JP3912533B2 - Conductive paste composition for ceramic circuit board - Google Patents
Conductive paste composition for ceramic circuit board Download PDFInfo
- Publication number
- JP3912533B2 JP3912533B2 JP2003051191A JP2003051191A JP3912533B2 JP 3912533 B2 JP3912533 B2 JP 3912533B2 JP 2003051191 A JP2003051191 A JP 2003051191A JP 2003051191 A JP2003051191 A JP 2003051191A JP 3912533 B2 JP3912533 B2 JP 3912533B2
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- weight
- monomer
- conductive paste
- paste composition
- 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.)
- Expired - Lifetime
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- 239000000203 mixture Substances 0.000 title claims description 77
- 239000000919 ceramic Substances 0.000 title claims description 37
- 239000000178 monomer Substances 0.000 claims description 72
- 239000011347 resin Substances 0.000 claims description 39
- 229920005989 resin Polymers 0.000 claims description 32
- 229920006026 co-polymeric resin Polymers 0.000 claims description 29
- 125000003277 amino group Chemical group 0.000 claims description 16
- 230000001588 bifunctional effect Effects 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 14
- 230000009477 glass transition Effects 0.000 claims description 12
- -1 alkyl methacrylate Chemical compound 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical group CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 6
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000003505 polymerization initiator Substances 0.000 claims description 4
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 description 14
- 238000007334 copolymerization reaction Methods 0.000 description 12
- 238000007639 printing Methods 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- 238000007650 screen-printing Methods 0.000 description 8
- 239000002952 polymeric resin Substances 0.000 description 7
- 239000001856 Ethyl cellulose Substances 0.000 description 6
- 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 6
- 229920001249 ethyl cellulose Polymers 0.000 description 6
- 235000019325 ethyl cellulose Nutrition 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 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 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 5
- 239000007869 azo polymerization initiator Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 239000010802 sludge Substances 0.000 description 5
- 229920003002 synthetic resin Polymers 0.000 description 5
- 230000037303 wrinkles Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- UODXCYZDMHPIJE-UHFFFAOYSA-N menthanol Chemical compound CC1CCC(C(C)(C)O)CC1 UODXCYZDMHPIJE-UHFFFAOYSA-N 0.000 description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000012776 electronic material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- RCEJCSULJQNRQQ-UHFFFAOYSA-N 2-methylbutanenitrile Chemical compound CCC(C)C#N RCEJCSULJQNRQQ-UHFFFAOYSA-N 0.000 description 1
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 241000953555 Theama Species 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical group CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 229920005684 linear copolymer Polymers 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 239000000693 micelle Substances 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
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Conductive Materials (AREA)
- Organic Insulating Materials (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、セラミック回路基板用の導電性ペースト組成物に関するものである。
【０００２】
【従来の技術】
この種の技術としては、従来よりエチルセルロース樹脂がバインダー樹脂として用いられているが、焼成時に分解残渣が残る問題があった。このような問題点を改良するために、特許文献１に記載されるようなセラミック回路基板用導電ペーストが知られている。即ち、比表面積が０．５〜３．０ｍ２／ｇの球状銅粉末を、セラミック生シートに含まれる有機バインダーと比べて樹脂成分の焼成時の飛散性が少なくとも劣らない有機バインダーを溶解した高沸点溶媒中に分散させるものである。具体的には、前記有機バインダーの樹脂成分がアクリル系樹脂であり、前記高沸点溶媒がテルピネオールであることが開示されている。そしてこのような導電性ペーストは、セラミック回路基板の導体特性および印刷精度が改善されるとしている。しかしながらこのような導電性のペーストは、スクリーン印刷に適した高粘度を発現させるために、共重合樹脂の分子量を上げる必要があり、このため高分子量に起因する糸引き性と称する問題があった。さらには、導電性ペーストとしての安定性にも問題点があった。
【０００３】
【特許文献１】
特開昭６０−１５３１９３号公報
【０００４】
【発明が解決しようとする課題】
本発明は、加熱分解性を良好なものとすることにより、より分解残渣が少なく、電気的特性に優れると共に、スクリーン印刷に要求される高粘度であっても糸引き性がなく印刷特性に優れ、さらに貯蔵安定性にも優れたセラミック回路基板用の導電性ペースト組成物を提供することを目的とする。
【０００５】
【課題を解決するための手段】
以上の課題を解決するためには、請求項１に記載されるように、下記化学式１で示されるメタクリル酸アルキルエステル単量体９４〜９９重量％、アミノ基含有メタクリル酸アルキルエステル０．１〜２．０重量％およびその他の共重合可能な単量体を含有する単量体混合物１００重量部に対して、２官能性単量体を０．０１〜２．０重量部或いは３官能性単量体を０．０１〜０．１重量部添加した単量体混合物を共重合して得られた、ガラス転移温度が４０〜８０℃で、重量平均分子量が３００００〜１５００００である共重合樹脂と、少なくとも導電性粉末を含有するセラミック回路基板用の導電性ペースト組成物。
【化１】
とすることによって、解決される。
【０００６】
また、請求項２に記載されるように、前記アミノ基含有メタクリル酸アルキルエステルが、メタクリル酸ジメチルアミノエチルおよび／またはメタクリル酸ジエチルアミノエチルである、請求項１に記載のセラミック回路基板用の導電性ペースト組成物とすることによって、解決される。
【０００７】
さらに、請求項３に記載されるように、前記共重合樹脂は、アゾ系の重合開始剤を前記単量体混合物１００質量部に対して、０．１〜３質量％を用いて懸濁重合法によって得られたものである請求項１または２に記載のセラミック回路基板用の導電性ペースト組成物とすることによって、解決される。
【０００８】
そして、請求項４に記載される前記共重合樹脂は、大気中または不活性ガス中において、１０℃／分の昇温速度で室温から５００℃まで加熱した場合の加熱分解残渣が、１．０重量％未満である請求項１〜３のいずれかに記載のセラミック回路基板用の導電性ペースト組成物とすることによって、解決される。
【０００９】
また、請求項５に記載されるように、前記導電性粉末１００質量部に対して、前記共重合樹脂がその固形分として５〜３０質量部添加された、請求項１〜４のいずれかに記載のセラミック回路基板用の導電性ペースト組成物とすることによって、解決される。
【００１０】
【発明の実施の形態】
以下に本発明を詳細に説明する。請求項１に記載される発明は、下記化学式１で示されるメタクリル酸アルキルエステル単量体９４〜９９重量％、アミノ基含有メタクリル酸アルキルエステル０．１〜２．０重量％およびその他の共重合可能な単量体を含有する単量体混合物１００重量部に対して、２官能性単量体を０．０１〜２．０重量部或いは３官能性単量体を０．０１〜０．１重量部添加した単量体混合物を共重合して得られた、ガラス転移温度が４０〜８０℃で、重量平均分子量が３００００〜１５００００である共重合樹脂と、少なくとも導電性粉末を含有するセラミック回路基板用の導電性ペースト組成物である。
【化１】
【００１１】
このように、化学式１で示されるメタクリル酸アルキルエステル単量体９４〜９９重量％、アミノ基含有メタクリル酸アルキルエステル０．１〜２．０重量％およびその他の共重合可能な単量体を含有する単量体混合物１００重量部に対して、２官能性単量体を０．０１〜２．０重量部或いは３官能性単量体を０．０１〜０．１重量部添加した単量体混合物を、共重合して得られた共重合樹脂であって、ガラス転移温度が４０〜８０℃で、重量平均分子量が３００００〜１５００００である、セラミック回路基板用の導電性ペースト組成物の共重合樹脂として用いられ、加熱分解性が良好となり、より分解残渣が少なく、電気的特性に優れると共に、スクリーン印刷時の糸引き性がない印刷特性に優れ、さらに貯蔵安定性にも優れたものとなり、セラミック回路基板の導電性ペースト組成物の共重合樹脂とすることができる。そして、前記導電性ペースト組成物は、少なくとも導電性粉末を混合することによって得られる。
【００１２】
即ち、前記メタクリル酸アルキルエステル単量体を、９４〜９９重量％を含有することにより、良好な加熱分解性を発現させることができる。そして、このメタクリル酸アルキルエステル単量体は、化学式１として示される構造を有するもので、Ｒが炭素数１〜８のメタクリル酸エステル類が加熱分解性の点で好ましい。具体的な例としては、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ノルマルブチル、メタクリル酸イソブチル、メタクリル酸ターシャリーブチル、メタクリル酸２−エチルヘキシル、メタクリル酸ベンジル、メタクリル酸シクロヘキシル、メタクリル酸イソボロニル等が挙げられ、これらの一種もしくは二種以上を混合して、用いることがきる。なお、前記メタクリル酸アルキルエステル単量体を９４〜９９重量％とするのは、この範囲を外れると加熱分解性が悪くなって、好ましくないためである。
【００１３】
さらに、前記アミノ基含有メタクリル酸アルキルエステルの添加量を、０．１重量％以上とすることで、導電性ペースト組成物の共重合樹脂に分散する導電性粉末の分散安定性を向上させることができ、２．０重量％以下とすることで加熱分解性も良好なものとすることができる。より好ましくは、０．５〜１．５重量％の範囲である。
【００１４】
また、前記アミノ基含有メタクリル酸アルキルエステルとして好ましいものは、請求項２に記載されるように、メタクリル酸ジメチルアミノエチル（ＤＭＭＡ）、メタクリル酸ジエチルアミノエチル（ＤＥＭＡ）であり、これらが単独で或いは併用して添加される。
【００１５】
本発明にはさらに、その他の共重合可能な単量体が添加されるが、前記メタクリル酸アルキルエステル単量体並びにアミノ基含有メタクリル酸アルキルエステル前記単量体の加熱分解性を低下させない範囲で添加される。その添加量は、単量体混合物の全体量として１００重量％を超えない範囲で配合される。概ね１０重量％以下である。具体的な例としては、メタクリル酸（ＭＭＡ）、メタクリル酸２−ヒドロキシエチル（ＨＥＭＡ）、アクリル酸メチル（ＭＡ）、アクリル酸エチル（ＥＡ）、スチレン、アクリロニトリル、アクリルアミド、メタクリルアミド、アクリル酸ブチル、メタクリル酸グリシジル、酢酸ビニル等が挙げられ、一種もしくは二種以上を混合して使用することができる。そして前記単量体混合物が、共重合樹脂のベース樹脂となる。そして、このベース樹脂を１００重量部として、その他の添加が加えられる。
【００１６】
また、ベース樹脂となる前記単量体混合物には、架橋成分を含有することが好ましい。これは架橋成分を含まない共重合体、即ち直鎖状共重合体で、本発明の重量平均分子量を有する共重合体を用いたセラミック回路基板用の導電性ペースト組成物では、スクリーン印刷後、刷版を被印刷面から剥がすときに、前記刷面と前記被印刷面との間で、導電性ペースト組成物の糸引き現象が起こり、良好な印刷ができないこととなる。このため架橋成分として２官能性単量体を、前記単量体混合物１００重量部に０．０１〜２．０重量部、或いは３官能性単量体を０．０１〜０．１重量部添加される。これは０．０１重量部未満の添加では、スクリーン印刷時の糸引き性のない共重合体を得ることができない。また前記２官能性単量体の場合は、２．０重量部を超えると、さらに３官能性単量体の場合は、０．１重量部を超えると、高沸点溶剤にも溶解しない共重合体となって、好ましくないためである。よって、前記２官能性単量体或いは３官能性単量体を併用する場合には、０．１重量部を超えないようにすることが、必要である。このような、２官能性単量体としては、ブチレングリコールジメタクリレート、1，６ヘキサンジオールジメタクリレート、１，３ブチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、エチレングリコールジメタクリレート、メタクリル酸アリル（ＡＭＡ）等が挙げられる。また３官能性単量体としては、トリメチロールプロパントリ（メタ）アクリレート（ＴＭＰＴＡ）、等が挙げられる。中でも、前記ＴＭＰＴＡや前記ＡＭＡが好ましいものである。このようなベース樹脂は、共重合させることによって導電性ペースト組成物用の共重合樹脂となる。
【００１７】
そして前記共重合樹脂は、アゾ系の重合開始剤を用いて行うのが好ましい。これは過酸化物系の重合開始剤を用いると、前記アミノ基含有メタクリル酸アルキルエステルの反応が進みにくくなり、好ましくないためである。具体的なアゾケ系の重合開始剤の例としては、２，２′−アゾビスイソブチロニトリル、２，２′−アゾビス（２−メチルブチルニトリル）、２，２′−アゾビス（２，４−ジメチルバレロニトリル）、１，１′−アゾビス（シクロヘキサンー１−カルボニトリル）、ジメチル２，２′−アゾビス（２−メチルプロピオネート）等が挙げられる。そしてその添加量は、前記単量体混合物１００重量部に対して、０．１〜３重量％とすることが好ましい。
【００１８】
そして、前記共重合樹脂の共重合方法としては、請求項３に記載されるように、前記アゾ系の重合開始剤を前記単量体混合物１００質量部に対して、０．１〜３質量％を用いた懸濁重合法とすることが、好ましい。これは、例えば溶液重合法では、溶剤中で単量体を重合するため、重合終了と同時に共重合樹脂を得ることができるが、高分子量の重合体を得にくいという問題があり、乳化重合法では、界面活性剤を溶解した水に乳化させた単量体をミセル中で重合するため、乳化状態のポリマーを析出分離もしくはスプレードライヤーによって水分を乾燥させ、得られたポリマーを溶剤に溶解させて共重合樹脂とするので、前記界面活性剤が共重合樹脂中に残り易く、加熱分解時の分解残渣が多くなる恐れがある。これに対し、前記の懸濁重合法では、分散剤を含む水中で単量体懸濁液を重合し、その後に洗浄により前記分散剤を洗い取るため、得られたビーズ状ポリマーは、高分子量の共重合体が得られると共に、分解残渣の少ないものとなり、溶剤に溶解した共重合樹脂は、セラミック回路基板用の導電性ペースト組成物の共重合樹脂として、好ましいものとすることができる。
【００１９】
また、前記共重合樹脂は、ガラス転移温度が４０〜８０℃で、重量平均分子量が３００００〜１５００００の範囲に入るものとするのが、好ましい。これは、セラミック回路基板用の導電性ペースト組成物の共重合樹脂としては、重量平均分子量を３万以上とすることによって、導電性粉末の分散がし易く、また導電性ペースト組成物中の前記導電性粉末の沈降を防止できる。また重量平均分子量を１５万以下程度とすることで、共重合樹脂中のゲル化物の発生を防ぐことができるので、好ましいものとなる。よって、前記共重合樹脂は、前記懸濁重合の条件等を選定して、重量平均分子量が３〜１５万程度になるように共重合させる。またガラス転移温度を４０〜８０℃とすることによって、印刷特性に関係する糸引き性が良好であり、また高沸点溶剤に溶け難くなるという問題もなくなる。
【００２０】
また、このようにして得られたセラミック回路基板用の導電性ペースト組成物の共重合樹脂は、請求項４に記載されるように、大気中または不活性ガス中において、１０℃／分の昇温速度で室温から５００℃まで加熱した場合の、加熱分解残渣が１．０重量％未満である導電性ペースト組成物用の共重合樹脂とすることができる。このようにスラッジ等の加熱分解残渣の少ないことにより、電気的特性の優れた導電性ペースト組成物となる。即ち、従来使用されていたエチルセルロース樹脂のように、５００℃以下の低温化での加熱分解ではスラッジと称する残渣が多く発生する不具合が生じ、さらに不活性ガス雰囲気中で加熱分解した場合、さらにスラッジが多く発生するので、電子材料用等の高純度の品質が必要な部分には使用できないという不都合がなくなる。このような不都合のない導電性ペースト組成物は、電子材料用等の高純度の品質が必要な部分にも使用できる。また、熱により酸化反応が進む金属フィラーや熱劣化を起こし易い金属酸化物、蛍光体等に好適である。なお、ここで、不活性雰囲気とは、多くの場合、窒素を用いるが、酸素と窒素の混合ガスでも良い。その他として、ヘリウム、ネオン、アルゴン等のガスである。
【００２１】
なお、セラミック回路基板用の導電性ペースト組成物とするためには、前記共重合樹脂と導電性粉末を、例えばジヒドロターピネオールのような有機溶剤に溶解、攪拌・分散させて導電性ペースト組成物とする。また前記導電性粉末としては、銅、銀、ニッケル等の金属等が用いられる。そして、前記導電性粉末と前記共重合樹脂との混合比は、請求項５に記載するように、請求項１〜４に記載されるセラミック回路基板用の導電性ペースト組成物には、それぞれ導電性粉末１００重量部に対して、共重合樹脂の固形分で５〜３０重量部を添加することが好ましい。これは前記共重合樹脂の固形分が５重量部未満であると、スクリーン印刷により形成された回路にクラックが発生する恐れがあり、また３０重量部を超えると、単位時間での分解残渣が残り易くなるためである。なお必要に応じて、可塑剤、分散剤、湿潤剤、消泡剤、帯電防止剤、減粘剤を添加しても良い。
【００２２】
【実施例】
以下に実験例１〜２６および従来例を示して、本発明の効果を説明する。表１（実施例）および表２（比較例および従来例）に示す、各種バンダー共重合樹脂を作製して、その分子量、ガラス転移温度、熱分解残渣、煤の有無、溶解性を、またこれらの共重合樹脂を用いて導電性ペースト組成物とし、その安定性、糸引き性、スクリーン印刷性を測定した。前記共重合樹脂の基本的な製法は、メタクリル酸アルキルエステル単量体、アミノ基含有メタクリル酸アルキルエステル、２或いは３官能性単量体、連鎖移動剤、重合開始剤を加えて、単量体混合物を用意した。つぎにポリビニルアルコール（クラレ社製、商品名：ＰＶＡ−２３５）をイオン交換水に溶解し、分散媒体とし、これに前記単量体混合物を加え、攪拌羽を３５０ｒｐｍで、７４℃、２時間の懸濁重合を行って、共重合を行った。得られた共重合物を、洗浄、脱水した後、乾燥して、共重合樹脂としたものである。
【００２３】
また、この共重合樹脂を用いた導電性ペースト組成物は、前記共重合樹脂８部（重量）をジヒドロターピネオール１００部（重量）に溶解した後、銅粉末（三井金属社製、「ｃｏｐｐｅｒ ｐｏｗｄｅｒ１１１０」）１００部（重量）を加え、三本ロールで分散して作製した。また従来例として、前記共重合樹脂に変えて、エチルセルロース（ハーキュリス社製、「Ｎ−４」）とした以外は前記と同様にして、作製した。
【００２４】
なお、表１および２に記載される記号は、以下の材料を示すものである。ＭＭＡはメタクリル酸メチル、ｉ−ＢＭＡはメタクリル酸イソブチル、ｎ−ＢＭＡはメタクリル酸ノルマルブチル、ＭＡはアクリル酸メチル、ＥＡはアクリル酸エチル、ＭＡＡはメタクリル酸、ＤＭＭＡはメタクリル酸ジメチルアミノエチル、ＨＥＭＡはメタクリル酸ヒドロキシエチル、ＡＭＡはメタクリル酸アリル、ＴＭＰＴＡはトリメチロールプロパントリアクリレート、ＡＩＢＮは２，２′−アゾビスイソブチロニトリル、ＬＭＣはラウリルメルカプタンである。
【００２５】
つぎに、前記評価方法について記載すると、重量平均分子量については、ゲルパーミエイションクロマトグラフィー（ＧＰＣ）を用いて測定した。加熱分解性については、得られた共重合樹脂を乾燥させ、サンプル量１０〜２０ｍｇをアルミ皿にのせ、熱重量分析（ＴＧＡ）で評価した。雰囲気は、窒素雰囲気中で１０℃／分で室温から５００℃まで昇温して測定を行った。○印は、５００℃における残量率が１．０重量％未満のものであり、×印は、５００℃における残量率が１．０重量％を超えたものである。また煤の有無に関しては、前記アルミ皿に煤があるか否かを目視によって確認し、見られないものは○印、確認できるものは×印とした。さらにガラス転移温度については、次のＦＯＸの式によって、求めた。１／Ｔｇ＝ΣＷｉ／Ｔｇｉ（但しＴｇは、゜Ｋ、Ｗは単量体の重量分率である。）
【００２６】
また、前記導電性ペースト組成物の評価方法について述べると、その安定性に関しては、得られた導電性ペースト組成物を室温で３日間放置し、粘度が２倍以上となったものを×印で、それ以外のものを合格として○印で表示した。糸引き性に関しては、スクリーン印刷を行った際に、従来例として記載したエチルセルロース系の共重合樹脂と、同程度の場合を合格として○印で、それ以外を不合格として×印で記載した。またスクリーン印刷性に関しては、印刷後の回路パターンの状態を比較し、従来例のエチルセルロース系の共重合樹脂と、同等であったものを合格として、○印で、それ以外を不合格として×印で表した。結果は、表１および２に示すとおりである。
【００２７】
【表１】
【表２】
表１から明らかなとおり、本発明の導電性ペースト組成物として用いる共重合樹脂（実験例１〜１５）の組成範囲は、５００℃における熱分解残量率が１．０重量％未満と、加熱分解性が良好であり、かつ煤の発生もなく、溶解性についても問題のないものであった。さらに、分子量についても重量平均分子量（Ｍｗ）が３〜１５万の範囲に入るものであり、ガラス転移温度も４０〜８０℃の範囲のものであった。より詳細に述べると、メタクリル酸アルキルエステル単量体が９４〜９９重量％範囲で、アミノ基含有メタクリル酸アルキルエステルを２重量％まで添加したもの、２官能性単量体を２．０重量部まで、または３官能性単量体を０．１重量部までの範囲で添加したもの、或いは２官能性単量体と３官能性単量体を併用したものを、共重合させた共重合樹脂は、実験例１〜１５に記載されるように、前記熱分解残量、煤の有無、溶解性、重量平均分子量並びにガラス転移温度特性の全てを、満足するものであることがわかる。
【００３０】
このように、前記共重合樹脂を用いた、セラミック回路基板用の導電性ペースト組成物は、溶解性、ペースト組成物の安定性、糸引き性易クリーン印刷性が、全て満足されるものであることがわかる。即ち、導電性ペースト組成物の安定性としては、室温で３日間放置しても粘度が２倍以上にはならず、糸引き性並びにスクリーン印刷を行った際の印刷性に関しても、従来のエチルセルロース系の共重合樹脂を用いたものと、ほぼ同程度の特性を有するものであった。しかも前述のように、特に加熱分解残量が１．０重量％未満と加熱分解性が良好であり、かつ煤の発生もない特性を有するものである。
【００３１】
これに対して、表２に示される比較例とした実験例１６〜２６および従来例のバインダー樹脂は、メタクリル酸アルキルエステル単量体が９４〜９９重量％の範囲を、アミノ基含有メタクリル酸アルキルエステルが０．１〜２．０重量％の範囲を、２官能性単量体が０．０１〜２．０重量部、また３官能性単量体量が０．０１〜０．１重量部の範囲を外れるものには、加熱分解残渣率が１重量％を超えるものがある。（実験例２４、２５）また、これらの実験例では、煤の発生も見られた。さらに２官能性単量体や３官能性単量体が、本発明の添加範囲を超えて配合されると、実験例１８や１９のようにゲル化物の発生が見られ、分子量測定が行えないようなバインダー共重合樹脂となる。また前記のバインダー樹脂を用いた導電性ペースト組成物も、実験例１６、１７、２０〜２３のように、印刷性に係わる糸引き性易クリーン印刷性が、従来のセルロース系バインダー樹脂を用いた導電性ペースト組成物と比較して、劣るものとなっていた。さらに実験例２０のように、アミノ基含有メタクリル酸アルキルエステルが含まれないので、導電性ペースト組成物の安定性に問題が生じるものもあった。また、実験例２６のように、アミノ基含有メタクリル酸アルキルエステルの添加量を、本発明の配合範囲を超えて多量に配合すると、懸濁重合が不安定になり共重合樹脂が得られなかった。よって、本発明の導電性ペースト組成物としては、前記組成範囲の共重合樹脂を用いるべきである。
【００３２】
【発明の効果】
以上詳述したように、本発明のセラミック回路基板用の導電性ペースト組成物は、化学式１で示されるメタクリル酸アルキルエステル単量体９４〜９９重量％、アミノ基含有メタクリル酸アルキルエステル０．１〜２．０重量％およびその他の共重合可能な単量体を含有する単量体混合物１００重量部に対して、２官能性単量体を０．０１〜２．０重量部或いは３官能性単量体を０．０１〜０．１重量部添加した単量体混合物を共重合して得られた、ガラス転移温度が４０〜８０℃で、重量平均分子量が３００００〜１５００００である共重合樹脂としたことによって、特に前記メタクリル酸アルキルエステル単量体が、メタクリル酸イソブチルである共重合樹脂とすることによって、熱分解残量率が極めて少なく電気的特性上の問題がない、また溶解性、印刷性にも優れたものとなる。さらには貯蔵安定性にも優れた、セラミック回路基板用の導電性ペースト組成物となる。
また、導電性ペースト組成物に用いる前記共重合樹脂は、ガラス転移温度が４０〜８０℃で、重量平均分子量が３００００〜１５００００であるから、印刷特性に関係する糸引き性が良好であり、また高沸点溶剤に溶け難くなるという問題もなくなる。さらに加熱分解残渣が少なく電気的特性に優れたものでもある。さらにまた貯蔵安定性にも優れた、セラミック回路基板用の導電性ペースト組成物として、十分実用的なものとなる。
【００３３】
さらに、前記アミノ基含有メタクリル酸アルキルエステルが、メタクリル酸ジメチルアミノエチルおよび／またはメタクリル酸ジエチルアミノエチルである、セラミック回路基板用の導電性ペースト組成物の共重合樹脂とすることによって、加熱分解性をより良好なものとすることができる。また得られた共重合樹脂は、熱分解残量率が１．０重量％未満の電気的特性上も問題がない、また溶解性、印刷性にも優れたものとなる。さらには貯蔵安定性にも優れた、セラミック回路基板用の導電性ペースト組成物の共重合樹脂として、提供できることになる。
【００３４】
また前記共重合樹脂は、アゾ系の重合開始剤を前記単量体混合物１００質量部に対して、０．１〜３質量％を用い、懸濁重合法によって得られたセラミック回路基板用の導電性ペースト組成物の共重合樹脂とすることによって、アゾ系の重合開始剤を特定量用いたことにより、分散剤を含む水中で単量体懸濁液を重合し、その後に洗浄により前記分散剤を洗い取るため、得られたビーズ状ポリマーは、高分子量の共重合体が得られると共に、分解残渣の少ないものとなり、溶剤に溶解した共重合樹脂は、セラミック回路基板用の導電性ペースト組成物として、好ましいものである。
【００３５】
そして、前記共重合樹脂は、大気中または不活性ガス中において、１０℃／分の昇温速度で室温から５００℃まで加熱した場合の加熱分解残渣が、１．０重量％未満である導電性ペースト組成物の共重合樹脂とすることによって、スラッジ等の加熱分解残渣の少ない電気的特性の優れたセラミック回路基板用の導電性ペースト組成物となる。即ち、従来使用されていたエチルセルロース樹脂やブチラール樹脂のように、５００℃以下の低温化での加熱分解ではスラッジと称する残渣が多く発生する不具合がなくなる。よって、電子材料用等の高純度の品質が必要な部分にも使用可能となる。そしてこのような共重合樹脂を用いた導電性ペースト組成物は、糸引き性易クリーン印刷性に優れ、さらに貯蔵安定性にも優れたセラミック回路基板用の導電性ペースト組成物とすることができる。
【００３６】
さらに、前記導電性粉末１００質量部に対して、前記共重合樹脂がその固形分として５〜３０質量部添加されたセラミック回路基板用の導電性ペースト組成物としたので、好ましいセラミック回路基板用の導電性ペースト組成物とすることができる。即ち、前記共重合樹脂の固形分が５重量部未満であると、スクリーン印刷により形成された回路にクラックが発生する恐れがあり、また３０重量部を超えると、単位時間での分解残渣が残り易くなるためである。 [0001]
BACKGROUND OF THE INVENTION
The present inventionConductive paste composition for ceramic circuit boardIt is about.
[0002]
[Prior art]
As this type of technology, an ethyl cellulose resin has been conventionally used as a binder resin, but there has been a problem that a decomposition residue remains during firing. In order to improve such problems, a conductive paste for a ceramic circuit board as described in Patent Document 1 is known.That isThe specific surface area is 0.5-3.0m2/ G of spherical copper powder is dispersed in a high-boiling solvent in which an organic binder that is not at least inferior in scattering property at the time of firing of the resin component as compared with the organic binder contained in the ceramic raw sheet is dissolved. Specifically, it is disclosed that the resin component of the organic binder is an acrylic resin, and the high boiling point solvent is terpineol. Such a conductive paste is said to improve the conductor characteristics and printing accuracy of the ceramic circuit board. However, such a conductive paste needs to increase the molecular weight of the copolymer resin in order to develop a high viscosity suitable for screen printing, and thus has a problem called stringiness due to the high molecular weight. . Furthermore, there is a problem in the stability as a conductive paste.
[0003]
[Patent Document 1]
JP 60-153193 A
[0004]
[Problems to be solved by the invention]
The present invention has less decomposition residue and better electrical characteristics by making the heat decomposability better, and also has excellent print characteristics without stringiness even at high viscosity required for screen printing. Excellent storage stabilityConductive paste composition for ceramic circuit boardThe purpose is to provide.
[0005]
[Means for Solving the Problems]
In order to solve the above problems, as described in claim 1, 94 to 99% by weight of a methacrylic acid alkyl ester monomer represented by the following chemical formula 1, an amino group-containing methacrylic acid alkyl ester 0.1 to The bifunctional monomer is added in an amount of 0.01 to 2.0 parts by weight or a trifunctional monomer based on 100 parts by weight of the monomer mixture containing 2.0% by weight and other copolymerizable monomers. A glass transition temperature obtained by copolymerizing a monomer mixture added with 0.01 to 0.1 part by weight of a monomer is 40 to 80 ° C., and a weight average molecular weight is 30,000 to 150,000.Conductive paste composition for ceramic circuit board containing copolymer resin and at least conductive powder.
[Chemical 1]
Is solved.
[0006]
Moreover, as described in claim 2, the amino group-containing methacrylic acid alkyl ester is dimethylaminoethyl methacrylate and / or diethylaminoethyl methacrylate.Conductive paste composition for ceramic circuit boardIs solved.
[0007]
Further, as described in claim 3,MemorandumPolymer resin isUsing 0.1 to 3% by mass of an azo polymerization initiator with respect to 100 parts by mass of the monomer mixture2. A product obtained by suspension polymerization.Or 2Described inConductive paste composition for ceramic circuit boardIs solved.
[0008]
And before being described in claim 4MemorandumThe polymerized resin has a thermal decomposition residue of less than 1.0% by weight when heated from room temperature to 500 ° C at a heating rate of 10 ° C / min in the air or in an inert gas. In anyConductive paste composition for ceramic circuit boardIs solved.
[0009]
Moreover, as described in claim 5, 5 to 30 parts by mass of the copolymer resin as a solid content thereof is added to 100 parts by mass of the conductive powder. This is solved by making the conductive paste composition for the ceramic circuit board described.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below. The invention described in claim 1 includes 94 to 99% by weight of a methacrylic acid alkyl ester monomer represented by the following chemical formula 1, 0.1 to 2.0% by weight of an amino group-containing methacrylic acid alkyl ester, and other copolymers. 0.01 to 2.0 parts by weight of a bifunctional monomer or 0.01 to 0.1 part of a trifunctional monomer with respect to 100 parts by weight of a monomer mixture containing possible monomers The glass transition temperature obtained by copolymerizing the monomer mixture added with parts by weight is 40 to 80 ° C., and the weight average molecular weight is 30,000 to 150,000.A conductive paste composition for a ceramic circuit board containing a copolymer resin and at least a conductive powder..
[Chemical 1]
[0011]
Thus, 94 to 99% by weight of the methacrylic acid alkyl ester monomer represented by Chemical Formula 1, 0.1 to 2.0% by weight of the amino group-containing methacrylic acid alkyl ester, and other copolymerizable monomers are contained. A monomer obtained by adding 0.01 to 2.0 parts by weight of a bifunctional monomer or 0.01 to 0.1 part by weight of a trifunctional monomer to 100 parts by weight of a monomer mixture Copolymerization of a conductive paste composition for a ceramic circuit board, which is a copolymer resin obtained by copolymerizing a mixture, having a glass transition temperature of 40 to 80 ° C. and a weight average molecular weight of 30,000 to 150,000. Used as a resin, heat decomposability is good, there are fewer decomposition residues, electrical properties are excellent, printing properties without stringiness during screen printing are excellent, and storage stability is also excellent. It may be a copolymer resin of the conductive paste composition of the ceramic circuit board. And the said electrically conductive paste composition is obtained by mixing an electroconductive powder at least.
[0012]
That isBy containing 94 to 99% by weight of the methacrylic acid alkyl ester monomer, good heat decomposability can be expressed. The methacrylic acid alkyl ester monomer has a structure represented by Chemical Formula 1, and R is preferably a methacrylic acid ester having 1 to 8 carbon atoms from the viewpoint of heat decomposability. Specific examples include methyl methacrylate, ethyl methacrylate, normal butyl methacrylate, isobutyl methacrylate, tertiary butyl methacrylate, 2-ethylhexyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, and the like. These can be used alone or in combination. The reason why the methacrylic acid alkyl ester monomer is 94 to 99% by weight is that it is not preferable to deviate from this range because the heat decomposability deteriorates.
[0013]
Furthermore, the addition amount of the amino group-containing methacrylic acid alkyl ester is 0.1 wt% or more,Copolymerization of conductive paste compositionThe dispersion stability of the conductive powder dispersed in the resin can be improved, and by making it 2.0% by weight or less, the heat decomposability can be improved. More preferably, it is in the range of 0.5 to 1.5% by weight.
[0014]
The preferred amino group-containing methacrylic acid alkyl ester is dimethylaminoethyl methacrylate (DMMA) or diethylaminoethyl methacrylate (DEMA) as described in claim 2, and these are used alone or in combination. Added.
[0015]
In the present invention, other copolymerizable monomers are further added, but within a range not deteriorating the heat decomposability of the methacrylic acid alkyl ester monomer and the amino group-containing methacrylic acid alkyl ester. Added. The addition amount is blended in a range not exceeding 100% by weight as the total amount of the monomer mixture. It is approximately 10% by weight or less. Specific examples include methacrylic acid (MMA), 2-hydroxyethyl methacrylate (HEMA), methyl acrylate (MA), ethyl acrylate (EA), styrene, acrylonitrile, acrylamide, methacrylamide, butyl acrylate, A glycidyl methacrylate, vinyl acetate, etc. are mentioned, It can use 1 type or in mixture of 2 or more types. And the monomer mixture isCopolymer resinThe base resin. And other addition is added for this base resin as 100 weight part.
[0016]
Moreover, it is preferable that the said monomer mixture used as base resin contains a crosslinking component. This is a copolymer containing no cross-linking component, that is, a linear copolymer, and the copolymer having the weight average molecular weight of the present invention was used.Conductive paste composition for ceramic circuit boardThen, after screen printing, when the printing plate is peeled off from the printing surface, a conductive paste is formed between the printing surface and the printing surface.CompositionAs a result, a stringing phenomenon occurs and good printing cannot be performed. For this reason, a bifunctional monomer is added as a crosslinking component, 0.01 to 2.0 parts by weight, or 0.01 to 0.1 parts by weight of a trifunctional monomer is added to 100 parts by weight of the monomer mixture. Is done. If the addition is less than 0.01 parts by weight, a copolymer having no stringiness during screen printing cannot be obtained. Further, in the case of the bifunctional monomer, if it exceeds 2.0 parts by weight, and in the case of the trifunctional monomer, if it exceeds 0.1 part by weight, the copolymer is not dissolved in the high boiling point solvent. It is because it becomes union and it is not preferable. Therefore, when the bifunctional monomer or the trifunctional monomer is used in combination, it is necessary not to exceed 0.1 parts by weight. Such bifunctional monomers include butylene glycol dimethacrylate, 1,6 hexanediol dimethacrylate, 1,3 butylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, allyl methacrylate (AMA). ) And the like. Examples of the trifunctional monomer include trimethylolpropane tri (meth) acrylate (TMPTA). Among them, the TMPTA and the AMA are preferable. Such base resin can be conductive paste by copolymerizationCompositionforofIt becomes a copolymer resin.
[0017]
And the copolymerresinIs preferably carried out using an azo polymerization initiator. This is because it is not preferable to use a peroxide polymerization initiator because the reaction of the amino group-containing methacrylic acid alkyl ester is difficult to proceed. Specific examples of the azoke-based polymerization initiator include 2, 2′-Azobisisobutyronitrile, 2,2′-Azobis (2-methylbutylnitrile), 2,2′-Azobis (2,4-dimethylvaleronitrile), 1,1′-Azobis (cyclohexane-1-carbonitrile), dimethyl 2,2′-Azobis (2-methylpropionate) etc. are mentioned. The addition amount is preferably 0.1 to 3% by weight with respect to 100 parts by weight of the monomer mixture.
[0018]
And beforeMemorandumAs a copolymerization method of the polymer resin, as described in claim 3,The azo polymerization initiator was used in an amount of 0.1 to 3% by mass with respect to 100 parts by mass of the monomer mixture.A suspension polymerization method is preferred. This is because, for example, in the solution polymerization method, the monomer is polymerized in a solvent,CopolymerizationResin can be obtained, but there is a problem that it is difficult to obtain a high molecular weight polymer. In the emulsion polymerization method, a monomer emulsified in water in which a surfactant is dissolved is polymerized in micelles. The polymer is precipitated and separated or dried with a spray dryer, and the resulting polymer is dissolved in a solvent.BothSince it is a polymerized resin, the surfactantBothIt tends to remain in the polymerized resin, and there is a possibility that the decomposition residue at the time of heat decomposition increases. On the other hand, in the above suspension polymerization method, the monomer suspension is polymerized in water containing a dispersant, and then the dispersant is washed away, so that the obtained bead polymer has a high molecular weight. Copolymer was obtained, and there were few decomposition residues, and it was dissolved in the solvent.CopolymerizationResin isFor ceramic circuit boardConductive pasteCopolymer resin of compositionCan be preferable.
[0019]
In addition,The copolymer resin preferably has a glass transition temperature of 40 to 80 ° C. and a weight average molecular weight of 30000 to 150,000. this is,Of conductive paste composition for ceramic circuit boardAs copolymer resinIsBy setting the weight average molecular weight to 30,000 or more, the conductive powder can be easily dispersed, and sedimentation of the conductive powder in the conductive paste composition can be prevented. In addition, by setting the weight average molecular weight to about 150,000 or less,CopolymerizationSince generation | occurrence | production of the gelled material in resin can be prevented, it becomes a preferable thing. Therefore,SaidThe copolymer resin is copolymerized so that the weight average molecular weight is about 3 to 150,000 by selecting the conditions for the suspension polymerization. Further, by setting the glass transition temperature to 40 to 80 ° C., the stringiness related to printing characteristics is good, and the problem that it is difficult to dissolve in a high boiling point solvent is eliminated.
[0020]
Also obtained in this wayOf conductive paste composition for ceramic circuit boardAs described in claim 4, the copolymer resin has a thermal decomposition residue of 1.0 when heated from room temperature to 500 ° C. at a temperature rising rate of 10 ° C./min in the air or in an inert gas. Conductive paste that is less than wt%CompositionforBothIt can be a polymerized resin. Thus, it becomes an electrically conductive paste composition excellent in electrical characteristics by having less heat decomposition residue such as sludge.That isAs in the case of ethyl cellulose resin that has been conventionally used, heat decomposition at a low temperature of 500 ° C. or less causes a problem that a lot of residue called sludge is generated. Further, when heat decomposition is performed in an inert gas atmosphere, the sludge further increases. Since it occurs frequently, there is no inconvenience that it cannot be used for parts that require high-purity quality such as for electronic materials. Such a conductive paste composition without any inconvenience can be used for parts that require high-purity quality such as for electronic materials. Moreover, it is suitable for a metal filler that undergoes an oxidation reaction by heat, a metal oxide that easily undergoes thermal degradation, a phosphor, and the like. Here, in many cases, nitrogen is used as the inert atmosphere, but a mixed gas of oxygen and nitrogen may be used. Other gases include helium, neon, and argon.
[0021]
Conductive paste for ceramic circuit boardsCompositionTo be beforeMemorandumConductive paste by dissolving polymer resin and conductive powder in organic solvent such as dihydroterpineol, stirring and dispersingCompositionAnd Moreover, as said electroconductive powder, metals, such as copper, silver, nickel, etc.Is used.AndSaidWith conductive powderSaidThe mixing ratio with the copolymer resin isAs described in claim 5, the conductive paste composition for a ceramic circuit board described in claims 1 to 4 has a solid content of the copolymer resin of 5 parts per 100 parts by weight of the conductive powder. It is preferable to add -30 parts by weight.This is beforeMemorandumIf the solid content of the polymer resin is less than 5 parts by weight, cracks may occur in the circuit formed by screen printing, and if it exceeds 30 parts by weight, the decomposition residue in unit time tends to remain. is there. In addition, you may add a plasticizer, a dispersing agent, a wetting agent, an antifoamer, an antistatic agent, and a viscosity reducing agent as needed.
[0022]
【Example】
The effects of the present invention will be described below with reference to Experimental Examples 1 to 26 and a conventional example. Various binder copolymer resins shown in Table 1 (Examples) and Table 2 (Comparative Examples and Conventional Examples) were prepared, and their molecular weight, glass transition temperature, thermal decomposition residue, presence or absence of wrinkles, solubility, and so on.BothConductive paste using polymerized resinCompositionThe stability, stringiness, and screen printability were measured. in frontMemorandumA basic method for producing a polymerization resin is to add a methacrylic acid alkyl ester monomer, an amino group-containing methacrylic acid alkyl ester, a bifunctional or trifunctional monomer, a chain transfer agent, a polymerization initiator, Prepared. Next, polyvinyl alcohol (manufactured by Kuraray Co., Ltd., trade name: PVA-235) is dissolved in ion-exchanged water to form a dispersion medium, to which the monomer mixture is added, and the stirring blade is 350 rpm at 74 ° C. for 2 hours. Suspension polymerization was performed to carry out copolymerization. The obtained copolymer is washed, dehydrated and dried.,BothIt is a polymerized resin.
[0023]
Also thisBothConductive paste using polymerized resinCompositionAfter dissolving 8 parts (by weight) of the copolymer resin in 100 parts (by weight) of dihydroterpineol, 100 parts (by weight) of copper powder (“copper powder 1110” manufactured by Mitsui Kinzoku Co., Ltd.) was added and dispersed with a three-roll. And produced. As a conventional example,MemorandumIt was produced in the same manner as described above except that ethyl cellulose (“N-4” manufactured by Herculis Co., Ltd.) was used instead of the polymer resin.
[0024]
In addition, the symbol described in Table 1 and 2 shows the following materials. MMA is methyl methacrylate, i-BMA is isobutyl methacrylate, n-BMA is normal butyl methacrylate, MA is methyl acrylate, EA is ethyl acrylate, MAA is methacrylic acid, DMMA is dimethylaminoethyl methacrylate, and HEMA Hydroxyethyl methacrylate, AMA is allyl methacrylate, TMPTA is trimethylolpropane triacrylate, AIBN is 2,2'-azobisisobutyronitrile, and LMC is lauryl mercaptan.
[0025]
Next, the evaluation method will be described. The weight average molecular weight was measured using gel permeation chromatography (GPC). About heat decomposability, it is obtainedTogetherThe polymer resin was dried and a sample amount of 10 to 20 mg was placed on an aluminum dish and evaluated by thermogravimetric analysis (TGA). The atmosphere was measured by raising the temperature from room temperature to 500 ° C. at 10 ° C./min in a nitrogen atmosphere. The symbol “◯” indicates that the remaining rate at 500 ° C. is less than 1.0% by weight, and the symbol “X” indicates that the remaining rate at 500 ° C. exceeds 1.0% by weight. In addition, regarding the presence or absence of wrinkles, whether or not wrinkles were found on the aluminum plate was visually confirmed. Further, the glass transition temperature was determined by the following FOX equation. 1 / Tg = ΣWi/ Tgi(However, Tg is ° K and W is the weight fraction of the monomer.)
[0026]
In addition, the conductive pasteCompositionAs for the evaluation method, the obtained conductive paste is related to its stability.CompositionWas allowed to stand at room temperature for 3 days, and those having a viscosity of 2 times or more were marked with x, and those with the others passed were marked with ○. Regarding the stringiness, when the screen printing was performed, the ethyl cellulose type described as the conventional example was used.CopolymerizationThe case of the same degree as that of the resin is indicated by a circle as a pass, and the other cases are indicated by a cross as a failure. In addition, regarding screen printability, the state of the circuit pattern after printing is compared, and the ethyl cellulose type of the conventional example is compared.CopolymerizationThose that were equivalent to the resin were indicated as “good” by “◯” and the others as “failed” by “x”. The results are as shown in Tables 1 and 2.
[0027]
[Table 1]
[Table 2]
As is apparent from Table 1, the present inventionUsed as a conductive paste compositionCopolymer resin (Experimental Examples 1-15)The composition range ofThe thermal decomposition residual rate at 500 ° C. was less than 1.0% by weight, the heat decomposition was good, no wrinkles were generated, and there was no problem with the solubility. Further, the molecular weight was within the range of 3 to 150,000 in the weight average molecular weight (Mw), and the glass transition temperature was within the range of 40 to 80 ° C. More specifically, methacrylic acid alkyl ester monomer is in the range of 94 to 99% by weight, amino group-containing methacrylic acid alkyl ester is added up to 2% by weight, and bifunctional monomer is 2.0 parts by weight. Or a trifunctional monomer added in an amount of up to 0.1 parts by weight, or a combination of a bifunctional monomer and a trifunctional monomerTogetherAs described in Experimental Examples 1 to 15, the polymerized resin satisfies all of the thermal decomposition remaining amount, the presence or absence of soot, solubility, weight average molecular weight, and glass transition temperature characteristics.
[0030]
Thus, saidUsing copolymer resin,For ceramic circuit boardConductive pasteCompositionIt can be seen that the solubility, the stability of the paste composition, and the ease of string drawing and easy printability are all satisfied.That is, Conductive pasteCompositionAs for the stability, the viscosity does not increase more than twice even when left at room temperature for 3 days.CopolymerizationIt had almost the same characteristics as those using resin. In addition, as described above, the thermal decomposition remaining amount is particularly less than 1.0% by weight, and the thermal decomposition property is good and there is no generation of soot.
[0031]
On the other hand, the experimental examples 16 to 26 and the conventional binder resins shown in Table 2 have an amino acid-containing alkyl methacrylate in the range of 94 to 99% by weight of the alkyl methacrylate ester monomer. Esters are in the range of 0.1 to 2.0% by weight, bifunctional monomers are 0.01 to 2.0 parts by weight, and trifunctional monomers are 0.01 to 0.1 parts by weight. Among these, there is one having a thermal decomposition residue ratio exceeding 1% by weight. (Experimental Examples 24 and 25) In these experimental examples, wrinkles were also observed. Furthermore, when a bifunctional monomer or a trifunctional monomer is blended beyond the addition range of the present invention, gelation is observed as in Experimental Examples 18 and 19, and the molecular weight cannot be measured. Such a binder copolymer resin is obtained. In addition, a conductive paste using the binder resinCompositionAlso, as in Experimental Examples 16, 17, 20-23, the stringiness and easy clean printability related to printability are inferior to those of conventional conductive paste compositions using a cellulose-based binder resin. It was. Further, as in Experimental Example 20, since an amino group-containing methacrylic acid alkyl ester was not included, there was a problem in which there was a problem in the stability of the conductive paste composition. Further, as in Experimental Example 26, when the addition amount of the amino group-containing methacrylic acid alkyl ester was blended in a large amount exceeding the blending range of the present invention, suspension polymerization became unstable and a copolymer resin could not be obtained. . Therefore, the present inventionAs the conductive paste composition, the composition rangeA copolymer resin should be used.
[0032]
【The invention's effect】
As detailed above,The conductive paste composition for a ceramic circuit board of the present invention isMonomer containing 94 to 99% by weight of methacrylic acid alkyl ester monomer represented by Chemical Formula 1, 0.1 to 2.0% by weight of amino group-containing methacrylic acid alkyl ester and other copolymerizable monomers Copolymerizes a monomer mixture obtained by adding 0.01 to 2.0 parts by weight of a bifunctional monomer or 0.01 to 0.1 part by weight of a trifunctional monomer to 100 parts by weight of the mixture. The glass transition temperature is 40 to 80 ° C. and the weight average molecular weight is 30,000 to 150,000.BothWith polymerized resinEspecially byThe alkyl methacrylate monomer is isobutyl methacrylate.BothBy using a polymerized resin, the thermal decomposition residual rate is extremely small, there is no problem in electrical characteristics, and the solubility and printability are excellent. Furthermore, it has excellent storage stability.For ceramic circuit boardConductive pasteCompositionIt becomes.
Moreover, the said used for an electrically conductive paste compositionSince the copolymer resin has a glass transition temperature of 40 to 80 ° C. and a weight average molecular weight of 30000 to 150,000, it has a good stringiness related to printing characteristics and is difficult to dissolve in a high boiling point solvent. Disappear. Furthermore, there are few residue of thermal decomposition and it is also excellent in electrical characteristics. Ceramic circuit board with excellent storage stabilityforConductive pasteCompositionAs such, it will be practical enough.
[0033]
Furthermore, the amino group-containing methacrylic acid alkyl ester is dimethylaminoethyl methacrylate and / or diethylaminoethyl methacrylate.For ceramic circuit boardConductive pasteOf compositionBy using a copolymer resin, the heat decomposability can be improved. Also obtainedTogetherThe polymerized resin has no problem in terms of electrical characteristics having a thermal decomposition residual ratio of less than 1.0% by weight, and has excellent solubility and printability. A ceramic circuit board with excellent storage stabilityforConductive pasteOf compositionIt can be provided as a copolymer resin.
[0034]
BeforeMemorandumPolymer resin isUsing 0.1 to 3% by mass of an azo polymerization initiator based on 100 parts by mass of the monomer mixture,Obtained by suspension polymerizationFor ceramic circuit boardConductive pasteOf compositionBy using a copolymer resin,By using a specific amount of azo polymerization initiator,In order to polymerize the monomer suspension in water containing the dispersant and then wash away the dispersant by washing, the resulting bead polymer is a high molecular weight copolymer, and the decomposition residue Less and dissolved in solventCopolymerizationResin isFor ceramic circuit boardConductive pasteCompositionIs preferable.
[0035]
And beforeMemorandumThe polymerization resin is a conductive paste having a thermal decomposition residue of less than 1.0% by weight when heated from room temperature to 500 ° C. at a rate of temperature increase of 10 ° C./min in the air or in an inert gas.Of compositionBy using a copolymer resin, it has excellent electrical characteristics with little thermal decomposition residue such as sludge.For ceramic circuit boardConductive pasteCompositionIt becomes.That isAs in the case of conventionally used ethyl cellulose resin and butyral resin, the heat decomposition at a low temperature of 500 ° C. or less eliminates the problem of generating a lot of residue called sludge. Therefore, it can also be used for parts that require high purity quality such as for electronic materials. And like thisNakyoConductive paste composition using polymerized resin is a ceramic circuit board with excellent stringiness, easy clean printability, and excellent storage stability.forConductive pasteCompositionIt can be.
[0036]
Furthermore, since it was set as the electroconductive paste composition for ceramic circuit boards in which the said copolymer resin was added 5-30 mass parts as the solid content with respect to 100 mass parts of said electroconductive powders, For preferable ceramic circuit boards It can be set as an electrically conductive paste composition. In other words, if the solid content of the copolymer resin is less than 5 parts by weight, there is a risk of cracks occurring in the circuit formed by screen printing, and if it exceeds 30 parts by weight, a decomposition residue remains in a unit time. This is because it becomes easier.
Claims (5)
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