derived from another ethylenically unsaturated monomer; a crosslinking resin having a crosslinking functional group that is capable of crosslinking the water-soluble resin; and water.
Description
本発明は、透明性、密着性、硬度、及び、耐湿熱性に優れる硬化物を得ることができ、かつ、環境への負荷を低減することができる硬化性樹脂組成物に関する。また、本発明は、該硬化性樹脂組成物を用いてなる表示素子に関する。
The present invention relates to a curable resin composition that can obtain a cured product that is excellent in transparency, adhesion, hardness, and heat-and-moisture resistance, and that can reduce the burden on the environment. The present invention also relates to a display element using the curable resin composition.
従来、液晶表示素子や有機ＥＬ表示素子に代表される表示素子の製造においては、ＴＦＴアレイやカラーフィルターの作製に用いられるレジスト材料を中心に多くのコーティング材料が使用されている。
例えば、特許文献１には、シロキサンポリマーと特定の２種類以上の有機溶媒とを含有するコーティング用組成物が開示されており、特許文献２には、樹脂と多官能モノマーと溶剤と光重合開始剤と有機化合物系紫外線吸収剤とを含有する感光性透明樹脂組成物が開示されている。これらの組成物は透明性に優れ、表示素子用途に好適に用いられるとされている。 Conventionally, in the manufacture of display elements such as liquid crystal display elements and organic EL display elements, many coating materials have been used mainly for resist materials used in the production of TFT arrays and color filters.
For example, Patent Document 1 discloses a coating composition containing a siloxane polymer and two or more types of organic solvents. Patent Document 2 discloses a resin, a polyfunctional monomer, a solvent, and photopolymerization initiation. A photosensitive transparent resin composition containing an agent and an organic compound-based ultraviolet absorber is disclosed. These compositions are excellent in transparency and are said to be suitably used for display device applications.
例えば、特許文献１には、シロキサンポリマーと特定の２種類以上の有機溶媒とを含有するコーティング用組成物が開示されており、特許文献２には、樹脂と多官能モノマーと溶剤と光重合開始剤と有機化合物系紫外線吸収剤とを含有する感光性透明樹脂組成物が開示されている。これらの組成物は透明性に優れ、表示素子用途に好適に用いられるとされている。 Conventionally, in the manufacture of display elements such as liquid crystal display elements and organic EL display elements, many coating materials have been used mainly for resist materials used in the production of TFT arrays and color filters.
For example, Patent Document 1 discloses a coating composition containing a siloxane polymer and two or more types of organic solvents. Patent Document 2 discloses a resin, a polyfunctional monomer, a solvent, and photopolymerization initiation. A photosensitive transparent resin composition containing an agent and an organic compound-based ultraviolet absorber is disclosed. These compositions are excellent in transparency and are said to be suitably used for display device applications.
しかしながら、特許文献１や特許文献２に開示されているような従来の樹脂組成物は、有機溶剤を含有するものであるため、環境への負荷を低減する等の観点から、有機溶剤を用いずに透明性に優れる樹脂組成物が求められていた。
However, since the conventional resin compositions disclosed in Patent Document 1 and Patent Document 2 contain an organic solvent, an organic solvent is not used from the viewpoint of reducing the burden on the environment. Therefore, a resin composition having excellent transparency has been demanded.
本発明は、透明性、密着性、硬度、及び、耐湿熱性に優れる硬化物を得ることができ、かつ、環境への負荷を低減することができる硬化性樹脂組成物を提供することを目的とする。また、本発明は、該硬化性樹脂組成物を用いてなる表示素子を提供することを目的とする。
An object of the present invention is to provide a curable resin composition capable of obtaining a cured product excellent in transparency, adhesion, hardness, and heat-and-moisture resistance, and capable of reducing the burden on the environment. To do. Moreover, an object of this invention is to provide the display element which uses this curable resin composition.
本発明は、カルボキシル基含有エチレン性不飽和単量体のカルボキシル基に由来する－Ｃ（＝Ｏ）ＯＸ基（Ｘは、水素又は塩形成カチオンである）を有するセグメントと、その他のエチレン性不飽和単量体に由来するセグメントとを有する共重合体である水溶性樹脂、上記水溶性樹脂を架橋することが可能な架橋性官能基を有する架橋性樹脂、及び、水を含有する硬化性樹脂組成物である。
以下に本発明を詳述する。 The present invention relates to a segment having a —C (═O) OX group (X is hydrogen or a salt-forming cation) derived from a carboxyl group of a carboxyl group-containing ethylenically unsaturated monomer, and other ethylenically unsaturated monomers. A water-soluble resin that is a copolymer having a segment derived from a saturated monomer, a cross-linkable resin having a cross-linkable functional group capable of cross-linking the water-soluble resin, and a curable resin containing water It is a composition.
The present invention is described in detail below.
以下に本発明を詳述する。 The present invention relates to a segment having a —C (═O) OX group (X is hydrogen or a salt-forming cation) derived from a carboxyl group of a carboxyl group-containing ethylenically unsaturated monomer, and other ethylenically unsaturated monomers. A water-soluble resin that is a copolymer having a segment derived from a saturated monomer, a cross-linkable resin having a cross-linkable functional group capable of cross-linking the water-soluble resin, and a curable resin containing water It is a composition.
The present invention is described in detail below.
本発明者らは、従来の樹脂組成物に用いられていた有機溶剤に代えて水を溶剤として用い、樹脂成分として水溶性樹脂を用いることにより、有機溶剤を用いず透明性に優れる樹脂組成物を得ることを試み、透明性に優れる水溶性樹脂として、カルボン酸又はその塩であるエチレン性不飽和単量体と、これと共重合可能なその他のエチレン性不飽和単量体とを単量体成分とする共重合体を用いることを検討した。しかしながら、得られた硬化物は、透明性には優れるものの、密着性や硬度や耐湿熱性に劣るという問題があった。
そこで本発明者らは更に鋭意検討した結果、上記水溶性樹脂を架橋することが可能な架橋性樹脂を用いて該水溶性樹脂を架橋することにより、硬化物が、透明性、密着性、硬度、及び、耐湿熱性に優れ、かつ、環境への負荷を低減することができる硬化性樹脂組成物を得ることができることを見出し、本発明を完成させるに至った。
また、本発明の硬化性樹脂組成物は、低温での加熱硬化が可能であるため、光照射や高温加熱によるデバイスへのダメージを防止することができる。
なお、本明細書において上記「透明」とは、へイズメーターを用いて測定した、全光線透過率が８５％以上であり、かつ、ヘイズ値（曇価）が１％以下であることを意味する。 The present inventors use water as a solvent in place of the organic solvent used in conventional resin compositions, and use a water-soluble resin as a resin component, so that the resin composition is excellent in transparency without using an organic solvent. As a water-soluble resin excellent in transparency, a single amount of an ethylenically unsaturated monomer that is a carboxylic acid or a salt thereof and another ethylenically unsaturated monomer copolymerizable therewith The use of a copolymer as a body component was examined. However, although the obtained cured product is excellent in transparency, there is a problem that it is inferior in adhesion, hardness, and heat-and-moisture resistance.
Therefore, as a result of further intensive studies, the present inventors cross-linked the water-soluble resin with a cross-linkable resin that can cross-link the water-soluble resin, so that the cured product has transparency, adhesion, hardness. And it discovered that it was excellent in moist heat resistance, and could obtain the curable resin composition which can reduce the load to an environment, and came to complete this invention.
Moreover, since the curable resin composition of the present invention can be cured by heating at a low temperature, damage to the device due to light irradiation or high-temperature heating can be prevented.
In the present specification, the above-mentioned “transparent” means that the total light transmittance measured with a haze meter is 85% or more and the haze value (cloudiness value) is 1% or less. To do.
そこで本発明者らは更に鋭意検討した結果、上記水溶性樹脂を架橋することが可能な架橋性樹脂を用いて該水溶性樹脂を架橋することにより、硬化物が、透明性、密着性、硬度、及び、耐湿熱性に優れ、かつ、環境への負荷を低減することができる硬化性樹脂組成物を得ることができることを見出し、本発明を完成させるに至った。
また、本発明の硬化性樹脂組成物は、低温での加熱硬化が可能であるため、光照射や高温加熱によるデバイスへのダメージを防止することができる。
なお、本明細書において上記「透明」とは、へイズメーターを用いて測定した、全光線透過率が８５％以上であり、かつ、ヘイズ値（曇価）が１％以下であることを意味する。 The present inventors use water as a solvent in place of the organic solvent used in conventional resin compositions, and use a water-soluble resin as a resin component, so that the resin composition is excellent in transparency without using an organic solvent. As a water-soluble resin excellent in transparency, a single amount of an ethylenically unsaturated monomer that is a carboxylic acid or a salt thereof and another ethylenically unsaturated monomer copolymerizable therewith The use of a copolymer as a body component was examined. However, although the obtained cured product is excellent in transparency, there is a problem that it is inferior in adhesion, hardness, and heat-and-moisture resistance.
Therefore, as a result of further intensive studies, the present inventors cross-linked the water-soluble resin with a cross-linkable resin that can cross-link the water-soluble resin, so that the cured product has transparency, adhesion, hardness. And it discovered that it was excellent in moist heat resistance, and could obtain the curable resin composition which can reduce the load to an environment, and came to complete this invention.
Moreover, since the curable resin composition of the present invention can be cured by heating at a low temperature, damage to the device due to light irradiation or high-temperature heating can be prevented.
In the present specification, the above-mentioned “transparent” means that the total light transmittance measured with a haze meter is 85% or more and the haze value (cloudiness value) is 1% or less. To do.
本発明の硬化性樹脂組成物は、水溶性樹脂を含有する。
上記水溶性樹脂は、カルボキシル基含有エチレン性不飽和単量体のカルボキシル基に由来する－Ｃ（＝Ｏ）ＯＸ基（Ｘは、水素又は塩形成カチオンである）を有するセグメントと、その他のエチレン性不飽和単量体に由来するセグメントとを有する共重合体（以下、「本発明にかかる水溶性樹脂」ともいう）である。本発明にかかる水溶性樹脂は、ランダム共重合体、ブロック共重合体、及び、グラフト共重合体のいずれであってもよい。
なお、本明細書において、上記「水溶性」とは、ｐＨ６からｐＨ９の概ね中性の範囲で水溶液を得ることができることを意味する。 The curable resin composition of the present invention contains a water-soluble resin.
The water-soluble resin includes a segment having a —C (═O) OX group (X is hydrogen or a salt-forming cation) derived from a carboxyl group of a carboxyl group-containing ethylenically unsaturated monomer, and other ethylene And a segment derived from a polymerizable unsaturated monomer (hereinafter also referred to as “water-soluble resin according to the present invention”). The water-soluble resin according to the present invention may be any of a random copolymer, a block copolymer, and a graft copolymer.
In the present specification, the term “water-soluble” means that an aqueous solution can be obtained in a neutral range of pH 6 to pH 9.
上記水溶性樹脂は、カルボキシル基含有エチレン性不飽和単量体のカルボキシル基に由来する－Ｃ（＝Ｏ）ＯＸ基（Ｘは、水素又は塩形成カチオンである）を有するセグメントと、その他のエチレン性不飽和単量体に由来するセグメントとを有する共重合体（以下、「本発明にかかる水溶性樹脂」ともいう）である。本発明にかかる水溶性樹脂は、ランダム共重合体、ブロック共重合体、及び、グラフト共重合体のいずれであってもよい。
なお、本明細書において、上記「水溶性」とは、ｐＨ６からｐＨ９の概ね中性の範囲で水溶液を得ることができることを意味する。 The curable resin composition of the present invention contains a water-soluble resin.
The water-soluble resin includes a segment having a —C (═O) OX group (X is hydrogen or a salt-forming cation) derived from a carboxyl group of a carboxyl group-containing ethylenically unsaturated monomer, and other ethylene And a segment derived from a polymerizable unsaturated monomer (hereinafter also referred to as “water-soluble resin according to the present invention”). The water-soluble resin according to the present invention may be any of a random copolymer, a block copolymer, and a graft copolymer.
In the present specification, the term “water-soluble” means that an aqueous solution can be obtained in a neutral range of pH 6 to pH 9.
上記－Ｃ（＝Ｏ）ＯＸ基を有するセグメントを有することにより、本発明にかかる水溶性樹脂は、水溶性及び架橋性樹脂との反応性に優れるものとなる。
By having the segment having the -C (= O) OX group, the water-soluble resin according to the present invention has excellent reactivity with water-soluble and crosslinkable resins.
上記－Ｃ（＝Ｏ）ＯＸ基を有するセグメントにおいて、該－Ｃ（＝Ｏ）ＯＸ基は、カルボキシル基含有エチレン性不飽和単量体のカルボキシル基に由来する。
上記カルボキシル基含有エチレン性不飽和単量体としては、例えば、アクリル酸、メタクリル酸、３－アクリロイルオキシプロピオン酸、フマル酸、イタコン酸、マレイン酸、クロトン酸等が挙げられる。なかでも、共重合性の観点から、アクリル酸、メタクリル酸が好ましい。 In the segment having the —C (═O) OX group, the —C (═O) OX group is derived from the carboxyl group of the carboxyl group-containing ethylenically unsaturated monomer.
Examples of the carboxyl group-containing ethylenically unsaturated monomer include acrylic acid, methacrylic acid, 3-acryloyloxypropionic acid, fumaric acid, itaconic acid, maleic acid, and crotonic acid. Of these, acrylic acid and methacrylic acid are preferable from the viewpoint of copolymerization.
上記カルボキシル基含有エチレン性不飽和単量体としては、例えば、アクリル酸、メタクリル酸、３－アクリロイルオキシプロピオン酸、フマル酸、イタコン酸、マレイン酸、クロトン酸等が挙げられる。なかでも、共重合性の観点から、アクリル酸、メタクリル酸が好ましい。 In the segment having the —C (═O) OX group, the —C (═O) OX group is derived from the carboxyl group of the carboxyl group-containing ethylenically unsaturated monomer.
Examples of the carboxyl group-containing ethylenically unsaturated monomer include acrylic acid, methacrylic acid, 3-acryloyloxypropionic acid, fumaric acid, itaconic acid, maleic acid, and crotonic acid. Of these, acrylic acid and methacrylic acid are preferable from the viewpoint of copolymerization.
上記－Ｃ（＝Ｏ）ＯＸ基において、Ｘは、水素又は塩形成カチオンである。
上記Ｘが塩形成カチオンである場合、該塩形成カチオンとしては、アンモニウムイオン、アルカリ金属イオン等が挙げられる。
なかでも、得られる水溶性樹脂がオキサゾリン基を有する架橋性樹脂との反応性により優れるものとなることから、上記Ｘは、水素又はアンモニウムイオンであることが好ましい。
なお、本明細書において上記「アンモニウムイオン」とは、アンモニア、一級アミン、二級アミン、又は、三級アミン由来のカチオンを意味する。
上記－Ｃ（＝Ｏ）ＯＸ基としては、具体的には例えば、－Ｃ（＝Ｏ）ＯＨ基、－Ｃ（＝Ｏ）Ｏ－ＮＨ３基、－Ｃ（＝Ｏ）Ｏ－ＮＨ２（ＣＨ３）基、－Ｃ（＝Ｏ）Ｏ－ＮＨ（ＣＨ３）２基、－Ｃ（＝Ｏ）Ｏ－Ｎ（ＣＨ３）３基、－Ｃ（＝Ｏ）ＯＮａ基、－Ｃ（＝Ｏ）ＯＫ基等が挙げられる。
なお、上記－Ｃ（＝Ｏ）ＯＸ基は、赤外分光装置を用いて確認することができる。 In the above-mentioned —C (═O) OX group, X is hydrogen or a salt-forming cation.
When X is a salt-forming cation, examples of the salt-forming cation include ammonium ions and alkali metal ions.
Especially, since the water-soluble resin obtained becomes more excellent by the reactivity with the crosslinkable resin which has an oxazoline group, it is preferable that said X is hydrogen or an ammonium ion.
In the present specification, the “ammonium ion” means a cation derived from ammonia, a primary amine, a secondary amine, or a tertiary amine.
Specific examples of the —C (═O) OX group include —C (═O) OH group, —C (═O) O—NH 3 group, —C (═O) O—NH 2 ( CH 3 ) group, —C (═O) O—NH (CH 3 ) 2 group, —C (═O) O—N (CH 3 ) 3 group, —C (═O) ONa group, —C (= O) OK group etc. are mentioned.
The —C (═O) OX group can be confirmed using an infrared spectrometer.
上記Ｘが塩形成カチオンである場合、該塩形成カチオンとしては、アンモニウムイオン、アルカリ金属イオン等が挙げられる。
なかでも、得られる水溶性樹脂がオキサゾリン基を有する架橋性樹脂との反応性により優れるものとなることから、上記Ｘは、水素又はアンモニウムイオンであることが好ましい。
なお、本明細書において上記「アンモニウムイオン」とは、アンモニア、一級アミン、二級アミン、又は、三級アミン由来のカチオンを意味する。
上記－Ｃ（＝Ｏ）ＯＸ基としては、具体的には例えば、－Ｃ（＝Ｏ）ＯＨ基、－Ｃ（＝Ｏ）Ｏ－ＮＨ３基、－Ｃ（＝Ｏ）Ｏ－ＮＨ２（ＣＨ３）基、－Ｃ（＝Ｏ）Ｏ－ＮＨ（ＣＨ３）２基、－Ｃ（＝Ｏ）Ｏ－Ｎ（ＣＨ３）３基、－Ｃ（＝Ｏ）ＯＮａ基、－Ｃ（＝Ｏ）ＯＫ基等が挙げられる。
なお、上記－Ｃ（＝Ｏ）ＯＸ基は、赤外分光装置を用いて確認することができる。 In the above-mentioned —C (═O) OX group, X is hydrogen or a salt-forming cation.
When X is a salt-forming cation, examples of the salt-forming cation include ammonium ions and alkali metal ions.
Especially, since the water-soluble resin obtained becomes more excellent by the reactivity with the crosslinkable resin which has an oxazoline group, it is preferable that said X is hydrogen or an ammonium ion.
In the present specification, the “ammonium ion” means a cation derived from ammonia, a primary amine, a secondary amine, or a tertiary amine.
Specific examples of the —C (═O) OX group include —C (═O) OH group, —C (═O) O—NH 3 group, —C (═O) O—NH 2 ( CH 3 ) group, —C (═O) O—NH (CH 3 ) 2 group, —C (═O) O—N (CH 3 ) 3 group, —C (═O) ONa group, —C (= O) OK group etc. are mentioned.
The —C (═O) OX group can be confirmed using an infrared spectrometer.
本発明にかかる水溶性樹脂中における上記－Ｃ（＝Ｏ）ＯＸ基を有するセグメントの含有割合の好ましい下限は５重量％、好ましい上限は２５重量％である。上記－Ｃ（＝Ｏ）ＯＸ基を有するセグメントの含有割合がこの範囲であることにより、耐水性や貯蔵安定性を悪化させることなく、得られる水溶性樹脂が、水溶性、及び、架橋性樹脂との反応性により優れるものとなる。上記－Ｃ（＝Ｏ）ＯＸ基を有するセグメントの含有割合のより好ましい下限は１０重量％、より好ましい上限は１５重量％である。
なお、上記－Ｃ（＝Ｏ）ＯＸ基を有するセグメントの含有割合は、１Ｈ－ＮＭＲ及び１３Ｃ－ＮＭＲにより求めることができる。 The preferable lower limit of the content ratio of the segment having —C (═O) OX group in the water-soluble resin according to the present invention is 5% by weight, and the preferable upper limit is 25% by weight. When the content ratio of the segment having the —C (═O) OX group is within this range, the obtained water-soluble resin is water-soluble and cross-linkable resin without deteriorating water resistance and storage stability. It becomes more excellent by the reactivity with. The more preferable lower limit of the content ratio of the segment having the —C (═O) OX group is 10% by weight, and the more preferable upper limit is 15% by weight.
The content ratio of the segment having the —C (═O) OX group can be determined by 1 H-NMR and 13 C-NMR.
なお、上記－Ｃ（＝Ｏ）ＯＸ基を有するセグメントの含有割合は、１Ｈ－ＮＭＲ及び１３Ｃ－ＮＭＲにより求めることができる。 The preferable lower limit of the content ratio of the segment having —C (═O) OX group in the water-soluble resin according to the present invention is 5% by weight, and the preferable upper limit is 25% by weight. When the content ratio of the segment having the —C (═O) OX group is within this range, the obtained water-soluble resin is water-soluble and cross-linkable resin without deteriorating water resistance and storage stability. It becomes more excellent by the reactivity with. The more preferable lower limit of the content ratio of the segment having the —C (═O) OX group is 10% by weight, and the more preferable upper limit is 15% by weight.
The content ratio of the segment having the —C (═O) OX group can be determined by 1 H-NMR and 13 C-NMR.
上記その他のエチレン性不飽和単量体としては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸２－メチルシクロヘキシル、（メタ）アクリル酸ジシクロペンタニルオキシエチル、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸ジシクロペンタニル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸４－ヒドロキシブチル等の（メタ）アクリル酸エステル系単量体や、スチレン、α－メチルスチレン、ｐ－メチルスチレン、ｐ－クロロスチレン等の芳香族ビニル系単量体や、アクリロニトリル、メタクリロニトリル等のシアン化ビニル系単量体等が挙げられる。
なお、本明細書において上記「（メタ）アクリル」は、アクリル又はメタクリルを意味する。 Examples of the other ethylenically unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate. Butyl, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, (meth) Isobornyl acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate (Meth) acrylic acid ester monomers such as styrene, α- Rusuchiren, p- methyl styrene, p- chlorostyrene, etc. aromatic vinyl monomers and, acrylonitrile, methacrylonitrile vinyl cyanide-based monomer, etc., and the like.
In the present specification, the “(meth) acryl” means acryl or methacryl.
なお、本明細書において上記「（メタ）アクリル」は、アクリル又はメタクリルを意味する。 Examples of the other ethylenically unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate. Butyl, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, (meth) Isobornyl acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate (Meth) acrylic acid ester monomers such as styrene, α- Rusuchiren, p- methyl styrene, p- chlorostyrene, etc. aromatic vinyl monomers and, acrylonitrile, methacrylonitrile vinyl cyanide-based monomer, etc., and the like.
In the present specification, the “(meth) acryl” means acryl or methacryl.
本発明にかかる水溶性樹脂中における上記その他のエチレン性不飽和単量体に由来するセグメントの含有割合の好ましい下限は７５重量％、好ましい上限は９５重量％である。上記その他のエチレン性不飽和単量体に由来するセグメントの含有割合がこの範囲であることにより、得られる硬化性樹脂組成物の硬化物が、耐湿熱性により優れるものとなる。上記その他のエチレン性不飽和単量体に由来するセグメントの含有割合のより好ましい下限は８０重量％、より好ましい上限は９０重量％である。
The preferable lower limit of the content ratio of the segment derived from the other ethylenically unsaturated monomer in the water-soluble resin according to the present invention is 75% by weight, and the preferable upper limit is 95% by weight. When the content ratio of the segment derived from the other ethylenically unsaturated monomer is within this range, the cured product of the obtained curable resin composition is more excellent in moisture and heat resistance. The minimum with more preferable content rate of the segment originating in the said other ethylenically unsaturated monomer is 80 weight%, and a more preferable upper limit is 90 weight%.
また、本発明にかかる水溶性樹脂は、Ｎ－フェニルマレイミド、Ｎ－ベンジルマレイミド、Ｎ－（１－ナフチル）マレイミド、ｏ－クロロフェニルマレイミド等の芳香族置換マレイミド系単量体や、Ｎ－メチルマレイミド、Ｎ－エチルマレイミド、Ｎ－プロピルマレイミド、Ｎ－イソプロピルマレイミド等のアルキル置換マレイミド系単量体等に由来するセグメントを有してもよい。
The water-soluble resin according to the present invention includes aromatic substituted maleimide monomers such as N-phenylmaleimide, N-benzylmaleimide, N- (1-naphthyl) maleimide, o-chlorophenylmaleimide, and N-methylmaleimide. , Segments derived from alkyl-substituted maleimide monomers such as N-ethylmaleimide, N-propylmaleimide and N-isopropylmaleimide.
本発明にかかる水溶性樹脂は、なかでも、側鎖に上記－Ｃ（＝Ｏ）ＯＸ基を有する（メタ）アクリル共重合体が好適である。
In particular, the water-soluble resin according to the present invention is preferably a (meth) acrylic copolymer having the above-mentioned —C (═O) OX group in the side chain.
本発明にかかる水溶性樹脂は、上記カルボキシル基含有エチレン性不飽和単量体に由来するセグメントと上記その他のエチレン性不飽和単量体に由来するセグメントとを有する共重合体であってもよいし、該共重合体を、アンモニアやアミン等の塩基により中和してカルボン酸塩としたものであってもよい。
The water-soluble resin according to the present invention may be a copolymer having a segment derived from the carboxyl group-containing ethylenically unsaturated monomer and a segment derived from the other ethylenically unsaturated monomer. The copolymer may be neutralized with a base such as ammonia or amine to form a carboxylate.
上記カルボキシル基含有エチレン性不飽和単量体に由来するセグメントと上記その他のエチレン性不飽和単量体に由来するセグメントとを有する共重合体を製造する方法としては、例えば、ラジカル重合開始剤及び必要に応じて分子量調整剤を用いて、上記カルボキシル基含有エチレン性不飽和単量体や上記その他のエチレン性不飽和単量体等の共重合体を構成する単量体成分を、塊状重合、溶液重合、懸濁重合、分散重合、乳化重合等の従来公知の方法により重合する方法が挙げられる。なかでも、溶液重合が好適である。
As a method for producing a copolymer having a segment derived from the carboxyl group-containing ethylenically unsaturated monomer and a segment derived from the other ethylenically unsaturated monomer, for example, a radical polymerization initiator and If necessary, using a molecular weight regulator, a monomer component constituting a copolymer such as the carboxyl group-containing ethylenically unsaturated monomer and the other ethylenically unsaturated monomer, bulk polymerization, Examples of the polymerization method include conventionally known methods such as solution polymerization, suspension polymerization, dispersion polymerization, and emulsion polymerization. Of these, solution polymerization is preferred.
上記溶液重合に用いられる溶媒としては、例えば、メタノール、エタノール、イソプロパノール、グリコール等の脂肪族アルコール類や、セロソルブ、ブチルセロソルブ等のセロソルブ類や、カルビトール、ブチルカルビトール等のカルビトール類や、酢酸セロソルブ、酢酸カルビトール、プロピレングリコールモノメチルエーテルアセテート等のエステル類や、ジエチレングリコールジメチルエーテル等のエーテル類や、テトラヒドロフラン等の環状エーテル、シクロヘキサノン、メチルエチルケトン、メチルイソブチルケトン等のケトン類や、ジメチルスルホキシド、ジメチルホルムアミド等の極性を有する有機溶剤等が挙げられる。
また、上記懸濁重合、上記分散重合、上記乳化重合等に用いられる媒体としては、例えば、ベンゼン、トルエン、ヘキサン、シクロヘキサン等の液状の炭化水素や、その他の非極性の有機溶剤等が挙げられる。 Examples of the solvent used in the solution polymerization include aliphatic alcohols such as methanol, ethanol, isopropanol and glycol, cellosolves such as cellosolve and butylcellosolve, carbitols such as carbitol and butylcarbitol, and acetic acid. Esters such as cellosolve, carbitol acetate, propylene glycol monomethyl ether acetate, ethers such as diethylene glycol dimethyl ether, cyclic ethers such as tetrahydrofuran, ketones such as cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl sulfoxide, dimethylformamide, etc. And organic solvents having the following polarity.
Examples of the medium used for the suspension polymerization, the dispersion polymerization, the emulsion polymerization, and the like include liquid hydrocarbons such as benzene, toluene, hexane, and cyclohexane, and other nonpolar organic solvents. .
また、上記懸濁重合、上記分散重合、上記乳化重合等に用いられる媒体としては、例えば、ベンゼン、トルエン、ヘキサン、シクロヘキサン等の液状の炭化水素や、その他の非極性の有機溶剤等が挙げられる。 Examples of the solvent used in the solution polymerization include aliphatic alcohols such as methanol, ethanol, isopropanol and glycol, cellosolves such as cellosolve and butylcellosolve, carbitols such as carbitol and butylcarbitol, and acetic acid. Esters such as cellosolve, carbitol acetate, propylene glycol monomethyl ether acetate, ethers such as diethylene glycol dimethyl ether, cyclic ethers such as tetrahydrofuran, ketones such as cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl sulfoxide, dimethylformamide, etc. And organic solvents having the following polarity.
Examples of the medium used for the suspension polymerization, the dispersion polymerization, the emulsion polymerization, and the like include liquid hydrocarbons such as benzene, toluene, hexane, and cyclohexane, and other nonpolar organic solvents. .
上記カルボキシル基含有エチレン性不飽和単量体に由来するセグメントと上記その他のエチレン性不飽和単量体に由来するセグメントとを有する共重合体を製造する際に有機溶剤を用いた場合は、得られた樹脂溶液に適当量の水を加えた後に減圧等により有機溶剤を留去することが好ましい。
When an organic solvent is used when producing a copolymer having a segment derived from the carboxyl group-containing ethylenically unsaturated monomer and a segment derived from the other ethylenically unsaturated monomer, it is obtained. It is preferable to add an appropriate amount of water to the obtained resin solution and then distill off the organic solvent by decompression or the like.
上記カルボキシル基含有エチレン性不飽和単量体に由来するセグメントと上記その他のエチレン性不飽和単量体に由来するセグメントとを有する共重合体を製造する際に用いるラジカル重合開始剤としては、例えば、過酸化物、アゾ開始剤等が挙げられる。
また、上記分子量調整剤としては、例えば、α－メチルスチレンダイマー、メルカプタン系の連鎖移動剤等が挙げられる。 As a radical polymerization initiator used when producing a copolymer having a segment derived from the carboxyl group-containing ethylenically unsaturated monomer and a segment derived from the other ethylenically unsaturated monomer, for example, , Peroxides, azo initiators, and the like.
Examples of the molecular weight modifier include α-methylstyrene dimer, mercaptan chain transfer agent, and the like.
また、上記分子量調整剤としては、例えば、α－メチルスチレンダイマー、メルカプタン系の連鎖移動剤等が挙げられる。 As a radical polymerization initiator used when producing a copolymer having a segment derived from the carboxyl group-containing ethylenically unsaturated monomer and a segment derived from the other ethylenically unsaturated monomer, for example, , Peroxides, azo initiators, and the like.
Examples of the molecular weight modifier include α-methylstyrene dimer, mercaptan chain transfer agent, and the like.
上記カルボキシル基含有エチレン性不飽和単量体に由来するセグメントと上記その他のエチレン性不飽和単量体に由来するセグメントとを有する共重合体を中和する際に用いることができるアミンとしては、例えば、メチルアミン、エチルアミン、プロピルアミン、イソプロピルアミン等の一級アミンや、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジイソプロピルアミン等の二級アミンや、トリメチルアミン、トリエチルアミン、Ｎ，Ｎ－ジメチルプロピルアミン、Ｎ，Ｎ－ジメチルイソプロピルアミン、Ｎ，Ｎ－ジイソプロピルメチルアミン、Ｎ，Ｎ－ジイソプロピルエチルアミン等の三級アミンが挙げられる。
As an amine that can be used when neutralizing a copolymer having a segment derived from the carboxyl group-containing ethylenically unsaturated monomer and a segment derived from the other ethylenically unsaturated monomer, For example, primary amines such as methylamine, ethylamine, propylamine, isopropylamine, secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, trimethylamine, triethylamine, N, N-dimethylpropylamine, N, Tertiary amines such as N-dimethylisopropylamine, N, N-diisopropylmethylamine, N, N-diisopropylethylamine and the like can be mentioned.
本発明にかかる水溶性樹脂の重量平均分子量の好ましい下限は５０００、好ましい上限は５万である。本発明にかかる水溶性樹脂の重量平均分子量がこの範囲であることにより、得られる硬化性樹脂組成物が密着性により優れるものとなる。本発明にかかる水溶性樹脂の重量平均分子量のより好ましい下限は１万、より好ましい上限は２万である。
なお、本明細書において上記重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定を行い、ポリスチレン換算により求められる値である。ＧＰＣによってポリスチレン換算による重量平均分子量を測定する際のカラムとしては、例えば、Ｓｈｏｄｅｘ ＬＦ－８０４（昭和電工社製）等が挙げられる。また、ＧＰＣで用いる溶媒としては、テトラヒドロフラン等が挙げられる。 The minimum with a preferable weight average molecular weight of the water-soluble resin concerning this invention is 5000, and a preferable upper limit is 50,000. When the weight average molecular weight of the water-soluble resin according to the present invention is within this range, the resulting curable resin composition has better adhesion. The minimum with a more preferable weight average molecular weight of the water-soluble resin concerning this invention is 10,000, and a more preferable upper limit is 20,000.
In addition, the said weight average molecular weight is a value calculated | required by polystyrene conversion by measuring with a gel permeation chromatography (GPC) in this specification. Examples of the column for measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK). Moreover, tetrahydrofuran etc. are mentioned as a solvent used by GPC.
なお、本明細書において上記重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定を行い、ポリスチレン換算により求められる値である。ＧＰＣによってポリスチレン換算による重量平均分子量を測定する際のカラムとしては、例えば、Ｓｈｏｄｅｘ ＬＦ－８０４（昭和電工社製）等が挙げられる。また、ＧＰＣで用いる溶媒としては、テトラヒドロフラン等が挙げられる。 The minimum with a preferable weight average molecular weight of the water-soluble resin concerning this invention is 5000, and a preferable upper limit is 50,000. When the weight average molecular weight of the water-soluble resin according to the present invention is within this range, the resulting curable resin composition has better adhesion. The minimum with a more preferable weight average molecular weight of the water-soluble resin concerning this invention is 10,000, and a more preferable upper limit is 20,000.
In addition, the said weight average molecular weight is a value calculated | required by polystyrene conversion by measuring with a gel permeation chromatography (GPC) in this specification. Examples of the column for measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK). Moreover, tetrahydrofuran etc. are mentioned as a solvent used by GPC.
本発明にかかる水溶性樹脂の－Ｃ（＝Ｏ）ＯＸ基当量の好ましい下限は２８８、好ましい上限は４０００である。本発明にかかる水溶性樹脂の－Ｃ（＝Ｏ）ＯＸ基当量がこの範囲であることにより、水溶性及び架橋性樹脂との反応性により優れるものとなる。本発明にかかる水溶性樹脂の－Ｃ（＝Ｏ）ＯＸ基当量のより好ましい下限は４８０、より好ましい上限は２０００である。
なお、本発明にかかる水溶性樹脂の－Ｃ（＝Ｏ）ＯＸ基当量は、本発明にかかる水溶性樹脂の重量（ｇ）を本発明にかかる水溶性樹脂に含まれる－Ｃ（＝Ｏ）ＯＸ基のモル数（ｍｏｌ）で除して求められる値である。 The preferable lower limit of the —C (═O) OX group equivalent of the water-soluble resin according to the present invention is 288, and the preferable upper limit is 4000. When the —C (═O) OX group equivalent of the water-soluble resin according to the present invention is within this range, the water-soluble resin and the reactivity with the cross-linkable resin are excellent. The more preferable lower limit of the —C (═O) OX group equivalent of the water-soluble resin according to the present invention is 480, and the more preferable upper limit is 2000.
Incidentally, the —C (═O) OX group equivalent of the water-soluble resin according to the present invention is such that the weight (g) of the water-soluble resin according to the present invention is the —C (═O) contained in the water-soluble resin according to the present invention. It is a value obtained by dividing by the number of moles (mol) of the OX group.
なお、本発明にかかる水溶性樹脂の－Ｃ（＝Ｏ）ＯＸ基当量は、本発明にかかる水溶性樹脂の重量（ｇ）を本発明にかかる水溶性樹脂に含まれる－Ｃ（＝Ｏ）ＯＸ基のモル数（ｍｏｌ）で除して求められる値である。 The preferable lower limit of the —C (═O) OX group equivalent of the water-soluble resin according to the present invention is 288, and the preferable upper limit is 4000. When the —C (═O) OX group equivalent of the water-soluble resin according to the present invention is within this range, the water-soluble resin and the reactivity with the cross-linkable resin are excellent. The more preferable lower limit of the —C (═O) OX group equivalent of the water-soluble resin according to the present invention is 480, and the more preferable upper limit is 2000.
Incidentally, the —C (═O) OX group equivalent of the water-soluble resin according to the present invention is such that the weight (g) of the water-soluble resin according to the present invention is the —C (═O) contained in the water-soluble resin according to the present invention. It is a value obtained by dividing by the number of moles (mol) of the OX group.
本発明にかかる水溶性樹脂としては、具体的には例えば、（メタ）アクリル酸／（メタ）アクリル酸メチル共重合体、（メタ）アクリル酸／（メタ）アクリル酸エチル共重合体、（メタ）アクリル酸／（メタ）アクリル酸プロピル共重合体、（メタ）アクリル酸／（メタ）アクリル酸イソプロピル共重合体、（メタ）アクリル酸／（メタ）アクリル酸ｎ－ブチル共重合体、（メタ）アクリル酸／（メタ）アクリル酸イソブチル共重合体、（メタ）アクリル酸／（メタ）アクリル酸２－エチルヘキシル共重合体、（メタ）アクリル酸／（メタ）アクリル酸シクロヘキシル共重合体、（メタ）アクリル酸／（メタ）アクリル酸２－メチルシクロヘキシル共重合体、（メタ）アクリル酸／（メタ）アクリル酸ジシクロペンタニルオキシエチル共重合体、（メタ）アクリル酸／（メタ）アクリル酸イソボルニル共重合体、（メタ）アクリル酸／（メタ）アクリル酸ジシクロペンタニル共重合体、（メタ）アクリル酸／（メタ）アクリル酸ベンジル共重合体、（メタ）アクリル酸／（メタ）アクリル酸２－ヒドロキシエチル共重合体、（メタ）アクリル酸／（メタ）アクリル酸２－ヒドロキシプロピル共重合体、（メタ）アクリル酸／（メタ）アクリル酸４－ヒドロキシブチル共重合体、（メタ）アクリル酸／スチレン／（メタ）アクリル酸メチル共重合体、（メタ）アクリル酸／（メタ）アクリル酸メチル／（メタ）アクリル酸２－ヒドロキシエチル共重合体、（メタ）アクリル酸／スチレン／（メタ）アクリル酸ベンジル共重合体、Ｎ－フェニルマレイミド／（メタ）アクリル酸／スチレン／（メタ）アクリル酸ベンジル共重合体、（メタ）アクリル酸／（メタ）アクリル酸メチル／（メタ）アクリル酸ｎ－ブチル共重合体、（メタ）アクリル酸／（メタ）アクリル酸メチル／（メタ）アクリル酸イソブチル共重合体、及び、これらについて上述した中和を行うことより得られるカルボン酸塩等が挙げられる。
Specific examples of the water-soluble resin according to the present invention include (meth) acrylic acid / (meth) methyl acrylate copolymer, (meth) acrylic acid / (meth) ethyl acrylate copolymer, (meth ) Acrylic acid / (meth) propyl propyl copolymer, (meth) acrylic acid / (meth) isopropyl acrylate copolymer, (meth) acrylic acid / (meth) acrylic acid n-butyl copolymer, (meth ) Acrylic acid / (meth) acrylic acid isobutyl copolymer, (meth) acrylic acid / (meth) acrylic acid 2-ethylhexyl copolymer, (meth) acrylic acid / (meth) acrylic acid cyclohexyl copolymer, (meta ) Acrylic acid / (meth) acrylic acid 2-methylcyclohexyl copolymer, (meth) acrylic acid / (meth) acrylic acid dicyclopentanyloxyethyl copolymer , (Meth) acrylic acid / (meth) acrylic acid isobornyl copolymer, (meth) acrylic acid / (meth) acrylic acid dicyclopentanyl copolymer, (meth) acrylic acid / (meth) acrylic acid benzyl copolymer Copolymer, (meth) acrylic acid / (meth) acrylic acid 2-hydroxyethyl copolymer, (meth) acrylic acid / (meth) acrylic acid 2-hydroxypropyl copolymer, (meth) acrylic acid / (meth) acrylic 4-hydroxybutyl copolymer, (meth) acrylic acid / styrene / methyl (meth) acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate Polymer, (meth) acrylic acid / styrene / (meth) acrylic acid benzyl copolymer, N-phenylmaleimide / (meth) acrylic acid / styre / (Meth) acrylic acid benzyl copolymer, (meth) acrylic acid / (meth) methyl acrylate / (meth) acrylic acid n-butyl copolymer, (meth) acrylic acid / methyl (meth) acrylate / ( Examples thereof include a (meth) acrylic acid isobutyl copolymer and a carboxylate obtained by performing the neutralization described above.
本発明にかかる水溶性樹脂は、予め水溶液の状態とした後に架橋性樹脂と混合してもよい。
本発明にかかる水溶性樹脂を含有する水溶液として市販されているものとしては、例えば、アクリット３ＳＱ－４２４、アクリット３ＳＱ－４２６（いずれも大成ファインケミカル社製）等が挙げられる。 The water-soluble resin according to the present invention may be mixed with a cross-linkable resin after being previously in an aqueous solution state.
Examples of commercially available aqueous solutions containing the water-soluble resin according to the present invention include Acryt 3SQ-424 and Acryt 3SQ-426 (both manufactured by Taisei Fine Chemical Co., Ltd.).
本発明にかかる水溶性樹脂を含有する水溶液として市販されているものとしては、例えば、アクリット３ＳＱ－４２４、アクリット３ＳＱ－４２６（いずれも大成ファインケミカル社製）等が挙げられる。 The water-soluble resin according to the present invention may be mixed with a cross-linkable resin after being previously in an aqueous solution state.
Examples of commercially available aqueous solutions containing the water-soluble resin according to the present invention include Acryt 3SQ-424 and Acryt 3SQ-426 (both manufactured by Taisei Fine Chemical Co., Ltd.).
本発明の硬化性樹脂組成物は、本発明にかかる水溶性樹脂を架橋することが可能な架橋性官能基を有する架橋性樹脂を含有する。上記架橋性樹脂を用いて本発明にかかる水溶性樹脂を架橋することにより、本発明の硬化性樹脂組成物の硬化物がガラス基板やアクリル系コーティング層との密着性、硬度、及び、耐湿熱性に優れるものとなる。また、上記架橋性樹脂は、本発明の硬化性樹脂組成物の硬化物にコーティングを施す場合の塗布時の濡れ性や密着性を向上させる効果も有する。
The curable resin composition of the present invention contains a crosslinkable resin having a crosslinkable functional group capable of crosslinking the water-soluble resin according to the present invention. By cross-linking the water-soluble resin according to the present invention using the cross-linkable resin, the cured product of the curable resin composition of the present invention has adhesion to a glass substrate or an acrylic coating layer, hardness, and heat and humidity resistance. It will be excellent. Moreover, the said crosslinkable resin also has the effect of improving the wettability at the time of application | coating in the case of coating the hardened | cured material of the curable resin composition of this invention, and adhesiveness.
上記架橋性樹脂の有する架橋性官能基としては、例えば、オキサゾリン基、エポキシ基、ヒドロキシ基、アミノ基、イソシアネート基、カルボジイミド基、アジリジン基等が挙げられる。なかでも、貯蔵安定性と加熱時の硬化性が良好であることから、オキサゾリン基が好ましい。
上記架橋性樹脂は、上記架橋性官能基を１分子中に２個以上有することが好ましい。 Examples of the crosslinkable functional group possessed by the crosslinkable resin include an oxazoline group, an epoxy group, a hydroxy group, an amino group, an isocyanate group, a carbodiimide group, and an aziridine group. Of these, an oxazoline group is preferred because of good storage stability and curability upon heating.
The crosslinkable resin preferably has two or more crosslinkable functional groups in one molecule.
上記架橋性樹脂は、上記架橋性官能基を１分子中に２個以上有することが好ましい。 Examples of the crosslinkable functional group possessed by the crosslinkable resin include an oxazoline group, an epoxy group, a hydroxy group, an amino group, an isocyanate group, a carbodiimide group, and an aziridine group. Of these, an oxazoline group is preferred because of good storage stability and curability upon heating.
The crosslinkable resin preferably has two or more crosslinkable functional groups in one molecule.
上記架橋性樹脂の架橋性官能基当量の好ましい下限は１００、好ましい上限は２０００である。上記架橋性樹脂の架橋性官能基当量がこの範囲であることにより、得られる硬化性樹脂組成物の硬化物が密着性、硬度、及び、耐湿熱性により優れるものとなる。上記架橋性樹脂の架橋性官能基当量のより好ましい下限は１２０、より好ましい上限は６００である。
なお、上記架橋性樹脂の架橋性官能基当量は、架橋性樹脂の重量（ｇ）を架橋性樹脂中に含まれる架橋性官能基のモル数（ｍｏｌ）で除して求められる値である。 The preferable lower limit of the crosslinkable functional group equivalent of the crosslinkable resin is 100, and the preferable upper limit is 2000. When the crosslinkable functional group equivalent of the crosslinkable resin is within this range, the cured product of the resulting curable resin composition is more excellent in adhesion, hardness, and moist heat resistance. The more preferable lower limit of the crosslinkable functional group equivalent of the crosslinkable resin is 120, and the more preferable upper limit is 600.
The crosslinkable functional group equivalent of the crosslinkable resin is a value obtained by dividing the weight (g) of the crosslinkable resin by the number of moles (mol) of the crosslinkable functional group contained in the crosslinkable resin.
なお、上記架橋性樹脂の架橋性官能基当量は、架橋性樹脂の重量（ｇ）を架橋性樹脂中に含まれる架橋性官能基のモル数（ｍｏｌ）で除して求められる値である。 The preferable lower limit of the crosslinkable functional group equivalent of the crosslinkable resin is 100, and the preferable upper limit is 2000. When the crosslinkable functional group equivalent of the crosslinkable resin is within this range, the cured product of the resulting curable resin composition is more excellent in adhesion, hardness, and moist heat resistance. The more preferable lower limit of the crosslinkable functional group equivalent of the crosslinkable resin is 120, and the more preferable upper limit is 600.
The crosslinkable functional group equivalent of the crosslinkable resin is a value obtained by dividing the weight (g) of the crosslinkable resin by the number of moles (mol) of the crosslinkable functional group contained in the crosslinkable resin.
上記架橋性樹脂は、水溶性であることが好ましい。
上記架橋性樹脂の樹脂骨格としては、例えば、ポリアクリル骨格、ポリエーテル骨格、ポリエステル骨格、ポリウレタン骨格、ポリアミド骨格、ポリイミド骨格、ポリスチレン骨格等が挙げられる。なかでも、ポリアクリル骨格が好ましい。 The crosslinkable resin is preferably water-soluble.
Examples of the resin skeleton of the crosslinkable resin include a polyacryl skeleton, a polyether skeleton, a polyester skeleton, a polyurethane skeleton, a polyamide skeleton, a polyimide skeleton, and a polystyrene skeleton. Of these, a polyacryl skeleton is preferable.
上記架橋性樹脂の樹脂骨格としては、例えば、ポリアクリル骨格、ポリエーテル骨格、ポリエステル骨格、ポリウレタン骨格、ポリアミド骨格、ポリイミド骨格、ポリスチレン骨格等が挙げられる。なかでも、ポリアクリル骨格が好ましい。 The crosslinkable resin is preferably water-soluble.
Examples of the resin skeleton of the crosslinkable resin include a polyacryl skeleton, a polyether skeleton, a polyester skeleton, a polyurethane skeleton, a polyamide skeleton, a polyimide skeleton, and a polystyrene skeleton. Of these, a polyacryl skeleton is preferable.
上記架橋性樹脂の重量平均分子量の好ましい下限は５００、好ましい上限は５０万である。上記架橋性樹脂の重量平均分子量がこの範囲であることにより、本発明にかかる水溶性樹脂をより均一に架橋することができる。上記架橋性樹脂の重量平均分子量のより好ましい下限は１万、より好ましい上限は２０万である。
The minimum with a preferable weight average molecular weight of the said crosslinkable resin is 500, and a preferable upper limit is 500,000. When the weight average molecular weight of the crosslinkable resin is within this range, the water-soluble resin according to the present invention can be more uniformly crosslinked. The minimum with a more preferable weight average molecular weight of the said crosslinkable resin is 10,000, and a more preferable upper limit is 200,000.
上記架橋性樹脂は、予め水溶液の状態とした後に本発明にかかる水溶性樹脂と混合してもよい。
上記架橋性樹脂を含有する水溶液として市販されているものとしては、例えば、エポクロスＫシリーズ、エポクロスＷＳシリーズ（いずれも日本触媒社製）等が挙げられる。 The crosslinkable resin may be mixed with the water-soluble resin according to the present invention after it is in an aqueous solution in advance.
As what is marketed as an aqueous solution containing the said crosslinkable resin, Epocross K series, Epocross WS series (all are the Nippon Shokubai company make) etc. are mentioned, for example.
上記架橋性樹脂を含有する水溶液として市販されているものとしては、例えば、エポクロスＫシリーズ、エポクロスＷＳシリーズ（いずれも日本触媒社製）等が挙げられる。 The crosslinkable resin may be mixed with the water-soluble resin according to the present invention after it is in an aqueous solution in advance.
As what is marketed as an aqueous solution containing the said crosslinkable resin, Epocross K series, Epocross WS series (all are the Nippon Shokubai company make) etc. are mentioned, for example.
本発明にかかる水溶性樹脂と上記架橋性樹脂との含有割合は、重量比で、本発明にかかる水溶性樹脂：架橋性樹脂＝１：０．０４～１：１．５であることが好ましい。本発明にかかる水溶性樹脂と上記架橋性樹脂との含有割合がこの範囲であることにより、得られる硬化性樹脂組成物の硬化物が密着性、硬度、及び、耐湿熱性により優れるものとなる。
硬度を重要特性とする場合、本発明にかかる水溶性樹脂と上記架橋性樹脂との含有割合は、重量比で、本発明にかかる水溶性樹脂：架橋性樹脂＝１：０．１～１：１．５であることが好ましく、本発明にかかる水溶性樹脂：架橋性樹脂＝１：０．２５～１：１であることがより好ましい。
貯蔵安定性を重要特性とする場合、本発明にかかる水溶性樹脂と上記架橋性樹脂との含有割合は、重量比で、本発明にかかる水溶性樹脂：架橋性樹脂＝１：０．０４～１：０．７であることが好ましく、本発明にかかる水溶性樹脂：架橋性樹脂＝１：０．０８～１：０．２５であることがより好ましい。 The content ratio of the water-soluble resin according to the present invention and the crosslinkable resin is preferably a weight ratio of water-soluble resin according to the present invention: crosslinkable resin = 1: 0.04 to 1: 1.5. . When the content ratio of the water-soluble resin according to the present invention and the crosslinkable resin is within this range, the cured product of the obtained curable resin composition is more excellent in adhesion, hardness, and moisture and heat resistance.
When hardness is an important characteristic, the content ratio of the water-soluble resin according to the present invention and the crosslinkable resin is a weight ratio, and the water-soluble resin according to the present invention: crosslinkable resin = 1: 0.1 to 1: 1.5 is preferable, and the water-soluble resin: crosslinkable resin according to the present invention is more preferably 1: 0.25 to 1: 1.
When storage stability is an important characteristic, the content ratio of the water-soluble resin according to the present invention and the cross-linkable resin is a weight ratio, and the water-soluble resin according to the present invention: cross-linkable resin = 1: 0.04 to The ratio is preferably 1: 0.7, more preferably water-soluble resin according to the present invention: crosslinkable resin = 1: 0.08 to 1: 0.25.
硬度を重要特性とする場合、本発明にかかる水溶性樹脂と上記架橋性樹脂との含有割合は、重量比で、本発明にかかる水溶性樹脂：架橋性樹脂＝１：０．１～１：１．５であることが好ましく、本発明にかかる水溶性樹脂：架橋性樹脂＝１：０．２５～１：１であることがより好ましい。
貯蔵安定性を重要特性とする場合、本発明にかかる水溶性樹脂と上記架橋性樹脂との含有割合は、重量比で、本発明にかかる水溶性樹脂：架橋性樹脂＝１：０．０４～１：０．７であることが好ましく、本発明にかかる水溶性樹脂：架橋性樹脂＝１：０．０８～１：０．２５であることがより好ましい。 The content ratio of the water-soluble resin according to the present invention and the crosslinkable resin is preferably a weight ratio of water-soluble resin according to the present invention: crosslinkable resin = 1: 0.04 to 1: 1.5. . When the content ratio of the water-soluble resin according to the present invention and the crosslinkable resin is within this range, the cured product of the obtained curable resin composition is more excellent in adhesion, hardness, and moisture and heat resistance.
When hardness is an important characteristic, the content ratio of the water-soluble resin according to the present invention and the crosslinkable resin is a weight ratio, and the water-soluble resin according to the present invention: crosslinkable resin = 1: 0.1 to 1: 1.5 is preferable, and the water-soluble resin: crosslinkable resin according to the present invention is more preferably 1: 0.25 to 1: 1.
When storage stability is an important characteristic, the content ratio of the water-soluble resin according to the present invention and the cross-linkable resin is a weight ratio, and the water-soluble resin according to the present invention: cross-linkable resin = 1: 0.04 to The ratio is preferably 1: 0.7, more preferably water-soluble resin according to the present invention: crosslinkable resin = 1: 0.08 to 1: 0.25.
また、本発明にかかる水溶性樹脂の有する－Ｃ（＝Ｏ）ＯＸ基と、架橋性樹脂の有する架橋性官能基とのモル比は、－Ｃ（＝Ｏ）ＯＸ基：架橋性官能基＝１：０．１～１：１０であることが好ましい。本発明にかかる水溶性樹脂の有する－Ｃ（＝Ｏ）ＯＸ基と、架橋性樹脂の有する架橋性官能基とのモル比がこの範囲であることにより、得られる硬化性樹脂組成物の硬化物が密着性、硬度、及び、耐湿熱性により優れるものとなる。本発明にかかる水溶性樹脂の有する－Ｃ（＝Ｏ）ＯＸ基と、架橋性樹脂の有する架橋性官能基とのモル比は、－Ｃ（＝Ｏ）ＯＸ基：架橋性官能基＝１：０．２～１：６であることがより好ましい。
貯蔵安定性を重要特性とする場合、本発明にかかる水溶性樹脂の有する－Ｃ（＝Ｏ）ＯＸ基と、架橋性樹脂の有する架橋性官能基とのモル比は、－Ｃ（＝Ｏ）ＯＸ基：架橋性官能基＝１：０．１～１：１であることが好ましく、－Ｃ（＝Ｏ）ＯＸ基：架橋性官能基＝１：０．２～１：０．５であることがより好ましい。
なお、本発明にかかる水溶性樹脂の有する－Ｃ（＝Ｏ）ＯＸ基と、架橋性樹脂の有する架橋性官能基とのモル比は、本発明にかかる水溶性樹脂の－Ｃ（＝Ｏ）ＯＸ基当量及び上記架橋性樹脂の架橋性官能基当量と、本発明にかかる水溶性樹脂と上記架橋性樹脂との含有割合とから求めることができる。 In addition, the molar ratio of —C (═O) OX group of the water-soluble resin according to the present invention to the crosslinkable functional group of the crosslinkable resin is —C (═O) OX group: crosslinkable functional group = It is preferably 1: 0.1 to 1:10. When the molar ratio of the —C (═O) OX group of the water-soluble resin according to the present invention to the crosslinkable functional group of the crosslinkable resin is within this range, a cured product of the resulting curable resin composition is obtained. Is superior in adhesion, hardness, and heat-and-moisture resistance. The molar ratio of the —C (═O) OX group of the water-soluble resin according to the present invention to the crosslinkable functional group of the crosslinkable resin is —C (═O) OX group: crosslinkable functional group = 1: More preferably, it is 0.2 to 1: 6.
When storage stability is an important characteristic, the molar ratio of the —C (═O) OX group of the water-soluble resin according to the present invention to the crosslinkable functional group of the crosslinkable resin is —C (═O). OX group: crosslinkable functional group = 1: 0.1 to 1: 1 is preferable, and —C (═O) OX group: crosslinkable functional group = 1: 0.2 to 1: 0.5. It is more preferable.
The molar ratio of the —C (═O) OX group of the water-soluble resin according to the present invention to the cross-linkable functional group of the cross-linkable resin is determined by the —C (═O) of the water-soluble resin according to the present invention. It can be determined from the OX group equivalent, the crosslinkable functional group equivalent of the crosslinkable resin, and the content ratio of the water-soluble resin and the crosslinkable resin according to the present invention.
貯蔵安定性を重要特性とする場合、本発明にかかる水溶性樹脂の有する－Ｃ（＝Ｏ）ＯＸ基と、架橋性樹脂の有する架橋性官能基とのモル比は、－Ｃ（＝Ｏ）ＯＸ基：架橋性官能基＝１：０．１～１：１であることが好ましく、－Ｃ（＝Ｏ）ＯＸ基：架橋性官能基＝１：０．２～１：０．５であることがより好ましい。
なお、本発明にかかる水溶性樹脂の有する－Ｃ（＝Ｏ）ＯＸ基と、架橋性樹脂の有する架橋性官能基とのモル比は、本発明にかかる水溶性樹脂の－Ｃ（＝Ｏ）ＯＸ基当量及び上記架橋性樹脂の架橋性官能基当量と、本発明にかかる水溶性樹脂と上記架橋性樹脂との含有割合とから求めることができる。 In addition, the molar ratio of —C (═O) OX group of the water-soluble resin according to the present invention to the crosslinkable functional group of the crosslinkable resin is —C (═O) OX group: crosslinkable functional group = It is preferably 1: 0.1 to 1:10. When the molar ratio of the —C (═O) OX group of the water-soluble resin according to the present invention to the crosslinkable functional group of the crosslinkable resin is within this range, a cured product of the resulting curable resin composition is obtained. Is superior in adhesion, hardness, and heat-and-moisture resistance. The molar ratio of the —C (═O) OX group of the water-soluble resin according to the present invention to the crosslinkable functional group of the crosslinkable resin is —C (═O) OX group: crosslinkable functional group = 1: More preferably, it is 0.2 to 1: 6.
When storage stability is an important characteristic, the molar ratio of the —C (═O) OX group of the water-soluble resin according to the present invention to the crosslinkable functional group of the crosslinkable resin is —C (═O). OX group: crosslinkable functional group = 1: 0.1 to 1: 1 is preferable, and —C (═O) OX group: crosslinkable functional group = 1: 0.2 to 1: 0.5. It is more preferable.
The molar ratio of the —C (═O) OX group of the water-soluble resin according to the present invention to the cross-linkable functional group of the cross-linkable resin is determined by the —C (═O) of the water-soluble resin according to the present invention. It can be determined from the OX group equivalent, the crosslinkable functional group equivalent of the crosslinkable resin, and the content ratio of the water-soluble resin and the crosslinkable resin according to the present invention.
本発明の硬化性樹脂組成物は、硬化物のクラック防止性を向上させること等を目的として、更に、－Ｎ（Ｈ）Ｃ（＝Ｏ）Ｙ基（Ｙは、炭素数１～３のアルキル基、水酸基、－ＯＮａ基、又は、水素基である）を有するエチレン性不飽和単量体に由来するセグメントを有する樹脂（以下、単に「－Ｎ（Ｈ）Ｃ（＝Ｏ）Ｙ基を有する樹脂」ともいう）を含有することが好ましい。
The curable resin composition of the present invention is further provided with a —N (H) C (═O) Y group (Y is an alkyl having 1 to 3 carbon atoms) for the purpose of improving the crack prevention property of the cured product. A resin having a segment derived from an ethylenically unsaturated monomer having a group, a hydroxyl group, a —ONa group, or a hydrogen group (hereinafter simply having “—N (H) C (═O) Y group” It is preferable to contain a resin.
上記－Ｎ（Ｈ）Ｃ（＝Ｏ）Ｙ基を有するエチレン性不飽和単量体としては、例えば、Ｎ－ビニルアセトアミド、Ｎ－ビニルプロピオンアミド、Ｎ－ビニルブチルアミド、Ｎ－ビニルカルバミド酸、Ｎ－ビニルカルバミド酸ナトリウム、Ｎ－ビニルホルムアミド等が挙げられる。なかでも、Ｎ－ビニルアセトアミドが好ましい。
Examples of the ethylenically unsaturated monomer having a —N (H) C (═O) Y group include N-vinylacetamide, N-vinylpropionamide, N-vinylbutyramide, N-vinylcarbamic acid, Examples include sodium N-vinylcarbamate and N-vinylformamide. Of these, N-vinylacetamide is preferable.
上記－Ｎ（Ｈ）Ｃ（＝Ｏ）Ｙ基を有する樹脂は、上記－Ｎ（Ｈ）Ｃ（＝Ｏ）Ｙ基を有するエチレン性不飽和単量体の単独重合体であってもよいし、上記－Ｎ（Ｈ）Ｃ（＝Ｏ）Ｙ基を有するエチレン性不飽和単量体とその他の単量体との共重合体であってもよい。上記その他の単量体としては、アクリルアミド、酢酸ビニル、（メタ）アクリル酸、（メタ）アクリル酸ナトリウム、（メタ）アクリル酸メチル、アクリロニトリル等、その他のエチレン性不飽和単量体と同様のものやその塩を用いることができる。また、得られた共重合体は、上述した、上記カルボキシル基含有エチレン性不飽和単量体に由来するセグメントと上記その他のエチレン性不飽和単量体に由来するセグメントとを有する共重合体を中和する方法と同様にして中和してもよい。
The resin having the —N (H) C (═O) Y group may be a homopolymer of an ethylenically unsaturated monomer having the —N (H) C (═O) Y group. A copolymer of the ethylenically unsaturated monomer having the —N (H) C (═O) Y group and other monomers may also be used. As said other monomer, the thing similar to other ethylenically unsaturated monomers, such as acrylamide, vinyl acetate, (meth) acrylic acid, sodium (meth) acrylate, methyl (meth) acrylate, acrylonitrile, etc. Or a salt thereof. Moreover, the obtained copolymer is the above-mentioned copolymer having a segment derived from the carboxyl group-containing ethylenically unsaturated monomer and a segment derived from the other ethylenically unsaturated monomer. You may neutralize like the method of neutralizing.
上記－Ｎ（Ｈ）Ｃ（＝Ｏ）Ｙ基を有する樹脂の重量平均分子量の好ましい下限は３万、好ましい上限は５００万である。上記－Ｎ（Ｈ）Ｃ（＝Ｏ）Ｙ基を有する樹脂の重量平均分子量がこの範囲であることにより、本発明の硬化性樹脂組成物の優れた塗布性や密着性等を維持したまま、硬化物がクラック防止性により優れるものとなる。上記－Ｎ（Ｈ）Ｃ（＝Ｏ）Ｙ基を有する樹脂の重量平均分子量のより好ましい下限は３０万、より好ましい上限は４００万である。
The preferable lower limit of the weight average molecular weight of the resin having the —N (H) C (═O) Y group is 30,000, and the preferable upper limit is 5 million. When the weight average molecular weight of the resin having the —N (H) C (═O) Y group is in this range, the excellent coating property and adhesion property of the curable resin composition of the present invention are maintained. The cured product is more excellent in crack prevention. The more preferable lower limit of the weight average molecular weight of the resin having the —N (H) C (═O) Y group is 300,000, and the more preferable upper limit is 4 million.
上記－Ｎ（Ｈ）Ｃ（＝Ｏ）Ｙ基を有する樹脂の含有割合は、重量比で、本発明にかかる水溶性樹脂と架橋性樹脂との合計：－Ｎ（Ｈ）Ｃ（＝Ｏ）Ｙ基を有する樹脂＝１００：１～１００：２０であることが好ましい。上記－Ｎ（Ｈ）Ｃ（＝Ｏ）Ｙ基を有する樹脂の含有量がこの範囲であることにより、本発明の硬化性樹脂組成物の優れた塗布性や密着性等を維持したまま、硬化物がクラック防止性により優れるものとなる。上記－Ｎ（Ｈ）Ｃ（＝Ｏ）Ｙ基を有する樹脂の含有割合は、重量比で、本発明にかかる水溶性樹脂と架橋性樹脂との合計：－Ｎ（Ｈ）Ｃ（＝Ｏ）Ｙ基を有する樹脂＝１００：５～１００：１５であることがより好ましい。
The content ratio of the resin having the —N (H) C (═O) Y group is the sum of the water-soluble resin and the crosslinkable resin according to the present invention in weight ratio: —N (H) C (═O) It is preferable that the resin having a Y group = 100: 1 to 100: 20. When the content of the resin having a —N (H) C (═O) Y group is within this range, curing can be performed while maintaining excellent coating properties and adhesion of the curable resin composition of the present invention. Things are superior due to crack prevention. The content ratio of the resin having the —N (H) C (═O) Y group is the sum of the water-soluble resin and the crosslinkable resin according to the present invention in weight ratio: —N (H) C (═O) It is more preferable that the resin having a Y group = 100: 5 to 100: 15.
本発明の硬化性樹脂組成物は、溶剤として水を含有する。
上記水を溶剤として用いることにより、硬化性樹脂組成物を塗工及び乾燥する際の、有機化学物質の排出等の環境への負荷、火災の危険性、及び、取扱者の健康への悪影響を低減することができる。
上述したように本発明にかかる水溶性樹脂及び上記架橋性樹脂は、それぞれ予め水溶液の状態とした後に混合してもよい。 The curable resin composition of the present invention contains water as a solvent.
By using the above water as a solvent, the impact on the environment, such as the discharge of organic chemicals, the danger of fire, and the health of the handler when coating and drying the curable resin composition are adversely affected. Can be reduced.
As described above, the water-soluble resin and the cross-linkable resin according to the present invention may be mixed after previously in the state of an aqueous solution.
上記水を溶剤として用いることにより、硬化性樹脂組成物を塗工及び乾燥する際の、有機化学物質の排出等の環境への負荷、火災の危険性、及び、取扱者の健康への悪影響を低減することができる。
上述したように本発明にかかる水溶性樹脂及び上記架橋性樹脂は、それぞれ予め水溶液の状態とした後に混合してもよい。 The curable resin composition of the present invention contains water as a solvent.
By using the above water as a solvent, the impact on the environment, such as the discharge of organic chemicals, the danger of fire, and the health of the handler when coating and drying the curable resin composition are adversely affected. Can be reduced.
As described above, the water-soluble resin and the cross-linkable resin according to the present invention may be mixed after previously in the state of an aqueous solution.
本発明の硬化性樹脂組成物における水の含有量は特に制限されず、塗布方法等に適した粘度となるように適宜設定されるが、固形分の濃度が１～５０重量％となる量であることが好ましく、１０～４０重量％となる量であることがより好ましい。
The content of water in the curable resin composition of the present invention is not particularly limited and is appropriately set so as to have a viscosity suitable for the coating method and the like, but in such an amount that the solid content concentration is 1 to 50% by weight. Preferably, the amount is 10 to 40% by weight.
本発明の硬化性樹脂組成物は、上記水に加えて有機溶剤等のその他の溶剤を含有してもよいが、環境への負荷を低減するという本発明の目的から、その他の溶剤を含有しないことが好ましい。上記その他の溶剤を含有する場合、その含有量は、溶剤全体の３０重量％以下であることが好ましく、１０重量％以下であることがより好ましい。
上記その他の溶剤の含有量が多くなりすぎる場合には、共沸等の適当な方法で上記その他の溶剤を除去することが好ましい。上記その他の溶剤の除去は、本発明にかかる水溶性樹脂及び上記架橋性樹脂と混合する前に行ってもよい。 The curable resin composition of the present invention may contain other solvents such as organic solvents in addition to the above water, but does not contain other solvents for the purpose of the present invention to reduce the burden on the environment. It is preferable. When it contains the said other solvent, it is preferable that the content is 30 weight% or less of the whole solvent, and it is more preferable that it is 10 weight% or less.
When the content of the other solvent is excessive, it is preferable to remove the other solvent by an appropriate method such as azeotropy. The removal of the other solvent may be performed before mixing with the water-soluble resin and the crosslinkable resin according to the present invention.
上記その他の溶剤の含有量が多くなりすぎる場合には、共沸等の適当な方法で上記その他の溶剤を除去することが好ましい。上記その他の溶剤の除去は、本発明にかかる水溶性樹脂及び上記架橋性樹脂と混合する前に行ってもよい。 The curable resin composition of the present invention may contain other solvents such as organic solvents in addition to the above water, but does not contain other solvents for the purpose of the present invention to reduce the burden on the environment. It is preferable. When it contains the said other solvent, it is preferable that the content is 30 weight% or less of the whole solvent, and it is more preferable that it is 10 weight% or less.
When the content of the other solvent is excessive, it is preferable to remove the other solvent by an appropriate method such as azeotropy. The removal of the other solvent may be performed before mixing with the water-soluble resin and the crosslinkable resin according to the present invention.
上記その他の溶剤としては、例えば、プロピレングリコールモノメチルエーテルアセテート等のプロピレングリコール類や、エチルアルコール、イソプロピルアルコール等のアルコール類等の有害性の低い有機溶剤が挙げられる。
As said other solvent, organic solvents with low toxicity, such as propylene glycols, such as propylene glycol monomethyl ether acetate, alcohols, such as ethyl alcohol and isopropyl alcohol, are mentioned, for example.
本発明の硬化性樹脂組成物は、本発明の目的を阻害しない範囲で、アンモニア水、水酸化ナトリウム等のｐＨ調整剤、粘度調整剤、紫外線吸収剤、酸化防止剤、消泡剤、レベリング剤、カップリング剤、顔料、染料等の公知の各種添加剤を含有してもよい。本発明の硬化性樹脂組成物は、増粘を抑制して貯蔵安定性を向上させるためにｐＨを調整することが好ましく、適度に高ｐＨ側へ調整することがより好ましい。
The curable resin composition of the present invention is a pH adjuster such as ammonia water and sodium hydroxide, a viscosity adjuster, an ultraviolet absorber, an antioxidant, an antifoaming agent, and a leveling agent as long as the object of the present invention is not impaired. Further, various known additives such as coupling agents, pigments, and dyes may be contained. In the curable resin composition of the present invention, it is preferable to adjust the pH in order to suppress thickening and improve storage stability, and it is more preferable to adjust the pH appropriately to the high pH side.
本発明の硬化性樹脂組成物を製造する方法としては、例えば、本発明にかかる水溶性樹脂と、上記架橋性樹脂と、上記水と、必要に応じて用いられる添加剤等とを、撹拌機を用いて混合する方法等が挙げられる。また、均一な混合物となるように、撹拌後、フィルターを用いて濾過を行うことが好ましい。
As a method for producing the curable resin composition of the present invention, for example, a water-soluble resin according to the present invention, the crosslinkable resin, the water, an additive used as necessary, and the like are mixed with a stirrer. And the like. Moreover, it is preferable to filter using a filter after stirring so that it may become a uniform mixture.
本発明の硬化性樹脂組成物をコーティング剤として用いる場合、コーティングの方法としては、例えば、スピンコート、スリットコート、スクリーン印刷、インクジェット塗布、静電塗布、バーコート、ダイコート、ロールコート等の公知のコーティング方法を用いることができ、所望の膜厚、及び、所定のコーティング方法に適した濃度、粘度に調整して使用することができる。
When the curable resin composition of the present invention is used as a coating agent, the coating method includes, for example, known methods such as spin coating, slit coating, screen printing, ink jet coating, electrostatic coating, bar coating, die coating, and roll coating. A coating method can be used, and it can be used by adjusting to a desired film thickness and a concentration and viscosity suitable for a predetermined coating method.
本発明の硬化性樹脂組成物は、低温での加熱により硬化させることができる。本発明の硬化性樹脂組成物を硬化させる際の加熱温度は特に限定されないが、通常は８０℃～２５０℃であり、熱処理時間を短縮するために好ましくは１００℃以上、加熱による黄変を抑制するために好ましくは２００℃以下である。
The curable resin composition of the present invention can be cured by heating at a low temperature. The heating temperature for curing the curable resin composition of the present invention is not particularly limited, but is usually 80 ° C. to 250 ° C., and preferably 100 ° C. or more to reduce the heat treatment time, thereby suppressing yellowing due to heating. Therefore, the temperature is preferably 200 ° C. or lower.
本発明の硬化性樹脂組成物からなる硬化物を有する表示素子もまた、本発明の１つである。
本発明の硬化性樹脂組成物からなる硬化物は、透明性、密着性、硬度、及び、耐湿熱性に優れるため、本発明の表示素子は、特に表示性能に優れるものとなる。 A display element having a cured product comprising the curable resin composition of the present invention is also one aspect of the present invention.
Since the cured product made of the curable resin composition of the present invention is excellent in transparency, adhesion, hardness, and heat-and-moisture resistance, the display element of the present invention is particularly excellent in display performance.
本発明の硬化性樹脂組成物からなる硬化物は、透明性、密着性、硬度、及び、耐湿熱性に優れるため、本発明の表示素子は、特に表示性能に優れるものとなる。 A display element having a cured product comprising the curable resin composition of the present invention is also one aspect of the present invention.
Since the cured product made of the curable resin composition of the present invention is excellent in transparency, adhesion, hardness, and heat-and-moisture resistance, the display element of the present invention is particularly excellent in display performance.
本発明によれば、透明性、密着性、硬度、及び、耐湿熱性に優れる硬化物を得ることができ、かつ、環境への負荷を低減することができる硬化性樹脂組成物を提供することができる。また、本発明によれば、該硬化性樹脂組成物を用いてなる表示素子を提供することができる。
According to the present invention, it is possible to provide a curable resin composition that can obtain a cured product that is excellent in transparency, adhesion, hardness, and heat-and-moisture resistance, and that can reduce the burden on the environment. it can. Moreover, according to this invention, the display element which uses this curable resin composition can be provided.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
（実施例１）
（１）水溶性樹脂Ａの調製
容量１０００ｍＬの四つ口セパラブルフラスコに、撹拌機、還流冷却器、温度計、窒素ガス導入管、及び、滴下漏斗を備えた反応装置を準備した。該フラスコ中にテトラヒドロフラン５０重量部を入れ、窒素ガスを導入してバブリングし、溶存酸素を除去した。カルボキシル基含有エチレン性不飽和単量体としてアクリル酸２０重量部と、その他のエチレン性不飽和単量体としてメタクリル酸メチル６０重量部及びアクリル酸２－ヒドロキシエチル３０重量部と、ラジカル重合開始剤としてｔ－ブチルパーオキシ－２－エチルへキサノエート１．３重量部と、溶剤としてテトラヒドロフラン５０重量部とを予め混合してモノマー溶液を調製し、上記テトラヒドロフランの入ったフラスコ内を撹拌しながら該モノマー溶液を１時間かけて滴下し、その後８０℃にて３時間還流して共重合反応を行い、樹脂溶液を得た。得られた樹脂溶液から共重合樹脂をメタノールで単離し、精製した後、減圧乾燥して樹脂固形物を得た。
次に、得られた樹脂固形物２０ｇに対して１ｍｏｌ／Ｌのアンモニア水３７重量部と水４３重量部とを添加し、中和しつつ８０℃で加熱撹拌して溶解し、水溶性樹脂Ａの水溶液（水溶性樹脂の重量平均分子量１２０００、水溶性樹脂中の－Ｃ（＝Ｏ）ＯＸ基当量３７７、固形分率２０重量％）を得た。 Example 1
(1) Preparation of water-soluble resin A A four-necked separable flask having a capacity of 1000 mL was equipped with a reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen gas inlet tube, and dropping funnel. 50 parts by weight of tetrahydrofuran was placed in the flask, and nitrogen gas was introduced and bubbled to remove dissolved oxygen. 20 parts by weight of acrylic acid as a carboxyl group-containing ethylenically unsaturated monomer, 60 parts by weight of methyl methacrylate and 30 parts by weight of 2-hydroxyethyl acrylate as other ethylenically unsaturated monomers, radical polymerization initiator A monomer solution was prepared by previously mixing 1.3 parts by weight of t-butylperoxy-2-ethylhexanoate as a solvent and 50 parts by weight of tetrahydrofuran as a solvent, and stirring the monomer in the flask containing the tetrahydrofuran. The solution was added dropwise over 1 hour, and then refluxed at 80 ° C. for 3 hours to carry out a copolymerization reaction to obtain a resin solution. The copolymer resin was isolated with methanol from the obtained resin solution, purified, and then dried under reduced pressure to obtain a resin solid.
Next, 37 parts by weight of 1 mol / L ammonia water and 43 parts by weight of water are added to 20 g of the obtained resin solid, and dissolved by heating and stirring at 80 ° C. while neutralizing. Solution (weight average molecular weight 12000 of water-soluble resin, —C (═O) OX group equivalent 377 in water-soluble resin, solid content 20% by weight).
（１）水溶性樹脂Ａの調製
容量１０００ｍＬの四つ口セパラブルフラスコに、撹拌機、還流冷却器、温度計、窒素ガス導入管、及び、滴下漏斗を備えた反応装置を準備した。該フラスコ中にテトラヒドロフラン５０重量部を入れ、窒素ガスを導入してバブリングし、溶存酸素を除去した。カルボキシル基含有エチレン性不飽和単量体としてアクリル酸２０重量部と、その他のエチレン性不飽和単量体としてメタクリル酸メチル６０重量部及びアクリル酸２－ヒドロキシエチル３０重量部と、ラジカル重合開始剤としてｔ－ブチルパーオキシ－２－エチルへキサノエート１．３重量部と、溶剤としてテトラヒドロフラン５０重量部とを予め混合してモノマー溶液を調製し、上記テトラヒドロフランの入ったフラスコ内を撹拌しながら該モノマー溶液を１時間かけて滴下し、その後８０℃にて３時間還流して共重合反応を行い、樹脂溶液を得た。得られた樹脂溶液から共重合樹脂をメタノールで単離し、精製した後、減圧乾燥して樹脂固形物を得た。
次に、得られた樹脂固形物２０ｇに対して１ｍｏｌ／Ｌのアンモニア水３７重量部と水４３重量部とを添加し、中和しつつ８０℃で加熱撹拌して溶解し、水溶性樹脂Ａの水溶液（水溶性樹脂の重量平均分子量１２０００、水溶性樹脂中の－Ｃ（＝Ｏ）ＯＸ基当量３７７、固形分率２０重量％）を得た。 Example 1
(1) Preparation of water-soluble resin A A four-necked separable flask having a capacity of 1000 mL was equipped with a reactor equipped with a stirrer, reflux condenser, thermometer, nitrogen gas inlet tube, and dropping funnel. 50 parts by weight of tetrahydrofuran was placed in the flask, and nitrogen gas was introduced and bubbled to remove dissolved oxygen. 20 parts by weight of acrylic acid as a carboxyl group-containing ethylenically unsaturated monomer, 60 parts by weight of methyl methacrylate and 30 parts by weight of 2-hydroxyethyl acrylate as other ethylenically unsaturated monomers, radical polymerization initiator A monomer solution was prepared by previously mixing 1.3 parts by weight of t-butylperoxy-2-ethylhexanoate as a solvent and 50 parts by weight of tetrahydrofuran as a solvent, and stirring the monomer in the flask containing the tetrahydrofuran. The solution was added dropwise over 1 hour, and then refluxed at 80 ° C. for 3 hours to carry out a copolymerization reaction to obtain a resin solution. The copolymer resin was isolated with methanol from the obtained resin solution, purified, and then dried under reduced pressure to obtain a resin solid.
Next, 37 parts by weight of 1 mol / L ammonia water and 43 parts by weight of water are added to 20 g of the obtained resin solid, and dissolved by heating and stirring at 80 ° C. while neutralizing. Solution (weight average molecular weight 12000 of water-soluble resin, —C (═O) OX group equivalent 377 in water-soluble resin, solid content 20% by weight).
（２）硬化性樹脂組成物の調製
上記「（１）水溶性樹脂Ａの調製」で得た水溶性樹脂Ａの水溶液１００重量部と、架橋性官能基としてオキサゾリン基を有する架橋性樹脂の水溶液（日本触媒社製、「エポクロスＷＳ－３００」、架橋性樹脂の重量平均分子量１２万、架橋性樹脂中のオキサゾリン基当量１３０、固形分率１０重量％）６９重量部とを、撹拌機で３０分間混合した後、孔径５μｍのメンブレンフィルターで濾過し、硬化性樹脂組成物を調製した。 (2) Preparation of curable resin composition 100 parts by weight of an aqueous solution of water-soluble resin A obtained in the above-mentioned "(1) Preparation of water-soluble resin A" and an aqueous solution of a crosslinkable resin having an oxazoline group as a crosslinkable functional group (Nippon Shokubai Co., Ltd., “Epocross WS-300”, weight average molecular weight 120,000 of crosslinkable resin, oxazoline group equivalent 130 in crosslinkable resin, solid content 10 wt%) 69 parts by weight with a stirrer After mixing for a minute, the mixture was filtered through a membrane filter having a pore size of 5 μm to prepare a curable resin composition.
上記「（１）水溶性樹脂Ａの調製」で得た水溶性樹脂Ａの水溶液１００重量部と、架橋性官能基としてオキサゾリン基を有する架橋性樹脂の水溶液（日本触媒社製、「エポクロスＷＳ－３００」、架橋性樹脂の重量平均分子量１２万、架橋性樹脂中のオキサゾリン基当量１３０、固形分率１０重量％）６９重量部とを、撹拌機で３０分間混合した後、孔径５μｍのメンブレンフィルターで濾過し、硬化性樹脂組成物を調製した。 (2) Preparation of curable resin composition 100 parts by weight of an aqueous solution of water-soluble resin A obtained in the above-mentioned "(1) Preparation of water-soluble resin A" and an aqueous solution of a crosslinkable resin having an oxazoline group as a crosslinkable functional group (Nippon Shokubai Co., Ltd., “Epocross WS-300”, weight average molecular weight 120,000 of crosslinkable resin, oxazoline group equivalent 130 in crosslinkable resin, solid content 10 wt%) 69 parts by weight with a stirrer After mixing for a minute, the mixture was filtered through a membrane filter having a pore size of 5 μm to prepare a curable resin composition.
（実施例２）
水溶性樹脂を含有する水溶液として「アクリット３ＳＱ－４２４」（大成ファインケミカル社製、カルボキシル基含有エチレン性不飽和単量体としてメタクリル酸１５重量％を含む共重合体をアンモニアで中和した水溶性樹脂の水溶液、水溶性樹脂の重量平均分子量１６０００、水溶性樹脂中の－Ｃ（＝Ｏ）ＯＸ基当量５９０、固形分率２５重量％）１００重量部と、架橋性樹脂を含有する水溶液として「エポクロスＷＳ－３００」１１０重量部とを、撹拌機で３０分間混合した後、孔径５μｍのメンブレンフィルターで濾過し、硬化性樹脂組成物を調製した。 (Example 2)
As an aqueous solution containing a water-soluble resin, “Acryt 3SQ-424” (manufactured by Taisei Fine Chemical Co., Ltd., a water-soluble resin obtained by neutralizing a copolymer containing 15% by weight of methacrylic acid as a carboxyl group-containing ethylenically unsaturated monomer with ammonia) As an aqueous solution containing 100 parts by weight of a water-soluble resin, a weight average molecular weight of 16000, a —C (═O) OX group equivalent weight of 590, a solid content of 25% by weight in the water-soluble resin, and “Epocross” 110 parts by weight of WS-300 was mixed with a stirrer for 30 minutes, and then filtered through a membrane filter having a pore size of 5 μm to prepare a curable resin composition.
水溶性樹脂を含有する水溶液として「アクリット３ＳＱ－４２４」（大成ファインケミカル社製、カルボキシル基含有エチレン性不飽和単量体としてメタクリル酸１５重量％を含む共重合体をアンモニアで中和した水溶性樹脂の水溶液、水溶性樹脂の重量平均分子量１６０００、水溶性樹脂中の－Ｃ（＝Ｏ）ＯＸ基当量５９０、固形分率２５重量％）１００重量部と、架橋性樹脂を含有する水溶液として「エポクロスＷＳ－３００」１１０重量部とを、撹拌機で３０分間混合した後、孔径５μｍのメンブレンフィルターで濾過し、硬化性樹脂組成物を調製した。 (Example 2)
As an aqueous solution containing a water-soluble resin, “Acryt 3SQ-424” (manufactured by Taisei Fine Chemical Co., Ltd., a water-soluble resin obtained by neutralizing a copolymer containing 15% by weight of methacrylic acid as a carboxyl group-containing ethylenically unsaturated monomer with ammonia) As an aqueous solution containing 100 parts by weight of a water-soluble resin, a weight average molecular weight of 16000, a —C (═O) OX group equivalent weight of 590, a solid content of 25% by weight in the water-soluble resin, and “Epocross” 110 parts by weight of WS-300 was mixed with a stirrer for 30 minutes, and then filtered through a membrane filter having a pore size of 5 μm to prepare a curable resin composition.
（実施例３）
水溶性樹脂を含有する水溶液として「アクリット３ＳＱ－４２６」（大成ファインケミカル社製、カルボキシル基含有エチレン性不飽和単量体としてメタクリル酸１５重量％を含む共重合体をアンモニアで中和した水溶性樹脂の水溶液、水溶性樹脂の重量平均分子量１６０００、水溶性樹脂中の－Ｃ（＝Ｏ）ＯＸ基当量５９０、固形分率２５重量％）１００重量部と、架橋性官能基としてオキサゾリン基を有する架橋性樹脂の水溶液として「エポクロスＷＳ－３００」１１０重量部とを、撹拌機で３０分間混合した後、孔径５μｍのメンブレンフィルターで濾過し、硬化性樹脂組成物を調製した。 (Example 3)
As an aqueous solution containing a water-soluble resin, “Acryt 3SQ-426” (manufactured by Taisei Fine Chemical Co., Ltd., a water-soluble resin obtained by neutralizing a copolymer containing 15% by weight of methacrylic acid as a carboxyl group-containing ethylenically unsaturated monomer with ammonia) A water-soluble resin having a weight average molecular weight of 16000, -C (= O) OX group equivalent weight of 590 in the water-soluble resin, solid content of 25 wt%) and 100 parts by weight of a crosslinkable functional group having an oxazoline group 110 parts by weight of “Epocross WS-300” as an aqueous solution of a curable resin was mixed with a stirrer for 30 minutes and then filtered through a membrane filter having a pore size of 5 μm to prepare a curable resin composition.
水溶性樹脂を含有する水溶液として「アクリット３ＳＱ－４２６」（大成ファインケミカル社製、カルボキシル基含有エチレン性不飽和単量体としてメタクリル酸１５重量％を含む共重合体をアンモニアで中和した水溶性樹脂の水溶液、水溶性樹脂の重量平均分子量１６０００、水溶性樹脂中の－Ｃ（＝Ｏ）ＯＸ基当量５９０、固形分率２５重量％）１００重量部と、架橋性官能基としてオキサゾリン基を有する架橋性樹脂の水溶液として「エポクロスＷＳ－３００」１１０重量部とを、撹拌機で３０分間混合した後、孔径５μｍのメンブレンフィルターで濾過し、硬化性樹脂組成物を調製した。 (Example 3)
As an aqueous solution containing a water-soluble resin, “Acryt 3SQ-426” (manufactured by Taisei Fine Chemical Co., Ltd., a water-soluble resin obtained by neutralizing a copolymer containing 15% by weight of methacrylic acid as a carboxyl group-containing ethylenically unsaturated monomer with ammonia) A water-soluble resin having a weight average molecular weight of 16000, -C (= O) OX group equivalent weight of 590 in the water-soluble resin, solid content of 25 wt%) and 100 parts by weight of a crosslinkable functional group having an oxazoline group 110 parts by weight of “Epocross WS-300” as an aqueous solution of a curable resin was mixed with a stirrer for 30 minutes and then filtered through a membrane filter having a pore size of 5 μm to prepare a curable resin composition.
（実施例４～６）
架橋性官能基としてオキサゾリン基を有する架橋性樹脂の水溶液である「エポクロスＷＳ－３００」の配合量を表１に示したように変更したこと以外は実施例３と同様にして、硬化性樹脂組成物を調製した。 (Examples 4 to 6)
A curable resin composition was obtained in the same manner as in Example 3 except that the blending amount of “Epocross WS-300” which is an aqueous solution of a crosslinkable resin having an oxazoline group as a crosslinkable functional group was changed as shown in Table 1. A product was prepared.
架橋性官能基としてオキサゾリン基を有する架橋性樹脂の水溶液である「エポクロスＷＳ－３００」の配合量を表１に示したように変更したこと以外は実施例３と同様にして、硬化性樹脂組成物を調製した。 (Examples 4 to 6)
A curable resin composition was obtained in the same manner as in Example 3 except that the blending amount of “Epocross WS-300” which is an aqueous solution of a crosslinkable resin having an oxazoline group as a crosslinkable functional group was changed as shown in Table 1. A product was prepared.
（実施例７）
実施例１の「（１）水溶性樹脂Ａの調製」で得た水溶性樹脂Ａの水溶液１００重量部と、架橋性樹脂を含有する水溶液（日本触媒社製、「エポクロスＷＳ－７００」、架橋性樹脂の重量平均分子量４万、架橋性樹脂中のオキサゾリン基当量２２０、固形分率２５重量％）７０重量部とを、撹拌機で３０分間混合した後、孔径５μｍのメンブレンフィルターで濾過し、硬化性樹脂組成物を調製した。 (Example 7)
100 parts by weight of an aqueous solution of the water-soluble resin A obtained in “(1) Preparation of water-soluble resin A” in Example 1 and an aqueous solution containing a crosslinkable resin (“Epocross WS-700” manufactured by Nippon Shokubai Co., Ltd.) 70 weight parts of the weight average molecular weight of the functional resin, 40,000 oxazoline group in the crosslinkable resin, solid content rate 25 weight%) was mixed for 30 minutes with a stirrer, and then filtered through a membrane filter having a pore size of 5 μm. A curable resin composition was prepared.
実施例１の「（１）水溶性樹脂Ａの調製」で得た水溶性樹脂Ａの水溶液１００重量部と、架橋性樹脂を含有する水溶液（日本触媒社製、「エポクロスＷＳ－７００」、架橋性樹脂の重量平均分子量４万、架橋性樹脂中のオキサゾリン基当量２２０、固形分率２５重量％）７０重量部とを、撹拌機で３０分間混合した後、孔径５μｍのメンブレンフィルターで濾過し、硬化性樹脂組成物を調製した。 (Example 7)
100 parts by weight of an aqueous solution of the water-soluble resin A obtained in “(1) Preparation of water-soluble resin A” in Example 1 and an aqueous solution containing a crosslinkable resin (“Epocross WS-700” manufactured by Nippon Shokubai Co., Ltd.) 70 weight parts of the weight average molecular weight of the functional resin, 40,000 oxazoline group in the crosslinkable resin, solid content rate 25 weight%) was mixed for 30 minutes with a stirrer, and then filtered through a membrane filter having a pore size of 5 μm. A curable resin composition was prepared.
（実施例８）
水溶性樹脂を含有する水溶液として「アクリット３ＳＱ－４２４」１００重量部と、架橋性樹脂を含有する水溶液として「エポクロスＷＳ－７００」１１２重量部とを、撹拌機で３０分間混合した後、孔径５μｍのメンブレンフィルターで濾過し、硬化性樹脂組成物を調製した。 (Example 8)
100 parts by weight of “Acryt 3SQ-424” as an aqueous solution containing a water-soluble resin and 112 parts by weight of “Epocross WS-700” as an aqueous solution containing a crosslinkable resin were mixed for 30 minutes with a stirrer, and then the pore diameter was 5 μm. The curable resin composition was prepared by filtering through a membrane filter.
水溶性樹脂を含有する水溶液として「アクリット３ＳＱ－４２４」１００重量部と、架橋性樹脂を含有する水溶液として「エポクロスＷＳ－７００」１１２重量部とを、撹拌機で３０分間混合した後、孔径５μｍのメンブレンフィルターで濾過し、硬化性樹脂組成物を調製した。 (Example 8)
100 parts by weight of “Acryt 3SQ-424” as an aqueous solution containing a water-soluble resin and 112 parts by weight of “Epocross WS-700” as an aqueous solution containing a crosslinkable resin were mixed for 30 minutes with a stirrer, and then the pore diameter was 5 μm. The curable resin composition was prepared by filtering through a membrane filter.
（実施例９）
水溶性樹脂を含有する水溶液として「アクリット３ＳＱ－４２６」１００重量部と、架橋性樹脂を含有する水溶液として「エポクロスＷＳ－７００」１１２重量部とを、撹拌機で３０分間混合した後、孔径５μｍのメンブレンフィルターで濾過し、硬化性樹脂組成物を調製した。 Example 9
100 parts by weight of “Acryt 3SQ-426” as an aqueous solution containing a water-soluble resin and 112 parts by weight of “Epocross WS-700” as an aqueous solution containing a crosslinkable resin were mixed for 30 minutes with a stirrer, and then the pore diameter was 5 μm. The curable resin composition was prepared by filtering through a membrane filter.
水溶性樹脂を含有する水溶液として「アクリット３ＳＱ－４２６」１００重量部と、架橋性樹脂を含有する水溶液として「エポクロスＷＳ－７００」１１２重量部とを、撹拌機で３０分間混合した後、孔径５μｍのメンブレンフィルターで濾過し、硬化性樹脂組成物を調製した。 Example 9
100 parts by weight of “Acryt 3SQ-426” as an aqueous solution containing a water-soluble resin and 112 parts by weight of “Epocross WS-700” as an aqueous solution containing a crosslinkable resin were mixed for 30 minutes with a stirrer, and then the pore diameter was 5 μm. The curable resin composition was prepared by filtering through a membrane filter.
（実施例１０）
水溶性樹脂を含有する水溶液として「アクリット３ＳＱ－４２６」１００重量部と、架橋性樹脂を含有する水溶液として「エポクロスＷＳ－７００」１８６重量部とを、撹拌機で３０分間混合した後、孔径５μｍのメンブレンフィルターで濾過し、硬化性樹脂組成物を調製した。 (Example 10)
100 parts by weight of “Acryt 3SQ-426” as an aqueous solution containing a water-soluble resin and 186 parts by weight of “Epocross WS-700” as an aqueous solution containing a crosslinkable resin were mixed for 30 minutes with a stirrer, and then the pore diameter was 5 μm. The curable resin composition was prepared by filtering through a membrane filter.
水溶性樹脂を含有する水溶液として「アクリット３ＳＱ－４２６」１００重量部と、架橋性樹脂を含有する水溶液として「エポクロスＷＳ－７００」１８６重量部とを、撹拌機で３０分間混合した後、孔径５μｍのメンブレンフィルターで濾過し、硬化性樹脂組成物を調製した。 (Example 10)
100 parts by weight of “Acryt 3SQ-426” as an aqueous solution containing a water-soluble resin and 186 parts by weight of “Epocross WS-700” as an aqueous solution containing a crosslinkable resin were mixed for 30 minutes with a stirrer, and then the pore diameter was 5 μm. The curable resin composition was prepared by filtering through a membrane filter.
（実施例１１）
実施例１の「（１）水溶性樹脂Ａの調製」で得た水溶性樹脂Ａの水溶液１００重量部と、架橋性樹脂（ナガセケムテックス社製、「デナコールＥＸ－５２１」、架橋性樹脂の重量平均分子量１２９４、架橋性樹脂中のエポキシ基当量１８３）１０重量部とを、撹拌機で３０分間混合した後、孔径５μｍのメンブレンフィルターで濾過し、硬化性樹脂組成物を調製した。 (Example 11)
100 parts by weight of an aqueous solution of water-soluble resin A obtained in “(1) Preparation of water-soluble resin A” in Example 1, crosslinkable resin (manufactured by Nagase ChemteX Corporation, “Denacol EX-521”, A weight average molecular weight of 1294 and 10 parts by weight of an epoxy group equivalent of 183 in the crosslinkable resin were mixed with a stirrer for 30 minutes, and then filtered through a membrane filter having a pore size of 5 μm to prepare a curable resin composition.
実施例１の「（１）水溶性樹脂Ａの調製」で得た水溶性樹脂Ａの水溶液１００重量部と、架橋性樹脂（ナガセケムテックス社製、「デナコールＥＸ－５２１」、架橋性樹脂の重量平均分子量１２９４、架橋性樹脂中のエポキシ基当量１８３）１０重量部とを、撹拌機で３０分間混合した後、孔径５μｍのメンブレンフィルターで濾過し、硬化性樹脂組成物を調製した。 (Example 11)
100 parts by weight of an aqueous solution of water-soluble resin A obtained in “(1) Preparation of water-soluble resin A” in Example 1, crosslinkable resin (manufactured by Nagase ChemteX Corporation, “Denacol EX-521”, A weight average molecular weight of 1294 and 10 parts by weight of an epoxy group equivalent of 183 in the crosslinkable resin were mixed with a stirrer for 30 minutes, and then filtered through a membrane filter having a pore size of 5 μm to prepare a curable resin composition.
（実施例１２）
－Ｎ（Ｈ）Ｃ（＝Ｏ）Ｙ基を有する樹脂を含有する水溶液として、「ＧＥ－１９１－０５３」（昭和電工社製、ポリ－Ｎ－ビニルアセトアミドの水溶液、ポリ－Ｎ－ビニルアセトアミドの重量平均分子量約１５０万、固形分率５重量％）４９重量部を配合したこと以外は、実施例１と同様にして、硬化性樹脂組成物を調製した。 Example 12
As an aqueous solution containing a resin having a —N (H) C (═O) Y group, “GE-191-053” (manufactured by Showa Denko KK, poly-N-vinylacetamide aqueous solution, poly-N-vinylacetamide A curable resin composition was prepared in the same manner as in Example 1 except that 49 parts by weight of a weight average molecular weight of about 1.5 million and a solid content of 5% by weight were blended.
－Ｎ（Ｈ）Ｃ（＝Ｏ）Ｙ基を有する樹脂を含有する水溶液として、「ＧＥ－１９１－０５３」（昭和電工社製、ポリ－Ｎ－ビニルアセトアミドの水溶液、ポリ－Ｎ－ビニルアセトアミドの重量平均分子量約１５０万、固形分率５重量％）４９重量部を配合したこと以外は、実施例１と同様にして、硬化性樹脂組成物を調製した。 Example 12
As an aqueous solution containing a resin having a —N (H) C (═O) Y group, “GE-191-053” (manufactured by Showa Denko KK, poly-N-vinylacetamide aqueous solution, poly-N-vinylacetamide A curable resin composition was prepared in the same manner as in Example 1 except that 49 parts by weight of a weight average molecular weight of about 1.5 million and a solid content of 5% by weight were blended.
（実施例１３）
「ＧＥ－１９１－０５３」の配合量を２１重量部に変更したこと以外は、実施例１２と同様にして、硬化性樹脂組成物を調製した。 (Example 13)
A curable resin composition was prepared in the same manner as in Example 12 except that the amount of “GE-191-053” was changed to 21 parts by weight.
「ＧＥ－１９１－０５３」の配合量を２１重量部に変更したこと以外は、実施例１２と同様にして、硬化性樹脂組成物を調製した。 (Example 13)
A curable resin composition was prepared in the same manner as in Example 12 except that the amount of “GE-191-053” was changed to 21 parts by weight.
（実施例１４）
「ＧＥ－１９１－０５３」の配合量を２３９重量部に変更したこと以外は、実施例１２と同様にして、硬化性樹脂組成物を調製した。 (Example 14)
A curable resin composition was prepared in the same manner as in Example 12 except that the amount of “GE-191-053” was changed to 239 parts by weight.
「ＧＥ－１９１－０５３」の配合量を２３９重量部に変更したこと以外は、実施例１２と同様にして、硬化性樹脂組成物を調製した。 (Example 14)
A curable resin composition was prepared in the same manner as in Example 12 except that the amount of “GE-191-053” was changed to 239 parts by weight.
（実施例１５）
－Ｎ（Ｈ）Ｃ（＝Ｏ）Ｙ基を有する樹脂を含有する水溶液として、「ＧＥ－１９１－１０３」（昭和電工社製、ポリ－Ｎ－ビニルアセトアミドの水溶液、ポリ－Ｎ－ビニルアセトアミドの重量平均分子量約９０万、固形分率１０重量％）２４重量部を配合したこと以外は、実施例１と同様にして、硬化性樹脂組成物を調製した。 (Example 15)
As an aqueous solution containing a resin having a —N (H) C (═O) Y group, “GE-191-103” (manufactured by Showa Denko KK, poly-N-vinylacetamide aqueous solution, poly-N-vinylacetamide A curable resin composition was prepared in the same manner as in Example 1 except that 24 parts by weight of a weight average molecular weight of about 900,000 and a solid content of 10% by weight were blended.
－Ｎ（Ｈ）Ｃ（＝Ｏ）Ｙ基を有する樹脂を含有する水溶液として、「ＧＥ－１９１－１０３」（昭和電工社製、ポリ－Ｎ－ビニルアセトアミドの水溶液、ポリ－Ｎ－ビニルアセトアミドの重量平均分子量約９０万、固形分率１０重量％）２４重量部を配合したこと以外は、実施例１と同様にして、硬化性樹脂組成物を調製した。 (Example 15)
As an aqueous solution containing a resin having a —N (H) C (═O) Y group, “GE-191-103” (manufactured by Showa Denko KK, poly-N-vinylacetamide aqueous solution, poly-N-vinylacetamide A curable resin composition was prepared in the same manner as in Example 1 except that 24 parts by weight of a weight average molecular weight of about 900,000 and a solid content of 10% by weight were blended.
（実施例１６）
－Ｎ（Ｈ）Ｃ（＝Ｏ）Ｙ基を有する樹脂を含有する水溶液として、「ＧＥ－１９１－１０４」（昭和電工社製、ポリ－Ｎ－ビニルアセトアミドの水溶液、ポリ－Ｎ－ビニルアセトアミドの重量平均分子量約３０万、固形分率１３重量％）１９重量部を配合したこと以外は、実施例１と同様にして、硬化性樹脂組成物を調製した。 (Example 16)
As an aqueous solution containing a resin having a —N (H) C (═O) Y group, “GE-191-104” (manufactured by Showa Denko KK, poly-N-vinylacetamide aqueous solution, poly-N-vinylacetamide A curable resin composition was prepared in the same manner as in Example 1 except that 19 parts by weight of a weight average molecular weight of about 300,000 and a solid content of 13% by weight were blended.
－Ｎ（Ｈ）Ｃ（＝Ｏ）Ｙ基を有する樹脂を含有する水溶液として、「ＧＥ－１９１－１０４」（昭和電工社製、ポリ－Ｎ－ビニルアセトアミドの水溶液、ポリ－Ｎ－ビニルアセトアミドの重量平均分子量約３０万、固形分率１３重量％）１９重量部を配合したこと以外は、実施例１と同様にして、硬化性樹脂組成物を調製した。 (Example 16)
As an aqueous solution containing a resin having a —N (H) C (═O) Y group, “GE-191-104” (manufactured by Showa Denko KK, poly-N-vinylacetamide aqueous solution, poly-N-vinylacetamide A curable resin composition was prepared in the same manner as in Example 1 except that 19 parts by weight of a weight average molecular weight of about 300,000 and a solid content of 13% by weight were blended.
（実施例１７）
－Ｎ（Ｈ）Ｃ（＝Ｏ）Ｙ基を有する樹脂を含有する水溶液として、「ＧＥ－１６７－０００」（昭和電工社製、Ｎ－ビニルアセトアミド・アクリル酸ナトリウム共重合体、共重合体の重量平均分子量約２６０万）を水に溶かして得られた固形分率５重量％の水溶液４９重量部を配合したこと以外は、実施例１と同様にして、硬化性樹脂組成物を調製した。 (Example 17)
As an aqueous solution containing a resin having a —N (H) C (═O) Y group, “GE-167-000” (manufactured by Showa Denko KK, N-vinylacetamide / sodium acrylate copolymer, A curable resin composition was prepared in the same manner as in Example 1 except that 49 parts by weight of an aqueous solution having a solid content of 5% by weight obtained by dissolving a weight average molecular weight of about 2.6 million) in water was blended.
－Ｎ（Ｈ）Ｃ（＝Ｏ）Ｙ基を有する樹脂を含有する水溶液として、「ＧＥ－１６７－０００」（昭和電工社製、Ｎ－ビニルアセトアミド・アクリル酸ナトリウム共重合体、共重合体の重量平均分子量約２６０万）を水に溶かして得られた固形分率５重量％の水溶液４９重量部を配合したこと以外は、実施例１と同様にして、硬化性樹脂組成物を調製した。 (Example 17)
As an aqueous solution containing a resin having a —N (H) C (═O) Y group, “GE-167-000” (manufactured by Showa Denko KK, N-vinylacetamide / sodium acrylate copolymer, A curable resin composition was prepared in the same manner as in Example 1 except that 49 parts by weight of an aqueous solution having a solid content of 5% by weight obtained by dissolving a weight average molecular weight of about 2.6 million) in water was blended.
（実施例１８）
水溶性樹脂を含有する水溶液として「アクリット３ＳＱ－４２６」１００重量部と、架橋性樹脂を含有する水溶液として「エポクロスＷＳ－３００」２０重量部とを、撹拌機で３０分間混合した後、孔径５μｍのメンブレンフィルターで濾過し、硬化性樹脂組成物を調製した。 (Example 18)
100 parts by weight of “Acryt 3SQ-426” as an aqueous solution containing a water-soluble resin and 20 parts by weight of “Epocross WS-300” as an aqueous solution containing a crosslinkable resin were mixed for 30 minutes with a stirrer, and then the pore diameter was 5 μm. The curable resin composition was prepared by filtering through a membrane filter.
水溶性樹脂を含有する水溶液として「アクリット３ＳＱ－４２６」１００重量部と、架橋性樹脂を含有する水溶液として「エポクロスＷＳ－３００」２０重量部とを、撹拌機で３０分間混合した後、孔径５μｍのメンブレンフィルターで濾過し、硬化性樹脂組成物を調製した。 (Example 18)
100 parts by weight of “Acryt 3SQ-426” as an aqueous solution containing a water-soluble resin and 20 parts by weight of “Epocross WS-300” as an aqueous solution containing a crosslinkable resin were mixed for 30 minutes with a stirrer, and then the pore diameter was 5 μm. The curable resin composition was prepared by filtering through a membrane filter.
（実施例１９）
水溶性樹脂を含有する水溶液として「アクリット３ＳＱ－４２６」１００重量部と、架橋性樹脂を含有する水溶液として「エポクロスＷＳ－７００」３０重量部とを、撹拌機で３０分間混合した後、孔径５μｍのメンブレンフィルターで濾過し、硬化性樹脂組成物を調製した。 (Example 19)
100 parts by weight of “Acryt 3SQ-426” as an aqueous solution containing a water-soluble resin and 30 parts by weight of “Epocross WS-700” as an aqueous solution containing a crosslinkable resin were mixed for 30 minutes with a stirrer, and then the pore diameter was 5 μm. The curable resin composition was prepared by filtering through a membrane filter.
水溶性樹脂を含有する水溶液として「アクリット３ＳＱ－４２６」１００重量部と、架橋性樹脂を含有する水溶液として「エポクロスＷＳ－７００」３０重量部とを、撹拌機で３０分間混合した後、孔径５μｍのメンブレンフィルターで濾過し、硬化性樹脂組成物を調製した。 (Example 19)
100 parts by weight of “Acryt 3SQ-426” as an aqueous solution containing a water-soluble resin and 30 parts by weight of “Epocross WS-700” as an aqueous solution containing a crosslinkable resin were mixed for 30 minutes with a stirrer, and then the pore diameter was 5 μm. The curable resin composition was prepared by filtering through a membrane filter.
（比較例１）
実施例１の「（１）水溶性樹脂Ａの調製」で得た水溶性樹脂Ａの水溶液を硬化性樹脂組成物として用意した。 (Comparative Example 1)
An aqueous solution of the water-soluble resin A obtained in “(1) Preparation of water-soluble resin A” in Example 1 was prepared as a curable resin composition.
実施例１の「（１）水溶性樹脂Ａの調製」で得た水溶性樹脂Ａの水溶液を硬化性樹脂組成物として用意した。 (Comparative Example 1)
An aqueous solution of the water-soluble resin A obtained in “(1) Preparation of water-soluble resin A” in Example 1 was prepared as a curable resin composition.
（比較例２）
「アクリット３ＳＱ－４２４」を硬化性樹脂組成物として用意した。 (Comparative Example 2)
“Acryt 3SQ-424” was prepared as a curable resin composition.
「アクリット３ＳＱ－４２４」を硬化性樹脂組成物として用意した。 (Comparative Example 2)
“Acryt 3SQ-424” was prepared as a curable resin composition.
（比較例３）
「アクリット３ＳＱ－４２６」を硬化性樹脂組成物として用意した。 (Comparative Example 3)
“Acryt 3SQ-426” was prepared as a curable resin composition.
「アクリット３ＳＱ－４２６」を硬化性樹脂組成物として用意した。 (Comparative Example 3)
“Acryt 3SQ-426” was prepared as a curable resin composition.
（比較例４）
「エポクロスＷＳ－３００」を硬化性樹脂組成物として用意した。 (Comparative Example 4)
“Epocross WS-300” was prepared as a curable resin composition.
「エポクロスＷＳ－３００」を硬化性樹脂組成物として用意した。 (Comparative Example 4)
“Epocross WS-300” was prepared as a curable resin composition.
（比較例５）
「エポクロスＷＳ－７００」を硬化性樹脂組成物として用意した。 (Comparative Example 5)
“Epocross WS-700” was prepared as a curable resin composition.
「エポクロスＷＳ－７００」を硬化性樹脂組成物として用意した。 (Comparative Example 5)
“Epocross WS-700” was prepared as a curable resin composition.
＜評価＞
実施例及び比較例で得られた各硬化性樹脂組成物について、以下の評価を行った。結果を表１～５に示した。 <Evaluation>
The following evaluation was performed about each curable resin composition obtained by the Example and the comparative example. The results are shown in Tables 1-5.
実施例及び比較例で得られた各硬化性樹脂組成物について、以下の評価を行った。結果を表１～５に示した。 <Evaluation>
The following evaluation was performed about each curable resin composition obtained by the Example and the comparative example. The results are shown in Tables 1-5.
（透明性）
実施例及び比較例で得られた各硬化性樹脂組成物を厚さ０．７ｍｍ、幅５０ｍｍ、長さ５０ｍｍの無アルカリガラス基板上にスピンコートにより塗布した後、１２０℃で１０分間乾燥し、膜厚が約１０μｍの塗膜を得た。得られたガラス基板上の塗膜について、へイズメーターを用いて全光線透過率とヘイズ値（曇価）の測定を行った。
透過率は、８５％以上であった場合を「○」、８５％未満であった場合を「×」とし、ヘイズ値は、１％以下であった場合を「○」、１％を超えた場合を「×」として透明性を評価した。 (transparency)
Each curable resin composition obtained in Examples and Comparative Examples was applied by spin coating on a non-alkali glass substrate having a thickness of 0.7 mm, a width of 50 mm, and a length of 50 mm, and then dried at 120 ° C. for 10 minutes. A coating film having a thickness of about 10 μm was obtained. About the coating film on the obtained glass substrate, the total light transmittance and the haze value (haze value) were measured using the haze meter.
When the transmittance was 85% or more, “◯”, when it was less than 85%, “x”, and when the haze value was 1% or less, “◯” exceeded 1%. Transparency was evaluated with “x” as the case.
実施例及び比較例で得られた各硬化性樹脂組成物を厚さ０．７ｍｍ、幅５０ｍｍ、長さ５０ｍｍの無アルカリガラス基板上にスピンコートにより塗布した後、１２０℃で１０分間乾燥し、膜厚が約１０μｍの塗膜を得た。得られたガラス基板上の塗膜について、へイズメーターを用いて全光線透過率とヘイズ値（曇価）の測定を行った。
透過率は、８５％以上であった場合を「○」、８５％未満であった場合を「×」とし、ヘイズ値は、１％以下であった場合を「○」、１％を超えた場合を「×」として透明性を評価した。 (transparency)
Each curable resin composition obtained in Examples and Comparative Examples was applied by spin coating on a non-alkali glass substrate having a thickness of 0.7 mm, a width of 50 mm, and a length of 50 mm, and then dried at 120 ° C. for 10 minutes. A coating film having a thickness of about 10 μm was obtained. About the coating film on the obtained glass substrate, the total light transmittance and the haze value (haze value) were measured using the haze meter.
When the transmittance was 85% or more, “◯”, when it was less than 85%, “x”, and when the haze value was 1% or less, “◯” exceeded 1%. Transparency was evaluated with “x” as the case.
（密着性）
「（透明性）」の評価に用いたガラス基板上に形成した塗膜について、ＪＩＳ Ｋ５４００に準拠して１ｍｍ間隔１００マス目の碁盤目剥離試験を行った。
テープ剥離後の塗膜の残存率が９５％以上であった場合を「○」、９５％未満８０％以上であった場合を「△」、８０％未満であった場合を「×」として密着性を評価した。 (Adhesion)
The coating film formed on the glass substrate used for the evaluation of “(transparency)” was subjected to a cross-cut peeling test having 100 squares at 1 mm intervals in accordance with JIS K5400.
When the remaining rate of the coated film after peeling off the tape is 95% or more, “○”, when less than 95% is 80% or more, “△”, and when less than 80%, “×” is adhered. Sex was evaluated.
「（透明性）」の評価に用いたガラス基板上に形成した塗膜について、ＪＩＳ Ｋ５４００に準拠して１ｍｍ間隔１００マス目の碁盤目剥離試験を行った。
テープ剥離後の塗膜の残存率が９５％以上であった場合を「○」、９５％未満８０％以上であった場合を「△」、８０％未満であった場合を「×」として密着性を評価した。 (Adhesion)
The coating film formed on the glass substrate used for the evaluation of “(transparency)” was subjected to a cross-cut peeling test having 100 squares at 1 mm intervals in accordance with JIS K5400.
When the remaining rate of the coated film after peeling off the tape is 95% or more, “○”, when less than 95% is 80% or more, “△”, and when less than 80%, “×” is adhered. Sex was evaluated.
（硬度）
「（透明性）」の評価に用いたガラス基板上に形成した塗膜について、ＪＩＳ Ｋ５４００に準拠して鉛筆硬度を測定した。 (hardness)
About the coating film formed on the glass substrate used for evaluation of "(transparency)", pencil hardness was measured based on JISK5400.
「（透明性）」の評価に用いたガラス基板上に形成した塗膜について、ＪＩＳ Ｋ５４００に準拠して鉛筆硬度を測定した。 (hardness)
About the coating film formed on the glass substrate used for evaluation of "(transparency)", pencil hardness was measured based on JISK5400.
（耐湿熱性）
「（透明性）」の評価に用いたガラス基板上に形成した塗膜について、温度８５℃、湿度８５％ＲＨに調整した恒温恒湿オーブン中で２４０時間保持する高温高湿試験を行った際の高温高湿試験前後における塗膜の状態を目視にて観察した。
高温高湿試験前後で塗膜に変化が見られなかった場合を「○」、高温高湿試験後の塗膜の一部に溶解、剥がれ、クラック、白化等の変化が見られた場合を「△」、高温高湿試験後の塗膜の広範囲に溶解、剥がれ、クラック、白化等の変化が見られた場合を「×」として耐湿熱性を評価した。 (Moisture and heat resistance)
When the coating film formed on the glass substrate used for the evaluation of “(transparency)” was subjected to a high temperature and high humidity test for 240 hours in a constant temperature and humidity oven adjusted to a temperature of 85 ° C. and a humidity of 85% RH. The state of the coating film before and after the high temperature and high humidity test was visually observed.
“○” indicates no change in the coating film before and after the high-temperature and high-humidity test, and “No” indicates a case where changes such as dissolution, peeling, cracking, and whitening are observed in a part of the coating film after the high-temperature and high-humidity test. [Delta] ", a case where changes such as dissolution, peeling, cracking, whitening, etc. were observed in a wide range of the coating film after the high temperature and high humidity test was evaluated as" x "to evaluate the heat and moisture resistance.
「（透明性）」の評価に用いたガラス基板上に形成した塗膜について、温度８５℃、湿度８５％ＲＨに調整した恒温恒湿オーブン中で２４０時間保持する高温高湿試験を行った際の高温高湿試験前後における塗膜の状態を目視にて観察した。
高温高湿試験前後で塗膜に変化が見られなかった場合を「○」、高温高湿試験後の塗膜の一部に溶解、剥がれ、クラック、白化等の変化が見られた場合を「△」、高温高湿試験後の塗膜の広範囲に溶解、剥がれ、クラック、白化等の変化が見られた場合を「×」として耐湿熱性を評価した。 (Moisture and heat resistance)
When the coating film formed on the glass substrate used for the evaluation of “(transparency)” was subjected to a high temperature and high humidity test for 240 hours in a constant temperature and humidity oven adjusted to a temperature of 85 ° C. and a humidity of 85% RH. The state of the coating film before and after the high temperature and high humidity test was visually observed.
“○” indicates no change in the coating film before and after the high-temperature and high-humidity test, and “No” indicates a case where changes such as dissolution, peeling, cracking, and whitening are observed in a part of the coating film after the high-temperature and high-humidity test. [Delta] ", a case where changes such as dissolution, peeling, cracking, whitening, etc. were observed in a wide range of the coating film after the high temperature and high humidity test was evaluated as" x "to evaluate the heat and moisture resistance.
（クラック防止性）
実施例１２～１７で得られた各硬化性樹脂組成物を厚さ０．７ｍｍ、幅５０ｍｍ、長さ５０ｍｍの無アルカリガラス基板上にスピンコートにより塗布した後、室温で１０分間放置した後、１２０℃で１０分間乾燥し、膜厚が約１０μｍの試験片を作製した。得られた試験片を目視にて観察し、全くクラックが確認されなかった場合を「○」、ごく僅かにクラックが確認された場合を「△」、はっきりとクラックが確認された場合を「×」としてクラック防止性を評価した。 (Crack prevention)
Each curable resin composition obtained in Examples 12 to 17 was applied on a non-alkali glass substrate having a thickness of 0.7 mm, a width of 50 mm, and a length of 50 mm by spin coating, and then allowed to stand at room temperature for 10 minutes. A test piece having a thickness of about 10 μm was produced by drying at 120 ° C. for 10 minutes. The obtained test piece was visually observed, “◯” when no cracks were confirmed, “△” when very slight cracks were confirmed, and “×” when cracks were clearly confirmed. The crack prevention property was evaluated.
実施例１２～１７で得られた各硬化性樹脂組成物を厚さ０．７ｍｍ、幅５０ｍｍ、長さ５０ｍｍの無アルカリガラス基板上にスピンコートにより塗布した後、室温で１０分間放置した後、１２０℃で１０分間乾燥し、膜厚が約１０μｍの試験片を作製した。得られた試験片を目視にて観察し、全くクラックが確認されなかった場合を「○」、ごく僅かにクラックが確認された場合を「△」、はっきりとクラックが確認された場合を「×」としてクラック防止性を評価した。 (Crack prevention)
Each curable resin composition obtained in Examples 12 to 17 was applied on a non-alkali glass substrate having a thickness of 0.7 mm, a width of 50 mm, and a length of 50 mm by spin coating, and then allowed to stand at room temperature for 10 minutes. A test piece having a thickness of about 10 μm was produced by drying at 120 ° C. for 10 minutes. The obtained test piece was visually observed, “◯” when no cracks were confirmed, “△” when very slight cracks were confirmed, and “×” when cracks were clearly confirmed. The crack prevention property was evaluated.
（貯蔵安定性）
実施例１８及び実施例１９で得られた各硬化性樹脂組成物の初期粘度及び２３℃にて１ヶ月放置した後の粘度を測定し、２３℃にて１ヶ月放置した後の粘度が初期粘度の１．３倍未満であった場合を「○」、１．３倍以上２倍未満であった場合を「△」、２倍以上５倍未満であった場合を「×」、５倍以上であった場合を「××」として貯蔵安定性を評価した。 (Storage stability)
The initial viscosity of each curable resin composition obtained in Example 18 and Example 19 and the viscosity after standing for 1 month at 23 ° C. were measured, and the viscosity after standing for 1 month at 23 ° C. was the initial viscosity. If it is less than 1.3 times, “◯”, if it is 1.3 times or more and less than 2 times, “△”, if it is 2 times or more and less than 5 times, “×”, if it is 5 times or more The storage stability was evaluated as “XX”.
実施例１８及び実施例１９で得られた各硬化性樹脂組成物の初期粘度及び２３℃にて１ヶ月放置した後の粘度を測定し、２３℃にて１ヶ月放置した後の粘度が初期粘度の１．３倍未満であった場合を「○」、１．３倍以上２倍未満であった場合を「△」、２倍以上５倍未満であった場合を「×」、５倍以上であった場合を「××」として貯蔵安定性を評価した。 (Storage stability)
The initial viscosity of each curable resin composition obtained in Example 18 and Example 19 and the viscosity after standing for 1 month at 23 ° C. were measured, and the viscosity after standing for 1 month at 23 ° C. was the initial viscosity. If it is less than 1.3 times, “◯”, if it is 1.3 times or more and less than 2 times, “△”, if it is 2 times or more and less than 5 times, “×”, if it is 5 times or more The storage stability was evaluated as “XX”.
本発明によれば、透明性、密着性、硬度、及び、耐湿熱性に優れる硬化物を得ることができ、かつ、環境への負荷を低減することができる硬化性樹脂組成物を提供することができる。また、本発明によれば、該硬化性樹脂組成物を用いてなる表示素子を提供することができる。
According to the present invention, it is possible to provide a curable resin composition that can obtain a cured product that is excellent in transparency, adhesion, hardness, and heat-and-moisture resistance, and that can reduce the burden on the environment. it can. Moreover, according to this invention, the display element which uses this curable resin composition can be provided.
Claims (6)
- カルボキシル基含有エチレン性不飽和単量体のカルボキシル基に由来する－Ｃ（＝Ｏ）ＯＸ基（Ｘは、水素又は塩形成カチオンである）を有するセグメントと、その他のエチレン性不飽和単量体に由来するセグメントとを有する共重合体である水溶性樹脂、前記水溶性樹脂を架橋することが可能な架橋性官能基を有する架橋性樹脂、及び、水を含有する
ことを特徴とする硬化性樹脂組成物。 Segments having a -C (= O) OX group (X is hydrogen or a salt-forming cation) derived from a carboxyl group of a carboxyl group-containing ethylenically unsaturated monomer, and other ethylenically unsaturated monomers A water-soluble resin that is a copolymer having a segment derived from the above, a cross-linkable resin having a cross-linkable functional group capable of cross-linking the water-soluble resin, and a curability characterized by containing water Resin composition. - 水溶性樹脂中における－Ｃ（＝Ｏ）ＯＸ基を有するセグメントの含有割合が５～２５重量％であることを特徴とする請求項１記載の硬化性樹脂組成物。 2. The curable resin composition according to claim 1, wherein the content ratio of the segment having —C (═O) OX group in the water-soluble resin is 5 to 25% by weight.
- 水溶性樹脂は、重量平均分子量が５０００～５万であることを特徴とする請求項１又は２記載の硬化性樹脂組成物。 3. The curable resin composition according to claim 1, wherein the water-soluble resin has a weight average molecular weight of 5,000 to 50,000.
- 水溶性樹脂の有する－Ｃ（＝Ｏ）ＯＸ基と、架橋性樹脂の有する架橋性官能基とのモル比が－Ｃ（＝Ｏ）ＯＸ基：架橋性官能基＝１：０．１～１：１０であることを特徴とする請求項１、２又は３記載の硬化性樹脂組成物。 The molar ratio of the —C (═O) OX group of the water-soluble resin to the crosslinkable functional group of the crosslinkable resin is —C (═O) OX group: crosslinkable functional group = 1: 0.1 to 1 The curable resin composition according to claim 1, 2 or 3.
- 更に、－Ｎ（Ｈ）Ｃ（＝Ｏ）Ｙ基（Ｙは、炭素数１～３のアルキル基、水酸基、－ＯＮａ基、又は、水素基である）を有するエチレン性不飽和単量体に由来するセグメントを有する樹脂を含有することを特徴とする請求項１、２、３又は４記載の硬化性樹脂組成物。 Further, an ethylenically unsaturated monomer having —N (H) C (═O) Y group (Y is an alkyl group having 1 to 3 carbon atoms, a hydroxyl group, an —ONa group, or a hydrogen group) The curable resin composition according to claim 1, comprising a resin having a segment derived therefrom.
- 請求項１、２、３、４又は５記載の硬化性樹脂組成物からなる硬化物を有することを特徴とする表示素子。 A display element comprising a cured product comprising the curable resin composition according to claim 1, 2, 3, 4 or 5.
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| JP2016564280A JPWO2017073365A1 (en) | 2015-10-27 | 2016-10-14 | Curable resin composition and display element |
| CN201680021555.1A CN107429030A (en) | 2015-10-27 | 2016-10-14 | Hardening resin composition and display element |
| KR1020177024938A KR20180074616A (en) | 2015-10-27 | 2016-10-14 | Curable resin composition and display element |
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| JP2015210813 | 2015-10-27 | ||
| JP2015-210813 | 2015-10-27 | ||
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| JP2016122162 | 2016-06-20 |
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| JP (1) | JPWO2017073365A1 (en) |
| KR (1) | KR20180074616A (en) |
| CN (1) | CN107429030A (en) |
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| CN113874408B (en) * | 2019-05-20 | 2023-09-15 | 株式会社力森诺科 | Composition for aqueous coating liquid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07118356A (en) * | 1994-03-28 | 1995-05-09 | Nippon Oil & Fats Co Ltd | Production of aqueous resin dispersion |
| JPH11158434A (en) * | 1997-11-28 | 1999-06-15 | Kansai Paint Co Ltd | Composition and process for hydrophilization treatment |
| JP2011039360A (en) * | 2009-08-14 | 2011-02-24 | Sumitomo Chemical Co Ltd | Polarizing plate and liquid crystal display device |
| JP2013511597A (en) * | 2009-11-23 | 2013-04-04 | スリーエム イノベイティブ プロパティズ カンパニー | Acrylic pressure sensitive adhesive having aziridinyl-epoxy crosslinking system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5290951B2 (en) * | 2007-02-23 | 2013-09-18 | 株式会社日本触媒 | Water-based resin composition for paint |
| CN102827518A (en) * | 2012-06-01 | 2012-12-19 | 安徽省金盾涂料有限责任公司 | Water paint composition |
| CN103481584B (en) * | 2012-06-11 | 2016-08-10 | 株式会社神户制钢所 | Thin-black-layer-coametal metal sheet |
| KR102301032B1 (en) * | 2013-10-28 | 2021-09-09 | 제온 코포레이션 | Slurry composition for negative electrodes of lithium ion secondary batteries, negative electrode for lithium ion secondary batteries, lithium ion secondary battery and production method |
-
2016
- 2016-10-14 JP JP2016564280A patent/JPWO2017073365A1/en active Pending
- 2016-10-14 CN CN201680021555.1A patent/CN107429030A/en active Pending
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- 2016-10-14 WO PCT/JP2016/080517 patent/WO2017073365A1/en active Application Filing
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07118356A (en) * | 1994-03-28 | 1995-05-09 | Nippon Oil & Fats Co Ltd | Production of aqueous resin dispersion |
| JPH11158434A (en) * | 1997-11-28 | 1999-06-15 | Kansai Paint Co Ltd | Composition and process for hydrophilization treatment |
| JP2011039360A (en) * | 2009-08-14 | 2011-02-24 | Sumitomo Chemical Co Ltd | Polarizing plate and liquid crystal display device |
| JP2013511597A (en) * | 2009-11-23 | 2013-04-04 | スリーエム イノベイティブ プロパティズ カンパニー | Acrylic pressure sensitive adhesive having aziridinyl-epoxy crosslinking system |
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|---|---|
| CN107429030A (en) | 2017-12-01 |
| JPWO2017073365A1 (en) | 2018-08-09 |
| TW201730265A (en) | 2017-09-01 |
| KR20180074616A (en) | 2018-07-03 |
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