JPH02184558A - Production of ceramic green sheet - Google Patents
Production of ceramic green sheetInfo
- Publication number
- JPH02184558A JPH02184558A JP1002777A JP277789A JPH02184558A JP H02184558 A JPH02184558 A JP H02184558A JP 1002777 A JP1002777 A JP 1002777A JP 277789 A JP277789 A JP 277789A JP H02184558 A JPH02184558 A JP H02184558A
- Authority
- JP
- Japan
- Prior art keywords
- addition
- polymer
- inorganic compound
- compound particles
- ceramic green
- 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 23
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 18
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 16
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 13
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011344 liquid material Substances 0.000 claims abstract description 8
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 125000000962 organic group Chemical group 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 5
- 125000002015 acyclic group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 239000011230 binding agent Substances 0.000 abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 125000003710 aryl alkyl group Chemical group 0.000 abstract description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 238000000034 method Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229960001019 oxacillin Drugs 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 3
- 239000002904 solvent Substances 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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 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
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000007864 aqueous solution Substances 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
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 239000012461 cellulose resin Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method 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
- 230000000694 effects Effects 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 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
- 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
- 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
- BQBSIHIZDSHADD-UHFFFAOYSA-N 2-ethenyl-4,5-dihydro-1,3-oxazole Chemical compound C=CC1=NCCO1 BQBSIHIZDSHADD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- NYEZZYQZRQDLEH-UHFFFAOYSA-N 2-ethyl-4,5-dihydro-1,3-oxazole Chemical compound CCC1=NCCO1 NYEZZYQZRQDLEH-UHFFFAOYSA-N 0.000 description 1
- -1 2-ethylhexyl Chemical group 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-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
- 239000005977 Ethylene Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- 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
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 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
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 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
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 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
- 229910052863 mullite Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000004711 α-olefin Substances 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〉
本発明はアルミナ、シリカ、ジルコニア、チタニア、チ
タン酸バリウム、炭化珪素、窒化珪素等の無機化合物粒
子を用いたセラミックス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 Application Field> The present invention relates to a method for manufacturing a ceramic green sheet using inorganic compound particles such as alumina, silica, zirconia, titania, barium titanate, silicon carbide, and silicon nitride. It is.
〈従来の技術および発明が改良しようとする問題点〉
従来から、セラミックスの成形法としてシート成形法が
多用されている。シート成形法は無機化合物粒子をバイ
ンダー、可塑剤を含む溶液に分散させてスラリーを作り
、これをキャリアーフィルム上にドクターブレード等を
用いて層状に塗布し乾燥し、得られたシート（グリーン
シートと呼ばれる−０）をロール状に巻いて保管し、必
要に応じて取り出して型で打ち抜き、更に焼成してパイ
ンダーを分解させると共に無機化合物粒子を焼結させセ
ラミックスとする方法が一般的である。この方法では、
従来バインダーとして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）アクリル系樹脂等が用いられて来た。しかしなが
ら、これらバインダーを用いると、無機化合物粒子の分
散性が不充分であり、粒子が二次凝集状態となるために
、粒子間の間隙が大きくなりシートに穴ができたり、表
面平滑性が劣ったものとなる。また、得られる成形品の
生密度が低い点でも改良が望まれている、近年、かかる
欠点を解消すべく数多くの提案がなされている（特開昭
５８−１６７４７１号、特開昭５９−１８２２６５号、
特開昭５９−１８２２６６号、特開昭６０−４６９６４
号）が、未だ充分な成果を得ていないのが現状である。<Prior art and problems to be improved by the invention> Conventionally, a sheet molding method has been frequently used as a method for molding ceramics. In the sheet forming method, inorganic compound particles are dispersed in a solution containing a binder and a plasticizer to create a slurry, and this is coated onto a carrier film in a layer using a doctor blade, etc., and dried, resulting in a sheet (green sheet). A common method is to store the material called -0) in a roll, take it out as needed, punch it out with a mold, and then fire it to decompose the binder and sinter the inorganic compound particles to make ceramics. in this way,
Conventional binders include butyral resins such as polyvinyl butyral, cellulose resins such as ethyl cellulose, (
Meta)acrylic resins have been used. However, when these binders are used, the dispersibility of the inorganic compound particles is insufficient, and the particles enter a secondary agglomerated state, resulting in large gaps between particles, resulting in holes in the sheet and poor surface smoothness. It becomes something. Furthermore, it is desired to improve the low green density of the obtained molded product.In recent years, many proposals have been made to eliminate this drawback (Japanese Patent Application Laid-Open No. 58-167471, JP-A No. 59-182265). issue,
JP-A-59-182266, JP-A-60-46964
However, the current situation is that sufficient results have not yet been obtained.
（問題を解決するための手段及び作用〉本発明者らはこ
のような現状に鑑み、鋭意研究を重ねた結果、付加重合
性オキサゾリンを用いて得られる重合体をバインダーと
して用いると、無機化合物粒子の分散が良好であり、表
面平滑性、生密度の改良されたセラミックスグリーンシ
ートが得られることを見出し、本発明を完成するに至っ
たものである。(Means and effects for solving the problem) In view of the current situation, the present inventors have conducted extensive research and found that when a polymer obtained using addition polymerizable oxazoline is used as a binder, inorganic compound particles The present inventors have discovered that a ceramic green sheet with good dispersion and improved surface smoothness and green density can be obtained, leading to the completion of the present invention.
すなわち、本発明は 一般式（Ｉ） Ｋ。That is, the present invention General formula (I) K.
（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ，はそれぞれ独立に水素
、ハロゲン、アルキル、アラルキル、フェニルまたは置
換フェニル基であり、Ｒ５は付加重合性不飽和結合を持
つ、非環状有機基である。）
で表わされる付加重合性オキサゾリン（ａ）を含んでな
る単量体成分を重合して得られる重合体（Ａ）および無
機化合物粒子（Ｂ）を含む液状物をキャリアーフィルム
上に塗布した後乾燥する事を特徴とするセラミックスグ
リーンシートの製造方法に関するものである。(In the formula, R1, R2, R3, and R are each independently hydrogen, halogen, alkyl, aralkyl, phenyl, or substituted phenyl group, and R5 is an acyclic organic group having an addition polymerizable unsaturated bond. ) A liquid material containing a polymer (A) obtained by polymerizing a monomer component containing an addition-polymerizable oxazoline (a) represented by (a) and inorganic compound particles (B) is applied onto a carrier film and then dried. The present invention relates to a method for manufacturing a ceramic green sheet, which is characterized by:
本発明において用いられる付加重合性オキサゾリン（ａ
）とは、前記一般式（Ｉ）で表わされるものであり、そ
の具体例としては１例えば２−ビニル−２−オキサゾリ
ン、２−ビニル−４−メチル−２−オキサシリン、２−
ビニル−５−メチル−２−オキサシリン、２−インプロ
ペニル−２−オキサゾリン、２−インプロペニル−４−
メチル−２−オキサシリン、２−インプロペニル−５−
エチル−２−オキサゾリン等を挙げることができ、これ
らの群から選ばれる１種または２種以上の混合物を使用
することができる。中でも、２−インプロペニル−２−
オキサゾリンが工業的にも入手しやすく好適である。付
加重合性オキサゾリン（ａ）の使用量は特に限定される
ものではないが、単量体成分中、０．５〜１００重量％
である事が好ましい、０．５重量％未満の量では無機化
合物粒子（Ｂ）の分散性がそこなわれる傾向にある。Addition-polymerizable oxazoline (a
) is represented by the above general formula (I), and specific examples thereof include 1, 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxacillin, 2-vinyl-4-methyl-2-oxacillin,
Vinyl-5-methyl-2-oxacillin, 2-impropenyl-2-oxazoline, 2-impropenyl-4-
Methyl-2-oxacillin, 2-impropenyl-5-
Examples include ethyl-2-oxazoline, and one type or a mixture of two or more types selected from these groups can be used. Among them, 2-impropenyl-2-
Oxazoline is preferred because it is industrially available. The amount of addition polymerizable oxazoline (a) used is not particularly limited, but is 0.5 to 100% by weight based on the monomer components.
If the amount is less than 0.5% by weight, the dispersibility of the inorganic compound particles (B) tends to be impaired.
単量体成分には必要により他の単量体（ｂ）が含まれて
いてもよい０本発明に用いられる他の単量体（ｂ）とし
ては、付加重合性オキサゾリン（ａ）と共重合可能なも
のであれば、特に制限はなく、例えば、（メタ）アクリ
ル酸メチル、（メタ）アクリル酸ブチル、（メタ）アク
リル酸２−エチルヘキシル等の（メタ）アクリル酸エス
テル類； （メタ）アクリル酸、イタコン酸、マレイン
酸等の不飽和カルボン酸類；（メタ）アクリロニトリル
等の不飽和ニトリル類； （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不飽和アミド
類：酢醜ビニル、プロピオン酸ビニル等のビニルエステ
ル類：メチルビニルエーテル、エチルビニルエーテル等
のビニルエーテル類；エチレン、プロピレン等のα−オ
レフィンＭ；塩化ビニル、塩化ビニリデン、フッ化ビニ
ル等の含ハロゲンα、β−不飽和モツマー類；スチレン
、α−メチルスチレン等のα、β−不飽和芳香族モツマ
ー類等が挙げられ、これらの１種または２種以上の混合
物を使用することができる。中でも、焼成の際残渣が残
らず、比較的低温で完全に分解する（メタ）アクリル酸
エステル類が好適である。The monomer component may contain other monomers (b) as necessary.Other monomers (b) used in the present invention include addition-polymerizable oxazolines (a) and copolymerizable There is no particular restriction as long as it is possible, for example, (meth)acrylic esters such as methyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate; (meth)acrylic acid, unsaturated carboxylic acids such as itaconic acid and maleic acid; unsaturated nitriles such as (meth)acrylonitrile; (meth)acrylamide, N
- Unsaturated amides such as methylol (meth)acrylamide; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefin M such as ethylene and propylene; vinyl chloride, chloride Examples include halogen-containing α, β-unsaturated motumers such as vinylidene and vinyl fluoride; α, β-unsaturated aromatic motumers such as styrene and α-methylstyrene; one or more of these Mixtures can be used. Among these, preferred are (meth)acrylic esters that do not leave any residue upon firing and are completely decomposed at relatively low temperatures.
重合体（Ａ）は付加重合性オキサゾリン（ａ）および必
要に応じて少なくとも１種の他の単量体（ｂ）を含む単
量体成分を従来公知の重合法、例えば懸濁重合、溶液重
合、乳化重合等により製造することができる。これら重
合法により製造される重合体（Ａ）は、通常溶媒に溶解
もしくは分散した液状物として得られるが、溶媒は分離
除去する事なくそのまま使用することもできる。Polymer (A) is prepared by polymerizing monomer components containing addition-polymerizable oxazoline (a) and, if necessary, at least one other monomer (b) using conventionally known polymerization methods such as suspension polymerization and solution polymerization. , emulsion polymerization, etc. The polymer (A) produced by these polymerization methods is usually obtained as a liquid product dissolved or dispersed in a solvent, but the solvent can also be used as it is without being separated and removed.
本発明に用いる無機化合物粒子（Ｂ）は従来からセラミ
ックスグリーンシートの製造に常用されるものであれば
特に制限されないが、アルミナ。The inorganic compound particles (B) used in the present invention are not particularly limited as long as they are conventionally used in the production of ceramic green sheets, including alumina.
シリカ、マグネシア、ジルコニア、チタニア、チタン酸
バリウム、チタン酸ジルコン酸鉛、炭化珪素、窒化珪素
、銅系フェロブスカイト、コージェライト、ムライト、
フェステライト、スピネル、窒化アルミニウム、結晶化
ガラス、ホウ珪酸ガラス、石英ガラスは重合体（Ａ）と
の親和性が特に優れたものであり、これらから選ばれる
少なくとも１種を用いると１表面平滑性が一段と高めら
れたセラミックスグリーンシートが得られるので好まし
い。Silica, magnesia, zirconia, titania, barium titanate, lead zirconate titanate, silicon carbide, silicon nitride, copper-based ferovskite, cordierite, mullite,
Festerite, spinel, aluminum nitride, crystallized glass, borosilicate glass, and quartz glass have particularly excellent affinity with the polymer (A), and when at least one selected from these is used, surface smoothness can be improved. This is preferable because it provides a ceramic green sheet with even higher properties.
本発明において、キャリアーフィルム上に塗布する液状
物は、前記重合体（Ａ）および無機化合物粒子（Ｂ）を
含んでなるものである。液状物中の重合体（Ａ）および
無機化合物粒子（Ｂ）の配合比率は従来から当業者が周
知の範囲内であればよいが。In the present invention, the liquid material applied onto the carrier film contains the polymer (A) and inorganic compound particles (B). The blending ratio of the polymer (A) and the inorganic compound particles (B) in the liquid may be within a range conventionally known to those skilled in the art.
キャリアーフィルム上へ塗布する際の作業性や得られる
セラミックスグリーンシートの表面平滑性を考慮すれば
、通常無機化合物粒子（Ｂ）１００重量部に対し、重合
体（Ａ） １〜３０重量部、好ましくは３〜２０重量部
（不揮発分換算）とするのが好適である。Considering the workability when coating onto the carrier film and the surface smoothness of the resulting ceramic green sheet, the polymer (A) is usually 1 to 30 parts by weight, preferably 1 to 100 parts by weight of the inorganic compound particles (B). is preferably 3 to 20 parts by weight (in terms of non-volatile content).
本発明の製造方法は、前記液状物をキャリアーフィルム
上に塗布した後乾燥する事により達成される０本発明の
製造方法を端的に表わす実施態様を挙げるならば、例え
ば無機化合物粒子（Ｂ）に溶剤、重合体（Ａ）および必
要であれば添加剤を加え混合、脱泡して液状物を調整し
、これをポリエステルフィルム等のキャリアーフィルム
上に塗布し、適宜加熱乾燥した後、キャリアーフィルム
から剥離してセラミックスグリーンシートを得る。The production method of the present invention is achieved by coating the liquid material on a carrier film and then drying it. A solvent, polymer (A), and additives if necessary are added, mixed, and defoamed to prepare a liquid material. This is applied onto a carrier film such as a polyester film, and after drying with appropriate heat, it is removed from the carrier film. Peel it off to obtain a ceramic green sheet.
この際必要に応じて用いられる添加剤としては、ブチラ
ール樹脂、セルロース系樹脂、（メタ）アクリル系樹脂
等の公知のバインダー成分；ジブチルフタレート、ブチ
ルベンジルフタレート等の可田剤：アルキルアリルボリ
エーテルアルコール。Additives that may be used as necessary include known binder components such as butyral resin, cellulose resin, and (meth)acrylic resin; plating agents such as dibutyl phthalate and butyl benzyl phthalate; and alkylaryl polyether alcohol. .
ポリエチレング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
リエーテル等の分散剤等を挙げることができる。Wetting agents such as polyethylene glycol ethyl ether; dispersing agents such as polyhydric alcohol ester polyethers such as glycerin and sorbitan; and the like.
本発明の製造方法により得られるセラミックスグリーン
シートは、そのまま焼成してシート状セラミックス成形
品としても良く、適宜所望の形状に影付した後焼成して
種々の形状のセラミックス成形品とする事もできる。The ceramic green sheet obtained by the production method of the present invention may be fired as it is to produce a sheet-like ceramic molded product, or it can be appropriately shaded into a desired shape and then fired to produce ceramic molded products in various shapes. .
〈発明の効果〉
本発明の製造方法により得られるセラミックスグリーン
シートは、重合体（Ａ）を用いる事により無機化合物粒
子（Ｂ）が極めて良く分散した液状物から得られる為に
、表面平滑性が良好で、しがも生密度の高いものである
。従って１本発明の製造方法によるセラミックスグリー
ンシートを用いて得られる各種セラミックス成形品は、
例えば、ＩＣ基板、ＩＣパッケージ、銹電体として好適
に用いることができる。<Effects of the Invention> The ceramic green sheet obtained by the production method of the present invention has excellent surface smoothness because it is obtained from a liquid material in which the inorganic compound particles (B) are extremely well dispersed by using the polymer (A). It is in good condition and has a high density. Therefore, various ceramic molded products obtained using the ceramic green sheet according to the manufacturing method of the present invention are as follows:
For example, it can be suitably used as an IC substrate, an IC package, or a galvanic body.
〈実施例〉
以下、実施例により本発明を具体的に説明するが、本発
明はこれらに限定されるものではない。<Examples> The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto.
なお、例中に特にことわりのない限り、％は重量％、部
は重量部を示す。In addition, unless otherwise specified in the examples, % indicates weight %, and parts indicate parts by weight.
参考例 １
攪拌機、還流冷却器、窒素導入管、温度計および滴下ロ
ートを備えたフラスコに、脱イオン水７８２．４部およ
びハイテノールＮ−０８（第一工業製薬■製）の１５％
水溶液１２８部を仕込み、適量のアンモニア水（２８％
）でｐＨ９に調整し、ゆるやかに窒素ガスを流しながら
７０℃に加熱した、そこへ過硫酸カリウムの５％水溶液
６４部を注入し、続いて予め調製しておいたアクリル酸
エチル１３９．５部、アクリル酸メチル４３６．５部お
よび２−インプロペニル−２−オキサゾリン６４部の単
量体混合物を３時間にわたって滴下した。Reference Example 1 782.4 parts of deionized water and 15% of Hytenol N-08 (manufactured by Daiichi Kogyo Seiyaku ■) were placed in a flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel.
Prepare 128 parts of aqueous solution and add appropriate amount of ammonia water (28%
) and heated to 70°C while slowly flowing nitrogen gas, into which 64 parts of a 5% aqueous solution of potassium persulfate was poured, followed by 139.5 parts of ethyl acrylate prepared in advance. , 436.5 parts of methyl acrylate, and 64 parts of 2-impropenyl-2-oxazoline were added dropwise over 3 hours.
反応中は窒素ガスを吹込み続は内温を７０部１℃に保っ
た０滴下絆了後も２時間同じ温度に保った後、内温を８
０℃に昇温させて１時間攪拌を続けて反応を完結させた
。その後冷却し、不揮発分３９．８％の重合体の水性分
散液〔１〕を得た。During the reaction, nitrogen gas was blown in and the internal temperature was maintained at 1°C by 70 parts.After the addition was completed, the internal temperature was kept at the same temperature for 2 hours, and then the internal temperature was reduced to 8°C.
The temperature was raised to 0°C and stirring was continued for 1 hour to complete the reaction. Thereafter, it was cooled to obtain an aqueous polymer dispersion [1] with a nonvolatile content of 39.8%.
参考例２〜３．比較参考例１
参考例１において、単量体混合物の組成を第１表に示し
た通りとした他は参考例１と同様の操作をくり返して重
合体の水性分散液〔２〕〜〔３〕及び比較重合体の水性
分散液〔１′〕を得た。Reference examples 2-3. Comparative Reference Example 1 The same operations as in Reference Example 1 were repeated except that the composition of the monomer mixture was changed as shown in Table 1 to prepare aqueous polymer dispersions [2] to [3]. An aqueous dispersion [1'] of a comparative polymer was obtained.
第１表
実施例１〜３．比較例１
アルミナ（昭和軽金属■製、商品名ＡＬ−１６ｏｓｃ）
ｉｏｏ部、水４０部および第２表に示す重合体の水性分
散液３０部をボールミルで２４時間混合した後、エバポ
レータを用い脱泡して液状物を調整した。この液状物を
ドクターブレードによりポリエステルフィルム上に乾燥
後の膜厚が０゜２１腸となる様キャスティングした。そ
の後５０”０で１時間、８０℃で３時間、１０５℃で２
時間遅次加熱乾燥し、セラミックスグリーンシートを得
た。これらのセラミックスグリーンシートの平滑性、生
密度の測定結果は第２表に示した。Table 1 Examples 1 to 3. Comparative Example 1 Alumina (manufactured by Showa Light Metal ■, trade name AL-16osc)
After mixing 30 parts of the aqueous dispersion of the polymer shown in Table 2 in a ball mill for 24 hours, the mixture was defoamed using an evaporator to prepare a liquid material. This liquid was cast onto a polyester film using a doctor blade so that the film thickness after drying was 0.21 mm. Then 1 hour at 50”0, 3 hours at 80℃, 2 hours at 105℃
A ceramic green sheet was obtained by slow heating and drying. The measurement results of the smoothness and green density of these ceramic green sheets are shown in Table 2.
なお、測定方法は以下の通りである。The measurement method is as follows.
生密度二次式により算出した。Calculated using the green density quadratic formula.
成形品の重量（ｇ） 生密度（ｇ／ｃ／）＝ 成形品の体積（（Ｉｆ＋） 平滑性：ＪＩＳＢＯ６０１に従って測定した。Weight of molded product (g) Green density (g/c/)= Volume of molded product ((If+) Smoothness: Measured according to JISBO601.
（鉢ｍにて表示）
第２表
参考例 ４
参考例１と同様の４つロフラスコに酢酸エチル１００部
を仕込み８０℃まで昇温した。そこへ窒素ガスを吹き込
みながら、アクリル酸エチル５０部、アクリル酸ブチル
１０部、メタクリル酸メチル２０部、２−インプロペニ
ル−２−オキサシリン２０部およびアゾビスイソブチロ
ニトリル１．５部からなる混合物を２時間にわたって滴
下ロートより滴下し、更に８０℃で６時間保持した後、
室温まで冷却して不揮発分５０．０％の重合体の有機溶
剤溶液〔４〕を得た。(Displayed in pot m) Table 2 Reference Example 4 100 parts of ethyl acetate was charged into a four-bottle flask similar to Reference Example 1, and the temperature was raised to 80°C. While blowing nitrogen gas therein, a mixture consisting of 50 parts of ethyl acrylate, 10 parts of butyl acrylate, 20 parts of methyl methacrylate, 20 parts of 2-impropenyl-2-oxacillin, and 1.5 parts of azobisisobutyronitrile was added. was added dropwise from the dropping funnel over 2 hours, and after further holding at 80°C for 6 hours,
It was cooled to room temperature to obtain a polymer organic solvent solution [4] with a nonvolatile content of 50.0%.
参考例５〜６．比較例２
参考例４において重合性単量体混合物の組成を第３表に
示した通りとした他は、参考例４と同様の操作をくり返
して重合体の有機溶剤溶液〔５〕〜〔６〕及び比較重合
体の有機溶剤溶液〔２′〕を得た。Reference examples 5-6. Comparative Example 2 The same operations as in Reference Example 4 were repeated except that the composition of the polymerizable monomer mixture in Reference Example 4 was changed as shown in Table 3 to prepare polymer organic solvent solutions [5] to [6]. ] and a comparative polymer solution [2'] in an organic solvent were obtained.
第 表 乾燥しセラミックスグリーンシートを得た。No. table It was dried to obtain a ceramic green sheet.
らのセラミックスグリーンシートの平滑性、度の測定結
果は第４表に示した。The results of measuring the smoothness and degree of the ceramic green sheets are shown in Table 4.
なお、測定方法は実施例１の方法に準じた。Note that the measurement method was based on the method of Example 1.
これ 生布 第４表 実施例４〜６．比較例２this raw cloth Table 4 Examples 4-6. Comparative example 2
Claims (2)
立に水素、ハロゲン、アルキル、フェニルまたは置換フ
ェニル基であり、Ｒ＿５は付加重合性不飽和結合を持つ
、非環状有機基である。） で表わされる付加重合性オキサゾリン（ａ）を含んでな
る単量体成分を重合して得られる重合体（Ａ）および無
機化合物粒子（Ｂ）を含む液状物をキャリアーフィルム
上に塗布した後乾燥する事を特徴とするセラミックスグ
リーンシートの製造方法。1. General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) A polymer (A) obtained by polymerizing a monomer component containing an addition-polymerizable oxazoline (a), which is an acyclic organic group having a polymerizable unsaturated bond; A method for producing a ceramic green sheet, which comprises applying a liquid material containing B) onto a carrier film and then drying it.
（Ａ）を１〜３０重量部（不揮発分換算）の割合で用い
る請求項１記載のセラミックスグリーンシートの製造方
法。2. 2. The method for producing a ceramic green sheet according to claim 1, wherein the polymer (A) is used in a ratio of 1 to 30 parts by weight (in terms of non-volatile content) based on 100 parts by weight of the inorganic compound particles (B).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1002777A JPH02184558A (en) | 1989-01-11 | 1989-01-11 | Production of ceramic green sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1002777A JPH02184558A (en) | 1989-01-11 | 1989-01-11 | Production of ceramic green sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02184558A true JPH02184558A (en) | 1990-07-19 |
Family
ID=11538774
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1002777A Pending JPH02184558A (en) | 1989-01-11 | 1989-01-11 | Production of ceramic green sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02184558A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003030192A2 (en) * | 2001-08-27 | 2003-04-10 | Motorola, Inc. | Low-pressure laminated ceramic devices |
-
1989
- 1989-01-11 JP JP1002777A patent/JPH02184558A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003030192A2 (en) * | 2001-08-27 | 2003-04-10 | Motorola, Inc. | Low-pressure laminated ceramic devices |
| WO2003030192A3 (en) * | 2001-08-27 | 2005-01-20 | Motorola Inc | Low-pressure laminated ceramic devices |
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