JPH01270559A - Production of ceramic green sheet - Google Patents
Production of ceramic green sheetInfo
- Publication number
- JPH01270559A JPH01270559A JP63094414A JP9441488A JPH01270559A JP H01270559 A JPH01270559 A JP H01270559A JP 63094414 A JP63094414 A JP 63094414A JP 9441488 A JP9441488 A JP 9441488A JP H01270559 A JPH01270559 A JP H01270559A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- meth
- fine powder
- binder
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000000178 monomer Substances 0.000 claims abstract description 45
- 239000000843 powder Substances 0.000 claims abstract description 25
- 239000011230 binding agent Substances 0.000 claims abstract description 20
- 239000002002 slurry Substances 0.000 claims abstract description 20
- 230000002378 acidificating effect Effects 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 239000006259 organic additive Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 18
- -1 veria Chemical compound 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 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
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003849 aromatic solvent 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
- 238000005266 casting Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- UDJZTGMLYITLIQ-UHFFFAOYSA-N 1-ethenylpyrrolidine Chemical compound C=CN1CCCC1 UDJZTGMLYITLIQ-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 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
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- QNZFKUWECYSYPS-UHFFFAOYSA-N lead zirconium Chemical compound [Zr].[Pb] QNZFKUWECYSYPS-UHFFFAOYSA-N 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052863 mullite Inorganic materials 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
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はセラミックグリーンシートの製造に関するもの
である。さらに具体的には、酸性を示すセラミック微粉
体を用いてグリーンシートを製造するに際し、特定組成
の溶剤型（メタ）アクリル系共重合体をバインダーとし
て用いてなる十分な密度、強度及び可撓性を有すると共
に表面平滑性にすぐれたグリーンシートの製造方法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to the production of ceramic green sheets. More specifically, when manufacturing green sheets using ceramic fine powder that exhibits acidity, we have developed a system that provides sufficient density, strength, and flexibility by using a solvent-based (meth)acrylic copolymer with a specific composition as a binder. The present invention relates to a method for producing a green sheet that has the following properties and has excellent surface smoothness.
セラミックグリーンシートはセラミック微粉体にバイン
ダー、有機溶剤及び必要に応じ分散剤、可塑剤等を添加
し所要時間混練して得たスラリーをキャリヤーフィルム
上にドクターブレードで厚みを調整してキャスティング
し、乾燥して製造する。Ceramic green sheets are made by adding a binder, an organic solvent, and if necessary a dispersant, a plasticizer, etc. to fine ceramic powder and kneading the resulting slurry for the required time, casting the slurry onto a carrier film with a doctor blade to adjust the thickness, and drying. and manufacture it.
かかる方法においてバインターとしてはポリビニルブチ
ラール等のブチラール樹脂、エチルセルロース等のセル
ロース系樹脂、（メタ）アクリル酸エステルを共重合［
〜だ（メタ）アクリル系樹脂等が用いられている。In this method, as a binder, a butyral resin such as polyvinyl butyral, a cellulose resin such as ethyl cellulose, and a (meth)acrylic acid ester are copolymerized [
-(meth)acrylic resin etc. are used.
しかしながら、セラミック微粉体のうち酸性を呈するも
のは通常のバインダーを用いて混練すると該酸性セラミ
ック微粉体の分散性が悪く、混練に長時間を要し且つ分
散が不十分で二次凝集状態の粒子がそのまま残存する。However, when ceramic fine powder exhibiting acidity is kneaded with a normal binder, the dispersibility of the acidic ceramic fine powder is poor, and kneading takes a long time, and the particles are not sufficiently dispersed and are in a secondary agglomerated state. remains as is.
その結果、粒子間のトの密度が低くなシ、強度及び可撓
性に劣るためシートの巻取り保管工程や打抜き等の加工
を行なう工程においてグリーンシートに割れやヒビが生
じるという欠点があった。As a result, the density of particles between particles is low, and the strength and flexibility are poor, resulting in cracks and cracks in the green sheet during the process of winding and storing the sheet, punching, etc. .
本発明者等はかかる現状の問題点を解決するため鋭意研
究を重ねた結果、本発明を完成するに至ったものである
。The present inventors have completed the present invention as a result of extensive research in order to solve the current problems.
即ち本発明は酸性微粉体にバインダー、有機溶剤及び必
要に応じ添加剤を加えて所要時間混練して得るスラリー
を用いてセラミックグリーンシートを製造する方法にお
いて、酸性セラミック微粉体１００重量部に対しバイン
ダーとして、塩基性不飽和単量体（１） ０．５〜２０
重量％、炭素数が１〜２０個のアルキル基を有する（メ
タ）アクリル酸アルキルエステル（２１３０〜９９．５
重ｉ％および該単量体（１）及び（２）と共重合可能な
その他の不飽和単癒体（３）０〜５０重量係からなる重
合性屯量体成分（但し、単量体（１） 、（２）及び（
３）の合計は１００重量％である。）を有機溶剤中で重
合して得られる（メタ）アクリル系共重合体を３〜３０
重量部の割合で用いることを特徴とするセラミックグリ
ーンシートの製造方法に関するものである。That is, the present invention provides a method for manufacturing a ceramic green sheet using a slurry obtained by adding a binder, an organic solvent, and additives as necessary to acidic fine powder and kneading the mixture for a required period of time. As, basic unsaturated monomer (1) 0.5-20
Weight%, (meth)acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms (2130 to 99.5
A polymerizable monomer component consisting of 0 to 50% by weight of other unsaturated monomers (3) copolymerizable with the monomers (1) and (2) (however, the monomer ( 1), (2) and (
The total of 3) is 100% by weight. ) in an organic solvent.
The present invention relates to a method for producing a ceramic green sheet, characterized in that the ceramic green sheet is used in parts by weight.
以下本発明を具体的に説明する。The present invention will be specifically explained below.
本発明に使用される酸性セラミック微粉体はこれを水に
分散したスラリー状物が酸性を呈するものであり、例え
ば微粉体２０重量部と水８０重量部を混合したスラリー
ＯＰＨ値が７を下廻るものである。スラリーのＰ Ｈ値
はセラミック微粉体の製法、添加物、不純物等によって
大きく影響され、また粉体の表面処理によっても調整す
ることができる。従って使用する粉体のＰＨ値が７を下
廻る値のものであればジルコニア、チタニア、アルミ力
、シリカ、ベリアなどの酸化物、コージェライト、ムラ
イト、スピネル、ステアタイト、フォルステライト、カ
オリ＃などの複合系酸化物、チタン酸バリウム、ジルコ
ニウムリタン酸鉛やＹＢａＣｕｂ、等銅系などのペロブ
スカイト系酸化物、炭化珪素、窒化珪素、窒化アルミニ
ウム、ホウ化ジルコニウムなどの非酸化物、ホウケイ酸
等のガラス質あるいはこれらの混合物等を使用すること
ができる。特に好ましくは、ジルコニア、窒化珪素、ア
ルミナ、チタニア及びシリカ、チタン酸バリウム等があ
る。The acidic ceramic fine powder used in the present invention is a slurry obtained by dispersing it in water and exhibits acidity. For example, a slurry obtained by mixing 20 parts by weight of the fine powder and 80 parts by weight of water has an OPH value of less than 7. It is something. The PH value of the slurry is greatly influenced by the manufacturing method of the ceramic fine powder, additives, impurities, etc., and can also be adjusted by surface treatment of the powder. Therefore, if the PH value of the powder used is less than 7, oxides such as zirconia, titania, aluminum, silica, veria, cordierite, mullite, spinel, steatite, forsterite, Kaori # etc. Composite oxides of barium titanate, perovskite oxides such as copper-based lead zirconium ritanate, YBaCub, etc., non-oxides such as silicon carbide, silicon nitride, aluminum nitride, zirconium boride, and glasses such as borosilicate. or a mixture thereof can be used. Particularly preferred are zirconia, silicon nitride, alumina, titania, silica, barium titanate, and the like.
本発明における塩基性不飽和単量体（１）としては、そ
の水溶液又は水分散液が塩基性を呈するものであれば制
限なく使用できるが、分子内に塩基性窒素原子を有する
単量体、その塩及びその四級化物が入手が容易でかつ効
果の上でも優れており好ましい。The basic unsaturated monomer (1) in the present invention can be used without any restriction as long as its aqueous solution or aqueous dispersion exhibits basicity, but monomers having a basic nitrogen atom in the molecule, Salts thereof and quaternized products thereof are preferred because they are easily available and have excellent effects.
分子内に塩基性窒素原子を有する単量体（以下、単量体
ｆａ）という。）としては、例えばアミンエチル（メタ
）アクリレート、アミノエチル（メタ）アクリルアミド
、アリルアミン等の如き１級アミンを有する単量体；Ｎ
−メチルアミノエチル（メタ）アクリｌ／−１−５Ｎ−
フェニルアミノエチル（メタ）アクリレート等の如き２
級アミンを有する単量体；Ｎ、Ｎ−ジメチルアミノエチ
ル（メタ）アクリレート、Ｎ、Ｎ−ジメチルアミノエチ
ル（メタ）アクリルアミド、Ｎ−ビニル−２−ピロリド
ン、Ｎ−ビニルピロリジン、アクリロイルモルホリン、
ビニルピリジン等の如き３級アミンを有する単量体等を
、該単量体（ａｌの塩としては、例えば該単量体（ａ）
と塩酸、硫酸、リン酸等の無機酸との塩やギ酸、酢酸、
蓚酸、プロピオン酸等の如き有機酸との塩を、該単量体
（ａ）の四級化物としては、例えば該単量体（ａｌのハ
ロゲン化炭化水素やアルキル硫酸等の周知の四級化剤に
よる四級化物等を挙げることができ、これらの１種以上
を用いることができる。A monomer having a basic nitrogen atom in the molecule (hereinafter referred to as monomer fa). ), monomers having a primary amine such as amine ethyl (meth)acrylate, aminoethyl (meth)acrylamide, allylamine;
-methylaminoethyl(meth)acrylic/-1-5N-
2 such as phenylaminoethyl (meth)acrylate etc.
monomer having a class amine; N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, N-vinyl-2-pyrrolidone, N-vinylpyrrolidine, acryloylmorpholine,
A monomer having a tertiary amine, such as vinylpyridine, etc., is used as a salt of the monomer (al), for example, the monomer (a).
and salts with inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid,
Examples of the quaternized product of the monomer (a) include salts with organic acids such as oxalic acid and propionic acid, and known quaternized products such as halogenated hydrocarbons and alkyl sulfates of the monomer (al). For example, quaternized products can be mentioned, and one or more of these can be used.
塩基性不飽和単量体（１）は得られる共重合体の酸性セ
ラミック微粉体へ対する濡れ性や吸着性を向上させるた
めのもので、重合性単量体成分中０５や吸着歇が低下し
て分散性が悪くなると共にバインダーとしての結合力が
低下する。２００重量％こえる場合にはバインダーの熱
分解性が低下しセラミック焼成時に長時間を要してコス
トに影響したシ、又、有機溶剤への溶解性が低下するた
めバインダーの溶液粘度が上昇する。そのためスラリー
を調整する場合に必要以上の有機溶剤を加えなければな
らず、コストに影響したシ、シート乾燥時に収縮が大き
くなってシートの仕上り状態に悪影響を及ぼす。The basic unsaturated monomer (1) is used to improve the wettability and adsorptivity of the obtained copolymer to acidic ceramic fine powder, and reduces the adsorption duration and 05 in the polymerizable monomer components. As a result, the dispersibility deteriorates and the binding strength as a binder decreases. If it exceeds 200% by weight, the thermal decomposition properties of the binder will decrease, which will require a long time during ceramic firing, which will affect the cost, and the solubility in organic solvents will decrease, resulting in an increase in the solution viscosity of the binder. Therefore, when preparing the slurry, it is necessary to add more organic solvent than necessary, which affects the cost, and increases shrinkage during sheet drying, which adversely affects the finished state of the sheet.
炭素数が１〜２０個のアルキル基を有する（メタ）アク
リル酸アルキルエステル（２）としては、例えばメチル
（メタ）アクリレート、エチル（メタ）アクリレート、
ｎ−プロピル（メタ）アクリレート、ｉ−プロピル（メ
タ）アクリレート、ｎ−ブチル（メタ）アクリレート、
ｉ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）
アクリレート、２−エチルヘキシル（メタ）アクリレー
ト、シクロヘキシル（メタ）アクリレート、ラウリル（
メタ）アクリレート、ステアリル（メタ）アクリレート
等を挙げることができ、これらの１種以上を用いること
ができる。このような炭素数が１〜２０個のアルキル基
を有する（メタ）アクリル酸アルキルエステル（２）は
重合性単量体成分中３０〜９９．５重量％の範囲で用い
られなければならない。３００重量％満の場合にはバイ
ンダーの熱分解性が低下しセラミック焼成時に長時間を
要してコストの上昇を招いたシ、又しばしば炭化成分が
残存し、セラミックの絶縁性、誘電柚特性等を阻害する
ので好ましくない。逆に９９５重量係をこえる場合には
塩基性不飽和単量体（１）の使用量が前記規定量に満た
なくなシ、セラミック微粉体の分散性が悪くなるので好
ましくない。Examples of the (meth)acrylic acid alkyl ester (2) having an alkyl group having 1 to 20 carbon atoms include methyl (meth)acrylate, ethyl (meth)acrylate,
n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate,
i-Butyl (meth)acrylate, t-butyl (meth)
Acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, lauryl (
Examples include meth)acrylate and stearyl (meth)acrylate, and one or more of these can be used. The (meth)acrylic acid alkyl ester (2) having an alkyl group having 1 to 20 carbon atoms must be used in an amount of 30 to 99.5% by weight in the polymerizable monomer component. If the content is less than 300% by weight, the thermal decomposition of the binder decreases, resulting in a long time required for firing the ceramic, resulting in an increase in cost.Also, carbonized components often remain, which deteriorates the insulating properties and dielectric properties of the ceramic. This is not preferable because it inhibits On the other hand, if it exceeds 995% by weight, the amount of basic unsaturated monomer (1) used will be less than the specified amount and the dispersibility of the ceramic fine powder will deteriorate, which is not preferable.
その他の不飽和単量体（３）としては、該単量体（１）
及び（２）と共重合しうるものであれば特に制限されず
、例えば（メタ）アクリル酸、イタコン酸、クロトン酸
、マレイン酸及びその半エステル、フマル酸及びその半
エステル等の如きカルボキシル基含有不飽和単量体；（
メタ）アクリロニトリル等の如き不飽和シアン；（メタ
）アクリルアミド、Ｎ−メチロール（メタ）アクリルア
ミド等の如き不飽和アミド及びその誘導体；２−ヒドロ
キシエチル（メタ）アクリレート、２−ヒドロキシプロ
ピル（メタ）アクリレート、ポリプロピレングリコール
（メタ）アクリレート、ポリエチレングリコール（メタ
）アクリレート等の如き水酸基含有不飽和単量体；その
他スチレーン、α−メチルスチレン、酢酸ビニル、フロ
ピオン酸ビニル、マレイン酸、フマル酸、イタコン酸の
ジエステル等を挙げることがそき、これらの１種以上用
いることができる。これら不飽和単量体（３）は必要に
応じて用いられるもので全共重合単量体１００重量係中
１Ｏ〜５０重量係の範囲で用いられる。５００重量％越
えるとバインダーの熱分解性が低下し、前述のような不
都合が生じる。Other unsaturated monomers (3) include the monomer (1)
There is no particular restriction as long as it can be copolymerized with Unsaturated monomer; (
Unsaturated cyanogens such as meth)acrylonitrile; unsaturated amides and derivatives thereof such as (meth)acrylamide, N-methylol (meth)acrylamide, etc.; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, Hydroxyl group-containing unsaturated monomers such as polypropylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate, etc.; Others such as styrene, α-methylstyrene, vinyl acetate, vinyl propionate, diesters of maleic acid, fumaric acid, itaconic acid, etc. One or more of these can be used. These unsaturated monomers (3) are used as necessary, and are used in an amount of 10 to 50 parts by weight based on 100 parts by weight of the total copolymerized monomers. If it exceeds 500% by weight, the thermal decomposition properties of the binder will decrease, causing the above-mentioned disadvantages.
本発明における（メタ）アクリル系共重合体は塩基性不
飽和単量体（１）炭素数が１〜２０個のアルキル基を有
する（メタ）アクリル酸アルキルエステル（２）及びそ
の他の不飽和単量体（３）からなる重合性単量体成分を
周知の溶液重合によシ共重合して得られる。The (meth)acrylic copolymer in the present invention comprises basic unsaturated monomers (1), (meth)acrylic acid alkyl esters having an alkyl group having 1 to 20 carbon atoms, and other unsaturated monomers. It is obtained by copolymerizing a polymerizable monomer component consisting of the polymer (3) by well-known solution polymerization.
その際、用いられる有機溶剤はトルエン、キシレン等の
芳香族溶剤；ＭＥＫ、ＭＩ ＢＫ１アノン等のケトン系
溶剤；酢酸エチル、酢酸ブチル、酢酸セロソルブ等のエ
ステル及びインプロパツール、ブタノール等のアルコー
ル類などでこれは単独又は混合して用いられる。重合開
始剤としではアゾビスイソブチロニトリノベベンゾイル
パーオキサイド、ジ；ターシャリーブチルパーオキサイ
ドなどのラジカル重合開始剤を用いることができる。In this case, the organic solvents used are aromatic solvents such as toluene and xylene; ketone solvents such as MEK and MI BK1 anone; esters such as ethyl acetate, butyl acetate, and cellosolve acetate, and alcohols such as Impropatol and butanol. These can be used alone or in combination. As the polymerization initiator, radical polymerization initiators such as azobisisobutyronitrinobebenzoyl peroxide and di-tertiary butyl peroxide can be used.
又、重合温度は６０〜１４０℃の範囲で自由に選択でき
る。Further, the polymerization temperature can be freely selected within the range of 60 to 140°C.
（メタ）アクリル系共重合体を得るに際して、重合性単
量体成分の組成はセラミックグリーンシートに所望の性
状に応じて前記で規定された範囲内で自由に選択すれば
良いが、得られる（メタ）アクリル系共重合体のガラス
転移温度が−２０’Ｃ〜３０℃の範囲、特に好ましくは
一５〜１５℃の範囲となる組成とするのが好ましい。ガ
ラス転移温度をこの範囲とすることにより、得られるグ
リーンシートはべたついたシ硬くなりすぎたりすること
がなく、加工時や離型時の作業性に優れると共に多量の
可塑剤を用いずとも成形性の優れたものとなる。又、分
子量は広い範囲とすることができるが、バインダーとし
ての結合力やスラリーの粘度を考慮して数平均分子量が
１万〜１０万の範囲とするのが好適である。When obtaining a (meth)acrylic copolymer, the composition of the polymerizable monomer component may be freely selected within the range specified above depending on the desired properties of the ceramic green sheet. It is preferable to use a composition in which the glass transition temperature of the meth)acrylic copolymer is in the range of -20'C to 30C, particularly preferably in the range of -5 to 15C. By keeping the glass transition temperature within this range, the resulting green sheet will not become sticky or too hard, and will have excellent workability during processing and mold release, as well as good moldability without using a large amount of plasticizer. It will be excellent. Although the molecular weight can be within a wide range, it is preferable that the number average molecular weight is in the range of 10,000 to 100,000 in consideration of the binding force as a binder and the viscosity of the slurry.
かくして得られた溶剤型（メタ）アクリル系共重合体は
、本発明の製造方法においてバインダーとして用いる。The solvent-type (meth)acrylic copolymer thus obtained is used as a binder in the production method of the present invention.
本発明の製造方法は、酸性セラミック微粉体にして得る
スラリーを周知の手順によりセラミックグリーンシート
とすることにより達成される。The manufacturing method of the present invention is achieved by converting a slurry obtained from acidic ceramic fine powder into a ceramic green sheet using a well-known procedure.
の範囲の量で用いる。バインダーの使用量が３重量部未
満の場合は得られるグリーンシートの成形性、強度、可
撓性が不十分であり、逆に３０重量部を越える場合はグ
リーンシートの加工性が劣ると共酸性セラミック微粉体
の充分な分散を可能にすると共に、該スラリーをキャス
ティングしてシート状とするのを容易にするために用い
るものである。Used in amounts within the range of . If the amount of binder used is less than 3 parts by weight, the moldability, strength, and flexibility of the resulting green sheet will be insufficient, and if it exceeds 30 parts by weight, the processability of the green sheet will be poor and co-acidic properties will occur. It is used to enable sufficient dispersion of the ceramic fine powder and to facilitate casting of the slurry into a sheet form.
その使用量に特に制限はないが、通常該スラＩＪ−重合
に用いる溶剤と同様に芳香族溶剤、ケトン系溶剤、エス
テル及びアルコール類等を挙げること引
≠を重合溶＃として用いて溶液重合して得られた場合は
、重合生成物である（メタ）アクリル系共剤
重合体の溶≠溶液をそのまま用いることができる。There is no particular restriction on the amount used, but aromatic solvents, ketone solvents, esters, alcohols, etc. can be mentioned as well as the solvents usually used in the slug IJ polymerization. In the case where the solution is obtained as is, the solution of the (meth)acrylic co-agent polymer which is the polymerization product can be used as it is.
判 もちろん、該共重合体の溶液に用いた溶薫と同種側 又は異種の情無を別途使用しても何らさしつかえない。judgment Of course, the same side as the melt used for the solution of the copolymer. Or there is nothing wrong with using different types of compassion separately.
又、スラリーを得る際の成分は前記成分だけであってか
まわないが、必要によシ従来から慣用の添加剤、例えば
ジブチルフタレート、ブチルベンジルフタレート等の可
塑剤、アルキルアリルポリエーテルアルコールやポリエ
チレンクリコールエチルエーテル等の湿潤剤、グリセリ
ン、ソルビタン等の多価アルコールエステル系ポリエー
テル等実施態様として、例えば下記の如き手順を例示す
ることができる。In addition, the ingredients for obtaining the slurry may be only the above-mentioned ingredients, but if necessary, conventional additives such as plasticizers such as dibutyl phthalate and butyl benzyl phthalate, alkylaryl polyether alcohol, and polyethylene chloride may be added. Examples of embodiments include wetting agents such as recall ethyl ether, polyhydric alcohol ester polyethers such as glycerin, sorbitan, etc., and the following procedure can be exemplified.
（記）
酸性セラミック微粉体１００重量部にバインダ置部、消
泡剤０へ一１重量部及び分散剤０〜２重量部を加えてボ
ールミルで１０〜５０時間混練してスラリーとした。次
いで脱泡しながら該スラリーの粘度を２０〜】００ポイ
ズの範囲、よシ好ましくは４０〜８０ポイズの範囲に調
整した後、一定の挟間を有するドクターブレードでキャ
リヤーフィルム上にシート状にキャスティングし、続い
て５０°Ｃ１８０℃、１２０°Ｃのような一定温度で、
あるいは順次連続的に加熱乾燥してセラミックグリーン
シートを得る。(Note) To 100 parts by weight of acidic ceramic fine powder, a binder, 0 to 11 parts by weight of an antifoaming agent, and 0 to 2 parts by weight of a dispersant were added and kneaded in a ball mill for 10 to 50 hours to obtain a slurry. Next, the viscosity of the slurry is adjusted to a range of 20 to 00 poise, preferably 40 to 80 poise while defoaming, and then cast into a sheet onto a carrier film using a doctor blade having a certain gap. , followed by constant temperature such as 50°C, 180°C, 120°C,
Alternatively, ceramic green sheets are obtained by successively heating and drying.
本発明の製造方法により得られるセラミックグリーンシ
ートは酸性セラミック微粉体に特定組成の（メタ）アク
リル系重合体をバインダーに用いてなるために十分な密
度、強度及び可撓性を有すると共に均一な厚みを有し、
表面平滑性にもすぐれたものである。The ceramic green sheet obtained by the manufacturing method of the present invention is made of acidic ceramic fine powder and a (meth)acrylic polymer of a specific composition as a binder, so it has sufficient density, strength and flexibility, and has a uniform thickness. has
It also has excellent surface smoothness.
従って本発明の製造方法によシ得られたセラミックグリ
ーンシートは適当な形状に賦形しかつ焼成して緻密で優
れた強度を有すると共に表面平滑性もすぐれたセラミッ
ク製品とすることができる。Therefore, the ceramic green sheet obtained by the manufacturing method of the present invention can be shaped into a suitable shape and fired to produce a ceramic product that is dense and has excellent strength and surface smoothness.
次いで本発明を参考例及び実施例によシ更に詳しく説明
するが、本発明はこれらの実施例等に限定されるもので
はない。なお、参考例及び実施例中の部及び係は特にこ
とわシのないかぎシ重置部、重量％を示すものとする。Next, the present invention will be explained in more detail with reference to Reference Examples and Examples, but the present invention is not limited to these Examples. In addition, in the reference examples and examples, the parts and sections indicate the overlapping parts and weight % unless otherwise specified.
参考例１
撹拌器、温度計、冷却管、窒素導入管、混合モノマー滴
下ロートを備えたフラスコに有機溶剤としてトルエン７
００重量部を入れフラスコ内の空モノマー滴下ロートに
仕込んだジメチルアミノエチルメタクリレート７０重量
部、ｎ−ブチルメタクリレート５２参重量部、２−エチ
ルへキシルアクリレート１０５重量部、アゾビスイソブ
チロニトリル２重量部からなる重合性単量体成分を７０
℃に保ったフラスコ中に３時間かけて滴下した。Reference Example 1 Toluene 7 was added as an organic solvent to a flask equipped with a stirrer, a thermometer, a cooling tube, a nitrogen introduction tube, and a mixing monomer dropping funnel.
70 parts by weight of dimethylaminoethyl methacrylate, 52 parts by weight of n-butyl methacrylate, 105 parts by weight of 2-ethylhexyl acrylate, and 2 parts by weight of azobisisobutyronitrile. The polymerizable monomer component consisting of 70 parts
The mixture was added dropwise over 3 hours into a flask kept at ℃.
その後８０℃で２時間、さらに１００℃で２時間加熱し
た後冷却し、固型分濃度５０％、溶液粘度４５ストーク
ス、数平均分子量２０，０００の（メタ）アクリル系共
重合体（ａ−ｉ）の溶液を得た。Thereafter, it was heated at 80°C for 2 hours and then at 100°C for 2 hours, and then cooled to produce a (meth)acrylic copolymer (a-i ) was obtained.
参考例２〜４及び比較参考例１〜３
参考例１において重合性単量体成分の組成を表Ｉに示し
た通りとする以外は参考例１と同様の操作をくシ返して
、固型分濃度が５０％の（メタ）アクリル系共重合体（
ａ−２）〜（ａ−４）及び比較用共重合体（ｂ−１）〜
（ｂ−３）の溶液を得た。Reference Examples 2 to 4 and Comparative Reference Examples 1 to 3 The same operations as in Reference Example 1 were repeated except that the composition of the polymerizable monomer component in Reference Example 1 was as shown in Table I. (meth)acrylic copolymer with a concentration of 50% (
a-2) to (a-4) and comparative copolymer (b-1) to
A solution of (b-3) was obtained.
実施例１
イツトリア３モル係を含有する粒子径が０．５μｍの酸
性セラミック微粉体（ＭＳ−３部日本触媒化学工業■製
）１００部と参考例１で得られた共重合体（ａ−１）の
溶液１０部、酢酸エチル１５部、メチルエチルケトン１
５部及び可塑剤としてジオクチルフタレート０．５部を
ボールミルの中に仕込み２４時間混練してスラリーを得
た。このスラリーを２００メツシユの金網を用いて濾過
し、４０ｒｐｍの速度で撹拌しながら熟成し、次いで減
圧脱泡して６０ポイズの粘度に調整した後ドクターブレ
ードを用いてＰＥＴフィルム上にキャスティングし、次
いで５０℃より昇温速度１℃／分で１１０℃まで昇温加
熱して厚さ４０μｍのセラミックグリーンシート（Ａ−
１）を得た。得られたセラミックグリーンシー） （Ａ
−１）の表面平滑性、１０朋φの棒への巻取シ性及び折
９曲げた後のシ張り破断時の伸びと強度を測定した。こ
れらの結果を表Ｈに示す。Example 1 100 parts of acidic ceramic fine powder (MS-3, manufactured by Nippon Shokubai Chemical Industry Co., Ltd.) containing 3 moles of ittria and having a particle size of 0.5 μm and the copolymer obtained in Reference Example 1 (a-1 ), 15 parts of ethyl acetate, 1 part of methyl ethyl ketone
5 parts and 0.5 parts of dioctyl phthalate as a plasticizer were placed in a ball mill and kneaded for 24 hours to obtain a slurry. This slurry was filtered using a 200-mesh wire mesh, aged while stirring at a speed of 40 rpm, degassed under reduced pressure to adjust the viscosity to 60 poise, and then cast onto a PET film using a doctor blade. Ceramic green sheets with a thickness of 40 μm (A-
1) was obtained. The obtained ceramic green sea) (A
The surface smoothness of -1), the winding property into a 10 mm diameter rod, and the elongation and strength at break after 9 bends were measured. These results are shown in Table H.
尚、用いたジルコニア球状微粉体２０部と水８０部を混
合したスラリーのｐＨは５．０であった。The pH of the slurry used was 5.0, which was a mixture of 20 parts of zirconia spherical fine powder and 80 parts of water.
実施例２〜４及び比較例１〜４
実施例１におけるスラリーの組成を表■に示した通りと
する以外は実施例１と同様にしてセラミックグリーンシ
ード（Ａ−２）〜（Ａ−４）及び比較用のセラミックグ
リーンシート（Ｂ−１）〜（Ｂ−４）を得た。得られた
各グリーンシートの物性を実施例１と同様にして測定し
た結果を表Ｈに示す。Examples 2 to 4 and Comparative Examples 1 to 4 Ceramic green seeds (A-2) to (A-4) were prepared in the same manner as in Example 1, except that the composition of the slurry in Example 1 was as shown in Table 1. And comparative ceramic green sheets (B-1) to (B-4) were obtained. Table H shows the results of measuring the physical properties of each of the obtained green sheets in the same manner as in Example 1.
Claims (5)
必要に応じ添加剤を加えて所要時間混練して得るスラリ
ーを用いてセラミックグリーンシートを製造する方法に
おいて、酸性セラミック微粉体１００重量部に対しバイ
ンダーとして、塩基性不飽和単量体（１）０．５〜２０
重量％、炭素数が１〜２０個のアルキル基を有する（メ
タ）アクリル酸アルキルエステル（２）３０〜９９．５
重量％および該単量体（１）及び（２）と共重合可能な
その他の不飽和単量体（３）０〜５０重量％からなる重
合性単量体成分（但し、単量体（１）、（２）及び（３
）の合計は１００重量％である。）を有機溶剤中で重合
して得られる（メタ）アクリル系共重合体を３〜３０重
量部の割合で用いることを特徴とするセラミックグリー
ンシートの製造方法。1. In a method for manufacturing a ceramic green sheet using a slurry obtained by adding a binder, an organic solvent, and additives as necessary to acidic ceramic fine powder and kneading the mixture for a required period of time, a base is added as a binder to 100 parts by weight of acidic ceramic fine powder. Sexually unsaturated monomer (1) 0.5-20
Weight %, (meth)acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms (2) 30 to 99.5
A polymerizable monomer component consisting of 0 to 50% by weight of other unsaturated monomers (3) copolymerizable with monomers (1) and (2) (however, monomer (1) ), (2) and (3
) is 100% by weight. ) is used in an organic solvent in an amount of 3 to 30 parts by weight of a (meth)acrylic copolymer.
体２０重量部と水８０重量部を混合したスラリーのＰＨ
値が７を下廻るものを用いる請求項１に記載の製造方法
。2. PH of a slurry prepared by mixing 20 parts by weight of acidic ceramic fine powder with 80 parts by weight of water as acidic ceramic fine powder
The manufacturing method according to claim 1, wherein a material having a value of less than 7 is used.
素原子を有する単量体、その塩及びその四級化物から選
ばれる１種以上を用いる請求項１に記載の製造方法。3. 2. The manufacturing method according to claim 1, wherein the basic unsaturated monomer (1) is one or more selected from monomers having a basic nitrogen atom in the molecule, salts thereof, and quaternized products thereof.
１に記載の製造方法。4. The manufacturing method according to claim 1, wherein the copolymer has a number average molecular weight of 10,000 to 100,000.
る請求項１に記載の製造方法。5. The manufacturing method according to claim 1, wherein the copolymer has a glass transition temperature of -20°C to 30°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63094414A JPH01270559A (en) | 1988-04-19 | 1988-04-19 | Production of ceramic green sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63094414A JPH01270559A (en) | 1988-04-19 | 1988-04-19 | Production of ceramic green sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01270559A true JPH01270559A (en) | 1989-10-27 |
Family
ID=14109583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63094414A Pending JPH01270559A (en) | 1988-04-19 | 1988-04-19 | Production of ceramic green sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01270559A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61101449A (en) * | 1984-10-24 | 1986-05-20 | 荒川化学工業株式会社 | Manufacture of ceramic green sheet |
| JPS61163163A (en) * | 1985-01-16 | 1986-07-23 | 株式会社日本触媒 | Ceramic forming binder |
-
1988
- 1988-04-19 JP JP63094414A patent/JPH01270559A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61101449A (en) * | 1984-10-24 | 1986-05-20 | 荒川化学工業株式会社 | Manufacture of ceramic green sheet |
| JPS61163163A (en) * | 1985-01-16 | 1986-07-23 | 株式会社日本触媒 | Ceramic forming binder |
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