WO2016125618A1 - Solvent composition for manufacturing electronic device - Google Patents
Solvent composition for manufacturing electronic device Download PDFInfo
- Publication number
- WO2016125618A1 WO2016125618A1 PCT/JP2016/052068 JP2016052068W WO2016125618A1 WO 2016125618 A1 WO2016125618 A1 WO 2016125618A1 JP 2016052068 W JP2016052068 W JP 2016052068W WO 2016125618 A1 WO2016125618 A1 WO 2016125618A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electronic device
- solvent
- ink
- formula
- solvent composition
- Prior art date
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- 239000002904 solvent Substances 0.000 title claims abstract description 116
- 239000000203 mixture Substances 0.000 title claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 47
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 42
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011230 binding agent Substances 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical group CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- DBUMQODMPXCGAY-UHFFFAOYSA-N 2-(2-butan-2-yloxypropoxy)propan-1-ol Chemical compound CCC(C)OC(C)COC(C)CO DBUMQODMPXCGAY-UHFFFAOYSA-N 0.000 claims description 6
- YYLLIJHXUHJATK-UHFFFAOYSA-N Cyclohexyl acetate Chemical compound CC(=O)OC1CCCCC1 YYLLIJHXUHJATK-UHFFFAOYSA-N 0.000 claims description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 6
- AKIIJALHGMKJEJ-UHFFFAOYSA-N (2-methylcyclohexyl) acetate Chemical compound CC1CCCCC1OC(C)=O AKIIJALHGMKJEJ-UHFFFAOYSA-N 0.000 claims description 5
- HBUKXWXYJOMLIP-UHFFFAOYSA-N 1-[2-(2-methoxypropoxy)propoxy]-3-methylbutane Chemical compound C(CC(C)C)OCC(OCC(C)OC)C HBUKXWXYJOMLIP-UHFFFAOYSA-N 0.000 claims description 5
- KJOVIRMWPFJSTR-UHFFFAOYSA-N 1-butan-2-yloxypropan-2-ol Chemical compound CCC(C)OCC(C)O KJOVIRMWPFJSTR-UHFFFAOYSA-N 0.000 claims description 5
- HGERSUQOJQWENV-UHFFFAOYSA-N 1-pentan-2-yloxypropan-2-ol Chemical compound CCCC(C)OCC(C)O HGERSUQOJQWENV-UHFFFAOYSA-N 0.000 claims description 5
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 claims description 5
- MBZRJSQZCBXRGK-UHFFFAOYSA-N 4-tert-Butylcyclohexyl acetate Chemical compound CC(=O)OC1CCC(C(C)(C)C)CC1 MBZRJSQZCBXRGK-UHFFFAOYSA-N 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000000304 alkynyl group Chemical group 0.000 claims description 5
- 239000003989 dielectric material Substances 0.000 claims description 5
- 239000011810 insulating material Substances 0.000 claims description 5
- 239000000696 magnetic material Substances 0.000 claims description 5
- 239000007769 metal material Substances 0.000 claims description 5
- 229940094933 n-dodecane Drugs 0.000 claims description 5
- 239000004065 semiconductor Substances 0.000 claims description 5
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 4
- GVJGVGAUZWVCBW-UHFFFAOYSA-N 2-[2-(2-butan-2-yloxypropoxy)propoxy]propan-1-ol Chemical compound CC(CC)OC(C)COC(C)COC(C)CO GVJGVGAUZWVCBW-UHFFFAOYSA-N 0.000 claims description 4
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract 2
- 239000000976 ink Substances 0.000 description 66
- 150000001412 amines Chemical class 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 19
- ZPAKUZKMGJJMAA-UHFFFAOYSA-N Cyclohexane-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)CC1C(O)=O ZPAKUZKMGJJMAA-UHFFFAOYSA-N 0.000 description 14
- -1 etc.) Substances 0.000 description 13
- 238000010304 firing Methods 0.000 description 13
- 239000001856 Ethyl cellulose Substances 0.000 description 11
- 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 11
- 229920001249 ethyl cellulose Polymers 0.000 description 11
- 235000019325 ethyl cellulose Nutrition 0.000 description 11
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 10
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 10
- 229940113162 oleylamide Drugs 0.000 description 10
- 230000032683 aging Effects 0.000 description 9
- RZIPTXDCNDIINL-UHFFFAOYSA-N cyclohexane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCCC1(C(O)=O)C(O)=O RZIPTXDCNDIINL-UHFFFAOYSA-N 0.000 description 9
- 239000002562 thickening agent Substances 0.000 description 9
- SADAOYKNIHVPHS-UHFFFAOYSA-N cyclohexane-1,1,2,2-tetracarbonyl chloride Chemical compound ClC(=O)C1(C(Cl)=O)CCCCC1(C(Cl)=O)C(Cl)=O SADAOYKNIHVPHS-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000011354 acetal resin Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 229920006324 polyoxymethylene Polymers 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 150000001718 carbodiimides Chemical class 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000003985 ceramic capacitor Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 2
- GTVGXWMIEPEVNL-UHFFFAOYSA-N 4,5-bis(2-ethylhexylcarbamoyl)cyclohexane-1,2-dicarboxylic acid Chemical compound C(C)C(CNC(=O)C1C(CC(C(C1)C(=O)O)C(=O)O)C(=O)NCC(CCCC)CC)CCCC GTVGXWMIEPEVNL-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229920013820 alkyl cellulose Polymers 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000012461 cellulose resin Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000011437 continuous method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- BGRWYRAHAFMIBJ-UHFFFAOYSA-N diisopropylcarbodiimide Natural products CC(C)NC(=O)NC(C)C BGRWYRAHAFMIBJ-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- BMFVGAAISNGQNM-UHFFFAOYSA-N isopentylamine Chemical compound CC(C)CCN BMFVGAAISNGQNM-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 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 2
- 239000000126 substance Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- AJYOAVGWPBRROO-ZUELCTOOSA-N 1-N,2-N-bis(2-ethylhexyl)-4-N,5-N-bis[(Z)-octadec-9-enyl]cyclohexane-1,2,4,5-tetracarboxamide Chemical compound C(CCCCCCC\C=C/CCCCCCCC)NC(=O)C1CC(C(CC1C(=O)NCCCCCCCC\C=C/CCCCCCCC)C(=O)NCC(CCCC)CC)C(=O)NCC(CCCC)CC AJYOAVGWPBRROO-ZUELCTOOSA-N 0.000 description 1
- DWNAUQMXBUXKSX-UHFFFAOYSA-N 1-N,2-N-bis(2-ethylhexyl)-4-N,5-N-dioctadecylcyclohexane-1,2,4,5-tetracarboxamide Chemical compound C(CCCCCCCCCCCCCCCCC)NC(=O)C1CC(C(CC1C(=O)NCCCCCCCCCCCCCCCCCC)C(=O)NCC(CCCC)CC)C(=O)NCC(CCCC)CC DWNAUQMXBUXKSX-UHFFFAOYSA-N 0.000 description 1
- WHIJWSNTWHJZJO-ZHTVLWRQSA-N 1-N,2-N-bis[(Z)-octadec-9-enyl]-4-N,5-N-dioctadecylcyclohexane-1,2,4,5-tetracarboxamide Chemical compound C(CCCCCCC\C=C/CCCCCCCC)NC(=O)C1CC(C(CC1C(=O)NCCCCCCCC\C=C/CCCCCCCC)C(=O)NCCCCCCCCCCCCCCCCCC)C(=O)NCCCCCCCCCCCCCCCCCC WHIJWSNTWHJZJO-ZHTVLWRQSA-N 0.000 description 1
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- CXBDYQVECUFKRK-UHFFFAOYSA-N 1-methoxybutane Chemical compound CCCCOC CXBDYQVECUFKRK-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- YVHDVDHZIITGIX-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]-1-propoxypropane Chemical compound C(CC)OCC(OCC(OCC(C)OC)C)C YVHDVDHZIITGIX-UHFFFAOYSA-N 0.000 description 1
- 125000006040 2-hexenyl group Chemical group 0.000 description 1
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000006041 3-hexenyl group Chemical group 0.000 description 1
- 125000006042 4-hexenyl group Chemical group 0.000 description 1
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- CIURCIMZEPBPPG-UHFFFAOYSA-N CC(CCC)OC(C)COC(C)CO Chemical compound CC(CCC)OC(C)COC(C)CO CIURCIMZEPBPPG-UHFFFAOYSA-N 0.000 description 1
- CQWSJIYHAIVZCB-UHFFFAOYSA-N CCCCCCCCCCCCCCCCCCNC(C(CC(C(C1)C(O)=O)C(O)=O)C1C(NCCCCCCCCCCCCCCCCCC)=O)=O Chemical compound CCCCCCCCCCCCCCCCCCNC(C(CC(C(C1)C(O)=O)C(O)=O)C1C(NCCCCCCCCCCCCCCCCCC)=O)=O CQWSJIYHAIVZCB-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 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
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- 125000005070 decynyl 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#C* 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000004090 dissolution Methods 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
- 230000000694 effects Effects 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000005980 hexynyl group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000001421 myristyl 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])[H] 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000001196 nonadecyl 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])C([H])([H])[H] 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005069 octynyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C#C* 0.000 description 1
- 125000001117 oleyl 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])=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])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical class C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 description 1
- 229940100684 pentylamine Drugs 0.000 description 1
- 125000005981 pentynyl group Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000123 polythiophene Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/228—Terminals
- H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
Definitions
- the present invention relates to a solvent composition used in an ink for forming a wiring or an electrode using a printing method in the production of an electronic device.
- This application claims the priority of Japanese Patent Application No. 2015-019637 for which it applied to Japan on February 3, 2015, and uses the content here.
- Electronic devices manufactured using the printing method include capacitors, inductors, varistors, thermistors, transistors, speakers, actuators, antennas, solid oxide fuel cells, and the like.
- a multilayer ceramic capacitor is generally manufactured through the following steps. 1.
- a green sheet is obtained by forming a slurry containing ceramic powder, a binder resin such as polyvinyl acetal resin, and a solvent into a sheet.
- An ink containing an electrical property imparting material for example, nickel, palladium, etc.
- a binder resin for example, ethyl cellulose, etc.
- an organic solvent for example, terpineol, etc.
- the applied ink is dried (drying process). 4).
- a green sheet on which wiring or the like is formed is cut into a predetermined size, and a plurality of sheets are stacked and pressed. 5. Firing (firing process).
- the binder resin contained in the ink has a function of fixing the electrical property imparting material on the green sheet and a function of imparting an appropriate viscosity to enable formation of a fine print pattern.
- ethyl cellulose has been mainly used as the binder resin.
- a member having a surface to be coated hereinafter sometimes referred to as a “surface to be coated”
- the carbon component remains ash after firing, which causes a decrease in conductivity.
- Patent Document 1 discloses that the amount of ash produced can be reduced by using polyvinyl acetal resin instead of ethyl cellulose. However, even if a polyvinyl acetal resin was used, satisfactory results were not obtained for these problems.
- an object of the present invention is a solvent composition used for ink for forming wiring and electrodes of electronic devices by a printing method, which can improve the printing accuracy of the ink and can be baked at a low temperature. It is possible to provide a solvent composition capable of suppressing the amount of ash generated after firing extremely low.
- Another object of the present invention is an ink for forming wiring and electrodes of an electronic device by a printing method, which is excellent in printing accuracy, can be fired at a low temperature, and has an extremely small amount of ash generated after firing, And a manufacturing method thereof.
- the present inventors have found that the compound represented by the following formula (1) self-assembles and forms a string-like aggregate when heated and dissolved in a solvent. It has been found that such a viscosity is produced, that it can be fired at a lower temperature than a binder resin such as ethyl cellulose, and that the residual amount of ash after firing is extremely small.
- the ink obtained through the step of heating and dissolving the compound represented by the above formula (1) and the solvent has a viscosity suitable for the formation of wiring and the like by the printing method, so that dripping is suppressed and highly accurate.
- a wiring pattern can be formed, and in the baking process, baking can be performed quickly at a lower temperature than in the case of baking an ink containing a binder resin such as ethyl cellulose. It has been found that it can be prevented from being softened and deformed by exposure, the residual amount of ash after firing can be remarkably reduced, and the deterioration of electrical characteristics caused by this can be suppressed.
- the present invention has been completed based on these findings.
- this invention is a solvent composition used for the ink for manufacturing an electronic device by a printing method, Comprising: A solvent and following formula (1) (In the formula, R represents an aliphatic hydrocarbon group having 1 or more carbon atoms. In the formula, all four Rs are the same group or two different groups.)
- the solvent composition for electronic device manufacture containing the compound represented by these is provided.
- the present invention also provides the above-mentioned solvent composition for producing an electronic device, wherein R in the formula (1) is a linear or branched alkyl group, alkenyl group, or alkynyl group having 6 to 18 carbon atoms. To do.
- the present invention also provides the above-mentioned solvent composition for producing an electronic device, wherein the SP value [(cal / cm 3 ) 0.5 ] at 25 ° C. of the solvent is 7.0 to 9.0.
- the solvent is n-decane, n-dodecane, propylene glycol methyl-n-propyl ether, propylene glycol methyl-n-butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, At least selected from the group consisting of propylene glycol methyl-n-butyl ether, dipropylene glycol methyl isoamyl ether, tripropylene glycol methyl-n-propyl ether, cyclohexyl acetate, 2-methylcyclohexyl acetate, and 4-t-butylcyclohexyl acetate
- One of the above-mentioned solvent compositions for producing an electronic device is provided.
- the present invention also provides the above-mentioned solvent composition for producing an electronic device, wherein the content of the compound represented by the formula (1) is 0.1 to 50 parts by weight with respect to 100 parts by weight of the solvent.
- the present invention also provides a method for producing an ink for producing an electronic device, which comprises a step of heating and dissolving the above-mentioned solvent composition for producing an electronic device at 30 to 90 ° C.
- the present invention also provides a solvent and the following formula (1):
- R represents an aliphatic hydrocarbon group having 1 or more carbon atoms.
- all four Rs are the same group or two different groups.
- An ink for producing an electronic device comprising a compound represented by the formula:
- the present invention further provides the above-described ink for manufacturing an electronic device, further comprising a conductive metal material, a semiconductor material, a magnetic material, a dielectric material, or an insulating material.
- the present invention also provides the above-mentioned ink for manufacturing an electronic device, wherein the binder resin content is 10% by weight or less.
- a solvent composition for use in an ink for producing an electronic device by a printing method comprising a solvent and a compound represented by formula (1).
- R in the formula (1) is a linear or branched alkyl group, alkenyl group, or alkynyl group having 6 to 18 carbon atoms.
- the compound represented by formula (1) is at least one compound selected from the compounds represented by formulas (1-2) to (1-5) The solvent composition for electronic device manufacture of description.
- the compound represented by the formula (1) is a compound represented by the formula (1-3) and / or a compound represented by the formula (1-4) [1] or [2] Solvent composition for manufacturing electronic devices.
- the solvent composition for producing an electronic device according to any one of [1] to [6], wherein the content of the solvent is 20.0 to 99.9% by weight of the total amount of the solvent composition for producing an electronic device. .
- the solvent is n-decane, n-dodecane, propylene glycol methyl-n-propyl ether, propylene glycol methyl-n-butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl.
- -At least one selected from the group consisting of n-butyl ether, dipropylene glycol methyl isoamyl ether, tripropylene glycol methyl n-propyl ether, cyclohexyl acetate, 2-methylcyclohexyl acetate, and 4-t-butylcyclohexyl acetate
- the solvent composition for producing an electronic device according to any one of [1] to [7].
- the solvent composition for producing an electronic device according to any one of [1] to [8], which is less than 50% by weight of the total solvent contained in the product.
- the electrical property imparting material is a conductive metal material, a semiconductor material, a magnetic material, a dielectric material, or an insulating material.
- the binder resin content is 10% by weight or less.
- the binder resin is a polymer compound having a molecular weight of 10,000 or more.
- a method for manufacturing an electronic device comprising a step of applying an ink for manufacturing an electronic device according to any one of [12] to [20] by a printing method, forming a wiring through a step of drying and baking. .
- the solvent composition for producing an electronic device of the present invention contains the compound represented by the above formula (1), an ink having a viscosity suitable for forming a wiring or the like by a printing method is produced through a step of heating and dissolving. can do. Moreover, the ink obtained using the solvent composition for manufacturing an electronic device of the present invention is not easily dripped, and a highly accurate wiring pattern can be formed by a printing method. Moreover, in a baking process, it can bake at lower temperature and it can prevent that a to-be-coated surface member is softened and deform
- solvent composition for manufacturing electronic devices The solvent composition for producing an electronic device of the present invention (hereinafter sometimes referred to as “solvent composition”) is a solvent composition used in an ink for producing an electronic device using a printing method, And a compound represented by the formula (1).
- the solvent composition of the present invention contains a compound represented by the following formula (1).
- R represents an aliphatic hydrocarbon group having 1 or more carbon atoms.
- all four Rs are the same group or two different groups.
- the compound represented by the following formula (1) acts as a thickener.
- R is an aliphatic hydrocarbon group having 1 or more carbon atoms.
- R is an aliphatic hydrocarbon group having 1 or more carbon atoms.
- Examples of the compound represented by the formula (1) include compounds represented by the following formulas (1-1) to (1-5).
- R 1 and R 2 are different from each other and represent an aliphatic hydrocarbon group having 1 or more carbon atoms, and examples can be given in the same manner as R.
- R ⁇ 1 > exists in a formula they show the same group. The same applies to R 2 .
- the compounds represented by the above formulas (1-2) to (1-5) are preferable from the viewpoint that the viscosity can be increased by adding a small amount.
- a compound represented by (1-3) and / or a compound represented by the above formula (1-4) is preferred.
- the evaporation temperature is 120 to 380 ° C. (preferably 150 to 330 ° C., more preferably 150 to 320 ° C., particularly preferably 150 to 315 ° C., and most preferably 170 ° C.).
- the evaporation temperature can be controlled by the type of side chain. When the evaporation temperature exceeds the above range, firing at a low temperature becomes difficult, and the coated surface member may be softened and deformed by being exposed to a high temperature for a long time. On the other hand, if the evaporation temperature is lower than the above range, the composition may change due to vaporization at the time of ink preparation or printing, and it tends to be difficult to stably form wirings and the like.
- the compound represented by the formula (1) can self-associate by hydrogen bonding at the amide bond site to form a fiber-like self-assembly. Furthermore, since the R group has an affinity for the solvent, the solvent can be thickened by being compatible with the solvent, and an ink for producing an electronic device that is stable over time can be formed.
- the content of the compound represented by the formula (1) in the solvent composition of the present invention (when two or more are contained, the total content) is, for example, 0.1 to 50 parts by weight with respect to 100 parts by weight of the solvent. Degree, preferably 0.5 to 30 parts by weight, particularly preferably 0.5 to 10 parts by weight.
- the content of the compound represented by the formula (1) is below the above range, it becomes difficult to stably maintain the viscosity of the ink, such as a decrease in viscosity due to a temperature change. It may be difficult to form.
- the content of the compound represented by the formula (1) exceeds the above range, the viscosity of the ink becomes too high, and it may be difficult to form a wiring or the like by a printing method.
- the compound represented by Formula (1) can be manufactured by the following method etc., for example.
- 1. A method of reacting cyclohexanetetracarboxylic acid with thionyl chloride to obtain cyclohexanetetracarboxylic acid tetrachloride, and reacting the resulting cyclohexanetetracarboxylic acid tetrachloride with an amine.
- Amine acid (1) is reacted with cyclohexanetetracarboxylic dianhydride to obtain an amic acid, and amine (2) (which may be the same as or different from amine (1)) is used with a condensing agent.
- 1,2,4,5-cyclohexanetetracarboxylic acid can be suitably used.
- Examples of the amine (R—NH 2 : R is the same as described above) used in the production method 1 above include, for example, butylamine, pentylamine, isopentylamine, hexylamine, octylamine, 2-ethylhexylamine, decylamine, laurylamine Aliphatic hydrocarbon groups having 1 or more carbon atoms (preferably 6 to 20 carbon atoms, particularly preferably 6 to 18 carbon atoms) such as myristylamine, stearylamine, oleylamine, etc. (for example, linear or branched alkyl) And an amine having a group, an alkenyl group, or an alkynyl group.
- the reaction between cyclohexanetetracarboxylic acid tetrachloride and amine can be carried out, for example, by dropping cyclohexanetetracarboxylic acid tetrachloride into a system charged with amine.
- One amine may be used alone, or two different amines may be used.
- the amount of amine to be used (the total amount when two different amines are used) is, for example, about 4 to 8 mol, preferably 4 to 6 mol, per 1 mol of cyclohexanetetracarboxylic acid tetrachloride.
- the reaction between cyclohexanetetracarboxylic acid tetrachloride and amine can be carried out in the presence or absence of a solvent.
- the solvent include saturated or unsaturated hydrocarbon solvents such as pentane, hexane, heptane, octane and petroleum ether; aromatic hydrocarbon solvents such as benzene, toluene and xylene; methylene chloride, chloroform, 1, 2 -Halogenated hydrocarbon solvents such as dichloroethane, chlorobenzene, bromobenzene; ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, cyclopentyl methyl ether; acetonitrile, benzonitrile, etc.
- Nitrile solvents such as dimethyl sulfoxide
- sulfolane solvents such as sulfolane
- amide solvents such as dimethylformamide
- high-boiling solvents such as silicone oil.
- the amount of the solvent used is, for example, about 50 to 300% by weight with respect to the total amount of cyclohexanetetracarboxylic acid tetrachloride and amine.
- concentration of a reaction component will become low and there exists a tendency for reaction rate to fall.
- the reaction between cyclohexanetetracarboxylic acid tetrachloride and amine is usually carried out under normal pressure.
- the atmosphere of the reaction is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like.
- the reaction temperature is, for example, about 30 to 60 ° C.
- the reaction time is, for example, about 0.5 to 20 hours.
- an aging step may be provided. When the aging step is provided, the aging temperature is, for example, about 30 to 60 ° C., and the aging time is, for example, about 1 to 5 hours.
- the reaction can be carried out by any method such as batch, semi-batch and continuous methods.
- the obtained reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, etc., or a combination means combining these.
- cyclohexanetetracarboxylic dianhydride, amine (1) and the following solvent are charged into the system and aged to form an amic acid, and then amine (2) and a condensing agent (
- a compound represented by formula (1) can be produced by charging and aging carbodiimide or a salt thereof.
- 1,2,4,5-cyclohexanetetracarboxylic acid-1,2: 4,5-dianhydride can be preferably used.
- Examples of the amines (1) and (2) include the same examples as amines that can be used in the above production method 1.
- the amount of amine (1) used is, for example, about 2 to 4 moles, preferably 2 to 3 moles per mole of cyclohexanetetracarboxylic dianhydride.
- the amount of amine (2) to be used is, for example, about 2 to 4 mol, preferably 2 to 3 mol, per 1 mol of cyclohexanetetracarboxylic dianhydride.
- R ′ and R ′′ are, for example, a linear or branched alkyl group having 3 to 8 carbon atoms which may have a heteroatom-containing substituent, or 3 to 8 membered Examples thereof include cycloalkyl groups.
- R ′ and R ′′ may be the same or different.
- R ′ and R ′′ may be bonded to each other to form a ring together with the (—N ⁇ C ⁇ N—) group in the above formula.
- linear or branched alkyl group having 3 to 8 carbon atoms examples include propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, s-pentyl, t-pentyl, Examples include hexyl, isohexyl, s-hexyl, t-hexyl groups and the like.
- Examples of the 3- to 8-membered cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.
- heteroatom-containing substituents examples include nitrogen atom-containing substituents such as di (C 1-3 ) alkylamino groups such as amino groups and dimethylamino groups.
- carbodiimide examples include diisopropylcarbodiimide, dicyclohexylcarbodiimide, N- (3-dimethylaminopropyl) -N′-ethylcarbodiimide, and the like.
- carbodiimide salt examples include hydrochloride (specifically, N- (3-dimethylaminopropyl) -N′-ethylcarbodiimide hydrochloride). These can be used alone or in combination of two or more.
- the amount of carbodiimide used is, for example, about 2 to 6 moles, preferably 2 to 4 moles per mole of cyclohexanetetracarboxylic dianhydride.
- a proton-accepting solvent for example, pyridine, triethylamine, tributylamine, etc.
- a proton-accepting solvent for example, pyridine, triethylamine, tributylamine, etc.
- the amount of the solvent used is, for example, about 50 to 300% by weight, preferably 100 to 250% by weight, based on the total amount of amic acid.
- concentration of a reaction component will become low and there exists a tendency for reaction rate to fall.
- the above reaction is usually performed under normal pressure.
- the atmosphere of the reaction is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like.
- the aging temperature (reaction temperature) is, for example, about 30 to 70 ° C.
- the aging time of cyclohexanetetracarboxylic dianhydride and amine is, for example, about 0.5 to 5 hours, and the aging time of amic acid and amine is, for example, about 0.5 to 20 hours.
- the reaction can be carried out by any method such as batch, semi-batch and continuous methods.
- the obtained reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, etc., or a combination means combining these.
- solvent As the solvent contained in the solvent composition of the present invention, it is preferable to use a solvent excellent in solubility of the compound represented by the above formula (1).
- Examples of the solvent include those having an SP value at 25 ° C. [(cal / cm 3 ) 0.5 : Fedors calculated value] of 7.0 to 9.0 (preferably 7.5 to 9.0). 1 or 2 or more are excellent in solubility of the compound represented by the above formula (1), and the heating temperature when dissolving the compound represented by the above formula (1) is lowered, for example, This is preferable in that it can be suppressed to about 50 to 90 ° C.
- a solvent having an SP value outside the above range has a low solubility of the compound represented by the above formula (1), and thus there is a tendency that heating at a higher temperature is required when the compound is dissolved.
- n-decane (SP value: 7.6), n-dodecane (SP value: 7.7), propylene glycol methyl-n-propyl ether (SP value: 8.1), propylene glycol.
- Methyl-n-butyl ether (SP value: 8.1), dipropylene glycol dimethyl ether (SP value: 8.4), dipropylene glycol methyl-n-propyl ether (SP value: 8.2), dipropylene glycol methyl- n-butyl ether (SP value: 8.2), dipropylene glycol methyl isoamyl ether (SP value: 8.0), tripropylene glycol methyl-n-propyl ether (SP value: 8.2), cyclohexyl acetate (SP value) : 8.9), 2-methylcyclohexyl acetate (SP value: 8.5), and 4-t Butylcyclohexyl acetate (SP value: 8.2) it is preferred to use at least one
- the content of the solvent in the solvent composition of the present invention (when two or more are contained, the total content) is, for example, 20.0 to 99.9% by weight, preferably 30.0 to 99.5% by weight, particularly It is preferably 40.0 to 99.5% by weight, most preferably 50.0 to 99.5% by weight, particularly preferably 70.0 to 99.5% by weight.
- the content of the solvent is below the above range, the viscosity of the ink becomes too high, and it may be difficult to form a wiring or the like by a printing method.
- the solvent composition of the present invention may be a solvent other than the above-mentioned solvent (hereinafter referred to as “other solvent” if necessary) as long as the effect is not impaired.
- other solvent a solvent other than the above-mentioned solvent
- a well-known and conventional solvent used for electronic device production applications may be added.
- the amount of other solvents added is, for example, less than 50% by weight, preferably 30% by weight or less, particularly preferably 20% by weight or less, most preferably, of the total solvent (100% by weight) contained in the solvent composition of the present invention. Is 10% by weight or less.
- the ink for manufacturing an electronic device of the present invention (hereinafter sometimes referred to as “ink”) is an ink for forming wiring and electrodes of an electronic device by application by a printing method. The compound represented by this is included.
- the ink of the present invention comprises, for example, a step of heating and dissolving the solvent composition at 30 to 90 ° C. (upper limit is preferably 80 ° C., lower limit is preferably 40 ° C., particularly preferably 50 ° C., most preferably 70 ° C.). It can be manufactured after that.
- the solvent composition is heated and dissolved at 30 to 90 ° C. (the upper limit is preferably 80 ° C., the lower limit is preferably 40 ° C., particularly preferably 50 ° C., most preferably 70 ° C.).
- the time required for dissolution by heating is, for example, about 3 to 60 minutes (preferably 10 to 30 minutes).
- room temperature eg, 1 to 30 ° C.
- the cooling may be performed gradually at room temperature or rapidly by ice cooling or the like.
- the ink of the present invention it is preferable to add at least one electrical property imparting material selected from the group consisting of conductive metal materials, semiconductor materials, magnetic materials, dielectric materials, and insulating materials.
- the content of the electrical property imparting material (the total amount when containing two or more types) is, for example, about 0.1 to 90% by weight of the total amount of ink (100% by weight).
- conductive metal material and magnetic material well-known and commonly used materials can be used.
- semiconductor materials can be used, such as pentacene, fullerene derivatives, polythiophene derivatives, metals (copper, indium, gallium, selenium, arsenic, cadmium, tellurium, and alloys thereof), silicon fine particles, etc. Can be mentioned.
- dielectric material and the insulating material well-known and customary materials can be used, and examples thereof include cycloolefin polymer, fluororesin, butyral resin, glass, paper, Teflon (registered trademark) and the like.
- the ink of the present invention obtained through the above steps contains a compound represented by the above formula (1), and the compound self-assembles in a solvent to form a string-like aggregate, which is viscous like a polymer compound. Therefore, even if the binder resin is not blended, it has an appropriate viscosity for accurately forming the wiring and electrodes of the electronic device by the printing method.
- the ink of the present invention has an appropriate viscosity, and the viscosity at 25 ° C. (at a shear rate of 0.5 s ⁇ 1 ) is, for example, about 0.01 to 1000 Pa ⁇ s, preferably 0.1 to 500 Pa ⁇ s, particularly preferably. Is 1 to 200 Pa ⁇ s.
- the ink of the present invention does not require the addition of a binder resin (for example, a polymer compound having a molecular weight of 10,000 or more such as an ethyl cellulose resin, an alkyl cellulose resin, a polyvinyl acetal resin, and an acrylic resin).
- a binder resin for example, a polymer compound having a molecular weight of 10,000 or more such as an ethyl cellulose resin, an alkyl cellulose resin, a polyvinyl acetal resin, and an acrylic resin.
- the amount added is, for example, 10% by weight or less of the total amount of ink (100%), preferably 5% by weight or less, more preferably less than 5% by weight, particularly preferably 3% by weight or less, and most preferably 1% by weight or less. is there. If the amount of the binder resin added exceeds the above range, the ash content derived from the binder resin caused by firing causes a decrease in electrical characteristics, which is not preferable.
- the string-like aggregate composed of the compound represented by the formula (1) contained in the ink of the present invention has excellent thermal decomposability and easily has a low molecular weight. Therefore, the ink of the present invention can be baked at a lower temperature (for example, 100 to 350 ° C., preferably 150 to 300 ° C., particularly preferably 150 to 250 ° C.) as compared with an ink to which a viscosity is imparted by a binder resin such as ethyl cellulose. It is possible to prevent softening and deformation of the coated surface member in the firing step.
- a lower temperature for example, 100 to 350 ° C., preferably 150 to 300 ° C., particularly preferably 150 to 250 ° C.
- the residual amount of ash after firing can be reduced extremely low (the residual amount of ash is, for example, 4.5% by weight or less, preferably 4.0% by weight or less, particularly preferably 3.0% by weight or less). , Most preferably 2.5% by weight or less), it is possible to suppress a decrease in electrical properties caused by ash.
- the ink of the present invention has excellent electrical characteristics (for example, conductivity or insulation) through the steps of coating, drying, and firing on a surface member (for example, ceramic substrate, green sheet, etc.) by a printing method. Wiring and the like can be formed with high accuracy. Therefore, the ink of the present invention is particularly useful as an ink for producing, for example, a capacitor, an inductor, a varistor, a thermistor, a speaker, an actuator, an antenna, a solid oxide fuel cell (SOFC), etc. (particularly, a multilayer ceramic capacitor).
- SOFC solid oxide fuel cell
- the obtained wet powder was recrystallized with CHCl 3 / CH 3 OH (70/30 (v / v)), and 1,2,4,5-cyclohexanetetracarboxylic acid di (2-ethylhexylamide) di ( Oleylamide) [1,2,4,5-cyclohexanetetracarboxylic acid-1,4-di (2-ethylhexylamide) -2,5-di (oleylamide) and 1,2,4,5-cyclohexanetetracarboxylic 11.9 g of a mixture of acid-1,5-di (2-ethylhexylamide) -2,4-di (oleylamide)] (yield: 61%). The structure of the reaction product was confirmed by 1 H-NMR.
- Example 1 The solvent composition obtained by adding the thickener (1) obtained in Preparation Example 1 to n-decane (manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent so that the concentration of the thickener is 1% by weight. (1) was obtained.
- the obtained solvent composition (1) was dissolved by heating at a liquid temperature of 80 ° C. for 0.5 hours and allowed to cool to room temperature (25 ° C.) to obtain a paste-like ink (1) (viscosity at 25 ° C. [ At a shear rate of 0.5 s ⁇ 1 ]: 6 Pa ⁇ s).
- Comparative Example 1 A solvent composition was obtained in the same manner as in Example 1 except that the composition (unit: wt%) shown in Table 1 was changed, and an ink was obtained.
- ethyl cellulose (trade name “Etocel STD200”, manufactured by Nisshin Kasei Co., Ltd.) was added instead of the thickener so that the resin concentration became 5% by weight, and the liquid temperature was 80 ° C. for 3 hours. It was dissolved by heating and allowed to cool at room temperature (25 ° C.) to obtain a paste-like ink.
- Solvent dekane n-decane (manufactured by Wako Pure Chemical Industries, Ltd., SP value: 7.6)
- DPMNP Dipropylene glycol methyl-n-propyl ether (manufactured by Daicel Corporation, SP value: 8.2)
- CHXA cyclohexyl acetate (manufactured by Daicel Corporation, SP value: 8.9)
- the solvent composition for producing an electronic device of the present invention can produce an ink having a viscosity suitable for forming a wiring or the like by a printing method through a step of dissolving by heating. Moreover, the ink obtained using the solvent composition for manufacturing an electronic device of the present invention is not easily dripped, and a highly accurate wiring pattern can be formed by a printing method. Moreover, in a baking process, it can bake at lower temperature and it can prevent that a to-be-coated surface member is softened and deform
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Abstract
The purpose of the present invention is to provide a solvent composition, for use in ink for forming wiring and electrodes in an electronic device by a printing method, the solvent composition making it possible: to improve ink printing precision; to perform calcining at low temperatures; and to keep the quantity of ash produced after calcining to an extremely low level. This solvent composition for manufacturing an electronic device is used in ink for manufacturing an electronic device by a printing method, and comprises a solvent and a compound represented by formula (1). In the formula, R represents an aliphatic hydrocarbon group with a carbon number of at least 1. The four R's in the formula are all the same group, or are two different groups.
Description
本発明は、電子デバイスの製造において、印刷法を用いて配線又は電極を形成するためのインクに用いられる溶剤組成物に関する。本願は、２０１５年２月３日に日本に出願した、特願２０１５－０１９６３７号の優先権を主張し、その内容をここに援用する。
The present invention relates to a solvent composition used in an ink for forming a wiring or an electrode using a printing method in the production of an electronic device. This application claims the priority of Japanese Patent Application No. 2015-019637 for which it applied to Japan on February 3, 2015, and uses the content here.
印刷法を用いて製造する電子デバイスにはコンデンサ、インダクタ、バリスタ、サーミスタ、トランジスタ、スピーカ、アクチュエータ、アンテナ、固体酸化物燃料電池等がある。
Electronic devices manufactured using the printing method include capacitors, inductors, varistors, thermistors, transistors, speakers, actuators, antennas, solid oxide fuel cells, and the like.
例えば積層セラミックコンデンサは、一般的に、次のような工程を経て製造される。
１．セラミックスの粉末、ポリビニルアセタール樹脂等のバインダー樹脂、及び溶剤を含むスラリーをシート状に成形してグリーンシートを得る。
２．電気特性付与材（例えば、ニッケル、パラジウム等）、バインダー樹脂（例えば、エチルセルロース等）、及び有機溶剤（例えば、ターピネオール等）を含むインクを、グリーンシート上に印刷法により塗布し導電回路の配線や電極等（以後、「配線等」と称する場合がある）を形成する（塗布工程）。
３．塗布されたインクを乾燥させる（乾燥工程）。
４．配線等が形成されたグリーンシートを所定寸法に切断し、複数枚積み重ねて圧着する。
５．焼成させる（焼成工程）。 For example, a multilayer ceramic capacitor is generally manufactured through the following steps.
1. A green sheet is obtained by forming a slurry containing ceramic powder, a binder resin such as polyvinyl acetal resin, and a solvent into a sheet.
2. An ink containing an electrical property imparting material (for example, nickel, palladium, etc.), a binder resin (for example, ethyl cellulose, etc.), and an organic solvent (for example, terpineol, etc.) is applied onto a green sheet by a printing method, An electrode or the like (hereinafter may be referred to as “wiring or the like”) is formed (application process).
3. The applied ink is dried (drying process).
4). A green sheet on which wiring or the like is formed is cut into a predetermined size, and a plurality of sheets are stacked and pressed.
5. Firing (firing process).
１．セラミックスの粉末、ポリビニルアセタール樹脂等のバインダー樹脂、及び溶剤を含むスラリーをシート状に成形してグリーンシートを得る。
２．電気特性付与材（例えば、ニッケル、パラジウム等）、バインダー樹脂（例えば、エチルセルロース等）、及び有機溶剤（例えば、ターピネオール等）を含むインクを、グリーンシート上に印刷法により塗布し導電回路の配線や電極等（以後、「配線等」と称する場合がある）を形成する（塗布工程）。
３．塗布されたインクを乾燥させる（乾燥工程）。
４．配線等が形成されたグリーンシートを所定寸法に切断し、複数枚積み重ねて圧着する。
５．焼成させる（焼成工程）。 For example, a multilayer ceramic capacitor is generally manufactured through the following steps.
1. A green sheet is obtained by forming a slurry containing ceramic powder, a binder resin such as polyvinyl acetal resin, and a solvent into a sheet.
2. An ink containing an electrical property imparting material (for example, nickel, palladium, etc.), a binder resin (for example, ethyl cellulose, etc.), and an organic solvent (for example, terpineol, etc.) is applied onto a green sheet by a printing method, An electrode or the like (hereinafter may be referred to as “wiring or the like”) is formed (application process).
3. The applied ink is dried (drying process).
4). A green sheet on which wiring or the like is formed is cut into a predetermined size, and a plurality of sheets are stacked and pressed.
5. Firing (firing process).
インクに含まれるバインダー樹脂は電気特性付与材をグリーンシート上に固定する働きや、適度な粘度を付与して微細な印刷パターンの形成を可能とする働きを有する。バインダー樹脂としては、従来、エチルセルロースが主に用いられてきた。しかし、エチルセルロースは熱分解性が低いため高温で焼成する必要があり、長時間高温に曝されることにより被塗布面を有する部材（以後、「被塗布面部材」と称する場合がある）が軟化、変形する場合があること、また、焼成後にカーボン成分が灰分として残留し、それにより導電性の低下が引き起こされることが問題であった。
The binder resin contained in the ink has a function of fixing the electrical property imparting material on the green sheet and a function of imparting an appropriate viscosity to enable formation of a fine print pattern. Conventionally, ethyl cellulose has been mainly used as the binder resin. However, since ethyl cellulose has low thermal decomposability, it must be fired at a high temperature, and a member having a surface to be coated (hereinafter sometimes referred to as a “surface to be coated”) is softened by being exposed to a high temperature for a long time. In some cases, the carbon component remains ash after firing, which causes a decrease in conductivity.
上記問題を解決するため、バインダー樹脂の改善が種々検討された。例えば、特許文献１には、エチルセルロースに代えてポリビニルアセタール樹脂を用いることで灰分の生成量を低減できることが開示されている。しかしながら、ポリビニルアセタール樹脂を使用しても、これらの問題について十分満足できる結果は得られなかった。
In order to solve the above problems, various improvements of the binder resin were studied. For example, Patent Document 1 discloses that the amount of ash produced can be reduced by using polyvinyl acetal resin instead of ethyl cellulose. However, even if a polyvinyl acetal resin was used, satisfactory results were not obtained for these problems.
従って、本発明の目的は、印刷法によって電子デバイスの配線や電極を形成するためのインクに使用する溶剤組成物であって、インクの印字精度を向上することができ、低温で焼成することができ、焼成後に生じる灰分量を極めて低く抑制することができる溶剤組成物を提供することにある。
本発明の他の目的は、印刷法によって電子デバイスの配線や電極を形成するためのインクであって、印字精度に優れ、低温で焼成することができ、焼成後に生じる灰分量が極めて少ないインク、及びその製造方法を提供することにある。 Accordingly, an object of the present invention is a solvent composition used for ink for forming wiring and electrodes of electronic devices by a printing method, which can improve the printing accuracy of the ink and can be baked at a low temperature. It is possible to provide a solvent composition capable of suppressing the amount of ash generated after firing extremely low.
Another object of the present invention is an ink for forming wiring and electrodes of an electronic device by a printing method, which is excellent in printing accuracy, can be fired at a low temperature, and has an extremely small amount of ash generated after firing, And a manufacturing method thereof.
本発明の他の目的は、印刷法によって電子デバイスの配線や電極を形成するためのインクであって、印字精度に優れ、低温で焼成することができ、焼成後に生じる灰分量が極めて少ないインク、及びその製造方法を提供することにある。 Accordingly, an object of the present invention is a solvent composition used for ink for forming wiring and electrodes of electronic devices by a printing method, which can improve the printing accuracy of the ink and can be baked at a low temperature. It is possible to provide a solvent composition capable of suppressing the amount of ash generated after firing extremely low.
Another object of the present invention is an ink for forming wiring and electrodes of an electronic device by a printing method, which is excellent in printing accuracy, can be fired at a low temperature, and has an extremely small amount of ash generated after firing, And a manufacturing method thereof.
本発明者等は上記課題を解決するため鋭意検討した結果、下記式（１）で表される化合物は、溶剤中で加熱溶解すると自己組織化してひも状会合体を形成し、高分子化合物のような粘性を生じること、エチルセルロース等のバインダー樹脂に比べ低温で焼成可能であること、焼成後の灰分の残留量が極めて少ないことを見いだした。
As a result of intensive studies to solve the above problems, the present inventors have found that the compound represented by the following formula (1) self-assembles and forms a string-like aggregate when heated and dissolved in a solvent. It has been found that such a viscosity is produced, that it can be fired at a lower temperature than a binder resin such as ethyl cellulose, and that the residual amount of ash after firing is extremely small.
そして、上記式（１）で表される化合物と溶剤を加熱溶解する工程を経て得られるインクは、印刷法による配線等の形成に適した粘性を有するため、液ダレが抑制され、高精度の配線パターンを形成することができること、焼成工程においては、エチルセルロース等のバインダー樹脂を含むインクを焼成する場合に比べて、より低温で速やかに焼成することができ、被塗布面部材が長時間高温に曝されることにより軟化、変形することを防止できること、焼成後の灰分の残留量を著しく低減することができ、これにより引き起こされていた電気特性の低下を抑制することができることを見いだした。本発明はこれらの知見に基づいて完成させたものである。
The ink obtained through the step of heating and dissolving the compound represented by the above formula (1) and the solvent has a viscosity suitable for the formation of wiring and the like by the printing method, so that dripping is suppressed and highly accurate. A wiring pattern can be formed, and in the baking process, baking can be performed quickly at a lower temperature than in the case of baking an ink containing a binder resin such as ethyl cellulose. It has been found that it can be prevented from being softened and deformed by exposure, the residual amount of ash after firing can be remarkably reduced, and the deterioration of electrical characteristics caused by this can be suppressed. The present invention has been completed based on these findings.
すなわち、本発明は、印刷法によって電子デバイスを製造するためのインクに用いられる溶剤組成物であって、溶剤と下記式（１）
（式中、Ｒは炭素数１以上の脂肪族炭化水素基を示す。尚、式中の４つのＲは全て同一の基、又は２種の異なる基である）
で表される化合物を含む電子デバイス製造用溶剤組成物を提供する。 That is, this invention is a solvent composition used for the ink for manufacturing an electronic device by a printing method, Comprising: A solvent and following formula (1)
(In the formula, R represents an aliphatic hydrocarbon group having 1 or more carbon atoms. In the formula, all four Rs are the same group or two different groups.)
The solvent composition for electronic device manufacture containing the compound represented by these is provided.
で表される化合物を含む電子デバイス製造用溶剤組成物を提供する。 That is, this invention is a solvent composition used for the ink for manufacturing an electronic device by a printing method, Comprising: A solvent and following formula (1)
The solvent composition for electronic device manufacture containing the compound represented by these is provided.
本発明は、また、式（１）中のＲが炭素数６～１８の直鎖状若しくは分岐鎖状のアルキル基、アルケニル基、又はアルキニル基である前記の電子デバイス製造用溶剤組成物を提供する。
The present invention also provides the above-mentioned solvent composition for producing an electronic device, wherein R in the formula (1) is a linear or branched alkyl group, alkenyl group, or alkynyl group having 6 to 18 carbon atoms. To do.
本発明は、また、溶剤の２５℃におけるＳＰ値［（ｃａｌ／ｃｍ3）0.5］が７．０～９．０である前記の電子デバイス製造用溶剤組成物を提供する。
The present invention also provides the above-mentioned solvent composition for producing an electronic device, wherein the SP value [(cal / cm 3 ) 0.5 ] at 25 ° C. of the solvent is 7.0 to 9.0.
本発明は、また、溶剤が、ｎ－デカン、ｎ－ドデカン、プロピレングリコールメチル－ｎ－プロピルエーテル、プロピレングリコールメチル－ｎ－ブチルエーテル、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールメチル－ｎ－プロピルエーテル、ジプロピレングリコールメチル－ｎ－ブチルエーテル、ジプロピレングリコールメチルイソアミルエーテル、トリプロピレングリコールメチル－ｎ－プロピルエーテル、シクロヘキシルアセテート、２－メチルシクロヘキシルアセテート、及び４－ｔ－ブチルシクロヘキシルアセテートからなる群より選択される少なくとも１つである前記の電子デバイス製造用溶剤組成物を提供する。
In the present invention, the solvent is n-decane, n-dodecane, propylene glycol methyl-n-propyl ether, propylene glycol methyl-n-butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, At least selected from the group consisting of propylene glycol methyl-n-butyl ether, dipropylene glycol methyl isoamyl ether, tripropylene glycol methyl-n-propyl ether, cyclohexyl acetate, 2-methylcyclohexyl acetate, and 4-t-butylcyclohexyl acetate One of the above-mentioned solvent compositions for producing an electronic device is provided.
本発明は、また、式（１）で表される化合物の含有量が、溶剤１００重量部に対して０．１～５０重量部である前記の電子デバイス製造用溶剤組成物を提供する。
The present invention also provides the above-mentioned solvent composition for producing an electronic device, wherein the content of the compound represented by the formula (1) is 0.1 to 50 parts by weight with respect to 100 parts by weight of the solvent.
本発明は、また、前記の電子デバイス製造用溶剤組成物を３０～９０℃で加熱溶解する工程を有する電子デバイス製造用インクの製造方法を提供する。
The present invention also provides a method for producing an ink for producing an electronic device, which comprises a step of heating and dissolving the above-mentioned solvent composition for producing an electronic device at 30 to 90 ° C.
本発明は、また、溶剤と下記式（１）
（式中、Ｒは炭素数１以上の脂肪族炭化水素基を示す。尚、式中の４つのＲは全て同一の基、又は２種の異なる基である）
で表される化合物を含む電子デバイス製造用インクを提供する。 The present invention also provides a solvent and the following formula (1):
(In the formula, R represents an aliphatic hydrocarbon group having 1 or more carbon atoms. In the formula, all four Rs are the same group or two different groups.)
An ink for producing an electronic device comprising a compound represented by the formula:
で表される化合物を含む電子デバイス製造用インクを提供する。 The present invention also provides a solvent and the following formula (1):
An ink for producing an electronic device comprising a compound represented by the formula:
本発明は、また、更に、導電性金属材料、半導体材料、磁性材料、誘電材料、又は絶縁材料を含む前記の電子デバイス製造用インクを提供する。
The present invention further provides the above-described ink for manufacturing an electronic device, further comprising a conductive metal material, a semiconductor material, a magnetic material, a dielectric material, or an insulating material.
本発明は、また、バインダー樹脂含有量が１０重量％以下である前記の電子デバイス製造用インクを提供する。
The present invention also provides the above-mentioned ink for manufacturing an electronic device, wherein the binder resin content is 10% by weight or less.
すなわち、本発明は以下に関する。
［１］ 印刷法によって電子デバイスを製造するためのインクに用いられる溶剤組成物であって、溶剤と式（１）で表される化合物を含む電子デバイス製造用溶剤組成物。
［２］ 式（１）中のＲが炭素数６～１８の直鎖状若しくは分岐鎖状のアルキル基、アルケニル基、又はアルキニル基である［１］に記載の電子デバイス製造用溶剤組成物。
［３］ 式（１）で表される化合物が、式（1-2）～（1-5）で表される化合物から選択される少なくとも１種の化合物である［１］又は［２］に記載の電子デバイス製造用溶剤組成物。
［４］ 式（１）で表される化合物が、式（1-3）で表される化合物及び／又は式（1-4）で表される化合物である［１］又は［２］に記載の電子デバイス製造用溶剤組成物。
［５］ 式（１）で表される化合物の蒸発温度が１２０～３８０℃である［１］～［４］の何れか１つに記載の電子デバイス製造用溶剤組成物。
［６］ 溶剤の２５℃におけるＳＰ値［（ｃａｌ／ｃｍ3）0.5］が７．０～９．０である［１］～［５］の何れか１つに記載の電子デバイス製造用溶剤組成物。
［７］ 溶剤の含有量が電子デバイス製造用溶剤組成物全量の２０．０～９９．９重量％である［１］～［６］の何れか１つに記載の電子デバイス製造用溶剤組成物。
［８］ 溶剤が、ｎ－デカン、ｎ－ドデカン、プロピレングリコールメチル－ｎ－プロピルエーテル、プロピレングリコールメチル－ｎ－ブチルエーテル、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールメチル－ｎ－プロピルエーテル、ジプロピレングリコールメチル－ｎ－ブチルエーテル、ジプロピレングリコールメチルイソアミルエーテル、トリプロピレングリコールメチル－ｎ－プロピルエーテル、シクロヘキシルアセテート、２－メチルシクロヘキシルアセテート、及び４－ｔ－ブチルシクロヘキシルアセテートからなる群より選択される少なくとも１つである［１］～［７］の何れか１つに記載の電子デバイス製造用溶剤組成物。
［９］ ｎ－デカン、ｎ－ドデカン、プロピレングリコールメチル－ｎ－プロピルエーテル、プロピレングリコールメチル－ｎ－ブチルエーテル、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールメチル－ｎ－プロピルエーテル、ジプロピレングリコールメチル－ｎ－ブチルエーテル、ジプロピレングリコールメチルイソアミルエーテル、トリプロピレングリコールメチル－ｎ－プロピルエーテル、シクロヘキシルアセテート、２－メチルシクロヘキシルアセテート、及び４－ｔ－ブチルシクロヘキシルアセテート以外の溶剤の含有量が、電子デバイス製造用溶剤組成物に含まれる全溶剤の５０重量％未満である［１］～［８］の何れか１つに記載の電子デバイス製造用溶剤組成物。
［１０］ 式（１）で表される化合物の含有量が、溶剤１００重量部に対して０．１～５０重量部である［１］～［９］の何れか１つに記載の電子デバイス製造用溶剤組成物。
［１１］ ［１］～［１０］の何れか１つに記載の電子デバイス製造用溶剤組成物を３０～９０℃で加熱溶解する工程を有する電子デバイス製造用インクの製造方法。
［１２］ ［１１］に記載の製造方法により得られる電子デバイス製造用インク。
［１３］ ［１］～［１０］の何れか１つに記載の電子デバイス製造用溶剤組成物を含む電子デバイス製造用インク。
［１４］ 溶剤と式（１）で表される化合物を含む電子デバイス製造用インク。
［１５］ 更に、電気特性付与材を含む［１２］～［１４］の何れか１つに記載の電子デバイス製造用インク。
［１６］ 電気特性付与材が、導電性金属材料、半導体材料、磁性材料、誘電材料、又は絶縁材料である［１５］に記載の電子デバイス製造用インク。
［１７］ バインダー樹脂含有量が１０重量％以下である［１２］～［１６］の何れか１つに記載の電子デバイス製造用インク。
［１８］ バインダー樹脂が、分子量１００００以上の高分子化合物である［１７］に記載の電子デバイス製造用インク。
［１９］ バインダー樹脂が、エチルセルロース樹脂、アルキルセルロース樹脂、ポリビニルアセタール樹脂、及びアクリル樹脂からなる群より選択される少なくとも１種である［１７］又は［１８］に記載の電子デバイス製造用インク。
［２０］ ２５℃における粘度［せん断速度０．５ｓ-1における］が０．０１～１０００Ｐａ・ｓである［１２］～［１９］の何れか１つに記載の電子デバイス製造用インク。
［２１］ ［１２］～［２０］の何れか１つに記載の電子デバイス製造用インクを印刷法により塗布し、乾燥後、焼成する工程を経て配線を形成する工程を有する電子デバイスの製造方法。
［２２］ 焼成温度が１００～３５０℃の範囲である［２１］に記載の電子デバイスの製造方法。
［２３］ 灰分の残存量が４．５重量％以下である配線を形成する［２１］又は［２２］に記載の電子デバイスの製造方法。
［２４］ 電子デバイスが積層セラミックコンデンサである［２１］～［２３］の何れか１つに記載の電子デバイスの製造方法。
［２５］ ［２１］～［２４］の何れか１つに記載の電子デバイスの製造方法により得られる電子デバイス。
［２６］ 灰分の残存量が４．５重量％以下である配線を有する［２５］に記載の電子デバイス。 That is, the present invention relates to the following.
[1] A solvent composition for use in an ink for producing an electronic device by a printing method, comprising a solvent and a compound represented by formula (1).
[2] The solvent composition for producing an electronic device according to [1], wherein R in the formula (1) is a linear or branched alkyl group, alkenyl group, or alkynyl group having 6 to 18 carbon atoms.
[3] In [1] or [2], the compound represented by formula (1) is at least one compound selected from the compounds represented by formulas (1-2) to (1-5) The solvent composition for electronic device manufacture of description.
[4] The compound represented by the formula (1) is a compound represented by the formula (1-3) and / or a compound represented by the formula (1-4) [1] or [2] Solvent composition for manufacturing electronic devices.
[5] The solvent composition for producing an electronic device according to any one of [1] to [4], wherein the evaporation temperature of the compound represented by the formula (1) is 120 to 380 ° C.
[6] The solvent composition for producing an electronic device according to any one of [1] to [5], wherein the SP value [(cal / cm 3 ) 0.5 ] at 25 ° C. of the solvent is 7.0 to 9.0. object.
[7] The solvent composition for producing an electronic device according to any one of [1] to [6], wherein the content of the solvent is 20.0 to 99.9% by weight of the total amount of the solvent composition for producing an electronic device. .
[8] The solvent is n-decane, n-dodecane, propylene glycol methyl-n-propyl ether, propylene glycol methyl-n-butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl. -At least one selected from the group consisting of n-butyl ether, dipropylene glycol methyl isoamyl ether, tripropylene glycol methyl n-propyl ether, cyclohexyl acetate, 2-methylcyclohexyl acetate, and 4-t-butylcyclohexyl acetate The solvent composition for producing an electronic device according to any one of [1] to [7].
[9] n-decane, n-dodecane, propylene glycol methyl-n-propyl ether, propylene glycol methyl-n-butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl-n- Solvent composition for manufacturing electronic devices, except for butyl ether, dipropylene glycol methyl isoamyl ether, tripropylene glycol methyl-n-propyl ether, cyclohexyl acetate, 2-methylcyclohexyl acetate, and 4-t-butylcyclohexyl acetate The solvent composition for producing an electronic device according to any one of [1] to [8], which is less than 50% by weight of the total solvent contained in the product.
[10] The electronic device according to any one of [1] to [9], wherein the content of the compound represented by the formula (1) is 0.1 to 50 parts by weight with respect to 100 parts by weight of the solvent. Solvent composition for production.
[11] A method for producing an ink for producing an electronic device, comprising a step of heating and dissolving the solvent composition for producing an electronic device according to any one of [1] to [10] at 30 to 90 ° C.
[12] An electronic device manufacturing ink obtained by the manufacturing method according to [11].
[13] An ink for producing an electronic device comprising the solvent composition for producing an electronic device according to any one of [1] to [10].
[14] An ink for producing an electronic device comprising a solvent and a compound represented by the formula (1).
[15] The ink for manufacturing an electronic device according to any one of [12] to [14], further including an electrical property imparting material.
[16] The ink for manufacturing an electronic device according to [15], wherein the electrical property imparting material is a conductive metal material, a semiconductor material, a magnetic material, a dielectric material, or an insulating material.
[17] The ink for manufacturing an electronic device according to any one of [12] to [16], wherein the binder resin content is 10% by weight or less.
[18] The ink for manufacturing an electronic device according to [17], wherein the binder resin is a polymer compound having a molecular weight of 10,000 or more.
[19] The ink for manufacturing an electronic device according to [17] or [18], wherein the binder resin is at least one selected from the group consisting of an ethyl cellulose resin, an alkyl cellulose resin, a polyvinyl acetal resin, and an acrylic resin.
[20] The ink for manufacturing an electronic device according to any one of [12] to [19], wherein a viscosity at 25 ° C. (at a shear rate of 0.5 s −1 ) is 0.01 to 1000 Pa · s.
[21] A method for manufacturing an electronic device comprising a step of applying an ink for manufacturing an electronic device according to any one of [12] to [20] by a printing method, forming a wiring through a step of drying and baking. .
[22] The method for manufacturing an electronic device according to [21], wherein the firing temperature is in the range of 100 to 350 ° C.
[23] The method for manufacturing an electronic device according to [21] or [22], wherein a wiring having a residual amount of ash of 4.5% by weight or less is formed.
[24] The method for manufacturing an electronic device according to any one of [21] to [23], wherein the electronic device is a multilayer ceramic capacitor.
[25] An electronic device obtained by the method for manufacturing an electronic device according to any one of [21] to [24].
[26] The electronic device according to [25], including a wiring having a residual amount of ash of 4.5% by weight or less.
［１］ 印刷法によって電子デバイスを製造するためのインクに用いられる溶剤組成物であって、溶剤と式（１）で表される化合物を含む電子デバイス製造用溶剤組成物。
［２］ 式（１）中のＲが炭素数６～１８の直鎖状若しくは分岐鎖状のアルキル基、アルケニル基、又はアルキニル基である［１］に記載の電子デバイス製造用溶剤組成物。
［３］ 式（１）で表される化合物が、式（1-2）～（1-5）で表される化合物から選択される少なくとも１種の化合物である［１］又は［２］に記載の電子デバイス製造用溶剤組成物。
［４］ 式（１）で表される化合物が、式（1-3）で表される化合物及び／又は式（1-4）で表される化合物である［１］又は［２］に記載の電子デバイス製造用溶剤組成物。
［５］ 式（１）で表される化合物の蒸発温度が１２０～３８０℃である［１］～［４］の何れか１つに記載の電子デバイス製造用溶剤組成物。
［６］ 溶剤の２５℃におけるＳＰ値［（ｃａｌ／ｃｍ3）0.5］が７．０～９．０である［１］～［５］の何れか１つに記載の電子デバイス製造用溶剤組成物。
［７］ 溶剤の含有量が電子デバイス製造用溶剤組成物全量の２０．０～９９．９重量％である［１］～［６］の何れか１つに記載の電子デバイス製造用溶剤組成物。
［８］ 溶剤が、ｎ－デカン、ｎ－ドデカン、プロピレングリコールメチル－ｎ－プロピルエーテル、プロピレングリコールメチル－ｎ－ブチルエーテル、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールメチル－ｎ－プロピルエーテル、ジプロピレングリコールメチル－ｎ－ブチルエーテル、ジプロピレングリコールメチルイソアミルエーテル、トリプロピレングリコールメチル－ｎ－プロピルエーテル、シクロヘキシルアセテート、２－メチルシクロヘキシルアセテート、及び４－ｔ－ブチルシクロヘキシルアセテートからなる群より選択される少なくとも１つである［１］～［７］の何れか１つに記載の電子デバイス製造用溶剤組成物。
［９］ ｎ－デカン、ｎ－ドデカン、プロピレングリコールメチル－ｎ－プロピルエーテル、プロピレングリコールメチル－ｎ－ブチルエーテル、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールメチル－ｎ－プロピルエーテル、ジプロピレングリコールメチル－ｎ－ブチルエーテル、ジプロピレングリコールメチルイソアミルエーテル、トリプロピレングリコールメチル－ｎ－プロピルエーテル、シクロヘキシルアセテート、２－メチルシクロヘキシルアセテート、及び４－ｔ－ブチルシクロヘキシルアセテート以外の溶剤の含有量が、電子デバイス製造用溶剤組成物に含まれる全溶剤の５０重量％未満である［１］～［８］の何れか１つに記載の電子デバイス製造用溶剤組成物。
［１０］ 式（１）で表される化合物の含有量が、溶剤１００重量部に対して０．１～５０重量部である［１］～［９］の何れか１つに記載の電子デバイス製造用溶剤組成物。
［１１］ ［１］～［１０］の何れか１つに記載の電子デバイス製造用溶剤組成物を３０～９０℃で加熱溶解する工程を有する電子デバイス製造用インクの製造方法。
［１２］ ［１１］に記載の製造方法により得られる電子デバイス製造用インク。
［１３］ ［１］～［１０］の何れか１つに記載の電子デバイス製造用溶剤組成物を含む電子デバイス製造用インク。
［１４］ 溶剤と式（１）で表される化合物を含む電子デバイス製造用インク。
［１５］ 更に、電気特性付与材を含む［１２］～［１４］の何れか１つに記載の電子デバイス製造用インク。
［１６］ 電気特性付与材が、導電性金属材料、半導体材料、磁性材料、誘電材料、又は絶縁材料である［１５］に記載の電子デバイス製造用インク。
［１７］ バインダー樹脂含有量が１０重量％以下である［１２］～［１６］の何れか１つに記載の電子デバイス製造用インク。
［１８］ バインダー樹脂が、分子量１００００以上の高分子化合物である［１７］に記載の電子デバイス製造用インク。
［１９］ バインダー樹脂が、エチルセルロース樹脂、アルキルセルロース樹脂、ポリビニルアセタール樹脂、及びアクリル樹脂からなる群より選択される少なくとも１種である［１７］又は［１８］に記載の電子デバイス製造用インク。
［２０］ ２５℃における粘度［せん断速度０．５ｓ-1における］が０．０１～１０００Ｐａ・ｓである［１２］～［１９］の何れか１つに記載の電子デバイス製造用インク。
［２１］ ［１２］～［２０］の何れか１つに記載の電子デバイス製造用インクを印刷法により塗布し、乾燥後、焼成する工程を経て配線を形成する工程を有する電子デバイスの製造方法。
［２２］ 焼成温度が１００～３５０℃の範囲である［２１］に記載の電子デバイスの製造方法。
［２３］ 灰分の残存量が４．５重量％以下である配線を形成する［２１］又は［２２］に記載の電子デバイスの製造方法。
［２４］ 電子デバイスが積層セラミックコンデンサである［２１］～［２３］の何れか１つに記載の電子デバイスの製造方法。
［２５］ ［２１］～［２４］の何れか１つに記載の電子デバイスの製造方法により得られる電子デバイス。
［２６］ 灰分の残存量が４．５重量％以下である配線を有する［２５］に記載の電子デバイス。 That is, the present invention relates to the following.
[1] A solvent composition for use in an ink for producing an electronic device by a printing method, comprising a solvent and a compound represented by formula (1).
[2] The solvent composition for producing an electronic device according to [1], wherein R in the formula (1) is a linear or branched alkyl group, alkenyl group, or alkynyl group having 6 to 18 carbon atoms.
[3] In [1] or [2], the compound represented by formula (1) is at least one compound selected from the compounds represented by formulas (1-2) to (1-5) The solvent composition for electronic device manufacture of description.
[4] The compound represented by the formula (1) is a compound represented by the formula (1-3) and / or a compound represented by the formula (1-4) [1] or [2] Solvent composition for manufacturing electronic devices.
[5] The solvent composition for producing an electronic device according to any one of [1] to [4], wherein the evaporation temperature of the compound represented by the formula (1) is 120 to 380 ° C.
[6] The solvent composition for producing an electronic device according to any one of [1] to [5], wherein the SP value [(cal / cm 3 ) 0.5 ] at 25 ° C. of the solvent is 7.0 to 9.0. object.
[7] The solvent composition for producing an electronic device according to any one of [1] to [6], wherein the content of the solvent is 20.0 to 99.9% by weight of the total amount of the solvent composition for producing an electronic device. .
[8] The solvent is n-decane, n-dodecane, propylene glycol methyl-n-propyl ether, propylene glycol methyl-n-butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl. -At least one selected from the group consisting of n-butyl ether, dipropylene glycol methyl isoamyl ether, tripropylene glycol methyl n-propyl ether, cyclohexyl acetate, 2-methylcyclohexyl acetate, and 4-t-butylcyclohexyl acetate The solvent composition for producing an electronic device according to any one of [1] to [7].
[9] n-decane, n-dodecane, propylene glycol methyl-n-propyl ether, propylene glycol methyl-n-butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl-n- Solvent composition for manufacturing electronic devices, except for butyl ether, dipropylene glycol methyl isoamyl ether, tripropylene glycol methyl-n-propyl ether, cyclohexyl acetate, 2-methylcyclohexyl acetate, and 4-t-butylcyclohexyl acetate The solvent composition for producing an electronic device according to any one of [1] to [8], which is less than 50% by weight of the total solvent contained in the product.
[10] The electronic device according to any one of [1] to [9], wherein the content of the compound represented by the formula (1) is 0.1 to 50 parts by weight with respect to 100 parts by weight of the solvent. Solvent composition for production.
[11] A method for producing an ink for producing an electronic device, comprising a step of heating and dissolving the solvent composition for producing an electronic device according to any one of [1] to [10] at 30 to 90 ° C.
[12] An electronic device manufacturing ink obtained by the manufacturing method according to [11].
[13] An ink for producing an electronic device comprising the solvent composition for producing an electronic device according to any one of [1] to [10].
[14] An ink for producing an electronic device comprising a solvent and a compound represented by the formula (1).
[15] The ink for manufacturing an electronic device according to any one of [12] to [14], further including an electrical property imparting material.
[16] The ink for manufacturing an electronic device according to [15], wherein the electrical property imparting material is a conductive metal material, a semiconductor material, a magnetic material, a dielectric material, or an insulating material.
[17] The ink for manufacturing an electronic device according to any one of [12] to [16], wherein the binder resin content is 10% by weight or less.
[18] The ink for manufacturing an electronic device according to [17], wherein the binder resin is a polymer compound having a molecular weight of 10,000 or more.
[19] The ink for manufacturing an electronic device according to [17] or [18], wherein the binder resin is at least one selected from the group consisting of an ethyl cellulose resin, an alkyl cellulose resin, a polyvinyl acetal resin, and an acrylic resin.
[20] The ink for manufacturing an electronic device according to any one of [12] to [19], wherein a viscosity at 25 ° C. (at a shear rate of 0.5 s −1 ) is 0.01 to 1000 Pa · s.
[21] A method for manufacturing an electronic device comprising a step of applying an ink for manufacturing an electronic device according to any one of [12] to [20] by a printing method, forming a wiring through a step of drying and baking. .
[22] The method for manufacturing an electronic device according to [21], wherein the firing temperature is in the range of 100 to 350 ° C.
[23] The method for manufacturing an electronic device according to [21] or [22], wherein a wiring having a residual amount of ash of 4.5% by weight or less is formed.
[24] The method for manufacturing an electronic device according to any one of [21] to [23], wherein the electronic device is a multilayer ceramic capacitor.
[25] An electronic device obtained by the method for manufacturing an electronic device according to any one of [21] to [24].
[26] The electronic device according to [25], including a wiring having a residual amount of ash of 4.5% by weight or less.
本発明の電子デバイス製造用溶剤組成物は、上記式（１）で表される化合物を含有するため、加熱溶解する工程を経て、印刷法による配線等の形成に適した粘性を有するインクを製造することができる。
また、本発明の電子デバイス製造用溶剤組成物を使用して得られるインクは液ダレしにくく、印刷法により高精度の配線パターンを形成することができる。また、焼成工程において、より低温で焼成することができ、被塗布面部材が長時間高温に曝されることにより軟化、変形することを防止できる。更に、焼成後の灰分の残留量を著しく低減することができ、これにより引き起こされていた電気特性の低下を抑制することができる。
従って、本発明の電子デバイス製造用溶剤組成物を使用すれば、印刷法により電気特性に優れた配線等を形成することができ、電気特性に優れた配線等を有する電子デバイスを効率よく製造することができる。 Since the solvent composition for producing an electronic device of the present invention contains the compound represented by the above formula (1), an ink having a viscosity suitable for forming a wiring or the like by a printing method is produced through a step of heating and dissolving. can do.
Moreover, the ink obtained using the solvent composition for manufacturing an electronic device of the present invention is not easily dripped, and a highly accurate wiring pattern can be formed by a printing method. Moreover, in a baking process, it can bake at lower temperature and it can prevent that a to-be-coated surface member is softened and deform | transformed by being exposed to high temperature for a long time. Furthermore, the residual amount of ash after baking can be remarkably reduced, and the deterioration of electrical characteristics caused by this can be suppressed.
Therefore, if the solvent composition for producing an electronic device of the present invention is used, a wiring having excellent electrical characteristics can be formed by a printing method, and an electronic device having a wiring having excellent electrical characteristics is efficiently produced. be able to.
また、本発明の電子デバイス製造用溶剤組成物を使用して得られるインクは液ダレしにくく、印刷法により高精度の配線パターンを形成することができる。また、焼成工程において、より低温で焼成することができ、被塗布面部材が長時間高温に曝されることにより軟化、変形することを防止できる。更に、焼成後の灰分の残留量を著しく低減することができ、これにより引き起こされていた電気特性の低下を抑制することができる。
従って、本発明の電子デバイス製造用溶剤組成物を使用すれば、印刷法により電気特性に優れた配線等を形成することができ、電気特性に優れた配線等を有する電子デバイスを効率よく製造することができる。 Since the solvent composition for producing an electronic device of the present invention contains the compound represented by the above formula (1), an ink having a viscosity suitable for forming a wiring or the like by a printing method is produced through a step of heating and dissolving. can do.
Moreover, the ink obtained using the solvent composition for manufacturing an electronic device of the present invention is not easily dripped, and a highly accurate wiring pattern can be formed by a printing method. Moreover, in a baking process, it can bake at lower temperature and it can prevent that a to-be-coated surface member is softened and deform | transformed by being exposed to high temperature for a long time. Furthermore, the residual amount of ash after baking can be remarkably reduced, and the deterioration of electrical characteristics caused by this can be suppressed.
Therefore, if the solvent composition for producing an electronic device of the present invention is used, a wiring having excellent electrical characteristics can be formed by a printing method, and an electronic device having a wiring having excellent electrical characteristics is efficiently produced. be able to.
［電子デバイス製造用溶剤組成物］
本発明の電子デバイス製造用溶剤組成物（以後、「溶剤組成物」と称する場合がある）は、印刷法を用いて電子デバイスを製造するためのインクに用いられる溶剤組成物であって、溶剤と式（１）で表される化合物を含む。 [Solvent composition for manufacturing electronic devices]
The solvent composition for producing an electronic device of the present invention (hereinafter sometimes referred to as “solvent composition”) is a solvent composition used in an ink for producing an electronic device using a printing method, And a compound represented by the formula (1).
本発明の電子デバイス製造用溶剤組成物（以後、「溶剤組成物」と称する場合がある）は、印刷法を用いて電子デバイスを製造するためのインクに用いられる溶剤組成物であって、溶剤と式（１）で表される化合物を含む。 [Solvent composition for manufacturing electronic devices]
The solvent composition for producing an electronic device of the present invention (hereinafter sometimes referred to as “solvent composition”) is a solvent composition used in an ink for producing an electronic device using a printing method, And a compound represented by the formula (1).
（式（１）で表される化合物）
本発明の溶剤組成物は、下記式（１）で表される化合物を含有する。式中、Ｒは炭素数１以上の脂肪族炭化水素基を示す。尚、式中の４つのＲは全て同一の基、又は２種の異なる基である。下記式（１）で表される化合物は増粘剤として作用する。
(Compound represented by Formula (1))
The solvent composition of the present invention contains a compound represented by the following formula (1). In the formula, R represents an aliphatic hydrocarbon group having 1 or more carbon atoms. In the formula, all four Rs are the same group or two different groups. The compound represented by the following formula (1) acts as a thickener.
本発明の溶剤組成物は、下記式（１）で表される化合物を含有する。式中、Ｒは炭素数１以上の脂肪族炭化水素基を示す。尚、式中の４つのＲは全て同一の基、又は２種の異なる基である。下記式（１）で表される化合物は増粘剤として作用する。
The solvent composition of the present invention contains a compound represented by the following formula (1). In the formula, R represents an aliphatic hydrocarbon group having 1 or more carbon atoms. In the formula, all four Rs are the same group or two different groups. The compound represented by the following formula (1) acts as a thickener.
式（１）中、Ｒは炭素数１以上の脂肪族炭化水素基であり、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、ｔ－ブチル、ペンチル、ヘキシル、オクチル、２－エチルヘキシル、デシル、ドデシル、ミリスチル、ステアリル、ノナデシル基等の炭素数１～２０程度（好ましくは６～１８）の直鎖状又は分岐鎖状アルキル基；ビニル、３－ブテニル、４－ペンテニル、２－ヘキセニル、３－ヘキセニル、４－ヘキセニル、５－ヘキセニル、７－オクテニル、９－デセニル、１１－ドデセニル、オレイル基等の炭素数２～２０程度（好ましくは６～１８、特に好ましくは１２～１８）の直鎖状又は分岐鎖状アルケニル基；ブチニル、ペンチニル、ヘキシニル、オクチニル、デシニル、ペンタデシニル、オクタデシニル基等の炭素数２～２０程度（好ましくは６～１８、特に好ましくは１２～１８）の直鎖状又は分岐鎖状アルキニル基等を挙げることができる。
In the formula (1), R is an aliphatic hydrocarbon group having 1 or more carbon atoms. For example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl A linear or branched alkyl group having about 1 to 20 carbon atoms (preferably 6 to 18) such as myristyl, stearyl, nonadecyl group, etc .; vinyl, 3-butenyl, 4-pentenyl, 2-hexenyl, 3-hexenyl , 4-hexenyl, 5-hexenyl, 7-octenyl, 9-decenyl, 11-dodecenyl, oleyl and the like having a straight chain of about 2-20 (preferably 6-18, particularly preferably 12-18) Branched alkenyl group; carbon number of butynyl, pentynyl, hexynyl, octynyl, decynyl, pentadecynyl, octadecynyl group, etc. About 1-20 (preferably 6-18, particularly preferably 12-18) and the like straight chain or branched chain alkynyl groups.
式（１）で表される化合物としては、例えば、下記式（1-1）～（1-5）で表される化合物等を挙げることができる。下記式中、Ｒ1、Ｒ2は互いに異なって炭素数１以上の脂肪族炭化水素基を示し、上記Ｒと同様に例を挙げることができる。尚、式中に複数のＲ1が存在する場合、それらは同じ基を示す。Ｒ2についても同様である。
Examples of the compound represented by the formula (1) include compounds represented by the following formulas (1-1) to (1-5). In the following formulae, R 1 and R 2 are different from each other and represent an aliphatic hydrocarbon group having 1 or more carbon atoms, and examples can be given in the same manner as R. In addition, when several R < 1 > exists in a formula, they show the same group. The same applies to R 2 .
本発明における式（１）で表される化合物としては、なかでも少量の添加で増粘できる点で上記式（1-2）～（1-5）で表される化合物が好ましく、特に上記式（1-3）で表される化合物及び／又は上記式（1-4）で表される化合物が好ましい。
As the compound represented by the formula (1) in the present invention, the compounds represented by the above formulas (1-2) to (1-5) are preferable from the viewpoint that the viscosity can be increased by adding a small amount. A compound represented by (1-3) and / or a compound represented by the above formula (1-4) is preferred.
式（１）で表される化合物としては、なかでも、蒸発温度が１２０～３８０℃（好ましくは１５０～３３０℃、更に好ましくは１５０～３２０℃、特に好ましくは１５０～３１５℃、最も好ましくは１７０～３１５℃）のものが好ましく、蒸発温度は、側鎖の種類によりコントロールすることができる。蒸発温度が上記範囲を上回ると、低温で焼成することが困難となり、被塗布面部材が長時間高温に曝されることにより軟化、変形する場合がある。一方、蒸発温度が上記範囲を下回ると、インク調製時若しくは印刷時に気化して組成が変動する恐れがあり、安定して配線等を形成することが困難となる傾向がある。
Among the compounds represented by the formula (1), the evaporation temperature is 120 to 380 ° C. (preferably 150 to 330 ° C., more preferably 150 to 320 ° C., particularly preferably 150 to 315 ° C., and most preferably 170 ° C.). The evaporation temperature can be controlled by the type of side chain. When the evaporation temperature exceeds the above range, firing at a low temperature becomes difficult, and the coated surface member may be softened and deformed by being exposed to a high temperature for a long time. On the other hand, if the evaporation temperature is lower than the above range, the composition may change due to vaporization at the time of ink preparation or printing, and it tends to be difficult to stably form wirings and the like.
式（１）で表される化合物は、アミド結合部位において水素結合により自己会合してファイバー状の自己組織体を形成することができる。更に、Ｒ基が溶剤に対して親和性を有するため、溶剤と相溶させることにより溶剤を増粘することができ、経時的に安定な電子デバイス製造用インクを形成することができる。
The compound represented by the formula (1) can self-associate by hydrogen bonding at the amide bond site to form a fiber-like self-assembly. Furthermore, since the R group has an affinity for the solvent, the solvent can be thickened by being compatible with the solvent, and an ink for producing an electronic device that is stable over time can be formed.
本発明の溶剤組成物中の式（１）で表される化合物の含有量（２種以上含有する場合は合計含有量）は、溶剤１００重量部に対して、例えば０．１～５０重量部程度、好ましくは０．５～３０重量部、特に好ましくは０．５～１０重量部である。式（１）で表される化合物の含有量が上記範囲を下回ると温度変化によって低粘度化する等、インクの粘度を安定的に維持することが困難となり、液ダレにより高精度の配線パターンを形成することが困難となる場合がある。一方、式（１）で表される化合物の含有量が上記範囲を上回ると、インクの粘度が高くなりすぎ、印刷法による配線等の形成が困難となる場合がある。
The content of the compound represented by the formula (1) in the solvent composition of the present invention (when two or more are contained, the total content) is, for example, 0.1 to 50 parts by weight with respect to 100 parts by weight of the solvent. Degree, preferably 0.5 to 30 parts by weight, particularly preferably 0.5 to 10 parts by weight. When the content of the compound represented by the formula (1) is below the above range, it becomes difficult to stably maintain the viscosity of the ink, such as a decrease in viscosity due to a temperature change. It may be difficult to form. On the other hand, when the content of the compound represented by the formula (1) exceeds the above range, the viscosity of the ink becomes too high, and it may be difficult to form a wiring or the like by a printing method.
式（１）で表される化合物は、例えば、下記方法等により製造することができる。
１．シクロヘキサンテトラカルボン酸を塩化チオニルと反応させてシクロヘキサンテトラカルボン酸テトラクロライドを得、得られたシクロヘキサンテトラカルボン酸テトラクロライドにアミンを反応させる方法
２．シクロヘキサンテトラカルボン酸二無水物にアミン（１）を反応させてアミック酸を得、更にアミン（２）（アミン（１）と同一であってもよく異なっていてもよい）を縮合剤を用いて縮合させる方法 The compound represented by Formula (1) can be manufactured by the following method etc., for example.
1. 1. A method of reacting cyclohexanetetracarboxylic acid with thionyl chloride to obtain cyclohexanetetracarboxylic acid tetrachloride, and reacting the resulting cyclohexanetetracarboxylic acid tetrachloride with an amine. Amine acid (1) is reacted with cyclohexanetetracarboxylic dianhydride to obtain an amic acid, and amine (2) (which may be the same as or different from amine (1)) is used with a condensing agent. Method of condensation
１．シクロヘキサンテトラカルボン酸を塩化チオニルと反応させてシクロヘキサンテトラカルボン酸テトラクロライドを得、得られたシクロヘキサンテトラカルボン酸テトラクロライドにアミンを反応させる方法
２．シクロヘキサンテトラカルボン酸二無水物にアミン（１）を反応させてアミック酸を得、更にアミン（２）（アミン（１）と同一であってもよく異なっていてもよい）を縮合剤を用いて縮合させる方法 The compound represented by Formula (1) can be manufactured by the following method etc., for example.
1. 1. A method of reacting cyclohexanetetracarboxylic acid with thionyl chloride to obtain cyclohexanetetracarboxylic acid tetrachloride, and reacting the resulting cyclohexanetetracarboxylic acid tetrachloride with an amine. Amine acid (1) is reacted with cyclohexanetetracarboxylic dianhydride to obtain an amic acid, and amine (2) (which may be the same as or different from amine (1)) is used with a condensing agent. Method of condensation
上記１の製造方法で使用するシクロヘキサンテトラカルボン酸としては、１，２，４，５－シクロヘキサンテトラカルボン酸を好適に使用することができる。
As the cyclohexanetetracarboxylic acid used in the above production method 1, 1,2,4,5-cyclohexanetetracarboxylic acid can be suitably used.
上記１の製造方法で使用するアミン（Ｒ－ＮＨ2：Ｒは前記に同じ）としては、例えば、ブチルアミン、ペンチルアミン、イソペンチルアミン、へキシルアミン、オクチルアミン、２－エチルヘキシルアミン、デシルアミン、ラウリルアミン、ミリスチルアミン、ステアリルアミン、オレイルアミン等の炭素数１以上（好ましくは炭素数６～２０、特に好ましくは炭素数６～１８）の脂肪族炭化水素基（例えば、直鎖状若しくは分岐鎖状のアルキル基、アルケニル基、又はアルキニル基）を有するアミンを挙げることができる。
Examples of the amine (R—NH 2 : R is the same as described above) used in the production method 1 above include, for example, butylamine, pentylamine, isopentylamine, hexylamine, octylamine, 2-ethylhexylamine, decylamine, laurylamine Aliphatic hydrocarbon groups having 1 or more carbon atoms (preferably 6 to 20 carbon atoms, particularly preferably 6 to 18 carbon atoms) such as myristylamine, stearylamine, oleylamine, etc. (for example, linear or branched alkyl) And an amine having a group, an alkenyl group, or an alkynyl group.
上記１の製造方法において、シクロヘキサンテトラカルボン酸テトラクロライドとアミンの反応は、例えばアミンを仕込んだ系内にシクロヘキサンテトラカルボン酸テトラクロライドを滴下することにより行うことができる。アミンは、１種を単独で使用しても良く、２種の異なるアミンを使用しても良い。
In the production method of 1 above, the reaction between cyclohexanetetracarboxylic acid tetrachloride and amine can be carried out, for example, by dropping cyclohexanetetracarboxylic acid tetrachloride into a system charged with amine. One amine may be used alone, or two different amines may be used.
アミンの使用量（２種の異なるアミンを使用する場合はその総量）は、シクロヘキサンテトラカルボン酸テトラクロライド１モルに対して、例えば４～８モル程度、好ましくは４～６モルである。
The amount of amine to be used (the total amount when two different amines are used) is, for example, about 4 to 8 mol, preferably 4 to 6 mol, per 1 mol of cyclohexanetetracarboxylic acid tetrachloride.
シクロヘキサンテトラカルボン酸テトラクロライドとアミンの反応は、溶媒の存在下又は非存在下で行うことができる。前記溶媒としては、例えば、ペンタン、ヘキサン、ヘプタン、オクタン、石油エーテル等の飽和又は不飽和炭化水素系溶媒；ベンゼン、トルエン、キシレン等の芳香族炭化水素系溶媒；塩化メチレン、クロロホルム、１，２－ジクロロエタン、クロロベンゼン、ブロモベンゼン等のハロゲン化炭化水素系溶媒；ジエチルエーテル、ジイソプロピルエーテル、ジブチルエーテル、テトラヒドロフラン、ジオキサン、１，２－ジメトキシエタン、シクロペンチルメチルエーテル等のエーテル系溶媒；アセトニトリル、ベンゾニトリル等のニトリル系溶媒；ジメチルスルホキシド等のスルホキシド系溶媒；スルホラン等のスルホラン系溶媒；ジメチルホルムアミド等のアミド系溶媒；シリコーンオイル等の高沸点溶媒等を挙げることができる。これらは１種を単独で、又は２種以上を組み合わせて使用することができる。
The reaction between cyclohexanetetracarboxylic acid tetrachloride and amine can be carried out in the presence or absence of a solvent. Examples of the solvent include saturated or unsaturated hydrocarbon solvents such as pentane, hexane, heptane, octane and petroleum ether; aromatic hydrocarbon solvents such as benzene, toluene and xylene; methylene chloride, chloroform, 1, 2 -Halogenated hydrocarbon solvents such as dichloroethane, chlorobenzene, bromobenzene; ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, cyclopentyl methyl ether; acetonitrile, benzonitrile, etc. Nitrile solvents; sulfoxide solvents such as dimethyl sulfoxide; sulfolane solvents such as sulfolane; amide solvents such as dimethylformamide; high-boiling solvents such as silicone oil. These can be used alone or in combination of two or more.
前記溶媒の使用量としては、シクロヘキサンテトラカルボン酸テトラクロライドとアミンの総量に対して、例えば５０～３００重量％程度である。溶媒の使用量が上記範囲を上回ると反応成分の濃度が低くなり、反応速度が低下する傾向がある。
The amount of the solvent used is, for example, about 50 to 300% by weight with respect to the total amount of cyclohexanetetracarboxylic acid tetrachloride and amine. When the usage-amount of a solvent exceeds the said range, the density | concentration of a reaction component will become low and there exists a tendency for reaction rate to fall.
シクロヘキサンテトラカルボン酸テトラクロライドとアミンの反応は、通常、常圧下で行われる。また、上記反応の雰囲気としては反応を阻害しない限り特に限定されず、例えば、空気雰囲気、窒素雰囲気、アルゴン雰囲気等の何れであってもよい。反応温度は、例えば３０～６０℃程度である。反応時間は、例えば０．５～２０時間程度である。反応終了後（＝滴下終了後）は、熟成工程を設けてもよい。熟成工程を設ける場合、熟成温度は例えば３０～６０℃程度、熟成時間は例えば１～５時間程度である。また、反応はバッチ式、セミバッチ式、連続式等の何れの方法でも行うことができる。
The reaction between cyclohexanetetracarboxylic acid tetrachloride and amine is usually carried out under normal pressure. Further, the atmosphere of the reaction is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. The reaction temperature is, for example, about 30 to 60 ° C. The reaction time is, for example, about 0.5 to 20 hours. After completion of the reaction (= after completion of dropping), an aging step may be provided. When the aging step is provided, the aging temperature is, for example, about 30 to 60 ° C., and the aging time is, for example, about 1 to 5 hours. The reaction can be carried out by any method such as batch, semi-batch and continuous methods.
反応終了後、得られた反応生成物は、例えば、濾過、濃縮、蒸留、抽出、晶析、吸着、再結晶、カラムクロマトグラフィー等の分離手段や、これらを組み合わせた分離手段により分離精製できる。
After completion of the reaction, the obtained reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, etc., or a combination means combining these.
上記２の製造方法では、例えば、シクロヘキサンテトラカルボン酸二無水物とアミン（１）及び下記溶媒を系内に仕込み、熟成させることによりアミック酸を形成し、その後、アミン（２）と縮合剤（例えば、カルボジイミド又はその塩等）を仕込み、熟成させることにより式（１）で表される化合物を製造することができる。
In the above production method 2, for example, cyclohexanetetracarboxylic dianhydride, amine (1) and the following solvent are charged into the system and aged to form an amic acid, and then amine (2) and a condensing agent ( For example, a compound represented by formula (1) can be produced by charging and aging carbodiimide or a salt thereof.
前記シクロヘキサンテトラカルボン酸二無水物としては、１，２，４，５－シクロヘキサンテトラカルボン酸－１，２：４，５－二無水物を好適に使用することができる。
As the cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid-1,2: 4,5-dianhydride can be preferably used.
前記アミン（１）、（２）としては、上記１の製造方法で使用できるアミンと同様の例を挙げることができる。
Examples of the amines (1) and (2) include the same examples as amines that can be used in the above production method 1.
アミン（１）の使用量としては、シクロヘキサンテトラカルボン酸二無水物１モルに対して、例えば２～４モル程度、好ましくは２～３モルである。また、アミン（２）の使用量としては、シクロヘキサンテトラカルボン酸二無水物１モルに対して、例えば２～４モル程度、好ましくは２～３モルである。
The amount of amine (1) used is, for example, about 2 to 4 moles, preferably 2 to 3 moles per mole of cyclohexanetetracarboxylic dianhydride. The amount of amine (2) to be used is, for example, about 2 to 4 mol, preferably 2 to 3 mol, per 1 mol of cyclohexanetetracarboxylic dianhydride.
前記カルボジイミドは下記式で表される。
Ｒ”－Ｎ＝Ｃ＝Ｎ－Ｒ’
上記式中、Ｒ’、Ｒ”としては、例えば、ヘテロ原子含有置換基を有していてもよい、炭素数３～８の直鎖状若しくは分岐鎖状のアルキル基、又は３～８員のシクロアルキル基を挙げることができる。Ｒ’、Ｒ”は同一であってもよく、異なっていてもよい。また、Ｒ’とＲ”は互いに結合して上記式中の（－Ｎ＝Ｃ＝Ｎ－）基と共に環を形成していてもよい。 The carbodiimide is represented by the following formula.
R "-N = C = N-R '
In the above formula, R ′ and R ″ are, for example, a linear or branched alkyl group having 3 to 8 carbon atoms which may have a heteroatom-containing substituent, or 3 to 8 membered Examples thereof include cycloalkyl groups. R ′ and R ″ may be the same or different. R ′ and R ″ may be bonded to each other to form a ring together with the (—N═C═N—) group in the above formula.
Ｒ”－Ｎ＝Ｃ＝Ｎ－Ｒ’
上記式中、Ｒ’、Ｒ”としては、例えば、ヘテロ原子含有置換基を有していてもよい、炭素数３～８の直鎖状若しくは分岐鎖状のアルキル基、又は３～８員のシクロアルキル基を挙げることができる。Ｒ’、Ｒ”は同一であってもよく、異なっていてもよい。また、Ｒ’とＲ”は互いに結合して上記式中の（－Ｎ＝Ｃ＝Ｎ－）基と共に環を形成していてもよい。 The carbodiimide is represented by the following formula.
R "-N = C = N-R '
In the above formula, R ′ and R ″ are, for example, a linear or branched alkyl group having 3 to 8 carbon atoms which may have a heteroatom-containing substituent, or 3 to 8 membered Examples thereof include cycloalkyl groups. R ′ and R ″ may be the same or different. R ′ and R ″ may be bonded to each other to form a ring together with the (—N═C═N—) group in the above formula.
前記炭素数３～８の直鎖状若しくは分岐鎖状のアルキル基としては、例えば、プロピル、イソプロピル、ブチル、イソブチル、ｓ－ブチル、ｔ－ブチル、ペンチル、イソペンチル、ｓ－ペンチル、ｔ－ペンチル、ヘキシル、イソヘキシル、ｓ－ヘキシル、ｔ－ヘキシル基等を挙げることができる。
Examples of the linear or branched alkyl group having 3 to 8 carbon atoms include propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, s-pentyl, t-pentyl, Examples include hexyl, isohexyl, s-hexyl, t-hexyl groups and the like.
前記３～８員のシクロアルキル基としては、例えば、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、シクロオクチル基等を挙げることができる。
Examples of the 3- to 8-membered cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.
前記ヘテロ原子含有置換基としては、アミノ基、ジメチルアミノ基等のジ（Ｃ1-3）アルキルアミノ基等の窒素原子含有置換基を挙げることができる。
Examples of the heteroatom-containing substituent include nitrogen atom-containing substituents such as di (C 1-3 ) alkylamino groups such as amino groups and dimethylamino groups.
カルボジイミドとしては、例えば、ジイソプロピルカルボジイミド、ジシクロヘキシルカルボジイミド、Ｎ－（３－ジメチルアミノプロピル）－Ｎ’－エチルカルボジイミド等を挙げることができる。また、カルボジイミドの塩としては、例えば、塩酸塩（具体的には、Ｎ－（３－ジメチルアミノプロピル）－Ｎ’－エチルカルボジイミド塩酸塩等）等を挙げることができる。これらは１種を単独で、又は２種以上を組み合わせて使用することができる。
Examples of the carbodiimide include diisopropylcarbodiimide, dicyclohexylcarbodiimide, N- (3-dimethylaminopropyl) -N′-ethylcarbodiimide, and the like. Examples of the carbodiimide salt include hydrochloride (specifically, N- (3-dimethylaminopropyl) -N′-ethylcarbodiimide hydrochloride). These can be used alone or in combination of two or more.
カルボジイミドの使用量としては、シクロヘキサンテトラカルボン酸二無水物１モルに対して、例えば２～６モル程度、好ましくは２～４モルである。
The amount of carbodiimide used is, for example, about 2 to 6 moles, preferably 2 to 4 moles per mole of cyclohexanetetracarboxylic dianhydride.
前記溶媒としては、アミック酸の溶解性に優れるプロトン受容性溶媒（例えば、ピリジン、トリエチルアミン、トリブチルアミン等）を使用することが好ましい。これらは１種を単独で、又は２種以上を混合して使用することができる。
As the solvent, it is preferable to use a proton-accepting solvent (for example, pyridine, triethylamine, tributylamine, etc.) excellent in solubility of amic acid. These can be used individually by 1 type or in mixture of 2 or more types.
前記溶媒の使用量としては、アミック酸の総量に対して、例えば５０～３００重量％程度、好ましくは１００～２５０重量％である。溶媒の使用量が上記範囲を上回ると反応成分の濃度が低くなり、反応速度が低下する傾向がある。
The amount of the solvent used is, for example, about 50 to 300% by weight, preferably 100 to 250% by weight, based on the total amount of amic acid. When the usage-amount of a solvent exceeds the said range, the density | concentration of a reaction component will become low and there exists a tendency for reaction rate to fall.
上記反応は、通常、常圧下で行われる。また、上記反応の雰囲気としては反応を阻害しない限り特に限定されず、例えば、空気雰囲気、窒素雰囲気、アルゴン雰囲気等の何れであってもよい。熟成温度（反応温度）は、例えば３０～７０℃程度である。シクロヘキサンテトラカルボン酸二無水物とアミンの熟成時間は、例えば０．５～５時間程度であり、アミック酸とアミンの熟成時間は、例えば０．５～２０時間程度である。また、反応はバッチ式、セミバッチ式、連続式等の何れの方法でも行うことができる。
The above reaction is usually performed under normal pressure. Further, the atmosphere of the reaction is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. The aging temperature (reaction temperature) is, for example, about 30 to 70 ° C. The aging time of cyclohexanetetracarboxylic dianhydride and amine is, for example, about 0.5 to 5 hours, and the aging time of amic acid and amine is, for example, about 0.5 to 20 hours. The reaction can be carried out by any method such as batch, semi-batch and continuous methods.
反応終了後、得られた反応生成物は、例えば、濾過、濃縮、蒸留、抽出、晶析、吸着、再結晶、カラムクロマトグラフィー等の分離手段や、これらを組み合わせた分離手段により分離精製できる。
After completion of the reaction, the obtained reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, etc., or a combination means combining these.
（溶剤）
本発明の溶剤組成物に含まれる溶剤としては、上記式（１）で表される化合物の溶解性に優れる溶剤を使用することが好ましい。 (solvent)
As the solvent contained in the solvent composition of the present invention, it is preferable to use a solvent excellent in solubility of the compound represented by the above formula (1).
本発明の溶剤組成物に含まれる溶剤としては、上記式（１）で表される化合物の溶解性に優れる溶剤を使用することが好ましい。 (solvent)
As the solvent contained in the solvent composition of the present invention, it is preferable to use a solvent excellent in solubility of the compound represented by the above formula (1).
前記溶剤としては、なかでも、２５℃におけるＳＰ値［（ｃａｌ／ｃｍ3）0.5：Ｆｅｄｏｒｓ計算値］が７．０～９．０（好ましくは７．５～９．０）の範囲にある溶剤を１種又は２種以上使用することが、上記式（１）で表される化合物の溶解性に優れ、且つ上記式（１）で表される化合物を溶解する際の加熱温度を低く、例えば５０～９０℃程度に抑制することができる点で好ましい。ＳＰ値が上記範囲を外れる溶剤は上記式（１）で表される化合物の溶解性が低いため、前記化合物を溶解する際に、より高い温度での加熱が必要となる傾向がある。
Examples of the solvent include those having an SP value at 25 ° C. [(cal / cm 3 ) 0.5 : Fedors calculated value] of 7.0 to 9.0 (preferably 7.5 to 9.0). 1 or 2 or more are excellent in solubility of the compound represented by the above formula (1), and the heating temperature when dissolving the compound represented by the above formula (1) is lowered, for example, This is preferable in that it can be suppressed to about 50 to 90 ° C. A solvent having an SP value outside the above range has a low solubility of the compound represented by the above formula (1), and thus there is a tendency that heating at a higher temperature is required when the compound is dissolved.
前記溶剤としては、例えば、ｎ－デカン（ＳＰ値：７．６）、ｎ－ドデカン（ＳＰ値：７．７）、プロピレングリコールメチル－ｎ－プロピルエーテル（ＳＰ値：８．１）、プロピレングリコールメチル－ｎ－ブチルエーテル（ＳＰ値：８．１）、ジプロピレングリコールジメチルエーテル（ＳＰ値：８．４）、ジプロピレングリコールメチル－ｎ－プロピルエーテル（ＳＰ値：８．２）、ジプロピレングリコールメチル－ｎ－ブチルエーテル（ＳＰ値：８．２）、ジプロピレングリコールメチルイソアミルエーテル（ＳＰ値：８．０）、トリプロピレングリコールメチル－ｎ－プロピルエーテル（ＳＰ値：８．２）、シクロヘキシルアセテート（ＳＰ値：８．９）、２－メチルシクロヘキシルアセテート（ＳＰ値：８．５）、及び４－ｔ－ブチルシクロヘキシルアセテート（ＳＰ値：８．２）からなる群より選択される少なくとも１種を使用することが好ましい。
Examples of the solvent include n-decane (SP value: 7.6), n-dodecane (SP value: 7.7), propylene glycol methyl-n-propyl ether (SP value: 8.1), propylene glycol. Methyl-n-butyl ether (SP value: 8.1), dipropylene glycol dimethyl ether (SP value: 8.4), dipropylene glycol methyl-n-propyl ether (SP value: 8.2), dipropylene glycol methyl- n-butyl ether (SP value: 8.2), dipropylene glycol methyl isoamyl ether (SP value: 8.0), tripropylene glycol methyl-n-propyl ether (SP value: 8.2), cyclohexyl acetate (SP value) : 8.9), 2-methylcyclohexyl acetate (SP value: 8.5), and 4-t Butylcyclohexyl acetate (SP value: 8.2) it is preferred to use at least one selected from the group consisting of.
本発明の溶剤組成物中の溶剤の含有量（２種以上含有する場合は合計含有量）は、例えば２０．０～９９．９重量％、好ましくは３０．０～９９．５重量％、特に好ましくは４０．０～９９．５重量％、最も好ましくは５０．０～９９．５重量％、とりわけ好ましくは７０．０～９９．５重量％である。溶剤の含有量が上記範囲を下回ると、インクの粘度が高くなりすぎ、印刷法によって配線等を形成することが困難となる場合がある。一方、溶剤の含有量が上記範囲を上回ると、温度変化によって低粘度化する等、インクの粘度を安定的に維持することが困難となり、液ダレ等により高精度の配線パターンを形成することが困難となる場合がある。
The content of the solvent in the solvent composition of the present invention (when two or more are contained, the total content) is, for example, 20.0 to 99.9% by weight, preferably 30.0 to 99.5% by weight, particularly It is preferably 40.0 to 99.5% by weight, most preferably 50.0 to 99.5% by weight, particularly preferably 70.0 to 99.5% by weight. When the content of the solvent is below the above range, the viscosity of the ink becomes too high, and it may be difficult to form a wiring or the like by a printing method. On the other hand, if the content of the solvent exceeds the above range, it becomes difficult to stably maintain the viscosity of the ink, such as a decrease in viscosity due to a temperature change, and a highly accurate wiring pattern can be formed by dripping. It can be difficult.
また、本発明の溶剤組成物には、その効果を損なわない範囲であれば、必要に応じて上記溶剤以外の溶剤（以後、「他の溶剤」と称する場合がある。他の溶剤には、電子デバイス製造用途に用いられる周知慣用の溶剤が含まれる）を添加していてもよい。他の溶剤の添加量としては、本発明の溶剤組成物に含まれる全溶剤（１００重量％）の、例えば５０重量％未満、好ましくは３０重量％以下、特に好ましくは２０重量％以下、最も好ましくは１０重量％以下である。
Further, the solvent composition of the present invention may be a solvent other than the above-mentioned solvent (hereinafter referred to as “other solvent” if necessary) as long as the effect is not impaired. A well-known and conventional solvent used for electronic device production applications may be added. The amount of other solvents added is, for example, less than 50% by weight, preferably 30% by weight or less, particularly preferably 20% by weight or less, most preferably, of the total solvent (100% by weight) contained in the solvent composition of the present invention. Is 10% by weight or less.
［電子デバイス製造用インク、及びその製造方法］
本発明の電子デバイス製造用インク（以後、「インク」と称する場合がある）は、印刷法によって塗布することにより電子デバイスの配線や電極を形成するためのインクであり、溶剤と上記式（１）で表される化合物を含む。 [Ink for manufacturing electronic device and manufacturing method thereof]
The ink for manufacturing an electronic device of the present invention (hereinafter sometimes referred to as “ink”) is an ink for forming wiring and electrodes of an electronic device by application by a printing method. The compound represented by this is included.
本発明の電子デバイス製造用インク（以後、「インク」と称する場合がある）は、印刷法によって塗布することにより電子デバイスの配線や電極を形成するためのインクであり、溶剤と上記式（１）で表される化合物を含む。 [Ink for manufacturing electronic device and manufacturing method thereof]
The ink for manufacturing an electronic device of the present invention (hereinafter sometimes referred to as “ink”) is an ink for forming wiring and electrodes of an electronic device by application by a printing method. The compound represented by this is included.
本発明のインクは、例えば、上記溶剤組成物を３０～９０℃（上限は好ましくは８０℃、下限は好ましくは４０℃、特に好ましくは５０℃、最も好ましくは７０℃）で加熱溶解する工程を経て製造することができる。
The ink of the present invention comprises, for example, a step of heating and dissolving the solvent composition at 30 to 90 ° C. (upper limit is preferably 80 ° C., lower limit is preferably 40 ° C., particularly preferably 50 ° C., most preferably 70 ° C.). It can be manufactured after that.
本発明のインクの製造方法は、上記溶剤組成物を３０～９０℃（上限は好ましくは８０℃、下限は好ましくは４０℃、特に好ましくは５０℃、最も好ましくは７０℃）で加熱溶解する工程を有する。
In the method for producing the ink of the present invention, the solvent composition is heated and dissolved at 30 to 90 ° C. (the upper limit is preferably 80 ° C., the lower limit is preferably 40 ° C., particularly preferably 50 ° C., most preferably 70 ° C.). Have
加熱溶解に要する時間は、例えば３～６０分間程度（好ましくは１０～３０分間）である。
The time required for dissolution by heating is, for example, about 3 to 60 minutes (preferably 10 to 30 minutes).
加熱溶解後は、室温（例えば、１～３０℃）以下にまで冷却する工程を有することが好ましい。冷却は、室温で徐々に冷却してもよいし、氷冷等により急速に冷却してもよい。
After heating and melting, it is preferable to have a step of cooling to room temperature (eg, 1 to 30 ° C.) or lower. The cooling may be performed gradually at room temperature or rapidly by ice cooling or the like.
本発明のインクには、更に、導電性金属材料、半導体材料、磁性材料、誘電材料、及びは絶縁材料からなる群より選択される少なくとも１種の電気特性付与材を添加することが好ましい。電気特性付与材の含有量（２種以上含有する場合はその総量）としては、インク全量（１００重量％）の例えば０．１～９０重量％程度である。
In the ink of the present invention, it is preferable to add at least one electrical property imparting material selected from the group consisting of conductive metal materials, semiconductor materials, magnetic materials, dielectric materials, and insulating materials. The content of the electrical property imparting material (the total amount when containing two or more types) is, for example, about 0.1 to 90% by weight of the total amount of ink (100% by weight).
前記導電性金属材料、磁性材料としては周知慣用のものを使用することができ、例えば、金、銀、銅、ニッケル、パラジウム、アルミニウム、鉄、白金、モリブデン、タングステン、亜鉛、鉛、コバルト、酸化鉄・酸化クロム、フェライト、及びこれらの合金等を挙げることができる。半導体材料としては周知慣用のものを使用することができ、例えば、ペンタセン、フラーレン誘導体、ポリチオフェン誘導体、金属（銅、インジウム、ガリウム、セレン、砒素、カドミウム、テルル、及びこれらの合金）、シリコン微粒子等を挙げることができる。誘電材料、絶縁材料としては周知慣用のものを使用することができ、例えば、シクロオレフィンポリマー、フッ素樹脂、ブチラール樹脂、ガラス、紙、テフロン（登録商標）等を挙げることができる。
As the conductive metal material and magnetic material, well-known and commonly used materials can be used. For example, gold, silver, copper, nickel, palladium, aluminum, iron, platinum, molybdenum, tungsten, zinc, lead, cobalt, oxidation Examples thereof include iron / chromium oxide, ferrite, and alloys thereof. Known and commonly used semiconductor materials can be used, such as pentacene, fullerene derivatives, polythiophene derivatives, metals (copper, indium, gallium, selenium, arsenic, cadmium, tellurium, and alloys thereof), silicon fine particles, etc. Can be mentioned. As the dielectric material and the insulating material, well-known and customary materials can be used, and examples thereof include cycloolefin polymer, fluororesin, butyral resin, glass, paper, Teflon (registered trademark) and the like.
上記工程を経て得られる本発明のインクは上記式（１）で表される化合物を含有し、前記化合物は溶剤中で自己組織化してひも状会合体を形成し、高分子化合物のような粘性を生じるため、バインダー樹脂を配合しなくても、印刷法によって電子デバイスの配線や電極を精度良く形成するのに適度な粘度を有する。
The ink of the present invention obtained through the above steps contains a compound represented by the above formula (1), and the compound self-assembles in a solvent to form a string-like aggregate, which is viscous like a polymer compound. Therefore, even if the binder resin is not blended, it has an appropriate viscosity for accurately forming the wiring and electrodes of the electronic device by the printing method.
本発明のインクは適度な粘性を有し、２５℃における粘度［せん断速度０．５ｓ-1における］は、例えば０．０１～１０００Ｐａ・ｓ程度、好ましくは０．１～５００Ｐａ・ｓ、特に好ましくは１～２００Ｐａ・ｓである。
The ink of the present invention has an appropriate viscosity, and the viscosity at 25 ° C. (at a shear rate of 0.5 s −1 ) is, for example, about 0.01 to 1000 Pa · s, preferably 0.1 to 500 Pa · s, particularly preferably. Is 1 to 200 Pa · s.
そのため、本発明のインクはバインダー樹脂（例えば、エチルセルロース樹脂、アルキルセルロース樹脂、ポリビニルアセタール樹脂、アクリル樹脂等の分子量１００００以上の高分子化合物）を添加する必要がなく、添加する場合であっても、添加量は、インク全量（１００重量）の例えば１０重量％以下であり、好ましくは５重量％以下、更に好ましくは５重量％未満、特に好ましくは３重量％以下、最も好ましくは１重量％以下である。バインダー樹脂の添加量が上記範囲を上回ると、焼成によって生じるバインダー樹脂由来の灰分によって、電気特性の低下が引き起こされるため好ましくない。
Therefore, the ink of the present invention does not require the addition of a binder resin (for example, a polymer compound having a molecular weight of 10,000 or more such as an ethyl cellulose resin, an alkyl cellulose resin, a polyvinyl acetal resin, and an acrylic resin). The amount added is, for example, 10% by weight or less of the total amount of ink (100%), preferably 5% by weight or less, more preferably less than 5% by weight, particularly preferably 3% by weight or less, and most preferably 1% by weight or less. is there. If the amount of the binder resin added exceeds the above range, the ash content derived from the binder resin caused by firing causes a decrease in electrical characteristics, which is not preferable.
また、本発明のインクに含まれる式（１）で表される化合物からなるひも状会合体は、熱分解性に優れ容易に低分子量化する。そのため、本発明のインクはエチルセルロース等のバインダー樹脂により粘度が付与されたインクに比べて低温（例えば１００～３５０℃、好ましくは１５０～３００℃、特に好ましくは１５０～２５０℃）で焼成することができ、焼成工程における被塗布面部材の軟化、変形を防止することができる。更に、焼成後の灰分の残留量を極めて低く低減することができ（灰分の残存量は、例えば４．５重量％以下、好ましくは４．０重量％以下、特に好ましくは３．０重量％以下、最も好ましくは２．５重量％以下）、灰分によって引き起こされる電気特性の低下を抑制することができる。
Further, the string-like aggregate composed of the compound represented by the formula (1) contained in the ink of the present invention has excellent thermal decomposability and easily has a low molecular weight. Therefore, the ink of the present invention can be baked at a lower temperature (for example, 100 to 350 ° C., preferably 150 to 300 ° C., particularly preferably 150 to 250 ° C.) as compared with an ink to which a viscosity is imparted by a binder resin such as ethyl cellulose. It is possible to prevent softening and deformation of the coated surface member in the firing step. Furthermore, the residual amount of ash after firing can be reduced extremely low (the residual amount of ash is, for example, 4.5% by weight or less, preferably 4.0% by weight or less, particularly preferably 3.0% by weight or less). , Most preferably 2.5% by weight or less), it is possible to suppress a decrease in electrical properties caused by ash.
本発明のインクによれば、印刷法により被塗布面部材（例えば、セラミック基板、グリーンシート等）に塗布、乾燥し、焼成する工程を経て電気特性（例えば、導電性又は絶縁性）に優れた配線等を精度良く形成することができる。従って、本発明のインクは、例えば、コンデンサ、インダクタ、バリスタ、サーミスタ、スピーカ、アクチュエータ、アンテナ、固体酸化物燃料電池（SOFC）等（特に、積層セラミックコンデンサ）の製造用インクとして特に有用である。
According to the ink of the present invention, it has excellent electrical characteristics (for example, conductivity or insulation) through the steps of coating, drying, and firing on a surface member (for example, ceramic substrate, green sheet, etc.) by a printing method. Wiring and the like can be formed with high accuracy. Therefore, the ink of the present invention is particularly useful as an ink for producing, for example, a capacitor, an inductor, a varistor, a thermistor, a speaker, an actuator, an antenna, a solid oxide fuel cell (SOFC), etc. (particularly, a multilayer ceramic capacitor).
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例により何ら限定されるものではない。
Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
調製例１［増粘剤（１）：１，２，４，５－シクロヘキサンテトラカルボン酸ジ（２－エチルヘキシルアミド）ジ（オレイルアミド）の合成］
ジムロート冷却管、窒素導入口、滴下ロート、熱電対を備えた１００ｍＬ４つ口セパラブルフラスコにピリジン２０ｍＬ、１，２，４，５－シクロヘキサンテトラカルボン酸－１，２：４，５－二無水物４．５ｇ（０．０２ｍｏｌ）、オレイルアミン１０．６ｇ（０．０４ｍｏｌ）を仕込み、系内温度を５０℃に設定して、３時間熟成した。
その後、２－エチルヘキシルアミン５．２ｇ（０．０４ｍｏｌ）、ジイソプロピルカルボジイミド５．５ｇ（０．０４４ｍｏｌ）を仕込み、更に８時間熟成を行った。
その後、得られた粗液の低沸分をエバポレータにて除去し、メタノールで洗浄し、淡黄色の湿粉を得た。更に得られた湿粉についてＣＨＣｌ3／ＣＨ3ＯＨ（７０／３０(v/v)）で再結晶を行い、１，２，４，５－シクロヘキサンテトラカルボン酸ジ（２－エチルヘキシルアミド）ジ（オレイルアミド）［１，２，４，５－シクロヘキサンテトラカルボン酸－１，４－ジ（２－エチルヘキシルアミド）－２，５－ジ（オレイルアミド）と１，２，４，５－シクロヘキサンテトラカルボン酸－１，５－ジ（２－エチルヘキシルアミド）－２，４－ジ（オレイルアミド）の混合物］を１１．９ｇ得た（収率：６１％）。反応生成物の構造は1Ｈ－ＮＭＲにより確認した。 Preparation Example 1 [Thickener (1): Synthesis of 1,2,4,5-cyclohexanetetracarboxylic acid di (2-ethylhexylamide) di (oleylamide)]
20 mL of pyridine, 1,2,4,5-cyclohexanetetracarboxylic acid-1,2: 4,5-dianhydride in a 100 mL four-necked separable flask equipped with a Dimroth condenser, nitrogen inlet, dropping funnel, thermocouple 4.5 g (0.02 mol) and 10.6 g (0.04 mol) of oleylamine were charged, the system temperature was set to 50 ° C., and the mixture was aged for 3 hours.
Thereafter, 5.2 g (0.04 mol) of 2-ethylhexylamine and 5.5 g (0.044 mol) of diisopropylcarbodiimide were added, followed by further aging for 8 hours.
Thereafter, the low boiling content of the obtained crude liquid was removed by an evaporator and washed with methanol to obtain a pale yellow wet powder. Further, the obtained wet powder was recrystallized with CHCl 3 / CH 3 OH (70/30 (v / v)), and 1,2,4,5-cyclohexanetetracarboxylic acid di (2-ethylhexylamide) di ( Oleylamide) [1,2,4,5-cyclohexanetetracarboxylic acid-1,4-di (2-ethylhexylamide) -2,5-di (oleylamide) and 1,2,4,5-cyclohexanetetracarboxylic 11.9 g of a mixture of acid-1,5-di (2-ethylhexylamide) -2,4-di (oleylamide)] (yield: 61%). The structure of the reaction product was confirmed by 1 H-NMR.
ジムロート冷却管、窒素導入口、滴下ロート、熱電対を備えた１００ｍＬ４つ口セパラブルフラスコにピリジン２０ｍＬ、１，２，４，５－シクロヘキサンテトラカルボン酸－１，２：４，５－二無水物４．５ｇ（０．０２ｍｏｌ）、オレイルアミン１０．６ｇ（０．０４ｍｏｌ）を仕込み、系内温度を５０℃に設定して、３時間熟成した。
その後、２－エチルヘキシルアミン５．２ｇ（０．０４ｍｏｌ）、ジイソプロピルカルボジイミド５．５ｇ（０．０４４ｍｏｌ）を仕込み、更に８時間熟成を行った。
その後、得られた粗液の低沸分をエバポレータにて除去し、メタノールで洗浄し、淡黄色の湿粉を得た。更に得られた湿粉についてＣＨＣｌ3／ＣＨ3ＯＨ（７０／３０(v/v)）で再結晶を行い、１，２，４，５－シクロヘキサンテトラカルボン酸ジ（２－エチルヘキシルアミド）ジ（オレイルアミド）［１，２，４，５－シクロヘキサンテトラカルボン酸－１，４－ジ（２－エチルヘキシルアミド）－２，５－ジ（オレイルアミド）と１，２，４，５－シクロヘキサンテトラカルボン酸－１，５－ジ（２－エチルヘキシルアミド）－２，４－ジ（オレイルアミド）の混合物］を１１．９ｇ得た（収率：６１％）。反応生成物の構造は1Ｈ－ＮＭＲにより確認した。 Preparation Example 1 [Thickener (1): Synthesis of 1,2,4,5-cyclohexanetetracarboxylic acid di (2-ethylhexylamide) di (oleylamide)]
20 mL of pyridine, 1,2,4,5-cyclohexanetetracarboxylic acid-1,2: 4,5-dianhydride in a 100 mL four-necked separable flask equipped with a Dimroth condenser, nitrogen inlet, dropping funnel, thermocouple 4.5 g (0.02 mol) and 10.6 g (0.04 mol) of oleylamine were charged, the system temperature was set to 50 ° C., and the mixture was aged for 3 hours.
Thereafter, 5.2 g (0.04 mol) of 2-ethylhexylamine and 5.5 g (0.044 mol) of diisopropylcarbodiimide were added, followed by further aging for 8 hours.
Thereafter, the low boiling content of the obtained crude liquid was removed by an evaporator and washed with methanol to obtain a pale yellow wet powder. Further, the obtained wet powder was recrystallized with CHCl 3 / CH 3 OH (70/30 (v / v)), and 1,2,4,5-cyclohexanetetracarboxylic acid di (2-ethylhexylamide) di ( Oleylamide) [1,2,4,5-cyclohexanetetracarboxylic acid-1,4-di (2-ethylhexylamide) -2,5-di (oleylamide) and 1,2,4,5-cyclohexanetetracarboxylic 11.9 g of a mixture of acid-1,5-di (2-ethylhexylamide) -2,4-di (oleylamide)] (yield: 61%). The structure of the reaction product was confirmed by 1 H-NMR.
調製例２［増粘剤（２）：１，２，４，５－シクロヘキサンテトラカルボン酸ジ（２－エチルヘキシルアミド）ジ（ステアリルアミド）の合成］
オレイルアミンに代えてステアリルアミン１０．７ｇ（０．０４ｍｏｌ）を使用した以外は調製例１と同様に行って、１，２，４，５－シクロヘキサンテトラカルボン酸ジ（２－エチルヘキシルアミド）ジ（ステアリルアミド）［１，２，４，５－シクロヘキサンテトラカルボン酸－１，４－ジ（２－エチルヘキシルアミド）－２，５－ジ（ステアリルアミド）と１，２，４，５－シクロヘキサンテトラカルボン酸－１，５－ジ（２－エチルヘキシルアミド）－２，４－ジ（ステアリルアミド）の混合物］を１１．２ｇ得た（収率：５７％）。 Preparation Example 2 [Thickener (2): Synthesis of 1,2,4,5-cyclohexanetetracarboxylic acid di (2-ethylhexylamide) di (stearylamide)]
1,2,4,5-Cyclohexanetetracarboxylic acid di (2-ethylhexylamide) di (stearyl), except that 10.7 g (0.04 mol) of stearylamine was used instead of oleylamine Amido) [1,2,4,5-cyclohexanetetracarboxylic acid-1,4-di (2-ethylhexylamide) -2,5-di (stearylamide) and 1,2,4,5-cyclohexanetetracarboxylic acid -1,5-di (2-ethylhexylamide) -2,4-di (stearylamide)] was obtained (11.2 g) (yield: 57%).
オレイルアミンに代えてステアリルアミン１０．７ｇ（０．０４ｍｏｌ）を使用した以外は調製例１と同様に行って、１，２，４，５－シクロヘキサンテトラカルボン酸ジ（２－エチルヘキシルアミド）ジ（ステアリルアミド）［１，２，４，５－シクロヘキサンテトラカルボン酸－１，４－ジ（２－エチルヘキシルアミド）－２，５－ジ（ステアリルアミド）と１，２，４，５－シクロヘキサンテトラカルボン酸－１，５－ジ（２－エチルヘキシルアミド）－２，４－ジ（ステアリルアミド）の混合物］を１１．２ｇ得た（収率：５７％）。 Preparation Example 2 [Thickener (2): Synthesis of 1,2,4,5-cyclohexanetetracarboxylic acid di (2-ethylhexylamide) di (stearylamide)]
1,2,4,5-Cyclohexanetetracarboxylic acid di (2-ethylhexylamide) di (stearyl), except that 10.7 g (0.04 mol) of stearylamine was used instead of oleylamine Amido) [1,2,4,5-cyclohexanetetracarboxylic acid-1,4-di (2-ethylhexylamide) -2,5-di (stearylamide) and 1,2,4,5-cyclohexanetetracarboxylic acid -1,5-di (2-ethylhexylamide) -2,4-di (stearylamide)] was obtained (11.2 g) (yield: 57%).
調製例３［増粘剤（３）：１，２，４，５－シクロヘキサンテトラカルボン酸ジ（ステアリルアミド）ジ（オレイルアミド）の合成］
２－エチルヘキシルアミンに代えてステアリルアミン１０．７ｇ（０．０４ｍｏｌ）を使用した以外は調製例１と同様に行って、１，２，４，５－シクロヘキサンテトラカルボン酸ジ（ステアリルアミド）ジ（オレイルアミド）［１，２，４，５－シクロヘキサンテトラカルボン酸－１，４－ジ（ステアリルアミド）－２，５－ジ（オレイルアミド）と１，２，４，５－シクロヘキサンテトラカルボン酸－１，５－ジ（ステアリルアミド）－２，４－ジ（オレイルアミド）の混合物］を１３．４ｇ得た（収率：５３％）。 Preparation Example 3 [Thickener (3): Synthesis of 1,2,4,5-cyclohexanetetracarboxylic acid di (stearylamide) di (oleylamide)]
The same procedure as in Preparation Example 1 was conducted except that 10.7 g (0.04 mol) of stearylamine was used instead of 2-ethylhexylamine, and 1,2,4,5-cyclohexanetetracarboxylic acid di (stearylamide) di ( Oleylamide) [1,2,4,5-cyclohexanetetracarboxylic acid-1,4-di (stearylamide) -2,5-di (oleylamide) and 1,2,4,5-cyclohexanetetracarboxylic acid- 13.4 g of a mixture of 1,5-di (stearylamide) -2,4-di (oleylamide) (yield: 53%).
２－エチルヘキシルアミンに代えてステアリルアミン１０．７ｇ（０．０４ｍｏｌ）を使用した以外は調製例１と同様に行って、１，２，４，５－シクロヘキサンテトラカルボン酸ジ（ステアリルアミド）ジ（オレイルアミド）［１，２，４，５－シクロヘキサンテトラカルボン酸－１，４－ジ（ステアリルアミド）－２，５－ジ（オレイルアミド）と１，２，４，５－シクロヘキサンテトラカルボン酸－１，５－ジ（ステアリルアミド）－２，４－ジ（オレイルアミド）の混合物］を１３．４ｇ得た（収率：５３％）。 Preparation Example 3 [Thickener (3): Synthesis of 1,2,4,5-cyclohexanetetracarboxylic acid di (stearylamide) di (oleylamide)]
The same procedure as in Preparation Example 1 was conducted except that 10.7 g (0.04 mol) of stearylamine was used instead of 2-ethylhexylamine, and 1,2,4,5-cyclohexanetetracarboxylic acid di (stearylamide) di ( Oleylamide) [1,2,4,5-cyclohexanetetracarboxylic acid-1,4-di (stearylamide) -2,5-di (oleylamide) and 1,2,4,5-cyclohexanetetracarboxylic acid- 13.4 g of a mixture of 1,5-di (stearylamide) -2,4-di (oleylamide) (yield: 53%).
調製例４［増粘剤（４）：１，２，４，５－シクロヘキサンテトラカルボン酸テトラ（オレイルアミド）の合成］
２－エチルヘキシルアミンに代えてオレイルアミン１０．７ｇ（０．０４ｍｏｌ）を使用した以外は調製例１と同様に行って、１，２，４，５－シクロヘキサンテトラカルボン酸テトラ（オレイルアミド）を１２．３ｇ得た（収率：４９％）。 Preparation Example 4 [Thickener (4): Synthesis of 1,2,4,5-cyclohexanetetracarboxylic acid tetra (oleylamide)]
The same procedure as in Preparation Example 1 was carried out except that 10.7 g (0.04 mol) of oleylamine was used in place of 2-ethylhexylamine to give 1,2,4,5-cyclohexanetetracarboxylic acid tetra (oleylamide). 3 g was obtained (yield: 49%).
２－エチルヘキシルアミンに代えてオレイルアミン１０．７ｇ（０．０４ｍｏｌ）を使用した以外は調製例１と同様に行って、１，２，４，５－シクロヘキサンテトラカルボン酸テトラ（オレイルアミド）を１２．３ｇ得た（収率：４９％）。 Preparation Example 4 [Thickener (4): Synthesis of 1,2,4,5-cyclohexanetetracarboxylic acid tetra (oleylamide)]
The same procedure as in Preparation Example 1 was carried out except that 10.7 g (0.04 mol) of oleylamine was used in place of 2-ethylhexylamine to give 1,2,4,5-cyclohexanetetracarboxylic acid tetra (oleylamide). 3 g was obtained (yield: 49%).
実施例１
調製例１で得られた増粘剤（１）を、溶剤としてのｎ－デカン（和光純薬工業（株）製）に増粘剤濃度が１重量％になるように添加して溶剤組成物（１）を得た。
得られた溶剤組成物（１）を液温８０℃で０．５時間加熱溶解し、室温（２５℃）まで放冷して、ペースト状のインク（１）を得た（２５℃における粘度［せん断速度０．５ｓ-1における］：６Ｐａ・ｓ）。 Example 1
The solvent composition obtained by adding the thickener (1) obtained in Preparation Example 1 to n-decane (manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent so that the concentration of the thickener is 1% by weight. (1) was obtained.
The obtained solvent composition (1) was dissolved by heating at a liquid temperature of 80 ° C. for 0.5 hours and allowed to cool to room temperature (25 ° C.) to obtain a paste-like ink (1) (viscosity at 25 ° C. [ At a shear rate of 0.5 s −1 ]: 6 Pa · s).
調製例１で得られた増粘剤（１）を、溶剤としてのｎ－デカン（和光純薬工業（株）製）に増粘剤濃度が１重量％になるように添加して溶剤組成物（１）を得た。
得られた溶剤組成物（１）を液温８０℃で０．５時間加熱溶解し、室温（２５℃）まで放冷して、ペースト状のインク（１）を得た（２５℃における粘度［せん断速度０．５ｓ-1における］：６Ｐａ・ｓ）。 Example 1
The solvent composition obtained by adding the thickener (1) obtained in Preparation Example 1 to n-decane (manufactured by Wako Pure Chemical Industries, Ltd.) as a solvent so that the concentration of the thickener is 1% by weight. (1) was obtained.
The obtained solvent composition (1) was dissolved by heating at a liquid temperature of 80 ° C. for 0.5 hours and allowed to cool to room temperature (25 ° C.) to obtain a paste-like ink (1) (viscosity at 25 ° C. [ At a shear rate of 0.5 s −1 ]: 6 Pa · s).
実施例２～６、比較例１
下記表１に記載の組成（単位：重量％）に変更した以外は実施例１と同様にして溶剤組成物を得、インクを得た。尚、比較例１では増粘剤に代えてエチルセルロース（商品名「エトセルＳＴＤ２００」、日新化成（株）製）を樹脂濃度が５重量％になるように添加し、液温８０℃で３時間加熱溶解し、室温（２５℃）で放冷してペースト状のインクを得た。 Examples 2 to 6, Comparative Example 1
A solvent composition was obtained in the same manner as in Example 1 except that the composition (unit: wt%) shown in Table 1 was changed, and an ink was obtained. In Comparative Example 1, ethyl cellulose (trade name “Etocel STD200”, manufactured by Nisshin Kasei Co., Ltd.) was added instead of the thickener so that the resin concentration became 5% by weight, and the liquid temperature was 80 ° C. for 3 hours. It was dissolved by heating and allowed to cool at room temperature (25 ° C.) to obtain a paste-like ink.
下記表１に記載の組成（単位：重量％）に変更した以外は実施例１と同様にして溶剤組成物を得、インクを得た。尚、比較例１では増粘剤に代えてエチルセルロース（商品名「エトセルＳＴＤ２００」、日新化成（株）製）を樹脂濃度が５重量％になるように添加し、液温８０℃で３時間加熱溶解し、室温（２５℃）で放冷してペースト状のインクを得た。 Examples 2 to 6, Comparative Example 1
A solvent composition was obtained in the same manner as in Example 1 except that the composition (unit: wt%) shown in Table 1 was changed, and an ink was obtained. In Comparative Example 1, ethyl cellulose (trade name “Etocel STD200”, manufactured by Nisshin Kasei Co., Ltd.) was added instead of the thickener so that the resin concentration became 5% by weight, and the liquid temperature was 80 ° C. for 3 hours. It was dissolved by heating and allowed to cool at room temperature (25 ° C.) to obtain a paste-like ink.
＜評価＞
実施例で及び比較例で得られたインクについて、下記方法により残留灰分量、及び塗布性について評価した。
残留灰分量：
インク各２０ｍｇを、ＴＧ－ＤＴＡにて２０℃から４００℃まで１０℃／分で昇温測定を行い、温度毎の重量を測定し、２５０℃における残留灰分量（インク全量に対する残留灰分の割合）を評価した。 <Evaluation>
About the ink obtained by the Example and the comparative example, the amount of residual ash and the applicability | paintability were evaluated by the following method.
Residual ash content:
20 mg of each ink was measured for temperature increase from 20 ° C. to 400 ° C. at 10 ° C./min with TG-DTA, the weight at each temperature was measured, and the amount of residual ash at 250 ° C. (the ratio of residual ash to the total amount of ink) Evaluated.
実施例で及び比較例で得られたインクについて、下記方法により残留灰分量、及び塗布性について評価した。
残留灰分量：
インク各２０ｍｇを、ＴＧ－ＤＴＡにて２０℃から４００℃まで１０℃／分で昇温測定を行い、温度毎の重量を測定し、２５０℃における残留灰分量（インク全量に対する残留灰分の割合）を評価した。 <Evaluation>
About the ink obtained by the Example and the comparative example, the amount of residual ash and the applicability | paintability were evaluated by the following method.
Residual ash content:
20 mg of each ink was measured for temperature increase from 20 ° C. to 400 ° C. at 10 ° C./min with TG-DTA, the weight at each temperature was measured, and the amount of residual ash at 250 ° C. (the ratio of residual ash to the total amount of ink) Evaluated.
塗布性：
スクリーン印刷機（商品名「ＬＳ－１５０型ＴＶスクリーン印刷機」、ニューロング精密工業（株）製）を用い、塗布できたものを「○」、塗布できなかったものを「×」とした。 Applicability:
Using a screen printer (trade name “LS-150 type TV screen printer”, manufactured by Neurong Seimitsu Kogyo Co., Ltd.), what was applied was “◯”, and what was not applied was “×”.
スクリーン印刷機（商品名「ＬＳ－１５０型ＴＶスクリーン印刷機」、ニューロング精密工業（株）製）を用い、塗布できたものを「○」、塗布できなかったものを「×」とした。 Applicability:
Using a screen printer (trade name “LS-150 type TV screen printer”, manufactured by Neurong Seimitsu Kogyo Co., Ltd.), what was applied was “◯”, and what was not applied was “×”.
結果を下記表にまとめて示す。
The results are summarized in the following table.
表１中の略号は以下の通りである。
増粘剤
１：１，２，４，５－シクロヘキサンテトラカルボン酸ジ（２－エチルヘキシルアミド）ジ（オレイルアミド）
２：１，２，４，５－シクロヘキサンテトラカルボン酸ジ（２－エチルヘキシルアミド）ジ（ステアリルアミド）
３：１，２，４，５－シクロヘキサンテトラカルボン酸ジ（ステアリルアミド）ジ（オレイルアミド）
４：１，２，４，５－シクロヘキサンテトラカルボン酸テトラ（オレイルアミド）
樹脂
ＥＣ２００：エチルセルロース、商品名「エトセルＳＴＤ２００」、日新化成（株）製
溶剤
ｄｅｃａｎｅ：ｎ－デカン（和光純薬工業（株）製、ＳＰ値：７．６）
ＤＰＭＮＰ：ジプロピレングリコールメチル－ｎ－プロピルエーテル（（株）ダイセル製、ＳＰ値：８．２）
ＣＨＸＡ：シクロヘキシルアセテート（（株）ダイセル製、ＳＰ値：８．９） Abbreviations in Table 1 are as follows.
Thickener 1: 1,2,4,5-cyclohexanetetracarboxylic acid di (2-ethylhexylamide) di (oleylamide)
2: 1,2,4,5-cyclohexanetetracarboxylic acid di (2-ethylhexylamide) di (stearylamide)
3: 1,2,4,5-cyclohexanetetracarboxylic acid di (stearylamide) di (oleylamide)
4: 1,2,4,5-cyclohexanetetracarboxylic acid tetra (oleylamide)
Resin EC200: Ethylcellulose, trade name “Etocel STD200”, manufactured by Nisshin Kasei Co., Ltd. Solvent dekane: n-decane (manufactured by Wako Pure Chemical Industries, Ltd., SP value: 7.6)
DPMNP: Dipropylene glycol methyl-n-propyl ether (manufactured by Daicel Corporation, SP value: 8.2)
CHXA: cyclohexyl acetate (manufactured by Daicel Corporation, SP value: 8.9)
増粘剤
１：１，２，４，５－シクロヘキサンテトラカルボン酸ジ（２－エチルヘキシルアミド）ジ（オレイルアミド）
２：１，２，４，５－シクロヘキサンテトラカルボン酸ジ（２－エチルヘキシルアミド）ジ（ステアリルアミド）
３：１，２，４，５－シクロヘキサンテトラカルボン酸ジ（ステアリルアミド）ジ（オレイルアミド）
４：１，２，４，５－シクロヘキサンテトラカルボン酸テトラ（オレイルアミド）
樹脂
ＥＣ２００：エチルセルロース、商品名「エトセルＳＴＤ２００」、日新化成（株）製
溶剤
ｄｅｃａｎｅ：ｎ－デカン（和光純薬工業（株）製、ＳＰ値：７．６）
ＤＰＭＮＰ：ジプロピレングリコールメチル－ｎ－プロピルエーテル（（株）ダイセル製、ＳＰ値：８．２）
ＣＨＸＡ：シクロヘキシルアセテート（（株）ダイセル製、ＳＰ値：８．９） Abbreviations in Table 1 are as follows.
Thickener 1: 1,2,4,5-cyclohexanetetracarboxylic acid di (2-ethylhexylamide) di (oleylamide)
2: 1,2,4,5-cyclohexanetetracarboxylic acid di (2-ethylhexylamide) di (stearylamide)
3: 1,2,4,5-cyclohexanetetracarboxylic acid di (stearylamide) di (oleylamide)
4: 1,2,4,5-cyclohexanetetracarboxylic acid tetra (oleylamide)
Resin EC200: Ethylcellulose, trade name “Etocel STD200”, manufactured by Nisshin Kasei Co., Ltd. Solvent dekane: n-decane (manufactured by Wako Pure Chemical Industries, Ltd., SP value: 7.6)
DPMNP: Dipropylene glycol methyl-n-propyl ether (manufactured by Daicel Corporation, SP value: 8.2)
CHXA: cyclohexyl acetate (manufactured by Daicel Corporation, SP value: 8.9)
実施例で得られたインクは何れも、比較例で得られたインクより低温で気化した。また、２５０℃の加熱によって、比較例で得られたインクはインク全体の４．６重量％が灰分として残ったのに対し、実施例で得られたインクの残留灰分はインク全体の２．１重量％以下であった。
All the inks obtained in the examples were vaporized at a lower temperature than the inks obtained in the comparative examples. In addition, by heating at 250 ° C., 4.6% by weight of the ink obtained in the comparative example remained as ash, whereas the residual ash of the ink obtained in the example was 2.1% of the total ink. % By weight or less.
本発明の電子デバイス製造用溶剤組成物は、加熱溶解する工程を経て、印刷法による配線等の形成に適した粘性を有するインクを製造することができる。
また、本発明の電子デバイス製造用溶剤組成物を使用して得られるインクは液ダレしにくく、印刷法により高精度の配線パターンを形成することができる。また、焼成工程において、より低温で焼成することができ、被塗布面部材が長時間高温に曝されることにより軟化、変形することを防止できる。更に、焼成後の灰分の残留量を著しく低減することができ、これにより引き起こされていた電気特性の低下を抑制することができる。
従って、本発明の電子デバイス製造用溶剤組成物を使用すれば、印刷法により電気特性に優れた配線等を形成することができ、電気特性に優れた配線等を有する電子デバイスを効率よく製造することができる。 The solvent composition for producing an electronic device of the present invention can produce an ink having a viscosity suitable for forming a wiring or the like by a printing method through a step of dissolving by heating.
Moreover, the ink obtained using the solvent composition for manufacturing an electronic device of the present invention is not easily dripped, and a highly accurate wiring pattern can be formed by a printing method. Moreover, in a baking process, it can bake at lower temperature and it can prevent that a to-be-coated surface member is softened and deform | transformed by being exposed to high temperature for a long time. Furthermore, the residual amount of ash after baking can be remarkably reduced, and the deterioration of electrical characteristics caused by this can be suppressed.
Therefore, if the solvent composition for producing an electronic device of the present invention is used, a wiring having excellent electrical characteristics can be formed by a printing method, and an electronic device having a wiring having excellent electrical characteristics is efficiently produced. be able to.
また、本発明の電子デバイス製造用溶剤組成物を使用して得られるインクは液ダレしにくく、印刷法により高精度の配線パターンを形成することができる。また、焼成工程において、より低温で焼成することができ、被塗布面部材が長時間高温に曝されることにより軟化、変形することを防止できる。更に、焼成後の灰分の残留量を著しく低減することができ、これにより引き起こされていた電気特性の低下を抑制することができる。
従って、本発明の電子デバイス製造用溶剤組成物を使用すれば、印刷法により電気特性に優れた配線等を形成することができ、電気特性に優れた配線等を有する電子デバイスを効率よく製造することができる。 The solvent composition for producing an electronic device of the present invention can produce an ink having a viscosity suitable for forming a wiring or the like by a printing method through a step of dissolving by heating.
Moreover, the ink obtained using the solvent composition for manufacturing an electronic device of the present invention is not easily dripped, and a highly accurate wiring pattern can be formed by a printing method. Moreover, in a baking process, it can bake at lower temperature and it can prevent that a to-be-coated surface member is softened and deform | transformed by being exposed to high temperature for a long time. Furthermore, the residual amount of ash after baking can be remarkably reduced, and the deterioration of electrical characteristics caused by this can be suppressed.
Therefore, if the solvent composition for producing an electronic device of the present invention is used, a wiring having excellent electrical characteristics can be formed by a printing method, and an electronic device having a wiring having excellent electrical characteristics is efficiently produced. be able to.
Claims (9)
- 印刷法によって電子デバイスを製造するためのインクに用いられる溶剤組成物であって、溶剤と下記式（１）
で表される化合物を含む電子デバイス製造用溶剤組成物。 A solvent composition used in an ink for producing an electronic device by a printing method, wherein the solvent and the following formula (1)
The solvent composition for electronic device manufacture containing the compound represented by these. - 式（１）中のＲが炭素数６～１８の直鎖状若しくは分岐鎖状のアルキル基、アルケニル基、又はアルキニル基である請求項１に記載の電子デバイス製造用溶剤組成物。 The solvent composition for producing an electronic device according to claim 1, wherein R in the formula (1) is a linear or branched alkyl group, alkenyl group, or alkynyl group having 6 to 18 carbon atoms.
- 溶剤の２５℃におけるＳＰ値［（ｃａｌ／ｃｍ3）0.5］が７．０～９．０である請求項１又は２に記載の電子デバイス製造用溶剤組成物。 3. The solvent composition for producing an electronic device according to claim 1, wherein the solvent has an SP value [(cal / cm 3 ) 0.5 ] at 25 ° C. of 7.0 to 9.0.
- 溶剤が、ｎ－デカン、ｎ－ドデカン、プロピレングリコールメチル－ｎ－プロピルエーテル、プロピレングリコールメチル－ｎ－ブチルエーテル、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールメチル－ｎ－プロピルエーテル、ジプロピレングリコールメチル－ｎ－ブチルエーテル、ジプロピレングリコールメチルイソアミルエーテル、トリプロピレングリコールメチル－ｎ－プロピルエーテル、シクロヘキシルアセテート、２－メチルシクロヘキシルアセテート、及び４－ｔ－ブチルシクロヘキシルアセテートからなる群より選択される少なくとも１つである請求項１～３の何れか１項に記載の電子デバイス製造用溶剤組成物。 Solvent is n-decane, n-dodecane, propylene glycol methyl-n-propyl ether, propylene glycol methyl-n-butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl-n- 6. At least one selected from the group consisting of butyl ether, dipropylene glycol methyl isoamyl ether, tripropylene glycol methyl-n-propyl ether, cyclohexyl acetate, 2-methylcyclohexyl acetate, and 4-t-butylcyclohexyl acetate. 4. The solvent composition for producing an electronic device according to any one of 1 to 3.
- 式（１）で表される化合物の含有量が、溶剤１００重量部に対して０．１～５０重量部である請求項１～４の何れか１項に記載の電子デバイス製造用溶剤組成物。 The solvent composition for producing an electronic device according to any one of claims 1 to 4, wherein the content of the compound represented by the formula (1) is 0.1 to 50 parts by weight with respect to 100 parts by weight of the solvent. .
- 請求項１～５の何れか１項に記載の電子デバイス製造用溶剤組成物を３０～９０℃で加熱溶解する工程を有する電子デバイス製造用インクの製造方法。 A method for producing an ink for producing an electronic device, comprising a step of heating and dissolving the solvent composition for producing an electronic device according to any one of claims 1 to 5 at 30 to 90 ° C.
- 溶剤と下記式（１）
で表される化合物を含む電子デバイス製造用インク。 Solvent and following formula (1)
The ink for electronic device manufacture containing the compound represented by these. - 更に、導電性金属材料、半導体材料、磁性材料、誘電材料、又は絶縁材料を含む請求項７に記載の電子デバイス製造用インク。 The ink for manufacturing an electronic device according to claim 7, further comprising a conductive metal material, a semiconductor material, a magnetic material, a dielectric material, or an insulating material.
- バインダー樹脂含有量が１０重量％以下である請求項７又は８に記載の電子デバイス製造用インク。 The ink for manufacturing an electronic device according to claim 7 or 8, wherein the binder resin content is 10% by weight or less.
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| JP7113008B2 (en) | 2017-04-28 | 2022-08-04 | 株式会社ダイセル | Electronic device manufacturing solvent composition |
| US11655381B2 (en) | 2017-04-28 | 2023-05-23 | Daicel Corporation | Solvent composition for electronic device production |
| KR102560882B1 (en) * | 2017-04-28 | 2023-07-31 | 주식회사 다이셀 | Solvent composition for electronic device manufacturing |
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| Publication number | Publication date |
|---|---|
| TWI682008B (en) | 2020-01-11 |
| TW201638247A (en) | 2016-11-01 |
| JP6652509B2 (en) | 2020-02-26 |
| JPWO2016125618A1 (en) | 2017-11-09 |
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