JP6220619B2 - Methacrylic copolymer for binder, inorganic fine particle dispersed paste composition, and inorganic fine particle dispersed sheet - Google Patents
Methacrylic copolymer for binder, inorganic fine particle dispersed paste composition, and inorganic fine particle dispersed sheet Download PDFInfo
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- JP6220619B2 JP6220619B2 JP2013205528A JP2013205528A JP6220619B2 JP 6220619 B2 JP6220619 B2 JP 6220619B2 JP 2013205528 A JP2013205528 A JP 2013205528A JP 2013205528 A JP2013205528 A JP 2013205528A JP 6220619 B2 JP6220619 B2 JP 6220619B2
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- Prior art keywords
- monomer
- methacrylic
- inorganic fine
- weight
- fine particle
- Prior art date
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- 239000010419 fine particle Substances 0.000 title claims description 58
- 239000000203 mixture Substances 0.000 title claims description 57
- 239000011230 binding agent Substances 0.000 title claims description 47
- 229920001577 copolymer Polymers 0.000 title claims description 40
- 239000000178 monomer Substances 0.000 claims description 96
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 46
- -1 polytetramethylene Polymers 0.000 claims description 27
- 230000009477 glass transition Effects 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 24
- 125000001424 substituent group Chemical group 0.000 claims description 19
- 239000011521 glass Substances 0.000 claims description 15
- 229920001519 homopolymer Polymers 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 11
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 10
- 125000005641 methacryl group Chemical group 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 7
- 150000002148 esters Chemical group 0.000 claims description 5
- 230000007704 transition Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 description 20
- 239000011347 resin Substances 0.000 description 18
- 229920005989 resin Polymers 0.000 description 18
- 239000010408 film Substances 0.000 description 16
- 239000000843 powder Substances 0.000 description 16
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical group CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 13
- 239000000919 ceramic Substances 0.000 description 13
- 238000000354 decomposition reaction Methods 0.000 description 13
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical group CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 10
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 125000000524 functional group Chemical group 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 8
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 6
- UODXCYZDMHPIJE-UHFFFAOYSA-N menthanol Chemical compound CC1CCC(C(C)(C)O)CC1 UODXCYZDMHPIJE-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005238 degreasing Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 239000002736 nonionic surfactant Substances 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000003985 ceramic capacitor Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000113 methacrylic resin Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 239000001716 (4-methyl-1-propan-2-yl-1-cyclohex-2-enyl) acetate Substances 0.000 description 3
- HBNHCGDYYBMKJN-UHFFFAOYSA-N 2-(4-methylcyclohexyl)propan-2-yl acetate Chemical compound CC1CCC(C(C)(C)OC(C)=O)CC1 HBNHCGDYYBMKJN-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- IGODOXYLBBXFDW-UHFFFAOYSA-N alpha-Terpinyl acetate Chemical compound CC(=O)OC(C)(C)C1CCC(C)=CC1 IGODOXYLBBXFDW-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical group CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 2
- YJTIFIMHZHDNQZ-UHFFFAOYSA-N 2-[2-(2-methylpropoxy)ethoxy]ethanol Chemical compound CC(C)COCCOCCO YJTIFIMHZHDNQZ-UHFFFAOYSA-N 0.000 description 2
- VHNJXLWRTQNIPD-UHFFFAOYSA-N 3-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(O)CCOC(=O)C(C)=C VHNJXLWRTQNIPD-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000013039 cover film Substances 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000013033 iniferter Substances 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
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- 229910052759 nickel Inorganic materials 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229940116411 terpineol Drugs 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DEUGOISHWHDTIR-UHFFFAOYSA-N (1-hydroxy-5,5-dimethylhexyl) 2-methylpropanoate Chemical compound C(C(C)C)(=O)OC(CCCC(C)(C)C)O DEUGOISHWHDTIR-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- ZQXIMYREBUZLPM-UHFFFAOYSA-N 1-aminoethanethiol Chemical compound CC(N)S ZQXIMYREBUZLPM-UHFFFAOYSA-N 0.000 description 1
- OEYNWAWWSZUGDU-UHFFFAOYSA-N 1-methoxypropane-1,2-diol Chemical compound COC(O)C(C)O OEYNWAWWSZUGDU-UHFFFAOYSA-N 0.000 description 1
- MZQZXSHFWDHNOW-UHFFFAOYSA-N 1-phenylpropane-1,2-diol Chemical compound CC(O)C(O)C1=CC=CC=C1 MZQZXSHFWDHNOW-UHFFFAOYSA-N 0.000 description 1
- VWNAITWBRLKIIS-UHFFFAOYSA-N 1-sulfanylpropane-1,1-diol Chemical compound CCC(O)(O)S VWNAITWBRLKIIS-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- HOASSJAMRDRLKQ-UHFFFAOYSA-N 2,2-dimethylpropane;2-methylprop-2-enoic acid Chemical compound CC(C)(C)C.CC(=C)C(O)=O HOASSJAMRDRLKQ-UHFFFAOYSA-N 0.000 description 1
- OOHZIRUJZFRULE-UHFFFAOYSA-N 2,2-dimethylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)C OOHZIRUJZFRULE-UHFFFAOYSA-N 0.000 description 1
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- MIRQGKQPLPBZQM-UHFFFAOYSA-N 2-hydroperoxy-2,4,4-trimethylpentane Chemical compound CC(C)(C)CC(C)(C)OO MIRQGKQPLPBZQM-UHFFFAOYSA-N 0.000 description 1
- XRXANEMIFVRKLN-UHFFFAOYSA-N 2-hydroperoxy-2-methylbutane Chemical compound CCC(C)(C)OO XRXANEMIFVRKLN-UHFFFAOYSA-N 0.000 description 1
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 1
- VBDJOKZUAHMALC-UHFFFAOYSA-N 2-methylbutane;2-methylprop-2-enoic acid Chemical compound CCC(C)C.CC(=C)C(O)=O VBDJOKZUAHMALC-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- ULYIFEQRRINMJQ-UHFFFAOYSA-N 3-methylbutyl 2-methylprop-2-enoate Chemical compound CC(C)CCOC(=O)C(C)=C ULYIFEQRRINMJQ-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- QZYUYQMJDDXMMK-UHFFFAOYSA-N 4-hydroperoxy-2,2,3-trimethylpentane Chemical compound OOC(C)C(C)C(C)(C)C QZYUYQMJDDXMMK-UHFFFAOYSA-N 0.000 description 1
- YKXAYLPDMSGWEV-UHFFFAOYSA-N 4-hydroxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCO YKXAYLPDMSGWEV-UHFFFAOYSA-N 0.000 description 1
- PRKPGWQEKNEVEU-UHFFFAOYSA-N 4-methyl-n-(3-triethoxysilylpropyl)pentan-2-imine Chemical compound CCO[Si](OCC)(OCC)CCCN=C(C)CC(C)C PRKPGWQEKNEVEU-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MURCDOXDAHPNRQ-ZJKZPDEISA-N L-685,458 Chemical compound C([C@@H]([C@H](O)C[C@H](C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CC=1C=CC=CC=1)C(N)=O)CC=1C=CC=CC=1)NC(=O)OC(C)(C)C)C1=CC=CC=C1 MURCDOXDAHPNRQ-ZJKZPDEISA-N 0.000 description 1
- 229910018091 Li 2 S Inorganic materials 0.000 description 1
- 229910008515 Li2O-P2O5-B2O3 Inorganic materials 0.000 description 1
- 229910008674 Li2O—P2O5—B2O3 Inorganic materials 0.000 description 1
- 229910008918 Li2O—V2O5—SiO2 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910012465 LiTi Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
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- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
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- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical group CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
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- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Laminated Bodies (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
Description
本発明は、無機微粒子分散ペースト組成物に使用した場合に、熱劣化が起こりにくく、低温分解性に優れ、かつ、機械的強度の高いシートを得ることが可能なバインダー用メタアクリル共重合体、無機微粒子分散ペースト組成物及び無機微粒子分散シートに関する。 The present invention is a methacrylic copolymer for a binder that, when used in an inorganic fine particle-dispersed paste composition, is less susceptible to thermal degradation, has excellent low-temperature decomposability, and can provide a sheet with high mechanical strength, The present invention relates to an inorganic fine particle dispersed paste composition and an inorganic fine particle dispersed sheet.
近年、導電性粉末、セラミック粉末、ガラス粒子等の無機微粒子をバインダー樹脂に分散させた無機微粒子分散ペースト組成物が、様々な形状の焼成体を得るために用いられている。例えば、導電性粉末として金属微粒子を分散させたペースト組成物は、回路形成やコンデンサーの製造等に用いられ、セラミック粉末やガラス粒子を分散させたセラミックペーストやガラスペーストは、プラズマディスプレイパネル（以下、ＰＤＰともいう）の誘電体層の製造や積層セラミックコンデンサの製造等に用いられている。 In recent years, an inorganic fine particle-dispersed paste composition in which inorganic fine particles such as conductive powder, ceramic powder, and glass particles are dispersed in a binder resin has been used to obtain fired bodies having various shapes. For example, a paste composition in which metal fine particles are dispersed as a conductive powder is used for circuit formation, capacitor production, etc., and ceramic paste or glass paste in which ceramic powder or glass particles are dispersed is a plasma display panel (hereinafter, (Also referred to as PDP) for manufacturing dielectric layers and multilayer ceramic capacitors.
積層セラミックコンデンサ等の積層型の電子部品は、例えば、特許文献１に開示されているように、一般に次のような工程を経て製造される。
まず、バインダー樹脂を有機溶剤に溶解した溶液に、可塑剤、分散剤等を添加した後、セラミック原料粉末を加える。次いで、ボールミル等により均一に混合し脱泡を行って一定粘度を有するセラミックスラリー組成物を得る。得られたセラミックスラリー組成物をドクターブレード、リバースロールコーター等を用いて、離型処理したポリエチレンテレフタレートフィルム又はステンレス鋼プレート等の支持体面で流延成形する。次いで、加熱等により有機溶剤等の揮発分を溜去させた後、支持体から剥離してセラミックグリーンシートを得る。
A multilayer electronic component such as a multilayer ceramic capacitor is generally manufactured through the following steps as disclosed in Patent Document 1, for example.
First, after adding a plasticizer, a dispersing agent, etc. to the solution which melt | dissolved binder resin in the organic solvent, ceramic raw material powder is added. Next, it is uniformly mixed by a ball mill or the like and defoamed to obtain a ceramic slurry composition having a constant viscosity. The obtained ceramic slurry composition is cast-molded on a support surface such as a polyethylene terephthalate film or a stainless steel plate which has been subjected to mold release treatment using a doctor blade, a reverse roll coater or the like. Next, volatile components such as an organic solvent are distilled off by heating or the like, and then peeled off from the support to obtain a ceramic green sheet.
得られたセラミックグリーンシート上に内部電極となる導電ペーストをスクリーン印刷等により塗工したものを交互に複数枚積み重ね、加熱圧着して積層体を製造する。この積層体中に含まれるバインダー樹脂成分等を熱分解させて除去する処理（いわゆる「脱脂処理」）を行った後、焼成して得られたセラミック焼成物の端面に外部電極を焼結によって形成させる工程を経て、積層セラミックコンデンサが得られる。 On the obtained ceramic green sheet, a plurality of conductive pastes applied as internal electrodes applied by screen printing or the like are alternately stacked and thermocompression bonded to produce a laminate. Forming external electrodes on the end face of the fired ceramic product after pyrolyzing and removing the binder resin component contained in the laminate (so-called “degreasing”) Through the process, a multilayer ceramic capacitor is obtained.
近年、積層セラミックコンデンサ等の電子部品に対しては、軽量小型化及び価格の低廉化が強く求められている。従って、これらを製造する際に必要となるセラミック積層体においては一層当たりのシート厚みを薄くしたり、さらなる多層化を推し進めたりすることが行われる一方、その内部電極を形成するにあたっては高価なＰｔ、Ｐｄ、Ａｇ等に代わる安価な卑金属材料、例えば、Ｎｉや高周波特性に優れたＣｕ等を主成分として含む導電性ペーストを使用することが行われている。 In recent years, electronic parts such as multilayer ceramic capacitors have been strongly demanded to be lighter, smaller and cheaper. Accordingly, in the ceramic laminate required for manufacturing these, it is possible to reduce the sheet thickness per layer or to further increase the number of layers. On the other hand, expensive Pt is required for forming the internal electrode. An inexpensive base metal material replacing Pd, Ag, or the like, for example, a conductive paste containing Ni or Cu having excellent high frequency characteristics as a main component is used.
このような卑金属材料を主成分とする導電性ペーストを用いて内部電極を形成する場合、製造工程の途中で、積層素体の脱バインダー処理及び焼成処理を非酸化性雰囲気中で行う必要があるが、特に、導電性ペーストがＣｕを主成分とするものである場合には、酸素含有雰囲気中で高温加熱すると、良質の絶縁体である酸化物が形成されてしまうため、非酸化性雰囲気中で焼成温度を低くして焼成する必要がある。
しかしながら、非酸化性雰囲気中での焼成を行った際には、グリーンシート中のバインダーが炭素として残存し、炭素の存在に起因して発生した気孔（ポア）が焼成体中に残ることになるため、製造後の電子部品における特性上の不都合が生じていた。
When forming an internal electrode using a conductive paste mainly composed of such a base metal material, it is necessary to perform a debinding process and a baking process of the multilayer body in a non-oxidizing atmosphere during the manufacturing process. However, particularly when the conductive paste is mainly composed of Cu, heating at a high temperature in an oxygen-containing atmosphere results in the formation of a high-quality insulator oxide. Therefore, it is necessary to lower the baking temperature.
However, when firing in a non-oxidizing atmosphere, the binder in the green sheet remains as carbon, and pores (pores) generated due to the presence of carbon remain in the fired body. For this reason, there has been a problem in characteristics of the electronic component after manufacture.
そこで、低温分解性に優れるアクリル樹脂をバインダーとして用いることが検討されている。即ち、アクリル樹脂は低温下においても解重合（重合体が単量体に分解する化学反応）を起こし得るから、グリーンシート中における炭素の残存率（以下、残炭率という）を低下させることが可能であると考えられるからである。例えば、特許文献２には、高温残留重量が極めて少ないアクリル系樹脂を用いる方法が開示されている。
しかし、特許文献２に記載の発明では、焼結温度が高温条件の場合に対応したものであり、４００℃以下の低温分解のプロセスには対応していないものであった。
Then, using the acrylic resin excellent in low temperature decomposability as a binder is examined. That is, the acrylic resin can undergo depolymerization (chemical reaction in which the polymer is decomposed into monomers) even at low temperatures, so that the carbon residual ratio (hereinafter referred to as the residual carbon ratio) in the green sheet can be reduced. This is because it is considered possible. For example, Patent Document 2 discloses a method using an acrylic resin having a very low high-temperature residual weight.
However, the invention described in Patent Document 2 corresponds to the case where the sintering temperature is a high temperature condition, and does not correspond to the low temperature decomposition process at 400 ° C. or lower.
また、アクリル樹脂は、例えば、非特許文献１に記載のように、ＩＴＯ等の透明電極にも使用されているが、３００℃以上の高温に曝されることで抵抗値が上昇したり、一部の焼結磁石でも４００℃の高温で磁性の低下が顕著になったりする等のように、バインダー脱脂プロセスで無機材料が熱劣化する問題が発生していた。 In addition, as described in Non-Patent Document 1, for example, acrylic resin is also used for transparent electrodes such as ITO. However, the resistance value increases when exposed to a high temperature of 300 ° C. or higher. Even in some sintered magnets, there was a problem that the inorganic material was thermally deteriorated in the binder degreasing process, such as a significant decrease in magnetism at a high temperature of 400 ° C.
本発明者らは、上記現状に鑑み、無機微粒子分散ペースト組成物に使用した場合に、熱劣化が起こりにくく、低温分解性に優れ、かつ、機械的強度の高いシートを得ることが可能なバインダー用メタアクリル共重合体、無機微粒子分散ペースト組成物及び無機微粒子分散シートを提供することを目的とする。 In view of the above situation, the present inventors, when used in an inorganic fine particle-dispersed paste composition, are less susceptible to thermal degradation, have excellent low-temperature decomposability, and can obtain a sheet having high mechanical strength. It is an object to provide a methacrylic copolymer, an inorganic fine particle dispersed paste composition, and an inorganic fine particle dispersed sheet.
本発明は、３種以上のメタアクリルモノマーから形成されるバインダー用メタアクリル共重合体であって、メタクリル酸ｎブチルに由来するセグメントを有し、前記メタクリル酸ｎブチルに由来するセグメントの含有量が２０〜６０重量％であり、かつ、ガラス転移温度が１０〜３５℃、重量平均分子量が１０万〜３００万であり、前記メタアクリルモノマーは、メタクリル酸エステル置換基に分岐構造を有する置換基を有し、かつ、前記分岐構造を有する置換基の主鎖の炭素数が３以上であるモノマーを含み、前記モノマーに由来するセグメントの含有量が４０重量％以上であり、メタアクリル酸エステル置換基にグリシジル基を有するモノマーを含み、かつ、前記メタアクリル酸エステル置換基にグリシジル基を有するモノマーに由来するセグメントの含有量が１〜１０重量％であるバインダー用メタアクリル共重合体である。
以下に本発明を詳述する。
The present invention is a methacrylic copolymer for binders formed from three or more kinds of methacrylic monomers, having a segment derived from n-butyl methacrylate, and a content of the segment derived from n-butyl methacrylate Is 20 to 60% by weight, the glass transition temperature is 10 to 35 ° C., the weight average molecular weight is 100,000 to 3 million, and the methacrylic monomer is a substituent having a branched structure in a methacrylic acid ester substituent. It has, and includes monomers carbon atoms in the main chain of the substituent having a branched structure is 3 or more state, and are content 40 wt% or more segments derived from said monomers, methacrylic acid ester A monomer having a glycidyl group as a substituent, and derived from a monomer having a glycidyl group in the methacrylic ester substituent Content segment as a binder for methacrylic copolymer from 1 to 10 wt%.
The present invention is described in detail below.
本発明者らは、鋭意検討した結果、メタクリル酸ｎブチルを含む３種以上のメタアクリルモノマーを共重合成分とするメタアクリル共重合体を、無機微粒子分散用のバインダー樹脂として用い、ガラス転移温度及び重量平均分子量を所定の範囲内とした場合、熱による劣化を最小限に止めつつ、低温分解性に優れ、かつ、機械的強度の高いシートを得ることが可能となることを見出し、本発明を完成させるに至った。 As a result of intensive studies, the present inventors have used a methacrylic copolymer having three or more methacrylic monomers containing n-butyl methacrylate as a copolymerization component as a binder resin for dispersing inorganic fine particles, and having a glass transition temperature. And when the weight average molecular weight is within a predetermined range, it has been found that it is possible to obtain a sheet having excellent low-temperature decomposability and high mechanical strength while minimizing deterioration due to heat. It came to complete.
本発明のバインダー用メタアクリル共重合体は、３種以上のメタアクリルモノマーを共重合成分とする。メタアクリルモノマーから重合されるポリマーは、そのモノマー固有の天井温度と言われる温度で分解を開始する。例えば、メタクリル酸メチルの天井温度は２００℃未満だが、真空中３０分間加熱した時のポリマー重量損失が５０％になる温度は３２７℃と天井温度と隔たりがある。これは天井温度以上の領域でも分解と再重合反応の平衡反応であるため、環境温度が上昇するに従い分解反応が優先されるためである。メタアクリルモノマーの天井温度はモノマー毎に大きく異なるため、複数のモノマーを組み合わせることによって、ある温度域で発生する分解モノマーの量を少なくすることで再結合する確率を低くすることができる。即ち、複数のモノマーと組み合わせることによって、天井温度と実際の分解温度との隔たりを小さくすることが出来る。 The methacrylic copolymer for a binder of the present invention contains three or more methacrylic monomers as a copolymerization component. The polymer polymerized from the methacrylic monomer starts to decompose at a temperature called the ceiling temperature unique to the monomer. For example, although the ceiling temperature of methyl methacrylate is less than 200 ° C., the temperature at which the polymer weight loss becomes 50% when heated in a vacuum for 30 minutes is 327 ° C., which is different from the ceiling temperature. This is because the decomposition reaction is prioritized as the environmental temperature rises because it is an equilibrium reaction between decomposition and repolymerization reaction even in the region above the ceiling temperature. Since the ceiling temperature of the methacrylic monomer varies greatly from monomer to monomer, the probability of recombination can be lowered by reducing the amount of decomposition monomer generated in a certain temperature range by combining a plurality of monomers. That is, by combining with a plurality of monomers, the distance between the ceiling temperature and the actual decomposition temperature can be reduced.
本発明のバインダー用メタアクリル共重合体は、メタクリル酸ｎブチルに由来するセグメントを有する。
上記セグメントを有することで、低温分解性に優れ、かつ、機械的強度の高いシートを得ることが可能となる。
メタクリル酸ｎブチルに由来するセグメントは焼結時に煤になることを防ぐ。同様の効果はメタクリル酸メチルでも得られるが、メタクリル酸メチルを用いた場合、セグメントのＴｇが高く、樹脂が脆くなりやすく、分解終了温度が高くなりやすい。その為、メタクリル酸メチルセグメントを導入するには後述するメタクリル酸エステル置換基に分岐構造を有するモノマーを多く導入しなければならない。その為、メタクリル酸メチルと合わせて用いることが望ましいセグメント成分が、メタクリル酸イソブチルである。
上記メタクリル酸ｎブチルに由来するセグメントは、セグメントのＴｇが適当であり、樹脂のＴｇが１０〜３０℃の樹脂組成を形成しやすくなることから、シートを強靱にすることが可能となる。
The methacrylic copolymer for binder of the present invention has a segment derived from n-butyl methacrylate.
By having the segment, it is possible to obtain a sheet having excellent low-temperature decomposability and high mechanical strength.
Segments derived from n-butyl methacrylate prevent wrinkling during sintering. The same effect can be obtained with methyl methacrylate, but when methyl methacrylate is used, the Tg of the segment is high, the resin tends to be brittle, and the decomposition end temperature tends to be high. Therefore, in order to introduce a methyl methacrylate segment, a large amount of monomers having a branched structure must be introduced into the methacrylate ester substituent described later. Therefore, a segment component that is preferably used in combination with methyl methacrylate is isobutyl methacrylate.
The segment derived from the above-mentioned n-butyl methacrylate has an appropriate Tg of the segment and can easily form a resin composition having a Tg of 10 to 30 ° C. Therefore, the sheet can be toughened.
上記メタクリル酸ｎブチルに由来するセグメントの含有量の下限は１０重量％、上限は６０重量％である。上記メタクリル酸ｎブチルに由来するセグメントの含有量が１０重量％未満であると、焼成後の有機残渣が多くなり、６０重量％を超えると、低温分解化させにくくなる。好ましい下限は３０重量％、好ましい上限は５０重量％である。 The lower limit of the content of the segment derived from n-butyl methacrylate is 10% by weight, and the upper limit is 60% by weight. When the content of the segment derived from n-butyl methacrylate is less than 10% by weight, the organic residue after firing increases, and when it exceeds 60% by weight, it is difficult to decompose at low temperature. A preferred lower limit is 30% by weight and a preferred upper limit is 50% by weight.
上記メタアクリルモノマーとしては、メタクリル酸ｎブチル以外に、メタクリル酸エステル置換基に分岐構造を有する置換基を有し、かつ、前記分岐構造を有する置換基の主鎖の炭素数が３以上であるモノマーを用いることが好ましい。このようなモノマーとメタクリル酸ｎブチルとを組み合わせた場合、３５０℃という低温条件でも分解可能なバインダー用メタアクリル共重合体が得られる。 As the methacrylic monomer, in addition to n-butyl methacrylate, the methacrylic acid ester substituent has a substituent having a branched structure, and the main chain of the substituent having the branched structure has 3 or more carbon atoms. It is preferable to use a monomer. When such a monomer and n-butyl methacrylate are combined, a methacrylic copolymer for a binder that can be decomposed even at a low temperature of 350 ° C. is obtained.
上記メタクリル酸エステル置換基に分岐構造を有する置換基を有し、かつ、前記分岐構造を有する置換基の主鎖の炭素数が３以上であるモノマーに由来するセグメントの含有量の好ましい下限は４０重量％、好ましい上限は８０重量％である。上記メタクリル酸エステル置換基に分岐構造を有する置換基を有し、かつ、前記分岐構造を有する置換基の主鎖の炭素数が３以上であるモノマーに由来するセグメントの含有量が４０重量％未満であると、低温分解化させられなくなることがあり、８０重量％を超えると、焼成後の有機残渣が多くなることがある。より好ましい下限は４５重量％、より好ましい上限は７０重量％、特に好ましい上限は６０重量％である。 The preferable lower limit of the content of the segment derived from the monomer having a substituent having a branched structure in the methacrylic acid ester substituent and having a main chain of 3 or more carbon atoms of the substituent having the branched structure is 40. The preferred upper limit is 80% by weight. The methacrylic acid ester substituent has a substituent having a branched structure, and the content of a segment derived from a monomer having a main chain having 3 or more carbon atoms of the substituent having the branched structure is less than 40% by weight If it is, it may become impossible to decompose at low temperature, and if it exceeds 80% by weight, the organic residue after firing may increase. A more preferred lower limit is 45% by weight, a more preferred upper limit is 70% by weight, and a particularly preferred upper limit is 60% by weight.
上記メタクリル酸エステル置換基に分岐構造を有する置換基を有し、かつ、前記分岐構造を有する置換基の主鎖の炭素数が３以上であるモノマーとしては、例えば、イソブチルメタクリレート、セクブチルメタクリレート、イソペンタンメタクリレート、イソペンチルメタクリレート、ネオペンタンメタクリレート、ネオペンチルメタクリレート、ターシャリーペンチルメタクリレート、イソデシルメタクリレート等が挙げられる。
なかでも、イソデシルメタクリレートは、後述するガラス転移温度を低下させることが可能となることから、好ましく用いることができる。
Examples of the monomer having a substituent having a branched structure in the methacrylate ester substituent and having 3 or more carbon atoms in the main chain of the substituent having the branched structure include isobutyl methacrylate, secbutyl methacrylate, Examples include isopentane methacrylate, isopentyl methacrylate, neopentane methacrylate, neopentyl methacrylate, tertiary pentyl methacrylate, and isodecyl methacrylate.
Among these, isodecyl methacrylate can be preferably used because it can lower the glass transition temperature described later.
上記メタアクリルモノマーとしては、さらに、メタクリル酸エステル置換基に炭素数が３以下の直鎖状若しくは分岐状のアルキル基、または、炭素数が６以下の環状のアルキル基を有し、かつ、ホモポリマーでのガラス転移温度が６５℃以上であるモノマーが好ましい。
上記メタクリル酸エステル置換基に炭素数が３以下の直鎖状若しくは分岐状のアルキル基、または、炭素数が６以下の環状のアルキル基を有し、かつ、ホモポリマーでのガラス転移温度が６５℃以上であるモノマーを用いることによって、バインダー用メタアクリル共重合体全体のガラス転移温度が低くても、バインダー用メタアクリル共重合体の弾性を高めて降伏点を持たせることが出来る。そのため、得られたバインダー用メタアクリル共重合体を含有する無機微粒子分散ペースト組成物を、無機微粒子分散シートに加工する際のハンドリング性が向上し、加工を容易にすることができる。
上記メタアクリルモノマーのホモポリマーでのガラス転移温度の好ましい上限は、１１０℃である。
The methacrylic monomer further includes a linear or branched alkyl group having 3 or less carbon atoms or a cyclic alkyl group having 6 or less carbon atoms in the methacrylate ester substituent, Monomers having a glass transition temperature of 65 ° C. or higher in the polymer are preferred.
The methacrylic acid ester substituent has a linear or branched alkyl group having 3 or less carbon atoms or a cyclic alkyl group having 6 or less carbon atoms, and has a glass transition temperature of 65 in a homopolymer. By using a monomer having a temperature of not lower than ° C., the elasticity of the binder methacrylic copolymer can be increased to give a yield point even if the glass transition temperature of the entire methacrylic copolymer for binder is low. Therefore, the handling property at the time of processing the obtained inorganic fine particle dispersed paste composition containing the obtained methacrylic copolymer for binder into an inorganic fine particle dispersed sheet is improved, and the processing can be facilitated.
The upper limit with a preferable glass transition temperature in the homopolymer of the said methacryl monomer is 110 degreeC.
上記、メタクリル酸エステル置換基に炭素数が３以下の直鎖状若しくは分岐状のアルキル基、または、炭素数が６以下の環状のアルキル基を有し、かつ、ホモポリマーでのガラス転移温度が６５℃以上であるメタアクリルモノマーとしては、特に限定されないが、例えば、メチルメタクリレート（ホモポリマーでのガラス転移温度１０５℃）、エチルメタクリレート（ホモポリマーでのガラス転移温度６５℃）、シクロヘキシルメタクリレート（ホモポリマーでのガラス転移温度６６℃）、イソプロピルメタクリレート（ホモポリマーでのガラス転移温度８１℃）からなる群より選択される少なくとも１種からなるメタアクリルモノマーが好ましい。
これらのなかでは、焼結時の残渣を少なくするためにも、単量体の分子量が小さく、分解時に揮発性が高い、メチルメタクリレートが特に好ましい。
上記、メタクリル酸エステル置換基に炭素数が３以下の直鎖状若しくは分岐状のアルキル基、または、炭素数が６以下の環状のアルキル基を有し、かつ、ホモポリマーでのガラス転移温度が６５℃以上であるメタアクリルモノマーに由来するセグメントの含有量の好ましい下限は１５重量％、好ましい上限は６０重量％である。上記メタクリル酸エステル置換基に炭素数が３以下の直鎖状若しくは分岐状のアルキル基、または、炭素数が６以下の環状のアルキル基を有し、かつ、ホモポリマーでのガラス転移温度が６５℃以上であるメタアクリルモノマーに由来するセグメントの含有量が、１５重量％未満であると、バインダー用メタアクリル共重合体の弾性を高める効果が低くなることがあり、６０重量％を超えると、バインダー用メタアクリル共重合体全体のＴｇが高くなりすぎ、バインダー用メタアクリル共重合体を含有する無機微粒子分散ペースト組成物を用いた無機微粒子分散シートが脆くなる可能性がある。より好ましい下限は２０重量％、より好ましい上限は５０重量％、特に好ましい上限は４０重量％である。
The methacrylic acid ester substituent has a linear or branched alkyl group having 3 or less carbon atoms or a cyclic alkyl group having 6 or less carbon atoms, and has a glass transition temperature in a homopolymer. The methacrylic monomer having a temperature of 65 ° C. or higher is not particularly limited. For example, methyl methacrylate (glass transition temperature of 105 ° C. in homopolymer), ethyl methacrylate (glass transition temperature of 65 ° C. in homopolymer), cyclohexyl methacrylate (homopolymer). A methacryl monomer consisting of at least one selected from the group consisting of a glass transition temperature of 66 ° C. in a polymer and isopropyl methacrylate (a glass transition temperature of 81 ° C. in a homopolymer) is preferable.
Among these, methyl methacrylate is particularly preferable because the molecular weight of the monomer is small and volatility is high during decomposition in order to reduce the residue during sintering.
The methacrylic acid ester substituent has a linear or branched alkyl group having 3 or less carbon atoms or a cyclic alkyl group having 6 or less carbon atoms, and has a glass transition temperature in a homopolymer. The minimum with preferable content of the segment derived from the methacryl monomer which is 65 degreeC or more is 15 weight%, and a preferable upper limit is 60 weight%. The methacrylic acid ester substituent has a linear or branched alkyl group having 3 or less carbon atoms or a cyclic alkyl group having 6 or less carbon atoms, and has a glass transition temperature of 65 in a homopolymer. When the content of the segment derived from the methacrylic monomer having a temperature of ℃ or higher is less than 15% by weight, the effect of increasing the elasticity of the methacrylic copolymer for the binder may be lowered. The Tg of the entire methacrylic copolymer for the binder becomes too high, and the inorganic fine particle dispersed sheet using the inorganic fine particle dispersed paste composition containing the methacrylic copolymer for the binder may become brittle. A more preferred lower limit is 20% by weight, a more preferred upper limit is 50% by weight, and a particularly preferred upper limit is 40% by weight.
上記メタアクリルモノマーとしては、さらに、メタアクリル酸エステル置換基に極性基を有するモノマーが好ましい。メタアクリル酸エステル置換基に極性基を有するモノマーを用いることによって、バインダー用メタアクリル共重合体中に水素結合またはイオン相互作用による強固な相互作用を形成することが出来、強度をさらに高めることが出来る。上記メタアクリル酸エステル置換基中の極性基としては、特に限定されないが、水酸基、カルボキシル基、アミノ基等が挙げられる。 As said methacryl monomer, the monomer which has a polar group in a methacrylic acid ester substituent further is preferable. By using a monomer having a polar group as a methacrylic acid ester substituent, a strong interaction by hydrogen bonding or ionic interaction can be formed in the methacrylic copolymer for binder, and the strength can be further increased. I can do it. Although it does not specifically limit as a polar group in the said methacrylic acid ester substituent, A hydroxyl group, a carboxyl group, an amino group, etc. are mentioned.
上記メタアクリル酸エステル置換基に極性基を有するモノマーとしては、特に限定されないが、例えば、２−ヒドロキシエチルメタクリレート、３−ヒドロキシプロピルメタクリレート、２−ヒドロキシプロピルメタクリレート、４−ヒドロキシブチルメタクリレート、２−ヒドロキシブチルメタクリレート、３−ヒドロキシブチルメタクリレート、グリシジルメタクリレート、グリセロールモノメタクリレート等が挙げられる。中でも、２−ヒドロキシプロピルメタクリレート、２−ヒドロキシブチルメタクリレート、３−ヒドロキシブチルメタクリレートはバインダー用メタアクリル共重合体のＴｇを下げることが出来るため、好ましい。 The monomer having a polar group in the methacrylic acid ester substituent is not particularly limited. For example, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxy Examples include butyl methacrylate, 3-hydroxybutyl methacrylate, glycidyl methacrylate, and glycerol monomethacrylate. Among these, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, and 3-hydroxybutyl methacrylate are preferable because Tg of the methacrylic copolymer for binder can be lowered.
上記メタアクリル酸エステル置換基に極性基を有するモノマーに由来するセグメントの含有量の好ましい下限は１重量％、好ましい上限は１０重量％である。上記メタアクリル酸エステル置換基に極性基を有するモノマーに由来するセグメントの含有量が、１重量％未満であると、相互作用の効果が低くなることがあり、１０重量％を超えると、低温での熱分解性が損なわれたり、無機微粒子に付着する煤が多くなり、焼結体の残留炭素が多くなったりすることがある。より好ましい下限は３重量％、より好ましい上限は８重量％である。 The minimum with preferable content of the segment originating in the monomer which has a polar group in the said methacrylic acid ester substituent is 1 weight%, and a preferable upper limit is 10 weight%. When the content of the segment derived from the monomer having a polar group in the methacrylic acid ester substituent is less than 1% by weight, the interaction effect may be lowered. In some cases, the thermal decomposability of the sintered body is impaired, the amount of soot adhering to the inorganic fine particles increases, and the residual carbon of the sintered body increases. A more preferred lower limit is 3% by weight, and a more preferred upper limit is 8% by weight.
上記メタクリルモノマーは、メタアクリル酸エステル置換基にグリシジル基を有するモノマーを含むことが好ましい。特に、上記グリシジル基を有することで、例えば、極性基を有するモノマーと併用した場合、グリシジル基と極性基とが乾燥プロセスにおいて化学結合を形成し、積層体を作製する際に、溶剤等で侵されにくくすることが可能となる。
本発明のバインダー用メタアクリル共重合体において、上記メタアクリル酸エステル置換基にグリシジル基を有するモノマーに由来するセグメントの含有量の好ましい下限は１重量％、好ましい上限は１０重量％である。上記メタアクリル酸エステル置換基にグリシジル基を有するモノマーに由来するセグメントの含有量が、１重量％未満であると、相互作用の効果が低くなることがあり、１０重量％を超えると、低温での熱分解性が損なわれたり、無機微粒子に付着する煤が多くなり、焼結体の残留炭素が多くなったりすることがある。より好ましい下限は３重量％、より好ましい上限は８重量％である。
The methacrylic monomer preferably includes a monomer having a glycidyl group in the methacrylic acid ester substituent. In particular, when the glycidyl group is used, for example, when used in combination with a monomer having a polar group, the glycidyl group and the polar group form a chemical bond in the drying process, so that a laminate or the like is eroded by a solvent. It becomes possible to make it difficult to be done.
In the methacrylic copolymer for a binder of the present invention, the preferable lower limit of the content of the segment derived from the monomer having a glycidyl group in the methacrylic ester substituent is 1% by weight, and the preferable upper limit is 10% by weight. When the content of the segment derived from the monomer having a glycidyl group in the methacrylic acid ester substituent is less than 1% by weight, the interaction effect may be lowered. When the content exceeds 10% by weight, In some cases, the thermal decomposability of the sintered body is impaired, the amount of soot adhering to the inorganic fine particles increases, and the residual carbon of the sintered body increases. A more preferred lower limit is 3% by weight, and a more preferred upper limit is 8% by weight.
上記メタアクリルモノマーとしては、その一部又は全部のエステル置換基にポリテトラメチレンオキシドのセグメントを含むモノマーが好ましい。このようなエーテル鎖を有するグラフトモノマーを用いることによって、より分解温度を低温化させることができ、バインダー樹脂のＴｇを飛躍的に下げることが出来る為、メタクリル樹脂の脆さを改善することができる。中でもポリテトラメチレングリコールのセグメントを有するモノマーは低残炭性と両立化させることが出来る為、好適に用いることが出来る。 As said methacryl monomer, the monomer which contains the segment of polytetramethylene oxide in the ester substituent of the one part or all part is preferable. By using such a graft monomer having an ether chain, the decomposition temperature can be further lowered, and the Tg of the binder resin can be drastically lowered, so that the brittleness of the methacrylic resin can be improved. . Among them, a monomer having a polytetramethylene glycol segment can be preferably used because it can be made compatible with low residual carbon.
上記ポリテトラメチレンオキシドのグラフトモノマーとしては、例えば、ポリテトラメチレングリコールモノメタクリレート、ポリ（エチレングリコール・ポリテトラメチレングリコール）モノメタクリレート、ポリ（プロピレングリコール・テトラメチレングリコール）モノメタクリレート、プロピレングリコール・ポリブチレングリコールモノメタクリレート、メトキシポリテトラメチレングリコールモノメタクリレート、メトキシポリ（エチレングリコール・ポリテトラメチレングリコール）モノメタクリレート、メトキシポリ（プロピレングリコール・テトラメチレングリコール）モノメタクリレート、メトキシプロピレングリコール・ポリブチレングリコールモノメタクリレート等を用いることができる。 Examples of the polytetramethylene oxide graft monomer include polytetramethylene glycol monomethacrylate, poly (ethylene glycol / polytetramethylene glycol) monomethacrylate, poly (propylene glycol / tetramethylene glycol) monomethacrylate, propylene glycol / polybutylene. Use glycol monomethacrylate, methoxypolytetramethylene glycol monomethacrylate, methoxypoly (ethylene glycol / polytetramethylene glycol) monomethacrylate, methoxypoly (propylene glycol / tetramethylene glycol) monomethacrylate, methoxypropylene glycol / polybutylene glycol monomethacrylate, etc. Can do.
上記ポリテトラメチレンオキシドのグラフトモノマーに由来するセグメントの含有量の好ましい下限は１重量％、好ましい上限は２０重量％である。上記ポリテトラメチレンオキシドのグラフトモノマーに由来するセグメントの含有量が１重量％未満であると、低温分解化効果が低くなることがあり、２０重量％を超えると、ペースト化した際に無機粉の分散性が悪くなることがある。より好ましい下限は２重量％、より好ましい上限は１０重量％である。 The preferable lower limit of the content of the segment derived from the graft monomer of the polytetramethylene oxide is 1% by weight, and the preferable upper limit is 20% by weight. When the content of the segment derived from the graft monomer of the polytetramethylene oxide is less than 1% by weight, the low-temperature decomposition effect may be lowered. When the content exceeds 20% by weight, Dispersibility may deteriorate. A more preferred lower limit is 2% by weight, and a more preferred upper limit is 10% by weight.
上記ポリテトラメチレンオキシドのテトラメチレンオキシドの繰り返し数の好ましい下限は２、好ましい上限は２０である。上記テトラメチレンオキシドの繰り返し数が２未満であると、低Ｔｇ化によるメタクリル樹脂の脆さを改善する効果が低くなることがあり、２０を超えると、重合した際にゲル化を起こしやすくなることがある。 The preferable lower limit of the tetramethylene oxide repeating number of the polytetramethylene oxide is 2, and the preferable upper limit is 20. If the number of repeating tetramethylene oxide is less than 2, the effect of improving the brittleness of the methacrylic resin due to the low Tg may be reduced, and if it exceeds 20, gelation is likely to occur during polymerization. There is.
上述したメタアクリルモノマーの組み合わせとしては、メタクリル酸ｎブチルと、メタクリル酸エステル置換基に分岐構造を有する置換基を有し、かつ、前記分岐構造を有する置換基の主鎖の炭素数が３以上であるモノマーとの組み合わせ、及び、メタクリル酸ｎブチルと、メタクリル酸エステル置換基に分岐構造を有する置換基を有し、かつ、前記分岐構造を有する置換基の主鎖の炭素数が３以上であるモノマーと、エステル置換基にポリテトラメチレンオキシドのセグメントを含むモノマーとの組み合わせが好ましい。
また、これらに、極性基を有するメタアクリルモノマーやエステル置換基の炭素数が１〜３のメタアクリルモノマーを加える組み合わせも好ましい。
具体的には、メタクリル酸ｎブチルとメタクリル酸イソブチルとメタクリル酸イソデシルとの組み合わせ、及び、メタクリル酸ｎブチルとメタクリル酸イソブチルとポリテトラメチレングリコールのセグメントを有するメタクリル系グラフトモノマーとの組み合わせが好ましい。
また、メタクリル酸ｎブチルとメタクリル酸イソブチルと２−ヒドロキシプロピルメタクリレートとの組み合わせ、及び、メタクリル酸ｎブチルとメタクリル酸メチルとメタクリル酸イソブチルとの組み合わせも好ましい。
更に、メタクリル酸イソデシル（ｉＤＭＡ）、イソプロピルメタクリレート（ｉＰＭＡ）、２−ヒドロキシエチルメタクリレート（ＨＥＭＡ）、グリシジルメタクリレート（ＧＭＡ）、２−ヒドロキシプロピルメタクリレート（２−ＨＰＭＡ）、ポリテトラメチレングリコールのセグメントを有するメタクリル系グラフトモノマー（ＰＴＭＯＡ）、及び、メタクリル酸エチルから選択される少なくとも１種のメタアクリルモノマーを加え、４種以上のメタアクリルモノマーを組み合わせてもよい。
As a combination of the above-mentioned methacrylic monomers, n-butyl methacrylate and a methacrylate ester substituent having a substituent having a branched structure, and the main chain of the substituent having the branched structure has 3 or more carbon atoms A combination of the monomer, and n-butyl methacrylate and a substituent having a branched structure in the methacrylate ester substituent, and the main chain of the substituent having the branched structure has 3 or more carbon atoms A combination of a monomer and a monomer containing a polytetramethylene oxide segment in the ester substituent is preferred.
A combination of a methacryl monomer having a polar group or a methacryl monomer having 1 to 3 carbon atoms in the ester substituent is also preferable.
Specifically, a combination of nbutyl methacrylate, isobutyl methacrylate and isodecyl methacrylate, and a combination of a methacrylic graft monomer having segments of nbutyl methacrylate, isobutyl methacrylate and polytetramethylene glycol are preferable.
A combination of nbutyl methacrylate, isobutyl methacrylate and 2-hydroxypropyl methacrylate and a combination of nbutyl methacrylate, methyl methacrylate and isobutyl methacrylate are also preferred.
Further, methacrylic acid having segments of isodecyl methacrylate (iDMA), isopropyl methacrylate (iPMA), 2-hydroxyethyl methacrylate (HEMA), glycidyl methacrylate (GMA), 2-hydroxypropyl methacrylate (2-HPMA), and polytetramethylene glycol. At least one methacrylic monomer selected from a system graft monomer (PTMOA) and ethyl methacrylate may be added, and four or more methacrylic monomers may be combined.
本発明のバインダー用メタアクリル共重合体は、ポリスチレン換算による重量平均分子量の下限が１０万、上限が３００万である。上記重量平均分子量が１０万未満であると、強度の低下や、ペースト作製時に粘度が充分に得られず貯蔵安定性が悪くなったり、シート化した際の強度が著しく低くなったりする。上記重量平均分子量が３００万を超えると、得られる無機微粒子分散ペースト組成物の糸曳性や溶媒への溶解性に問題が生じる。好ましい下限は１０万、好ましい上限は１００万である。
なお、ポリスチレン換算による重量平均分子量の測定は、カラムとして例えばＳＨＯＫＯ社製カラムＬＦ−８０４等を用いてゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定を行うことで得ることができる。
The lower limit of the weight average molecular weight in terms of polystyrene of the methacrylic copolymer for binder of the present invention is 100,000, and the upper limit is 3 million. When the weight average molecular weight is less than 100,000, the strength is lowered, the viscosity is not sufficiently obtained at the time of preparing the paste, the storage stability is deteriorated, or the strength when formed into a sheet is remarkably lowered. When the weight average molecular weight exceeds 3 million, problems arise in stringiness and solubility in a solvent of the obtained inorganic fine particle dispersed paste composition. The preferable lower limit is 100,000, and the preferable upper limit is 1,000,000.
In addition, the measurement of the weight average molecular weight by polystyrene conversion can be obtained by performing a gel permeation chromatography (GPC) measurement using, for example, a column LF-804 manufactured by SHOKO as a column.
本発明のバインダー用メタアクリル共重合体は、ガラス転移温度の好ましい下限が１０℃、好ましい上限が３５℃である。上記ガラス転移温度が１０℃未満であると、無機粉末とバインダーからなるシートに成形した際に柔らかすぎて取り扱い性に劣ることがある。上記ガラス転移温度が３５℃を超えると、得られるシートが脆くなり、取り扱い性が悪くなることがある。より好ましい下限は１５℃、より好ましい上限は３０℃である。
なお、本発明のバインダー用メタアクリル共重合体のガラス転移温度は、メタアクリルモノマーの組成と、構成モノマーをホモポリマーとした場合のガラス転移温度とから概算することが可能である。具体的には、本発明のバインダー用メタアクリル共重合体のガラス転移温度は、構成モノマーをホモポリマーとした場合のガラス転移温度に、それぞれの割合を掛けたものの合計として計算される。
メタアクリルモノマーのホモポリマーとした場合のガラス転移温度は以下の通りである。
メチルメタクリレート（ＭＭＡ）：１０５℃、エチルメタクリレート（ＥＭＡ）：６５℃、イソプロピルメタクリレート（ｉＰＭＡ）：８１℃、ｎ−ブチルメタクリレート（ＢＭＡ）：２０℃、イソブチルメタクリレート（ｉＢＭＡ）：５３℃、２−ヒドロキシエチルメタクリレート（ＨＥＭＡ）：５５℃、２−ヒドロキシプロピルメタクリレート（ＨＰＭＡ）：２６℃、イソデシルメタクリレート（ＩＤＭＡ）：−４１℃、グリシジルメタクリレート（ＧＭＡ）：４１℃
The preferable lower limit of the glass transition temperature of the methacrylic copolymer for binder of the present invention is 10 ° C, and the preferable upper limit is 35 ° C. When the glass transition temperature is less than 10 ° C., it may be too soft and inferior in handleability when formed into a sheet composed of an inorganic powder and a binder. When the said glass transition temperature exceeds 35 degreeC, the sheet | seat obtained will become weak and handleability may worsen. A more preferred lower limit is 15 ° C., and a more preferred upper limit is 30 ° C.
The glass transition temperature of the methacrylic copolymer for binders of the present invention can be estimated from the composition of the methacrylic monomer and the glass transition temperature when the constituent monomer is a homopolymer. Specifically, the glass transition temperature of the methacrylic copolymer for binder of the present invention is calculated as the sum of the glass transition temperatures when the constituent monomers are homopolymers multiplied by the respective proportions.
The glass transition temperature of the methacryl monomer homopolymer is as follows.
Methyl methacrylate (MMA): 105 ° C., ethyl methacrylate (EMA): 65 ° C., isopropyl methacrylate (iPMA): 81 ° C., n-butyl methacrylate (BMA): 20 ° C., isobutyl methacrylate (iBMA): 53 ° C., 2-hydroxy Ethyl methacrylate (HEMA): 55 ° C., 2-hydroxypropyl methacrylate (HPMA): 26 ° C., isodecyl methacrylate (IDMA): −41 ° C., glycidyl methacrylate (GMA): 41 ° C.
本発明のバインダー用メタアクリル共重合体は、９０％分解温度が３５０℃以下であることが好ましく、より好ましくは９０％分解温度が３００℃以下である。９０％分解温度が３５０℃を超えると、焼成時に無機粉が熱劣化することがある。なお、上記９０％分解温度は、熱重量測定装置ＴＧ−ＤＴＡによって測定することができる。 The 90% decomposition temperature of the methacrylic copolymer for binder of the present invention is preferably 350 ° C. or lower, more preferably 300 ° C. or lower. If the 90% decomposition temperature exceeds 350 ° C., the inorganic powder may be thermally deteriorated during firing. The 90% decomposition temperature can be measured by a thermogravimetric measuring device TG-DTA.
本発明のバインダー用メタアクリル共重合体を製造する方法としては特に限定されず、例えば、メタクリル酸ｎブチルを所定量含む３種以上のメタアクリルモノマーを原料モノマーとし、連鎖移動剤及び有機溶剤等を含有するモノマー混合液を調製した後、該モノマー混合液に重合開始剤を添加し、上記原料モノマーを共重合させる方法が挙げられる。 The method for producing the methacrylic copolymer for binder of the present invention is not particularly limited. For example, three or more methacrylic monomers containing a predetermined amount of n-butyl methacrylate are used as a raw material monomer, a chain transfer agent, an organic solvent, etc. A method of preparing a monomer mixed solution containing, followed by adding a polymerization initiator to the monomer mixed solution and copolymerizing the raw material monomers.
また、本発明のバインダー用メタアクリル共重合体の分子末端のみに水素結合性官能基を導入する方法としては、例えば、水素結合性官能基を有する連鎖移動剤のもとで、上述したメタクリル酸ｎブチルを所定量含む３種以上のメタアクリルモノマーからなる原料モノマーをフリーラジカル重合法、リビングラジカル重合法、イニファーター重合法、アニオン重合法、リビングアニオン重合法等の従来公知の方法で共重合する方法や、水素結合性官能基を有する重合開始剤のもとで、上述したモノマーをフリーラジカル重合法、リビングラジカル重合法、イニファーター重合法、アニオン重合法、リビングアニオン重合法等の従来公知の方法で共重合する方法が挙げられる。なお、これらの方法は併用してもよい。
また、バインダー用メタアクリル共重合体の分子末端のみに水素結合性官能基が導入されたことは、例えば、１３Ｃ−ＮＭＲにより確認することができる。
Moreover, as a method for introducing a hydrogen bonding functional group only into the molecular terminal of the methacrylic copolymer for binder of the present invention, for example, the above-mentioned methacrylic acid under a chain transfer agent having a hydrogen bonding functional group is used. Copolymerize raw material monomers consisting of 3 or more methacrylic monomers containing n-butyl by a known method such as free radical polymerization, living radical polymerization, iniferter polymerization, anion polymerization, and living anion polymerization. And a conventional initiator such as a free radical polymerization method, a living radical polymerization method, an iniferter polymerization method, an anionic polymerization method, or a living anion polymerization method under the polymerization initiator having a hydrogen bonding functional group. The method of copolymerizing by the method of this is mentioned. These methods may be used in combination.
Moreover, it can confirm by 13 C-NMR that the hydrogen bondable functional group was introduce | transduced only into the molecular terminal of the methacrylic copolymer for binders.
上記水素結合性官能基を有する連鎖移動剤としては、特に限定されず、例えば、水素結合性官能基として水酸基を有するメルカプトプロパンジオール、水素結合性官能基としてカルボキシル基を有するチオグリセロール、メルカプトコハク酸、メルカプト酢酸、水素結合性官能基としてアミノ基を有するアミノエタンチオール等が挙げられる。 The chain transfer agent having a hydrogen bonding functional group is not particularly limited. For example, mercaptopropanediol having a hydroxyl group as a hydrogen bonding functional group, thioglycerol having a carboxyl group as a hydrogen bonding functional group, mercaptosuccinic acid , Mercaptoacetic acid, aminoethanethiol having an amino group as a hydrogen bonding functional group, and the like.
上記水素結合性官能基を有する重合開始剤としては、特に限定されず、例えば、Ｐ−メンタンヒドロペルオキシド（日油社製「パーメンタＨ」）、ジイソプロピルベンゼンヒドロペルオキシド（日油社製「パークミルＰ」）、１，２，３，３−テトラメチルブチルヒドロペルオキシド（日油社製「パーオクタＨ」）、クメンヒドロペルオキシド（日油社製「パークミルＨ−８０」）、ｔ−ブチルヒドロペルオキシド（日油社製「パーブチルＨ−６９」）、過酸化シクロヘキサノン（日油社製「パーヘキサＨ」）、１，１，３，３−テトラメチルブチルヒドロパーオキサイド、ｔ−ブチルヒドロパーオキサイド、ｔ−アミルヒドロパーオキサイド、Ｄｉｓｕｃｃｉｎｉｃ ａｃｉｄ ｐｅｒｏｘｉｄｅ（パーロイルＳＡ）等が挙げられる。 The polymerization initiator having a hydrogen bonding functional group is not particularly limited, and examples thereof include P-menthane hydroperoxide (“Permenta H” manufactured by NOF Corporation), diisopropylbenzene hydroperoxide (“PARK Mill P” manufactured by NOF Corporation). ), 1,2,3,3-tetramethylbutyl hydroperoxide (“Perocta H” manufactured by NOF Corporation), cumene hydroperoxide (“PARK Mill H-80” manufactured by NOF Corporation), t-butyl hydroperoxide (NOF Corporation) “Perbutyl H-69”), cyclohexanone peroxide (“Perhexa H” manufactured by NOF Corporation), 1,1,3,3-tetramethylbutyl hydroperoxide, t-butyl hydroperoxide, t-amyl hydro Peroxide, Disuccinic acid peroxide (Perroyl SA), etc. are mentioned.
また、本発明のバインダー用メタアクリル共重合体と、有機溶剤と、無機微粒子とを用いて無機微粒子分散ペースト組成物を作製することができる。
本発明のバインダー用メタアクリル共重合体、有機溶剤、及び、無機微粒子を含有する無機微粒子分散ペースト組成物もまた、本発明の１つである。
In addition, an inorganic fine particle-dispersed paste composition can be prepared using the methacrylic copolymer for binder of the present invention, an organic solvent, and inorganic fine particles.
The inorganic fine particle-dispersed paste composition containing the methacrylic copolymer for binder of the present invention, an organic solvent, and inorganic fine particles is also one aspect of the present invention.
本発明の無機微粒子分散ペースト組成物は、無機微粒子を含有する。
上記無機微粒子としては特に限定されず、例えば、ＩＴＯ、ＦＴＯ、銅、銀、ニッケル、パラジウム、アルミナ、ジルコニア、酸化チタン、チタン酸バリウム、窒化アルミナ、窒化ケイ素、窒化ホウ素、ケイ酸塩ガラス、鉛ガラス、ＣａＯ・Ａｌ２Ｏ３・ＳｉＯ２系無機ガラス、ＭｇＯ・Ａｌ２Ｏ３・ＳｉＯ２系無機ガラス、ＬｉＯ２・Ａｌ２Ｏ３・ＳｉＯ２系無機ガラス等の低融点ガラス、Ｌｉ２Ｓ−ＭｘＳｙ（Ｍ＝Ｂ、Ｓｉ、Ｇｃ、Ｐ）等のリチウム硫黄系ガラス、ＬｉＣｏＯ２等のリチウムコバルト複合酸化物やＬｉＭｎＯ４等のリチウムマンガン複合酸化物、リチウムニッケル複合酸化物、リチウムバナジウム複合酸化物、リチウムジルコニウム複合酸化物、リチウムハフニウム複合酸化物、ケイリン酸リチウム（Ｌｉ３．５ＳｉＯ．５ＰＯ．５Ｏ４）、リン酸チタンリチウム（ＬｉＴｉ２（ＰＯ４）３）、チタン酸リチウム（Ｌｉ４Ｔｉ５Ｏ１２）、リン酸ゲルマニウムリチウム（ＬｉＧｅ２（ＰＯ４）３）、Ｌｉ２Ｏ−ＳｉＯ２、Ｌｉ２Ｏ−Ｖ２Ｏ５−ＳｉＯ２、Ｌｉ２Ｏ−Ｐ２Ｏ５−Ｂ２Ｏ３、Ｌｉ２Ｏ−ＧｅＯ２Ｂａなどの酸化リチウム化合物、酸化ニオブ、酸化バナジウム、酸化タングステン、ＭｇＡｌ１０Ｏ１７：Ｅｕ、Ｚｎ２ＳｉＯ４：Ｍｎ、（Ｙ、Ｇｄ）ＢＯ３：Ｅｕ等の蛍光体、種々のカーボンブラック、カーボンナノチューブ、金属錯体等が挙げられる。
なお、上記無機微粒子の平均粒子径は０．０５〜５０μｍが好ましい。
The inorganic fine particle-dispersed paste composition of the present invention contains inorganic fine particles.
The inorganic fine particles are not particularly limited. For example, ITO, FTO, copper, silver, nickel, palladium, alumina, zirconia, titanium oxide, barium titanate, alumina nitride, silicon nitride, boron nitride, silicate glass, lead glass, CaO · Al 2 O 3 · SiO 2 type inorganic glass, MgO · Al 2 O 3 · SiO 2 type inorganic glass, LiO 2 · Al 2 O 3 · SiO 2 type low melting point glass such as inorganic glass, Li 2 S -M x S y (M = B , Si, Gc, P) lithium-sulfur-based glass, lithium-cobalt composite oxide such as LiCoO 2 or LiMnO lithium-manganese composite oxides such as 4, such as, lithium nickel composite oxide, lithium Vanadium composite oxide, lithium zirconium composite oxide, lithium hafnium composite oxide, lithium silicate (L 3 .5SiO.5PO.5O 4), titanium phosphate lithium (LiTi 2 (PO 4) 3 ), lithium titanate (Li 4 Ti 5 O 12) , phosphoric acid germanium lithium (LiGe 2 (PO 4) 3 ), Li 2 O—SiO 2 , Li 2 O—V 2 O 5 —SiO 2 , Li 2 O—P 2 O 5 —B 2 O 3 , lithium oxide compounds such as Li 2 O—GeO 2 Ba, niobium oxide, oxidation Examples include phosphors such as vanadium, tungsten oxide, MgAl 10 O 17 : Eu, Zn 2 SiO 4 : Mn, (Y, Gd) BO 3 : Eu, various carbon blacks, carbon nanotubes, metal complexes, and the like.
The average particle size of the inorganic fine particles is preferably 0.05 to 50 μm.
本発明の無機微粒子分散ペースト組成物における上記無機微粒子の含有量としては特に限定されないが、好ましい下限が１０重量％、好ましい上限が９０重量％である。１０重量％未満であると、粘度が充分に得られないことがあり、塗工性が低下することがあり、９０重量％を超えると、無機微粒子を分散させることが困難になることがある。 The content of the inorganic fine particles in the inorganic fine particle-dispersed paste composition of the present invention is not particularly limited, but a preferred lower limit is 10% by weight and a preferred upper limit is 90% by weight. If the amount is less than 10% by weight, the viscosity may not be sufficiently obtained, and coatability may be lowered. If the amount exceeds 90% by weight, it may be difficult to disperse the inorganic fine particles.
本発明の無機微粒子分散ペースト組成物は、有機溶剤を含有する。
上記有機溶剤としては特に限定されず、例えば、トルエン、酢酸エチル、酢酸ブチル、イソプロパノール、メチルイソブチルケトン、メチルエチルケトン、メチルイソブチルケトン、エチレングリコールエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノイソブチルエーテル、トリメチルペンタンジオールモノイソブチレート、ブチルカルビトール、ブチルカルビトールアセテート、テルピネオール、テルピネオールアセテート、ジヒドロテルピネオール、ジヒドロテルピネオールアセテートテキサノール、イソホロン、乳酸ブチル、ジオクチルフタレート、ジオクチルアジペート、ベンジルアルコール、フェニルプロピレングリコール、クレゾール等が挙げられる。なかでも、テルピネオールアセテート、ジヒドロテルピネオール、ジヒドロテルピネオールアセテート、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノイソブチルエーテル、ブチルカルビトール、ブチルカルビトールアセテート、テキサノールが好ましく、テルピネオール、テルピネオールアセテート、ジヒドロテルピネオール、ジヒドロテルピネオールアセテートがより好ましい。なお、これらの有機溶剤は単独で用いてもよく、２種以上を併用してもよい。
The inorganic fine particle dispersed paste composition of the present invention contains an organic solvent.
The organic solvent is not particularly limited. For example, toluene, ethyl acetate, butyl acetate, isopropanol, methyl isobutyl ketone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol Monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisobutyl ether, trimethylpentanediol monoisobutyrate, butyl carbitol, butyl carbitol acetate, terpineol, terpineol acetate, dihydroterpineol, dihydroterpineol acetate texanol, isophorone, butyl lactate, dioctyl Phthalate, geo Chiruajipeto, benzyl alcohol, phenyl propylene glycol, cresol, and the like. Among them, terpineol acetate, dihydroterpineol acetate, dihydroterpineol acetate, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisobutyl ether, butyl carbitol, butyl carbitol acetate, and texanol are preferable, and terpineol, terpineol acetate, dihydroterpineol, dihydroterpineol. Acetate is more preferred. In addition, these organic solvents may be used independently and may use 2 or more types together.
本発明の無機微粒子分散ペースト組成物におけるバインダー用メタアクリル共重合体の含有量としては特に限定されないが、好ましい下限が５重量％、好ましい上限が３０重量％である。上記バインダー用メタアクリル共重合体の含有量が、上記範囲内であると、低温で焼成しても脱脂可能な無機微粒子分散ペースト組成物を作製することができる。 Although it does not specifically limit as content of the methacrylic copolymer for binders in the inorganic fine particle dispersion paste composition of this invention, A preferable minimum is 5 weight% and a preferable upper limit is 30 weight%. When the content of the methacrylic copolymer for binder is within the above range, an inorganic fine particle-dispersed paste composition that can be degreased even when fired at a low temperature can be produced.
本発明の無機微粒子分散ペースト組成物における上記有機溶剤の含有量としては特に限定されないが、好ましい下限は１０重量％、好ましい上限は６０重量％である。この範囲を外れると、塗工性が低下したり、無機微粒子を分散させることが困難となったりすることがある。 Although it does not specifically limit as content of the said organic solvent in the inorganic fine particle dispersion paste composition of this invention, A preferable minimum is 10 weight% and a preferable upper limit is 60 weight%. If it is out of this range, the coatability may be lowered or it may be difficult to disperse the inorganic fine particles.
本発明の無機微粒子分散ペースト組成物は、密着促進剤を含有してもよい。
上記密着促進剤としては、特に限定されないが、アミノシラン系シランカップリング剤が好適に用いられる。
上記アミノシラン系シランカップリング剤としては、Ｎ−２−（アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリエトキシシラン、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−トリエトキシシリル−Ｎ−（１，３−ジメチル−ブチリデン）プロピルアミン、Ｎ−フェニル−３−アミノプロピルトリメトキシシランが挙げられる。
アミノシラン系シランカップリング剤以外にも、グリシジルシラン系シランカップリング剤である３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、３−グリシドキシプロピルトリエトキシシラン、その他シランカップリング剤であるジメチルジメトキシシラン、テトラメトキシシラン、テトラエトキシシラン、フェニルトリメトキシシラン、ジフェニルジメトキシシラン等も好適に用いることができ、これらを複数用いても良い。
The inorganic fine particle dispersed paste composition of the present invention may contain an adhesion promoter.
The adhesion promoter is not particularly limited, but an aminosilane-based silane coupling agent is preferably used.
Examples of the aminosilane-based silane coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and N-2- (amino Ethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl -3-aminopropyltrimethoxysilane.
Besides aminosilane silane coupling agents, glycidylsilane silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, In addition, dimethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, and the like, which are silane coupling agents, can be suitably used, and a plurality of these may be used.
本発明の無機微粒子分散ペースト組成物は、塗工後のレベリングを促進させる目的でノニオン系界面活性剤を含有することが好ましい。
上記ノニオン系界面活性剤としては特に限定されないが、ＨＬＢ値が１０以上２０以下のノニオン系界面活性剤であることが好ましい。ここで、ＨＬＢ値とは、界面活性剤の親水性、親油性を表す指標として用いられるものであって、計算方法がいくつか提案されており、例えば、エステル系の界面活性剤について、鹸化価をＳ、界面活性剤を構成する脂肪酸の酸価をＡとし、ＨＬＢ値を２０（１−Ｓ／Ａ）等の定義がある。具体的には、脂肪鎖にアルキレンエーテルを付加させたポリエチレンオキサイドを有するノニオン系界面活性剤が好適であり、具体的には例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンセチルエーテル等が好適に用いられる。なお、上記ノニオン系界面活性剤は、熱分解性がよいが、大量に添加すると無機微粒子分散ペースト組成物の熱分解性が低下することがあるため、含有量の好ましい上限は５重量％である。
The inorganic fine particle-dispersed paste composition of the present invention preferably contains a nonionic surfactant for the purpose of promoting leveling after coating.
The nonionic surfactant is not particularly limited, but is preferably a nonionic surfactant having an HLB value of 10 or more and 20 or less. Here, the HLB value is used as an index representing the hydrophilicity and lipophilicity of a surfactant, and several calculation methods have been proposed. For example, saponification value of an ester-based surfactant And S, the acid value of the fatty acid constituting the surfactant is A, and the HLB value is 20 (1-S / A). Specifically, a nonionic surfactant having a polyethylene oxide in which an alkylene ether is added to an aliphatic chain is preferable. Specifically, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, and the like are preferably used. It is done. The nonionic surfactant has good thermal decomposability, but if added in a large amount, the thermal decomposability of the inorganic fine particle-dispersed paste composition may be lowered. Therefore, the preferable upper limit of the content is 5% by weight. .
また、本発明の無機微粒子分散ペースト組成物では、更に、添加剤として、可塑剤、粘着付与剤、保存安定剤、消泡剤、熱分解促進剤、酸化防止剤等を含有させてもよい。これらの添加剤は、特に限定されるものではなく、この分野で通常用いられるものを適宜選択することができる。 Further, the inorganic fine particle dispersed paste composition of the present invention may further contain, as additives, a plasticizer, a tackifier, a storage stabilizer, an antifoaming agent, a thermal decomposition accelerator, an antioxidant and the like. These additives are not particularly limited, and those commonly used in this field can be appropriately selected.
本発明の無機微粒子分散ペースト組成物の製造方法としては特に限定されず、従来公知の方法が挙げられ、各成分をボールミル、ブレンダーミル、３本ロール等の各種混合機を用いて混合する方法等が挙げられる。 The method for producing the inorganic fine particle-dispersed paste composition of the present invention is not particularly limited, and includes conventionally known methods, such as a method of mixing each component using various mixers such as a ball mill, a blender mill, and a three roll. Is mentioned.
本発明の無機微粒子分散ペースト組成物は、無機微粒子としてガラス粉末を用いた場合、ガラスペースト組成物として好適に使用することができる。また、無機微粒子としてセラミック粉末を用いた場合はセラミックペースト組成物、無機微粒子として蛍光体粉末を用いた場合は蛍光体ペースト組成物、無機微粒子として導電性粉末を用いた場合は導電ペースト組成物として好適に使用することができる。 The inorganic fine particle-dispersed paste composition of the present invention can be suitably used as a glass paste composition when glass powder is used as the inorganic fine particles. In addition, when ceramic powder is used as the inorganic fine particles, a ceramic paste composition is used. When phosphor powder is used as the inorganic fine particles, a phosphor paste composition is used. When conductive powder is used as the inorganic fine particles, a conductive paste composition is used. It can be preferably used.
無機微粒子としてガラス粉末又はセラミックス粉末を用いることで、グリーンシートの材料として好適に使用することができる。また、リチウム元素を含んだガラスシートの製造にも好適に用いることが出来る。これらの用途で本発明の無機微粒子分散ペースト組成物（以下、グリーンシート形成用無機微粒子分散ペースト組成物ともいう）を用いることで、低温での脱脂が可能となり、焼結時における無機微粒子の焼結中の酸化や熱履歴を最低限度に抑えることが可能となる。 By using glass powder or ceramic powder as the inorganic fine particles, it can be suitably used as a material for the green sheet. Moreover, it can use suitably also for manufacture of the glass sheet containing a lithium element. In these applications, the inorganic fine particle dispersed paste composition of the present invention (hereinafter also referred to as “inorganic fine particle dispersed paste composition for forming a green sheet”) can be degreased at a low temperature, and the inorganic fine particles can be sintered during sintering. It becomes possible to suppress the oxidation and thermal history during sintering to a minimum.
上記グリーンシート形成用無機微粒子分散ペースト組成物に用いられる溶剤としては、特にトルエンや酢酸ブチル、イソプロパノール、メチルイソブチルケトン等が好ましい。また、上記溶剤の添加量は用いる塗工プロセスによって適宜選択することが望ましく、特に限定されるものではない。更に、本発明のグリーンシート形成用無機微粒子分散ペースト組成物における上記無機微粒子及び無機微粒子の含有量としては特に限定されないが、好ましい下限が５０重量％、好ましい上限が９５重量％である。５０重量％未満であると、樹脂分が多く焼結性に問題が発生する可能性があり９５重量％を超えると、無機微粒子等を分散させることが困難でシート化できないことがある。 As the solvent used for the above-mentioned inorganic fine particle dispersed paste composition for forming a green sheet, toluene, butyl acetate, isopropanol, methyl isobutyl ketone, and the like are particularly preferable. The amount of the solvent added is preferably selected as appropriate depending on the coating process used, and is not particularly limited. Further, the content of the inorganic fine particles and the inorganic fine particles in the inorganic fine particle-dispersed paste composition for forming a green sheet of the present invention is not particularly limited, but a preferable lower limit is 50% by weight and a preferable upper limit is 95% by weight. If it is less than 50% by weight, there is a possibility that a large amount of resin is present and a problem may occur in the sinterability.
上記グリーンシート形成用無機微粒子分散ペースト組成物を、片面離型処理を施した支持フィルム上に塗工し、溶剤を乾燥させ、シート状に成形することで、無機微粒子分散シートを製造することができる。このような無機微粒子分散シートもまた本発明の１つである。
本発明の無機微粒子分散シートの製造方法としては、例えば、本発明のバインダー用メタアクリル共重合体を溶剤に溶解させ、界面活性剤や分散剤、可塑剤等を添加し、攪拌、均一なビヒクルを作成した後、無機微粒子を添加し、ボールミルの分散装置を用いて均一に分散させる。得られた無機微粒子分散ペースト組成物をロールコーター、ダイコーター、スクイズコーター、カーテンコーター等の塗工方式によって支持フィルム上に均一に塗膜を形成する方法等が挙げられる。
The inorganic fine particle-dispersed paste composition for forming a green sheet is coated on a support film that has been subjected to a single-sided release treatment, and the solvent is dried and formed into a sheet shape to produce an inorganic fine particle-dispersed sheet. it can. Such an inorganic fine particle dispersed sheet is also one aspect of the present invention.
The method for producing the inorganic fine particle-dispersed sheet of the present invention includes, for example, dissolving the methacrylic copolymer for binder of the present invention in a solvent, adding a surfactant, a dispersant, a plasticizer, etc., stirring, and uniform vehicle. Then, inorganic fine particles are added and dispersed uniformly using a ball mill dispersing device. Examples thereof include a method of uniformly forming a coating film on a support film by applying the obtained inorganic fine particle dispersed paste composition by a coating method such as a roll coater, a die coater, a squeeze coater, or a curtain coater.
本発明の無機微粒子分散シートを製造する際に用いる支持フィルムは、耐熱性及び耐溶剤性を有すると共に可撓性を有する樹脂フィルムであることが好ましい。支持フィルムが可撓性を有することにより、ロールコーター、ブレードコーターなどによって支持フィルムの表面にグリーンシート形成用無機微粒子分散ペースト組成物を塗布することができ、得られるグリーンシート形成フィルムをロール状に巻回した状態で保存し、供給することができる。 The support film used when producing the inorganic fine particle-dispersed sheet of the present invention is preferably a resin film having heat resistance and solvent resistance and flexibility. Since the support film is flexible, the inorganic fine particle dispersed paste composition for forming a green sheet can be applied to the surface of the support film by a roll coater, a blade coater, or the like, and the resulting green sheet forming film is rolled. It can be stored and supplied in a wound state.
上記支持フィルムを形成する樹脂としては、例えばポリエチレンテレフタレート、ポリエステル、ポリエチレン、ポリプロピレン、ポリスチレン、ポリイミド、ポリビニルアルコール、ポリ塩化ビニル、ポリフロロエチレン等の含フッ素樹脂、ナイロン、セルロース等が挙げられる。
上記支持フィルムの厚みは、例えば、２０〜１００μｍが好ましい。
また、支持フィルムの表面には離型処理が施されていることが好ましく、これにより、転写工程において、支持フィルムの剥離操作を容易に行うことができる。
なお、本発明の無機微粒子分散ペースト組成物を用いて得られる無機微粒子分散シートもまた本発明の１つである。
Examples of the resin that forms the support film include polyethylene terephthalate, polyester, polyethylene, polypropylene, polystyrene, polyimide, polyvinyl alcohol, polyvinyl chloride, polyfluoroethylene, and other fluorine-containing resins, nylon, and cellulose.
As for the thickness of the said support film, 20-100 micrometers is preferable, for example.
Moreover, it is preferable that the surface of the support film is subjected to a mold release treatment, whereby the support film can be easily peeled off in the transfer step.
An inorganic fine particle dispersed sheet obtained using the inorganic fine particle dispersed paste composition of the present invention is also one aspect of the present invention.
本発明によれば、無機微粒子分散ペースト組成物に使用した場合に、熱劣化が起こりにくく、低温分解性に優れ、かつ、機械的強度の高いシートを得ることが可能なバインダー用メタアクリル共重合体、無機微粒子分散ペースト組成物及び無機微粒子分散シートを提供することができる。 According to the present invention, when used in an inorganic fine particle-dispersed paste composition, a methacrylic copolymer for a binder that is less susceptible to thermal degradation, has excellent low-temperature decomposability, and has a high mechanical strength. A coalescence, an inorganic fine particle dispersion paste composition, and an inorganic fine particle dispersion sheet 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るものではない。 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）バインダー樹脂、無機微粒子分散ペースト組成物の調製
攪拌機、冷却器、温度計、湯浴及び、窒素ガス導入口を備えた２Ｌセパラプルフラスコに、メタクリル酸ｎブチル（ｎ−ＢＭＡ）４５重量部、イソブチルメタクリレート（ｉＢＭＡ）２５重量部、イソデシルメタクリレート（ｉＤＭＡ）３０重量部、有機溶剤として酢酸ブチル１００重量部とを混合し、モノマー混合液を得た。
Example 1
(1) Preparation of binder resin and inorganic fine particle-dispersed paste composition In a 2 L separable flask equipped with a stirrer, cooler, thermometer, hot water bath, and nitrogen gas inlet, n-butyl methacrylate (n-BMA) 45 weight Parts, 25 parts by weight of isobutyl methacrylate (iBMA), 30 parts by weight of isodecyl methacrylate (iDMA), and 100 parts by weight of butyl acetate as an organic solvent were mixed to obtain a monomer mixture.
得られたモノマー混合液を、窒素ガスを用いて２０分間バブリングすることにより溶存酸素を除去した後、セパラブルフラスコ系内を窒素ガスで置換し攪拌しながら湯浴が沸騰するまで昇温した。重合開始剤を酢酸ブチルで希釈した溶液を加えた。また重合中に重合開始剤を含む酢酸ブチル溶液を数回添加した。 The obtained monomer mixture was bubbled with nitrogen gas for 20 minutes to remove dissolved oxygen, and then the temperature inside the separable flask system was replaced with nitrogen gas and heated until the hot water bath boiled with stirring. A solution obtained by diluting the polymerization initiator with butyl acetate was added. Further, a butyl acetate solution containing a polymerization initiator was added several times during the polymerization.
重合開始から７時間後、室温まで冷却し重合を終了させた。これにより、メタアクリル樹脂の酢酸ブチル溶液を得た。得られた重合体について、カラムとしてＳＨＯＫＯ社製カラムＬＦ−８０４を用い、ゲルパーミエーションクロマトグラフィーによる分析を行ったところ、ポリスチレン換算による重量平均分子量は表１のとおりであった。
このようにして得られたメタアクリル樹脂の酢酸ブチル溶液５０重量部に、無機粉体としてＬｉＳ−Ｐ２Ｓ５系ガラス（平均粒子径２．０μｍ）５０重量部を添加し、高速攪拌機で混練し、無機微粒子分散ペースト組成物を得た。
Seven hours after the start of polymerization, the polymerization was terminated by cooling to room temperature. As a result, a butyl acetate solution of a methacrylic resin was obtained. The obtained polymer was analyzed by gel permeation chromatography using a column LF-804 manufactured by SHOKO as a column, and the weight average molecular weight in terms of polystyrene was as shown in Table 1.
50 parts by weight of LiS-P 2 S 5 glass (average particle size 2.0 μm) was added as inorganic powder to 50 parts by weight of the butyl acetate solution of the methacrylic resin thus obtained, and kneaded with a high-speed stirrer. Thus, an inorganic fine particle dispersed paste composition was obtained.
（２）シートの作製
得られた無機微粒子分散ペースト組成物を、予め離型処理したポリエチレンテレフタレート（ＰＥＴ）よりなる支持フィルム（幅４００ｍｍ，長さ３０ｍ，厚さ３８μｍ）上にブレードコーターを用いて塗布し、形成された塗膜を１００℃で１０分間乾燥することにより溶剤を除去することにより、厚さ５０μｍの無機粉体含有樹脂層を支持フィルム上に形成した。次いで、前記無機粉体含有樹脂層上に、予め離型処理したＰＥＴよりなるカバーフィルム（幅４００ｍｍ，長さ３０ｍ，厚さ２５μｍ）を貼り付けることにより、グリーンシートを製造した。
(2) Production of Sheet Using the blade coater on the support film (width 400 mm, length 30 m, thickness 38 μm) made of polyethylene terephthalate (PET), which was previously subjected to mold release treatment, the obtained inorganic fine particle dispersed paste composition. The solvent was removed by drying the coated film thus formed at 100 ° C. for 10 minutes, thereby forming an inorganic powder-containing resin layer having a thickness of 50 μm on the support film. Next, a green sheet was manufactured by pasting a cover film (width 400 mm, length 30 m, thickness 25 μm) made of PET, which was previously subjected to mold release treatment, on the inorganic powder-containing resin layer.
（実施例２〜８、比較例１〜３）
実施例１におけるアクリルモノマー混合液の組成を表１に記載の内容に変更し、実施例１と同じ方法で無機微粒子分散ペースト組成物、シートを作製した。
表１中、ＢＭＡはメタクリル酸ｎブチル（ｎ−ＢＭＡ）、ｉＢＭＡはイソブチルメタクリレート、ｉＤＭＡはイソデシルメタクリレート、ＰＴＭＯＭＡはポリテトラメチレングリコールのセグメントを有するメタクリル系グラフトモノマー（ブレンマー（登録商標）５５ＰＥＴ−８００、日油社製）、２−ＨＰＭＡは２−ヒドロキシプロピルメタクリレート、ＧＭＡはグリシジルメタクリレート、ｉＰＭＡはイソプロピルメタクリレート、ＨＥＭＡは２−ヒドロキシエチルメタクリレート、ＭＭＡはメチルメタクリレートである。
ｉＢＭＡ、ｉＤＭＡは、メタクリル酸エステル置換基に分岐構造を有する置換基を有し、かつ、前記分岐構造を有する置換基の主鎖の炭素数が３以上であるモノマー（表１中、モノマーＡとする。）である。ＭＭＡ、ｉＰＭＡは、メタクリル酸エステル置換基に炭素数が３以下の直鎖状若しくは分岐状のアルキル基、または、炭素数が６以下の環状のアルキル基を有し、かつ、ホモポリマーでのガラス転移温度が６５℃以上であるモノマー（表１中、モノマーＢとする。）である。ＧＭＡ、ＨＥＭＡ、２−ＨＰＭＡは、メタアクリル酸エステル置換基に極性基またはグリシジル基を有するモノマー（表１中、モノマーＣとする。）である。
(Examples 2-8, Comparative Examples 1-3)
The composition of the acrylic monomer mixture in Example 1 was changed to the contents shown in Table 1, and an inorganic fine particle-dispersed paste composition and a sheet were produced in the same manner as in Example 1.
In Table 1, BMA is n-butyl methacrylate (n-BMA), iBMA is isobutyl methacrylate, iDMA is isodecyl methacrylate, and PTMOMA is a methacrylic graft monomer having a segment of polytetramethylene glycol (Blemmer (registered trademark) 55 PET-800). 2-HPMA is 2-hydroxypropyl methacrylate, GMA is glycidyl methacrylate, iPMA is isopropyl methacrylate, HEMA is 2-hydroxyethyl methacrylate, and MMA is methyl methacrylate.
iBMA and iDMA are monomers having a substituent having a branched structure in a methacrylate ester substituent, and having 3 or more carbon atoms in the main chain of the substituent having the branched structure (in Table 1, monomer A and ). MMA and iPMA have a linear or branched alkyl group having 3 or less carbon atoms or a cyclic alkyl group having 6 or less carbon atoms in a methacrylic acid ester substituent, and glass with a homopolymer A monomer having a transition temperature of 65 ° C. or higher (referred to as monomer B in Table 1). GMA, HEMA, and 2-HPMA are monomers having a polar group or a glycidyl group as a methacrylic acid ester substituent (referred to as monomer C in Table 1).
＜評価＞
実施例１〜８及び比較例１〜３で得られた重合体、無機微粒子分散ペースト組成物及びシートについて以下の評価を行った。結果を表２に示した。
<Evaluation>
The following evaluation was performed about the polymer, inorganic fine particle dispersion paste composition, and sheet which were obtained in Examples 1-8 and Comparative Examples 1-3. The results are shown in Table 2.
（１）樹脂のガラス転移温度測定
得られた重合体について、示差走査熱量計（ＤＳＣ）を用いてガラス転移温度を測定した。
(1) Measurement of glass transition temperature of resin The glass transition temperature of the obtained polymer was measured using a differential scanning calorimeter (DSC).
（２）樹脂伸長性
実施例、比較例で作製した重合体の酢酸ブチル溶液を離型処理したＰＥＴフィルムにアプリケーターを用いて塗工し、１００℃送風オーブンで１０分間乾燥させ、樹脂シートを作成した。樹脂シートの厚みは２０μであった。方眼紙をカバーフィルムとして用い、はさみで幅１ｃｍの短冊片を作製した。２３℃、５０ＲＨ条件下で島津製作所社製オートグラフＡＧ−ＩＳを用いてチャック間距離３ｃｍ、引張速度１０ｍｍ／ｍｉｎにて引張試験を行い、破断に要した歪みを評価した。
破断歪みが５０％以上である場合を「○」、５０％未満である場合を「×」とした。
(2) Resin extensibility: A butyl acetate solution of a polymer prepared in Examples and Comparative Examples was applied to a PET film which had been subjected to mold release treatment using an applicator, and dried in a 100 ° C. blowing oven for 10 minutes to prepare a resin sheet. did. The thickness of the resin sheet was 20 μm. Graph paper was used as a cover film, and a strip of 1 cm width was produced with scissors. A tensile test was performed under the conditions of 23 ° C. and 50 RH using an autograph AG-IS manufactured by Shimadzu Corporation at a distance between chucks of 3 cm and a tensile speed of 10 mm / min to evaluate the strain required for breaking.
The case where the breaking strain was 50% or more was rated as “◯”, and the case where it was less than 50% was regarded as “x”.
（３）焼結性
実施例、比較例で作製した無機微粒子分散ペースト組成物をＴＧ−ＤＴＡのアルミナパンに詰め、１０℃／ｍｉｎにて昇温し、溶媒を蒸発、樹脂を熱分解させた。脱脂が終了した（重量が５０％を示した）温度を評価した。脱脂が終了した温度は、無機微粒子分散ペースト組成物中に占める無機微粒子以外の割合に相当する重量減少がなされたと推測される温度を、測定結果から読み取った。これは無機微粒子分散ペースト組成物中のメタアクリル共重合体成分が９０％以上分解する分解終了温度に相当する。
(3) Sinterability The inorganic fine particle-dispersed paste compositions prepared in Examples and Comparative Examples were packed in an TG-DTA alumina pan, heated at 10 ° C./min, the solvent was evaporated, and the resin was thermally decomposed. . The temperature at which the degreasing was completed (weight showed 50%) was evaluated. The temperature at which the degreasing was completed was read from the measurement results as the temperature at which the weight reduction corresponding to the proportion other than the inorganic fine particles in the inorganic fine particle-dispersed paste composition was estimated. This corresponds to a decomposition end temperature at which 90% or more of the methacrylic copolymer component in the inorganic fine particle dispersed paste composition is decomposed.
（４）熱劣化評価
実施例、比較例で作製したシートをマッフル炉にてＴＧ−ＤＴＡにて得られたそれぞれの脱脂終了温度で３０時間焼成を行った
得られた試料についてＸ線回折評価装置（リガク社製、ＲＩＮＴ２４００）を用いて広角Ｘ線回折評価を行った。即ち、焼成された試料に５０ｋＶ、１００ｍＡの条件で発生させた（ＣｕＫα）Ｘ線を６０分照射し、散乱スペクトルを得た。縦軸に散乱強度Ｉ、横軸に散乱角を２θプロットし、それぞれの軸を対数表示に変換して２θ＝６〜３０（ｄｅｇ）付近の散乱ピークあるいはショルダーの有無を確認した。
２θ＝２７度の熱劣化に起因する結晶性ピークが生じなかった場合を「○」、ピークが見られた場合を「×」とした。
(4) Thermal degradation evaluation apparatus X-ray diffraction evaluation apparatus for samples obtained by firing sheets prepared in Examples and Comparative Examples for 30 hours at respective degreasing end temperatures obtained by TG-DTA in a muffle furnace Wide angle X-ray diffraction evaluation was performed using RINT2400 (manufactured by Rigaku Corporation). That is, the fired sample was irradiated with (CuKα) X-rays generated under conditions of 50 kV and 100 mA for 60 minutes to obtain a scattering spectrum. The scattering intensity I is plotted on the vertical axis and the scattering angle is plotted 2θ on the horizontal axis, and each axis is converted into a logarithmic display to confirm the presence or absence of a scattering peak or shoulder near 2θ = 6 to 30 (deg).
The case where no crystallinity peak due to thermal degradation of 2θ = 27 degrees occurred was “◯”, and the case where a peak was observed was “x”.
本発明によれば、無機微粒子分散ペースト組成物に使用した場合に、熱劣化が起こりにくく、低温分解性に優れ、かつ、機械的強度の高いシートを得ることが可能なバインダー用メタアクリル共重合体、無機微粒子分散ペースト組成物及び無機微粒子分散シートを提供することができる。
According to the present invention, when used in an inorganic fine particle-dispersed paste composition, a methacrylic copolymer for a binder that is less susceptible to thermal degradation, has excellent low-temperature decomposability, and has a high mechanical strength. A coalescence, an inorganic fine particle dispersion paste composition, and an inorganic fine particle dispersion sheet can be provided.
Claims (6)
メタクリル酸ｎブチルに由来するセグメントを有し、前記メタクリル酸ｎブチルに由来するセグメントの含有量が２０〜６０重量％であり、かつ、
ガラス転移温度が１０〜３５℃、重量平均分子量が１０万〜３００万であり、
前記メタアクリルモノマーは、メタクリル酸エステル置換基に分岐構造を有する置換基を有し、かつ、前記分岐構造を有する置換基の主鎖の炭素数が３以上であるモノマーを含み、前記モノマーに由来するセグメントの含有量が４０重量％以上であり、メタアクリル酸エステル置換基にグリシジル基を有するモノマーを含み、かつ、前記メタアクリル酸エステル置換基にグリシジル基を有するモノマーに由来するセグメントの含有量が１〜１０重量％である
ことを特徴とするバインダー用メタアクリル共重合体。 A methacrylic copolymer for binders formed from three or more methacrylic monomers,
It has a segment derived from n-butyl methacrylate, the content of the segment derived from n-butyl methacrylate is 20 to 60% by weight, and
The glass transition temperature is 10 to 35 ° C., the weight average molecular weight is 100,000 to 3 million,
The methacrylic monomer includes a monomer having a substituent having a branched structure in a methacrylic acid ester substituent, and a main chain of the substituent having the branched structure having 3 or more carbon atoms, and is derived from the monomer der content segment 40% by weight or more of is, include monomers having a glycidyl group in methacrylic acid ester substituent, and containing a segment derived from a monomer having a glycidyl group in the methacrylic acid ester substituent A methacrylic copolymer for a binder, characterized in that the amount is from 1 to 10% by weight .
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