JP2017165630A - Resin composition for molding ceramic green sheet and material for molding ceramic green sheet - Google Patents
Resin composition for molding ceramic green sheet and material for molding ceramic green sheet Download PDFInfo
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- JP2017165630A JP2017165630A JP2016054314A JP2016054314A JP2017165630A JP 2017165630 A JP2017165630 A JP 2017165630A JP 2016054314 A JP2016054314 A JP 2016054314A JP 2016054314 A JP2016054314 A JP 2016054314A JP 2017165630 A JP2017165630 A JP 2017165630A
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- ceramic green
- molecular weight
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- green sheet
- low molecular
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- 239000000919 ceramic Substances 0.000 title claims abstract description 86
- 239000011342 resin composition Substances 0.000 title claims abstract description 28
- 238000000465 moulding Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 title abstract description 21
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 64
- 229920005989 resin Polymers 0.000 claims abstract description 49
- 239000011347 resin Substances 0.000 claims abstract description 49
- 230000009477 glass transition Effects 0.000 claims abstract description 28
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 15
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 15
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims description 20
- 239000012778 molding material Substances 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 32
- 239000004014 plasticizer Substances 0.000 description 26
- -1 methacryloyl group Chemical group 0.000 description 18
- 239000000178 monomer Substances 0.000 description 16
- 239000002270 dispersing agent Substances 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical group CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N Diethylhexyl phthalate Natural products CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-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
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-BGYRXZFFSA-N 1-o-[(2r)-2-ethylhexyl] 2-o-[(2s)-2-ethylhexyl] benzene-1,2-dicarboxylate Chemical compound CCCC[C@H](CC)COC(=O)C1=CC=CC=C1C(=O)OC[C@H](CC)CCCC BJQHLKABXJIVAM-BGYRXZFFSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 description 1
- MBGYSHXGENGTBP-UHFFFAOYSA-N 6-(2-ethylhexoxy)-6-oxohexanoic acid Chemical compound CCCCC(CC)COC(=O)CCCCC(O)=O MBGYSHXGENGTBP-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-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
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 1
- 101000663183 Homo sapiens Scavenger receptor class F member 1 Proteins 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 102100037081 Scavenger receptor class F member 1 Human genes 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 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
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 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
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
Description
本発明は、セラミックグリーンシート成形用樹脂組成物およびセラミックグリーンシート成形用材料に関する。 The present invention relates to a ceramic green sheet molding resin composition and a ceramic green sheet molding material.
セラミック多層配線基板等のセラミックパッケージの製造に、セラミックグリーンシートが使用されている。セラミックグリーンシートは、例えば、無機粉体とバインダと有機溶剤と添加剤とを均一に混合してスラリーを調製し、このスラリーを支持体に塗布した後、有機溶剤を乾燥除去し、支持体を剥離することによって得られる。このようなセラミックグリーンシート上に、内部電極を形成するための導電性組成物を所定のパターンに印刷し、これを複数枚重ねて加熱圧縮して積層体とし、これを焼成すると、セラミックグリーンシート中のバインダが熱分解して除去され、セラミック多層配線基板が得られる。 Ceramic green sheets are used in the manufacture of ceramic packages such as ceramic multilayer wiring boards. The ceramic green sheet is prepared, for example, by uniformly mixing an inorganic powder, a binder, an organic solvent, and an additive, and preparing a slurry. After applying the slurry to the support, the organic solvent is removed by drying, and the support is removed. Obtained by peeling. On such a ceramic green sheet, a conductive composition for forming an internal electrode is printed in a predetermined pattern, and a plurality of these are stacked and heat-compressed to form a laminate. The binder inside is thermally decomposed and removed, and a ceramic multilayer wiring board is obtained.
セラミックグリーンシートには、強度、伸度等の機械的物性、バインダの熱分解性等が求められている。そこで、セラミックグリーンシートのバインダとして、強度に優れたブチラール樹脂が使用されたり、熱分解性に優れたアクリル樹脂が使用されたりしている。また、セラミックグリーンシートの伸度の向上のため、可塑剤が添加されている。可塑剤としては、フタル酸ジブチル等のフタル酸エステル系のものが汎用されている（例えば特許文献１）。
しかし、可塑剤を添加することで伸度は向上するが、強度は不充分である。
Ceramic green sheets are required to have mechanical properties such as strength and elongation, and thermal decomposability of the binder. Therefore, a butyral resin having excellent strength or an acrylic resin having excellent thermal decomposability is used as a binder for the ceramic green sheet. In addition, a plasticizer is added to improve the elongation of the ceramic green sheet. As the plasticizer, phthalate esters such as dibutyl phthalate are widely used (for example, Patent Document 1).
However, the addition of a plasticizer improves the elongation, but the strength is insufficient.
本発明は、上記事情に鑑みてなされたものであって、伸度および強度が共に優れたセラミックグリーンシートが得られるセラミックグリーンシート成形用樹脂組成物およびセラミックグリーンシート成形用材料を提供することを目的とする。 The present invention has been made in view of the above circumstances, and provides a ceramic green sheet molding resin composition and a ceramic green sheet molding material from which a ceramic green sheet excellent in both elongation and strength can be obtained. Objective.
本発明は、以下の態様を有する。
［１］重量平均分子量が１０，０００以下、ガラス転移温度が−２０℃以下である低分子量アクリル重合体（Ａ）と、アクリル樹脂およびブチラール樹脂からなる群から選ばれる少なくとも１種の樹脂であって重量平均分子量が１００，０００〜１，０００，０００、ガラス転移温度が４０℃以上である樹脂（Ｂ）と、を含むことを特徴とするセラミックグリーンシート成形用樹脂組成物。
［２］前記低分子量アクリル重合体（Ａ）と前記樹脂（Ｂ）との質量比が、前記低分子量アクリル重合体（Ａ）／前記樹脂（Ｂ）＝５／９５〜５０／５０の範囲内である［１］に記載のセラミックグリーンシート成形用樹脂組成物。
［３］重量平均分子量が１０，０００以下、ガラス転移温度が−２０℃以下である低分子量アクリル重合体（Ａ）と、アクリル樹脂およびブチラール樹脂からなる群から選ばれる少なくとも１種の樹脂であって重量平均分子量が１００，０００〜１，０００，０００、ガラス転移温度が４０℃以上である樹脂（Ｂ）と、無機粉体（Ｃ）と、を含むことを特徴とするセラミックグリーンシート成形用材料。
The present invention has the following aspects.
[1] It is at least one resin selected from the group consisting of a low molecular weight acrylic polymer (A) having a weight average molecular weight of 10,000 or less and a glass transition temperature of −20 ° C. or less, and an acrylic resin and a butyral resin. And a resin (B) having a weight average molecular weight of 100,000 to 1,000,000 and a glass transition temperature of 40 ° C. or higher, and a resin composition for forming a ceramic green sheet.
[2] The mass ratio of the low molecular weight acrylic polymer (A) to the resin (B) is within the range of the low molecular weight acrylic polymer (A) / the resin (B) = 5/95 to 50/50. The resin composition for forming a ceramic green sheet according to [1].
[3] At least one resin selected from the group consisting of a low molecular weight acrylic polymer (A) having a weight average molecular weight of 10,000 or less and a glass transition temperature of −20 ° C. or less, and an acrylic resin and a butyral resin. A ceramic green sheet comprising: a resin (B) having a weight average molecular weight of 100,000 to 1,000,000 and a glass transition temperature of 40 ° C. or higher; and an inorganic powder (C). material.
本発明のセラミックグリーンシート成形用樹脂組成物およびセラミックグリーンシート成形用材料によれば、伸度および強度が共に優れたセラミックグリーンシートが得られる。 According to the resin composition for molding a ceramic green sheet and the material for molding a ceramic green sheet of the present invention, a ceramic green sheet having excellent elongation and strength can be obtained.
≪セラミックグリーンシート成形用樹脂組成物≫
本発明のセラミックグリーンシート成形用樹脂組成物（以下、「本樹脂組成物」とも記す。）は、低分子量アクリル重合体（Ａ）と樹脂（Ｂ）とを含む。
本樹脂組成物は、必要に応じて、本発明の効果を損なわない範囲で、低分子量アクリル重合体（Ａ）および樹脂（Ｂ）以外の他の成分をさらに含んでいてもよい。ただし本樹脂組成物は、無機粉体（Ｃ）を含まないものとする。
本樹脂組成物は、必要に応じて、有機溶剤を含んでもよい。
≪Resin composition for forming ceramic green sheets≫
The resin composition for molding a ceramic green sheet of the present invention (hereinafter also referred to as “the present resin composition”) includes a low molecular weight acrylic polymer (A) and a resin (B).
The present resin composition may further contain other components other than the low molecular weight acrylic polymer (A) and the resin (B) as required, as long as the effects of the present invention are not impaired. However, this resin composition does not contain inorganic powder (C).
The present resin composition may contain an organic solvent as necessary.
＜低分子量アクリル重合体（Ａ）＞
低分子量アクリル重合体（Ａ）において「アクリル重合体」とは、アクリル系単量体に基づく構成単位（単量体単位）を有する重合体である。アクリル系単量体とは、（メタ）アクリロイル基を有する単量体を示す。「（メタ）アクリロイル基」は、アクリロイル基およびメタクリロイル基の総称である。
<Low molecular weight acrylic polymer (A)>
In the low molecular weight acrylic polymer (A), the “acrylic polymer” is a polymer having a structural unit (monomer unit) based on an acrylic monomer. An acrylic monomer refers to a monomer having a (meth) acryloyl group. “(Meth) acryloyl group” is a general term for an acryloyl group and a methacryloyl group.
低分子量アクリル重合体（Ａ）を形成するアクリル系単量体としては、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ｎ−ブチル、（メタ）アクリル酸ｉ−ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸へプチル、（メタ）アクリル酸オクチル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ｎ−ラウリル等の（メタ）アクリル酸アルキルエステル；（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等の水酸基含有（メタ）アクリル酸エステル；アクリル酸、メタクリル酸等が挙げられる。「（メタ）アクリル酸」は、アクリル酸およびメタクリル酸の総称である。これらはいずれか１種を単独で用いてもよく２種以上を併用してもよい。 Examples of the acrylic monomer that forms the low molecular weight acrylic polymer (A) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid i. -Butyl, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isodecyl (meth) acrylate, (meth ) (Meth) acrylic acid alkyl esters such as n-lauryl acrylate; hydroxyl-containing (meth) acrylic esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; acrylic acid, methacrylic An acid etc. are mentioned. “(Meth) acrylic acid” is a general term for acrylic acid and methacrylic acid. Any of these may be used alone or in combination of two or more.
低分子量アクリル重合体（Ａ）は、好ましいガラス転移温度に調整する観点で、アクリル酸アルキルエステルに基づく構成単位を有することが好ましい。
アクリル酸アルキルエステルとしては、アルキル基の炭素数が１〜１２であるものが好ましい。
The low molecular weight acrylic polymer (A) preferably has a structural unit based on an alkyl acrylate ester from the viewpoint of adjusting to a preferred glass transition temperature.
As the alkyl acrylate ester, those in which the alkyl group has 1 to 12 carbon atoms are preferable.
低分子量アクリル重合体（Ａ）は、無機粉体（Ｃ）の分散性の点では、水酸基含有（メタ）アクリル酸エステル、アクリル酸およびメタクリル酸からなる群から選ばれる少なくとも１種の単量体（以下、単量体（ａ２）とも記す。）に基づく構成単位を有することが好ましい。
従来のセラミックグリーンシートには通常、スラリー調製時の無機粉体の分散性の向上のために、分散剤が配合されている。低分子量アクリル重合体（Ａ）が単量体（ａ２）に基づく構成単位を有する場合、低分子量アクリル重合体（Ａ）は分散剤としても機能する。そのため、分散剤を別途配合しなくても、スラリー中に無機粉体（Ｃ）が良好に分散し、得られるセラミックグリーンシート中の無機粉体（Ｃ）の分散均一性が良好になる。分散剤を配合しないことで、セラミックグリーンシートの材料を削減し、生産コストを低減できる。
The low molecular weight acrylic polymer (A) is at least one monomer selected from the group consisting of a hydroxyl group-containing (meth) acrylic acid ester, acrylic acid and methacrylic acid in terms of dispersibility of the inorganic powder (C). It is preferable to have a structural unit based on (hereinafter also referred to as monomer (a2)).
Conventional ceramic green sheets are usually mixed with a dispersant to improve the dispersibility of the inorganic powder during slurry preparation. When the low molecular weight acrylic polymer (A) has a structural unit based on the monomer (a2), the low molecular weight acrylic polymer (A) also functions as a dispersant. Therefore, even if a dispersant is not added separately, the inorganic powder (C) is well dispersed in the slurry, and the dispersion uniformity of the inorganic powder (C) in the obtained ceramic green sheet is improved. By not blending the dispersant, the material of the ceramic green sheet can be reduced and the production cost can be reduced.
低分子量アクリル重合体（Ａ）が（メタ）アクリル酸アルキルエステルに基づく構成単位を有する場合、（メタ）アクリル酸アルキルエステルに基づく構成単位の含有量は、低分子量アクリル重合体（Ａ）を構成する全構成単位の合計に対し、２５〜１００質量％が好ましい。 When the low molecular weight acrylic polymer (A) has a structural unit based on (meth) acrylic acid alkyl ester, the content of the structural unit based on (meth) acrylic acid alkyl ester constitutes the low molecular weight acrylic polymer (A). The total content of all structural units is preferably 25 to 100% by mass.
低分子量アクリル重合体（Ａ）中、単量体（ａ２）に基づく構成単位の含有量は、低分子量アクリル重合体（Ａ）を構成する全構成単位の合計に対し、０〜７５質量％が好ましい。また、１０質量％以上であれば、無機粉体（Ｃ）の分散性がより優れる。 In the low molecular weight acrylic polymer (A), the content of the structural unit based on the monomer (a2) is 0 to 75% by mass with respect to the total of all the structural units constituting the low molecular weight acrylic polymer (A). preferable. Moreover, if it is 10 mass% or more, the dispersibility of inorganic powder (C) will be more excellent.
低分子量アクリル重合体（Ａ）の重量平均分子量（Ｍｗ）は１０，０００以下であり、５０００以下であることが好ましい。重量平均分子量（Ｍｗ）が上記上限値以下であれば、低分子量アクリル重合体（Ａ）が樹脂（Ｂ）に対して可塑剤として機能し、本樹脂組成物から得られるセラミックグリーンシートの伸度が優れる。
低分子量アクリル重合体（Ａ）の重量平均分子量（Ｍｗ）の下限は、可塑剤としての機能の点では特に限定されないが、典型的には１，０００以上である。
低分子量アクリル重合体（Ａ）の重量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）により測定される標準ポリスチレン換算の値である。
The weight average molecular weight (Mw) of the low molecular weight acrylic polymer (A) is 10,000 or less, preferably 5000 or less. If the weight average molecular weight (Mw) is not more than the above upper limit, the low molecular weight acrylic polymer (A) functions as a plasticizer for the resin (B), and the elongation of the ceramic green sheet obtained from the resin composition Is excellent.
The lower limit of the weight average molecular weight (Mw) of the low molecular weight acrylic polymer (A) is not particularly limited in terms of the function as a plasticizer, but is typically 1,000 or more.
The weight average molecular weight (Mw) of the low molecular weight acrylic polymer (A) is a standard polystyrene equivalent value measured by gel permeation chromatography (GPC).
低分子量アクリル重合体（Ａ）のガラス転移温度（Ｔｇ）は−２０℃以下であり、−４０℃以下であることが好ましい。ガラス転移温度（Ｔｇ）が上記上限値以下であれば、低分子量アクリル重合体（Ａ）が樹脂（Ｂ）に対して可塑剤として機能し、本樹脂組成物から得られるセラミックグリーンシートの伸度が優れたものとなる。また、フタル酸エステル系可塑剤等の従来汎用の可塑剤を用いる場合に比べて、得られるセラミックグリーンシートの強度が高まる。
低分子量アクリル重合体（Ａ）のガラス転移温度（Ｔｇ）の下限は、可塑剤としての機能の点では特に限定されないが、典型的には−７５℃以上である。
低分子量アクリル重合体（Ａ）のガラス転移温度（Ｔｇ）は、示差走査熱量計（島津製作所社製、ＤＳＣ−６０）により測定される値である。
低分子量アクリル重合体（Ａ）のガラス転移温度（Ｔｇ）は、低分子量アクリル重合体（Ａ）を形成する単量体の種類、組成、低分子量アクリル重合体（Ａ）の重量平均分子量（Ｍｗ）等により調整できる。
The glass transition temperature (Tg) of the low molecular weight acrylic polymer (A) is −20 ° C. or lower, and preferably −40 ° C. or lower. If the glass transition temperature (Tg) is not more than the above upper limit, the low molecular weight acrylic polymer (A) functions as a plasticizer for the resin (B), and the elongation of the ceramic green sheet obtained from the resin composition Will be excellent. In addition, the strength of the obtained ceramic green sheet is increased as compared with the case of using a conventional general plasticizer such as a phthalate ester plasticizer.
The lower limit of the glass transition temperature (Tg) of the low molecular weight acrylic polymer (A) is not particularly limited in terms of the function as a plasticizer, but is typically −75 ° C. or higher.
The glass transition temperature (Tg) of the low molecular weight acrylic polymer (A) is a value measured by a differential scanning calorimeter (manufactured by Shimadzu Corporation, DSC-60).
The glass transition temperature (Tg) of the low molecular weight acrylic polymer (A) is the type and composition of the monomer that forms the low molecular weight acrylic polymer (A), and the weight average molecular weight (Mw) of the low molecular weight acrylic polymer (A). ) Etc.
低分子量アクリル重合体（Ａ）は、常法により製造できる。例えばアクリル系単量体を、溶液重合法、懸濁重合法等によって重合して得ることができる。重合には通常、ラジカル重合開始剤の存在下で行われる。重合の際、連鎖移動剤を用いてもよい。ラジカル重合開始剤や連鎖移動剤の使用量、溶媒の種類、重合温度等によって低分子量アクリル重合体（Ａ）の重量平均分子量（Ｍｗ）を調整できる。 A low molecular weight acrylic polymer (A) can be manufactured by a conventional method. For example, an acrylic monomer can be obtained by polymerizing by a solution polymerization method, a suspension polymerization method or the like. The polymerization is usually performed in the presence of a radical polymerization initiator. A chain transfer agent may be used during the polymerization. The weight average molecular weight (Mw) of the low molecular weight acrylic polymer (A) can be adjusted by the amount of radical polymerization initiator and chain transfer agent used, the type of solvent, the polymerization temperature, and the like.
＜樹脂（Ｂ）＞
樹脂（Ｂ）は、アクリル樹脂およびブチラール樹脂からなる群から選ばれる少なくとも１種である。
<Resin (B)>
The resin (B) is at least one selected from the group consisting of acrylic resins and butyral resins.
アクリル樹脂は、アクリル系単量体に基づく構成単位（単量体単位）を有する重合体である。
アクリル樹脂を形成するアクリル系単量体としては、特に限定されず、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ｎ−プロピル、（メタ）アクリル酸ｉ−プロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸ｉ−ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸へプチル、（メタ）アクリル酸オクチル等の（メタ）アクリル酸アルキルエステル；（メタ）アクリル酸２−メトキシエチル、（メタ）アクリル酸２−エトキシエチル、（メタ）アクリル酸２−（ｎ−プロポキシ）エチル、（メタ）アクリル酸２−（ｎ−ブトキシ）エチル、（メタ）アクリル酸３−メトキシプロピル、（メタ）アクリル酸３−エトキシプロピル、（メタ）アクリル酸２−（ｎ−プロポキシ）プロピル、（メタ）アクリル酸２−（ｎ−ブトキシ）プロピル等の（メタ）アクリル酸アルコキシアルキルエステル；（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ジシクロペンタニル、（メタ）アクリル酸イソボルニル等の脂環式基含有（メタ）アクリル酸エステル、（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等の水酸基含有（メタ）アクリル酸エステル；アクリル酸、メタクリル酸等が挙げられる。これらはいずれか１種を単独で用いてもよく２種以上を併用してもよい。
The acrylic resin is a polymer having a structural unit (monomer unit) based on an acrylic monomer.
The acrylic monomer that forms the acrylic resin is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate. N-butyl (meth) acrylate, i-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, (Meth) acrylic acid alkyl esters such as octyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (n-propoxy) ethyl (meth) acrylate, (Meth) acrylic acid 2- (n-butoxy) ethyl, (meth) acrylic acid 3-methoxypropyl, (meth) acrylic acid 3- (Meth) acrylic acid alkoxyalkyl esters such as toxipropyl, 2- (n-propoxy) propyl (meth) acrylate, 2- (n-butoxy) propyl (meth) acrylate; cyclohexyl (meth) acrylate, (meth ) Alicyclic group-containing (meth) acrylic esters such as dicyclopentanyl acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. Containing (meth) acrylic acid ester; acrylic acid, methacrylic acid and the like. Any of these may be used alone or in combination of two or more.
ブチラール樹脂は、ブチラール基を含む構成単位を有する重合体であり、工業的に用いられる一般的なものを使用でき、例えばポリビニルブチラール樹脂が挙げられる。ポリビニルブチラール樹脂は、ポリビニルアルコールとブチルアルデヒドとの反応生成物であり、例えばポリビニルアルコールとブチルアルデヒドとを酸触媒の存在下で反応させて得られる。具体的には積水化学工業株式会社製のエスレック（登録商標）ＢＭ−１、 エスレックＢＭ−２、 エスレックＢＭ−５、 エスレックＢＭ−Ｓ、 エスレックＢＨ−３、エスレックＢＨ−６、 エスレックＢＨ−Ｓ、 エスレックＢＸ−１、 エスレックＢＸ−５、等が挙げられる。 The butyral resin is a polymer having a structural unit containing a butyral group, and a general industrially used one can be used, for example, a polyvinyl butyral resin. The polyvinyl butyral resin is a reaction product of polyvinyl alcohol and butyraldehyde, and can be obtained, for example, by reacting polyvinyl alcohol and butyraldehyde in the presence of an acid catalyst. Specifically, SREC (registered trademark) BM-1, ESREC BM-2, ESREC BM-5, ESREC BM-S, ESREC BH-3, ESREC BH-6, ESREC BH-S, manufactured by Sekisui Chemical Co., Ltd. ESREC BX-1, ESREC BX-5, etc. are mentioned.
樹脂（Ｂ）の重量平均分子量（Ｍｗ）は、１００，０００〜１，０００，０００であることが好ましい。樹脂（Ｂ）の重量平均分子量（Ｍｗ）が上記下限値以上であれば、本樹脂組成物から得られるセラミックグリーンシートの強度が優れる。樹脂（Ｂ）の重量平均分子量（Ｍｗ）が上記上限値以下であれば、本樹脂組成物から得られるセラミックグリーンシートの伸度が優れる。
樹脂（Ｂ）の重量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）により測定される標準ポリスチレン換算の値である。
The weight average molecular weight (Mw) of the resin (B) is preferably 100,000 to 1,000,000. If the weight average molecular weight (Mw) of resin (B) is more than the said lower limit, the intensity | strength of the ceramic green sheet obtained from this resin composition will be excellent. When the weight average molecular weight (Mw) of the resin (B) is not more than the above upper limit, the elongation of the ceramic green sheet obtained from the resin composition is excellent.
The weight average molecular weight (Mw) of the resin (B) is a standard polystyrene equivalent value measured by gel permeation chromatography (GPC).
樹脂（Ｂ）のガラス転移温度（Ｔｇ）は、４０℃以上であり、５０℃以上であることが好ましい。樹脂（Ｂ）ガラス転移温度（Ｔｇ）が上記下限値以上であれば、得られるセラミックグリーンシートの強度が優れる。
樹脂（Ｂ）のガラス転移温度（Ｔｇ）の上限は、セラミックグリーンシートの強度の点では特に限定されないが、１２０℃以下であることが、より高伸度のセラミックグリーンシートが得られる点で好ましい。
樹脂（Ｂ）のガラス転移温度（Ｔｇ）は、示差走査熱量計（島津製作所社製、ＤＳＣ−６０）により測定される値である。
The glass transition temperature (Tg) of the resin (B) is 40 ° C. or higher, and preferably 50 ° C. or higher. If resin (B) glass transition temperature (Tg) is more than the said lower limit, the intensity | strength of the ceramic green sheet obtained will be excellent.
The upper limit of the glass transition temperature (Tg) of the resin (B) is not particularly limited in terms of the strength of the ceramic green sheet, but it is preferably 120 ° C. or less from the viewpoint of obtaining a higher elongation ceramic green sheet. .
The glass transition temperature (Tg) of the resin (B) is a value measured by a differential scanning calorimeter (manufactured by Shimadzu Corporation, DSC-60).
＜他の成分＞
本樹脂組成物が含んでいてもよい他の成分としては、後述する本発明のセラミックグリーンシート成形用材料が含んでいてもよい他の成分と同様のものが挙げられる。
<Other ingredients>
Examples of the other components that may be contained in the resin composition include the same components as other components that may be contained in the ceramic green sheet molding material of the present invention described later.
＜有機溶剤＞
本樹脂組成物が含んでいてもよい有機溶剤としては、後述する本発明のセラミックグリーンシート成形用材料が含んでいてもよい有機溶剤と同様のものが挙げられる。
<Organic solvent>
As an organic solvent which this resin composition may contain, the thing similar to the organic solvent which the ceramic green sheet molding material of this invention mentioned later may contain is mentioned.
＜各成分の含有量＞
本樹脂組成物において、低分子量アクリル重合体（Ａ）と樹脂（Ｂ）との質量比は、低分子量アクリル重合体（Ａ）／樹脂（Ｂ）（以下、「Ａ／Ｂ」とも記す。）＝５／９５〜５０／５０の範囲内であることが好ましく、１０／９０〜４０／６０の範囲内であることがより好ましい。Ａ／Ｂが前記範囲内であれば、セラミックグリーンシートの伸度、強度がより優れる。
<Content of each component>
In this resin composition, the mass ratio between the low molecular weight acrylic polymer (A) and the resin (B) is low molecular weight acrylic polymer (A) / resin (B) (hereinafter also referred to as “A / B”). = Preferably within the range of 5/95 to 50/50, more preferably within the range of 10/90 to 40/60. When A / B is within the above range, the elongation and strength of the ceramic green sheet are more excellent.
＜用途＞
本樹脂組成物は、セラミックグリーンシートの成形に用いられる。例えば本樹脂組成物と、無機粉体（Ｃ）とを混合することで、後述する本発明のセラミックグリーンシート成形用材料とすることができ、この材料をシート状に成形することでセラミックグリーンシートが得られる。
<Application>
The resin composition is used for forming a ceramic green sheet. For example, by mixing the resin composition and the inorganic powder (C), it can be used as a ceramic green sheet molding material of the present invention described later. By molding this material into a sheet shape, the ceramic green sheet Is obtained.
＜作用効果＞
本樹脂組成物において、樹脂（Ｂ）は、無機粉体（Ｃ）を結合するバインダとして機能し、低分子量アクリル重合体（Ａ）は、樹脂（Ｂ）の可塑剤として機能する。
低分子量アクリル重合体（Ａ）を用いることで、従来のセラミックグリーンシートに汎用されているフタル酸エステル系可塑剤を用いる場合に比べて、得られるセラミックグリーンシートの強度がより優れる。また、伸度も、従来と同等以上の優れたものとなる。
<Effect>
In the present resin composition, the resin (B) functions as a binder for binding the inorganic powder (C), and the low molecular weight acrylic polymer (A) functions as a plasticizer for the resin (B).
By using the low molecular weight acrylic polymer (A), the strength of the obtained ceramic green sheet is more excellent as compared with the case of using a phthalate ester plasticizer that is widely used in conventional ceramic green sheets. In addition, the elongation is also superior to that of the conventional one.
≪セラミックグリーンシート成形用材料≫
本発明のセラミックグリーンシート成形用材料（以下、「本材料」とも記す。）は、低分子量アクリル重合体（Ａ）と樹脂（Ｂ）と無機粉体（Ｃ）とを含む。
低分子量アクリル重合体（Ａ）、樹脂（Ｂ）はそれぞれ、本樹脂組成物における低分子量アクリル重合体（Ａ）、樹脂（Ｂ）と同様であり、好ましい態様も同様である。
本材料は、必要に応じて、本発明の効果を損なわない範囲で、低分子量アクリル重合体（Ａ）、樹脂（Ｂ）および無機粉体（Ｃ）以外の他の成分をさらに含んでいてもよい。
本材料は、必要に応じて、有機溶剤を含んでもよい。
≪Material for forming ceramic green sheet≫
The ceramic green sheet molding material of the present invention (hereinafter also referred to as “the present material”) includes a low molecular weight acrylic polymer (A), a resin (B), and an inorganic powder (C).
The low molecular weight acrylic polymer (A) and the resin (B) are the same as the low molecular weight acrylic polymer (A) and the resin (B) in the present resin composition, respectively, and the preferred embodiments are also the same.
This material may further contain other components other than the low molecular weight acrylic polymer (A), the resin (B), and the inorganic powder (C) as necessary, as long as the effects of the present invention are not impaired. Good.
The material may contain an organic solvent as necessary.
＜無機粉体（Ｃ）＞
無機粉体（Ｃ）としては、特に限定されず、セラミックグリーンシート用途において公知のものであってよい。具体例としては、アルミナ、ジルコニア、ケイ酸アルミニウム、酸化チタン、酸化亜鉛、チタン酸バリウム、炭化珪素、窒化珪素、窒化アルミニウム等が挙げられる。これらはいずれか１種を単独で用いてもよく２種以上を併用してもよい。
<Inorganic powder (C)>
The inorganic powder (C) is not particularly limited and may be a known one for ceramic green sheet applications. Specific examples include alumina, zirconia, aluminum silicate, titanium oxide, zinc oxide, barium titanate, silicon carbide, silicon nitride, and aluminum nitride. Any of these may be used alone or in combination of two or more.
＜他の成分＞
他の成分としては、例えば、分散剤（ただし低分子量アクリル重合体（Ａ）を除く。）、可塑剤（ただし低分子量アクリル重合体（Ａ）を除く。）、湿潤剤、消泡剤、帯電防止剤、減粘剤等が挙げられる。これらの添加剤はいずれか１種を単独で用いてもよく２種以上を併用してもよい。
分散剤としては、塗料用として一般的に用いられるものであればよく、市販品のもので構わない。例えば、楠本化学社製ディスパロン１２１０、ディスパロン２１５０、ディスパロンＫＳ−８６０、ディスパロンＫＳ８７３Ｎ等、サンノプコ社製ノプコスパース０９２、ＳＮディパーサント９２２８、ＳＮスパース７０等、味の素ファインテクノ社製アジスパーＰＮ４１１、アジスパーＰＡ１１１等が挙げられる。
可塑剤としては、特に限定されず、例えばフタル酸ジメチル、フタル酸ジエチル、フタル酸ジブチル、フタル酸ジエチルヘキシル、フタル酸ジオクチル、フタル酸ジイソデシル、フタル酸ブチルベンジル等のフタル酸エステル系の可塑剤；アジピン酸２−エチルヘキシル、アジピン酸ジオクチル、アジピン酸ジイソデシル等のアジピン酸エステル系の可塑剤；リン酸トリエチル、リン酸トリス−２−エチルヘキシル、リン酸トリフェニル等のリン酸エステル系の可塑剤等が挙げられる。
<Other ingredients>
Other components include, for example, a dispersant (excluding the low molecular weight acrylic polymer (A)), a plasticizer (excluding the low molecular weight acrylic polymer (A)), a wetting agent, an antifoaming agent, and a charge. An inhibitor, a viscosity reducing agent, etc. are mentioned. Any one of these additives may be used alone, or two or more thereof may be used in combination.
Any dispersing agent may be used as long as it is generally used for coatings, and any commercially available product may be used. For example, Disparon 1210, Disparon 2150, Disparon KS-860, Disparon KS873N, etc. manufactured by Enomoto Chemical Co., Ltd. .
The plasticizer is not particularly limited, and examples thereof include phthalate plasticizers such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diethylhexyl phthalate, dioctyl phthalate, diisodecyl phthalate, and butyl benzyl phthalate; Adipate plasticizers such as 2-ethylhexyl adipate, dioctyl adipate, diisodecyl adipate; phosphate plasticizers such as triethyl phosphate, tris-2-ethylhexyl phosphate, triphenyl phosphate, etc. Can be mentioned.
＜有機溶剤＞
有機溶剤としては、例えば酢酸エチル、酢酸ブチル、酢酸イソブチル、トルエン、キシレン、メチルシクロヘキサン、エタノール、ｎ−ブタノール、アセトン、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モノエチルエーテル、プロピレングリコールモノメチルエーテル等が挙げられる。
<Organic solvent>
Examples of the organic solvent include ethyl acetate, butyl acetate, isobutyl acetate, toluene, xylene, methylcyclohexane, ethanol, n-butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and the like. .
＜各成分の含有量＞
本材料における低分子量アクリル重合体（Ａ）と樹脂（Ｂ）との質量比（Ａ／Ｂ）の好ましい範囲は、本樹脂組成物におけるＡ／Ｂの好ましい範囲と同様である。
<Content of each component>
The preferred range of the mass ratio (A / B) of the low molecular weight acrylic polymer (A) and the resin (B) in the present material is the same as the preferred range of A / B in the present resin composition.
本材料中の無機粉体（Ｃ）の含有量は、低分子量アクリル重合体（Ａ）と樹脂（Ｂ）との合計１００質量部に対し、３００〜２０００質量部が好ましい。無機粉体（Ｃ）の含有量が前記範囲の上限値以下であれば、セラミックグリーンシートの強度、伸度がより優れる。無機粉体（Ｃ）の含有量が前記範囲の下限値以上であれば、セラミックグリーンシートを焼結する際の収縮を抑制できる。 The content of the inorganic powder (C) in the material is preferably 300 to 2000 parts by mass with respect to 100 parts by mass in total of the low molecular weight acrylic polymer (A) and the resin (B). If content of inorganic powder (C) is below the upper limit of the said range, the intensity | strength and elongation of a ceramic green sheet will be more excellent. If content of inorganic powder (C) is more than the lower limit of the said range, the shrinkage | contraction at the time of sintering a ceramic green sheet can be suppressed.
本材料中の他の成分の含有量は、他の成分の種類に応じて、本発明の効果を損なわない範囲で適宜設定でき、特に限定されないが、低分子量アクリル重合体（Ａ）と樹脂（Ｂ）との合計１００質量部に対し、５０質量部以下が好ましい。 The content of other components in the material can be appropriately set within a range not impairing the effects of the present invention, depending on the type of the other components, and is not particularly limited. However, the low molecular weight acrylic polymer (A) and the resin ( 50 parts by mass or less is preferable with respect to 100 parts by mass in total with B).
本材料は、例えば、低分子量アクリル重合体（Ａ）と、樹脂（Ｂ）と、無機粉体（Ｃ）と、必要に応じて他の成分と、有機溶剤とを混合することにより調製できる。各材料の混合は、ボールミル等の公知の混合装置を用いて行うことができる。各材料の混合順序は特に限定されない。 This material can be prepared by, for example, mixing a low molecular weight acrylic polymer (A), a resin (B), an inorganic powder (C), other components as necessary, and an organic solvent. The mixing of each material can be performed using a known mixing apparatus such as a ball mill. The mixing order of each material is not particularly limited.
＜用途＞
本材料は、セラミックグリーンシートの成形に用いられる。
セラミックグリーンシートの成形は、公知の方法により行うことができる。例えば本材料が有機溶剤を含む場合、スラリー状の本材料をドクターブレード法等によって支持体上に塗布し、乾燥させて有機溶剤を除去し、支持体を剥離する方法、本材料の粒子を乾式プレス法等で成形する方法等が挙げられる。支持体としては、表面が平滑で剥離性を有するものが好ましく、例えば、離型処理されたポリエチレンテレフタレートフィルム（ＰＥＴフィルム）が挙げられる。
<Application>
This material is used for forming ceramic green sheets.
The ceramic green sheet can be formed by a known method. For example, when this material contains an organic solvent, a slurry-like material is applied onto a support by a doctor blade method, etc., dried to remove the organic solvent, and the support is peeled off. Examples of the method include molding by a pressing method. As the support, those having a smooth surface and peelability are preferable, and examples thereof include a polyethylene terephthalate film (PET film) subjected to a release treatment.
本材料から得られたセラミックグリーンシートは、打ち抜き加工等の加工が必要に応じて施され、セラミックパッケージの製造に使用される。例えば、該セラミックグリーンシートに、内部電極を形成するための導電性組成物をスクリーン印刷法等により所定のパターンに印刷して印刷層付きグリーンシートとし、これを複数枚重ねて加熱圧縮して積層体とし、これを焼成すると、セラミックグリーンシート中の低分子量アクリル重合体（Ａ）および樹脂（Ｂ）が熱分解して除去され、セラミック多層配線基板が得られる。 The ceramic green sheet obtained from this material is subjected to processing such as punching as required, and is used for manufacturing a ceramic package. For example, a conductive sheet for forming internal electrodes is printed on the ceramic green sheet in a predetermined pattern by a screen printing method or the like to obtain a green sheet with a printed layer, and a plurality of these are stacked and heated and compressed to be laminated. When the body is fired, the low molecular weight acrylic polymer (A) and the resin (B) in the ceramic green sheet are thermally decomposed and removed, and a ceramic multilayer wiring board is obtained.
＜作用効果＞
本材料において、樹脂（Ｂ）は、無機粉体（Ｃ）を結合するバインダとして機能し、低分子量アクリル重合体（Ａ）は、樹脂（Ｂ）の可塑剤として機能する。
低分子量アクリル重合体（Ａ）を用いることで、従来のセラミックグリーンシートに汎用されているフタル酸エステル系可塑剤を用いる場合に比べて、得られるセラミックグリーンシートの強度がより優れる。また、伸度も、従来と同等以上の優れたものとなる。
<Effect>
In this material, the resin (B) functions as a binder for binding the inorganic powder (C), and the low molecular weight acrylic polymer (A) functions as a plasticizer for the resin (B).
By using the low molecular weight acrylic polymer (A), the strength of the obtained ceramic green sheet is more excellent as compared with the case of using a phthalate ester plasticizer that is widely used in conventional ceramic green sheets. In addition, the elongation is also superior to that of the conventional one.
以下、実施例により本発明をさらに詳しく説明する。ただし本発明は、以下の実施例に限定されるものではない。
なお、以下の各例中、「部」は「質量部」を示す。
低分子量アクリル重合体およびアクリル樹脂の重量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）により、標準ポリスチレン換算の値を測定し、ガラス転移温度（Ｔｇ）は、示差走査熱量計（島津製作所社製、ＤＳＣ−６０）により求めた。
ブチラール樹脂の重量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）の値を測定し、ガラス転移温度（Ｔｇ）は、示差走査熱量計（島津製作所社製、ＤＳＣ−６０）により求めた。
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
In the following examples, “part” represents “part by mass”.
The weight average molecular weight (Mw) of the low molecular weight acrylic polymer and the acrylic resin is a standard polystyrene conversion value measured by gel permeation chromatography (GPC), and the glass transition temperature (Tg) is a differential scanning calorimeter (Shimadzu Corporation). It was determined by DSC-60).
The weight average molecular weight (Mw) of the butyral resin was measured by gel permeation chromatography (GPC), and the glass transition temperature (Tg) was determined by a differential scanning calorimeter (manufactured by Shimadzu Corporation, DSC-60).
＜製造例Ａ１：低分子量アクリル重合体（Ａ１）の製造＞
重合用の攪拌羽を装着した攪拌棒、温度計、窒素パージ用のガラス管を備えたセパラブルフラスコに、アクリル酸ｎ−ブチル１００部、トルエン２５０部および重合開始剤（２，２’−アゾビス（２−メチルプロピオニトリル））１５．０部を加え、窒素雰囲気下、撹拌しながら９５℃で８時間保持して溶液重合を行い、重量平均分子量（Ｍｗ）が３，０００、ガラス転移温度（Ｔｇ）が−７５℃の低分子量アクリル重合体（Ａ１）の溶液を得た。
<Production Example A1: Production of Low Molecular Weight Acrylic Polymer (A1)>
In a separable flask equipped with a stirring rod equipped with a stirring blade for polymerization, a thermometer, and a glass tube for purging nitrogen, 100 parts of n-butyl acrylate, 250 parts of toluene and a polymerization initiator (2,2′-azobis) (2-methylpropionitrile)) 15.0 parts was added, and the solution polymerization was carried out by stirring at 95 ° C. for 8 hours under stirring in a nitrogen atmosphere. The weight average molecular weight (Mw) was 3,000, and the glass transition temperature. A solution of a low molecular weight acrylic polymer (A1) having a (Tg) of −75 ° C. was obtained.
＜製造例Ａ２〜Ａ５＞
重合する単量体の種類と量（部）、重合開始剤の量（部）を表１に示すように変更した以外は製造例Ａ１と同様にして、低分子量アクリル重合体（Ａ１）〜（Ａ５）の溶液を得た。低分子量アクリル重合体（Ａ１）〜（Ａ５）の重量平均分子量（Ｍｗ）およびガラス転移温度（Ｔｇ）を表１に示す。
<Production Examples A2 to A5>
Low molecular weight acrylic polymers (A1) to (A1) to (A) are produced in the same manner as in Production Example A1, except that the type and amount (parts) of the monomer to be polymerized and the amount (parts) of the polymerization initiator are changed as shown in Table 1. A solution of A5) was obtained. Table 1 shows the weight average molecular weight (Mw) and glass transition temperature (Tg) of the low molecular weight acrylic polymers (A1) to (A5).
＜製造例Ｂ１：アクリル樹脂（Ｂ１）の製造＞
重合用の攪拌羽を装着した攪拌棒、温度計を備えたセパラブルフラスコに、イオン交換水３００部およびノニオン系分散剤（株式会社クラレ製、「ＰＶＡ２３５」）０．３部を加えた後、メタクリル酸メチル９９．０部、メタクリル酸１．０部、連鎖移動剤（ｎ−ドデシルメルカプタン）０．０５部および重合開始剤（過酸化ベンゾイル）２．２部を加え、撹拌しながら８０℃で２時間保持して懸濁重合を行い、重合体の懸濁液を得た。
得られた懸濁液を３０℃まで冷却し、遠心脱水機で脱水し、５０℃、２４時間の条件で乾燥させて、重量平均分子量（Ｍｗ）が３００，０００、ガラス転移温度（Ｔｇ）が１１０℃のアクリル樹脂（Ｂ１）を得た。
<Production Example B1: Production of acrylic resin (B1)>
After adding 300 parts of ion-exchanged water and nonionic dispersant (manufactured by Kuraray Co., Ltd., “PVA235”) to a separable flask equipped with a stirring bar equipped with a stirring blade for polymerization and a thermometer, Add 99.0 parts of methyl methacrylate, 1.0 part of methacrylic acid, 0.05 part of chain transfer agent (n-dodecyl mercaptan) and 2.2 parts of polymerization initiator (benzoyl peroxide) at 80 ° C. with stirring. Suspension polymerization was carried out for 2 hours to obtain a polymer suspension.
The obtained suspension was cooled to 30 ° C., dehydrated with a centrifugal dehydrator, and dried at 50 ° C. for 24 hours. The weight average molecular weight (Mw) was 300,000, and the glass transition temperature (Tg) was An acrylic resin (B1) at 110 ° C. was obtained.
＜製造例Ｂ２、Ｂ３、Ｂ５〜Ｂ１０＞
重合する単量体の種類と量（部）、重合開始剤および連鎖移動剤の量（部）を表２に示すように変更した以外は製造例Ｂ１と同様にして、アクリル樹脂（Ｂ１）、（Ｂ２）、（Ｂ５）〜（Ｂ１０）を得た。アクリル樹脂（Ｂ１）、（Ｂ２）、（Ｂ５）〜（Ｂ１０）の重量平均分子量（Ｍｗ）およびガラス転移温度（Ｔｇ）を表２に示す。
<Production Examples B2, B3, B5 to B10>
Acrylic resin (B1), in the same manner as in Production Example B1, except that the type and amount (parts) of monomers to be polymerized, and the amount (parts) of polymerization initiator and chain transfer agent were changed as shown in Table 2. (B2) and (B5) to (B10) were obtained. Table 2 shows the weight average molecular weight (Mw) and glass transition temperature (Tg) of the acrylic resins (B1), (B2), and (B5) to (B10).
＜ブチラール樹脂（Ｂ４）＞
積水化学工業株式会社製のエスレックＢＭ−Ｓをブチラール樹脂（Ｂ４）とした。
<Butyral resin (B4)>
SLECK BM-S manufactured by Sekisui Chemical Co., Ltd. was used as butyral resin (B4).
＜実施例１＞
（セラミックグリーンシート成形用材料の調製およびセラミックグリーンシートの製造）
低分子量アクリル重合体（Ａ１）３５部と、アクリル樹脂（Ｂ１）６５部と、分散剤（サンノプコ株式会社製、ＳＮディスパーサント９２２８、ノニオン系分散剤）７．３部と、トルエン５３３部と、エタノール１３３部と、チタン酸バリウム（堺化学工業株式会社製、ＢＴ−０３）７３３部とを配合し、ボールミル分散機（中央化工機株式会社製）により４８時間攪拌混合してセラミックグリーンシート成形用のスラリーを得た。
次いで、このスラリーを、ドクターブレードを使用して支持体（パナック社製、剥離性ポリエチレンテレフタレートフィルム ＳＰ−ＰＥＴ１００−０１ＢＵ）上に塗布し、その塗膜を１００℃で３０分間乾燥し、その後、支持体を剥離して、厚さ３０μｍのセラミックグリーンシートを得た。
<Example 1>
(Preparation of ceramic green sheet molding material and production of ceramic green sheet)
35 parts of low molecular weight acrylic polymer (A1), 65 parts of acrylic resin (B1), 7.3 parts of a dispersant (manufactured by San Nopco, SN Dispersant 9228, nonionic dispersant), 533 parts of toluene, 133 parts of ethanol and 733 parts of barium titanate (manufactured by Sakai Chemical Industry Co., Ltd., BT-03) are blended and mixed for 48 hours with a ball mill disperser (manufactured by Chuo Kako Co., Ltd.) for forming a ceramic green sheet. A slurry of was obtained.
Then, this slurry was applied onto a support (manufactured by Panac Corporation, peelable polyethylene terephthalate film SP-PET100-01BU) using a doctor blade, the coating film was dried at 100 ° C. for 30 minutes, and then supported. The body was peeled off to obtain a ceramic green sheet having a thickness of 30 μm.
＜実施例２〜１３、比較例１〜５＞
低分子量アクリル重合体（Ａ）の種類、樹脂（Ｂ）の種類およびそれらの質量比（Ａ／Ｂ）を表３〜５に示すように変更した以外は実施例１と同様にして、厚さ３０μｍのセラミックグリーンシートを得た。
<Examples 2 to 13 and Comparative Examples 1 to 5>
The thickness of the low molecular weight acrylic polymer (A), the type of the resin (B), and the mass ratio (A / B) thereof were changed in the same manner as in Example 1 except that they were changed as shown in Tables 3 to 5. A 30 μm ceramic green sheet was obtained.
＜実施例１４＞
分散剤（サンノプコ株式会社製、ＳＮディスパーサント９２２８）を配合しなかった以外は実施例３と同様にして、厚さ３０μｍのセラミックグリーンシートを得た。
<Example 14>
A ceramic green sheet having a thickness of 30 μm was obtained in the same manner as in Example 3 except that the dispersant (manufactured by San Nopco, SN Dispersant 9228) was not blended.
得られたセラミックグリーンシートを以下の評価方法により評価した。結果を表３〜５に示す。
（評価方法）
各例で得られたセラミックグリーンシートの破断強度および伸度を、引張試験機（株式会社東洋精機製作所製、ＳＴＲＯＧＲＡＰＨ ＶＧ１−Ｅ）により測定した。測定条件は、温度２３℃、湿度５０％下で、引張試験機の引張そくどを１０ｍｍ／ｍｉｎとした。
別途、各例における低分子量アクリル重合体（Ａ）を可塑剤（フタル酸ジブチル）に置き換えて、厚さ３０μｍの可塑剤含有セラミックグリーンシートを得た。この可塑剤含有セラミックグリーンシートについて、上記と同様にして破断強度および伸度を測定した。
これらの結果から、各例のセラミックグリーンシートの破断強度および伸度をそれぞれ、以下の評価基準にて評価した。
「破断強度」
〇：破断強度が、対応する可塑剤含有セラミックグリーンシートの破断強度よりも高い値。
×：破断強度が、対応する可塑剤含有セラミックグリーンシートの破断強度と同じ値またはそれよりも低い値。
「伸度」
〇：伸度が、対応する可塑剤含有セラミックグリーンシートの伸度と同じ値またはそれよりも高い値。
×：伸度が、対応する可塑剤含有セラミックグリーンシートの伸度よりも低い値。
The obtained ceramic green sheet was evaluated by the following evaluation methods. The results are shown in Tables 3-5.
(Evaluation method)
The breaking strength and elongation of the ceramic green sheets obtained in each example were measured with a tensile tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., STROGRAPH VG1-E). The measurement conditions were a temperature of 23 ° C. and a humidity of 50%, and the tensile temperature of the tensile tester was 10 mm / min.
Separately, the low molecular weight acrylic polymer (A) in each example was replaced with a plasticizer (dibutyl phthalate) to obtain a plasticizer-containing ceramic green sheet having a thickness of 30 μm. With respect to this plasticizer-containing ceramic green sheet, the breaking strength and elongation were measured in the same manner as described above.
From these results, the breaking strength and elongation of the ceramic green sheet of each example were evaluated according to the following evaluation criteria.
"Breaking strength"
◯: The value at which the breaking strength is higher than the breaking strength of the corresponding plasticizer-containing ceramic green sheet.
X: The value at which the breaking strength is the same as or lower than the breaking strength of the corresponding plasticizer-containing ceramic green sheet.
"Elongation"
◯: The elongation is the same value or higher than the elongation of the corresponding plasticizer-containing ceramic green sheet.
X: The elongation is a value lower than the elongation of the corresponding plasticizer-containing ceramic green sheet.
上記結果に示すとおり、実施例１〜１３のセラミックグリーンシートは、フタル酸エステル系可塑剤を使用した比較例１のセラミックグリーンシートよりも高強度であり、伸度も同等以上であった。特に、Ａ／Ｂが５／９５〜５０／５０の範囲内の実施例１〜１２では、破断強度が優れていた。
また、分散剤を配合しなかった実施例１４でも良好な結果が得られた。このことから、低分子アクリル重合体（Ａ）が分散剤としての効果を有することも確認できた。
低分子量アクリル重合体（Ａ）の重量平均分子量（Ｍｗ）が１０，０００超の比較例１のセラミックグリーンシートは、伸度に劣っていた。
低分子量アクリル重合体（Ａ）のガラス転移温度が−２０℃よりも高い比較例２のセラミックグリーンシートは、強度、伸度ともに劣っていた。
樹脂（Ｂ）の重量平均分子量が１００，０００未満の比較例３のセラミックグリーンシートは、強度に劣っていた。
樹脂（Ｂ）の重量平均分子量が１，０００，０００超の比較例４のセラミックグリーンシートは、伸度に劣っていた。
樹脂（Ｂ）のガラス転移温度が４０℃未満の比較例５のセラミックグリーンシートは、強度に劣っていた。
As shown in the above results, the ceramic green sheets of Examples 1 to 13 were higher in strength than the ceramic green sheet of Comparative Example 1 using a phthalate ester plasticizer, and the elongation was equal or higher. In particular, in Examples 1 to 12 in which A / B was in the range of 5/95 to 50/50, the breaking strength was excellent.
Moreover, the favorable result was obtained also in Example 14 which did not mix | blend a dispersing agent. From this, it was also confirmed that the low molecular weight acrylic polymer (A) has an effect as a dispersant.
The ceramic green sheet of Comparative Example 1 in which the weight average molecular weight (Mw) of the low molecular weight acrylic polymer (A) was more than 10,000 was inferior in elongation.
The ceramic green sheet of Comparative Example 2 in which the glass transition temperature of the low molecular weight acrylic polymer (A) was higher than −20 ° C. was inferior in both strength and elongation.
The ceramic green sheet of Comparative Example 3 in which the weight average molecular weight of the resin (B) was less than 100,000 was inferior in strength.
The ceramic green sheet of Comparative Example 4 in which the weight average molecular weight of the resin (B) exceeds 1,000,000 was inferior in elongation.
The ceramic green sheet of Comparative Example 5 in which the glass transition temperature of the resin (B) was less than 40 ° C. was inferior in strength.
Claims (3)
アクリル樹脂およびブチラール樹脂からなる群から選ばれる少なくとも１種の樹脂であって重量平均分子量が１００，０００〜１，０００，０００、ガラス転移温度が４０℃以上である樹脂（Ｂ）と、
を含むことを特徴とするセラミックグリーンシート成形用樹脂組成物。 A low molecular weight acrylic polymer (A) having a weight average molecular weight of 10,000 or less and a glass transition temperature of −20 ° C. or less;
A resin (B) which is at least one resin selected from the group consisting of an acrylic resin and a butyral resin and has a weight average molecular weight of 100,000 to 1,000,000 and a glass transition temperature of 40 ° C. or higher;
A ceramic green sheet molding resin composition comprising:
アクリル樹脂およびブチラール樹脂からなる群から選ばれる少なくとも１種の樹脂であって重量平均分子量が１００，０００〜１，０００，０００、ガラス転移温度が４０℃以上である樹脂（Ｂ）と、
無機粉体（Ｃ）と、
を含むことを特徴とするセラミックグリーンシート成形用材料。 A low molecular weight acrylic polymer (A) having a weight average molecular weight of 10,000 or less and a glass transition temperature of −20 ° C. or less;
A resin (B) which is at least one resin selected from the group consisting of an acrylic resin and a butyral resin and has a weight average molecular weight of 100,000 to 1,000,000 and a glass transition temperature of 40 ° C. or higher;
Inorganic powder (C);
A ceramic green sheet molding material comprising:
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