JP4389202B2 - Photosensitive conductive paste - Google Patents
Photosensitive conductive paste Download PDFInfo
- Publication number
- JP4389202B2 JP4389202B2 JP2003391807A JP2003391807A JP4389202B2 JP 4389202 B2 JP4389202 B2 JP 4389202B2 JP 2003391807 A JP2003391807 A JP 2003391807A JP 2003391807 A JP2003391807 A JP 2003391807A JP 4389202 B2 JP4389202 B2 JP 4389202B2
- Authority
- JP
- Japan
- Prior art keywords
- metal powder
- powder
- conductive paste
- lightness
- photosensitive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000843 powder Substances 0.000 claims description 122
- 229910052751 metal Inorganic materials 0.000 claims description 84
- 239000002184 metal Substances 0.000 claims description 84
- 239000002245 particle Substances 0.000 claims description 19
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 206010034972 Photosensitivity reaction Diseases 0.000 claims 1
- 230000036211 photosensitivity Effects 0.000 claims 1
- 238000000034 method Methods 0.000 description 24
- 239000011248 coating agent Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 17
- 239000011521 glass Substances 0.000 description 15
- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- 239000011812 mixed powder Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- -1 maleic acid ester Chemical class 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000007650 screen-printing Methods 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 238000000206 photolithography Methods 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000007847 structural defect Effects 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 1
- RUJPNZNXGCHGID-UHFFFAOYSA-N (Z)-beta-Terpineol Natural products CC(=C)C1CCC(C)(O)CC1 RUJPNZNXGCHGID-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 description 1
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical class C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical class NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BVVRPVFKRUVCJX-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)CO Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)CO BVVRPVFKRUVCJX-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910020443 SiO2—PbO—B2O3 Inorganic materials 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- INXWLSDYDXPENO-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CO)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C INXWLSDYDXPENO-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
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- 238000010894 electron beam technology Methods 0.000 description 1
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- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 1
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- 239000007791 liquid phase Substances 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
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- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
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- 150000003505 terpenes Chemical class 0.000 description 1
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- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、感光性導電ペーストに関する。 The present invention relates to a photosensitive conductive paste.
近年、電子機器の小型化や高速信号化に伴い、当該電子機器に備えられる基板や部品等へ形成される導電パターンに対しても、その高密度化、高精細化、高信頼性等の要求がますます高まっており、より一層の導電パターン加工技術の向上が求められている。 In recent years, with the downsizing of electronic devices and the increase in the speed of signals, demands for higher density, higher definition, higher reliability, etc. are also required for conductive patterns formed on substrates and components provided in such electronic devices. However, there is a demand for further improvement in conductive pattern processing technology.
こうした電子機器の一例として、プラズマディスプレイパネル（PDP）がある。PDPは、液晶パネルに比べて高速の表示が可能であり、かつ大型化が容易であることから、壁掛けテレビ等の薄型高品位フルカラー表示装置としても主流に成り得るものとして期待されている。 An example of such an electronic device is a plasma display panel (PDP). A PDP is expected to be mainstream as a thin high-definition full-color display device such as a wall-mounted television because it can display at a higher speed than a liquid crystal panel and can be easily enlarged.
PDPのパネル構造は、典型的には、前面ガラス基板と背面ガラス基板とを一定の空間を隔てて対向させ、この空間内に基板上に設けられるリブ（ガラス隔壁）によって複数のセルが形成され、このセル内に蛍光体が塗布される。一方、基板上には透明電極、バス電極、アドレス電極といった電極が配され、これらの電極間に適宜の電圧を印加することにより、所望のセル内にプラズマ放電を発生させ、各セル内に封入されているNe、Xe等の放電ガスの放電により生じる紫外線によって当該セル内の蛍光体が励起され、３原色の可視光を発生させるようになっている。 In a PDP panel structure, typically, a front glass substrate and a back glass substrate are opposed to each other with a certain space therebetween, and a plurality of cells are formed in the space by ribs (glass partition walls) provided on the substrate. In this cell, a phosphor is applied. On the other hand, electrodes such as transparent electrodes, bus electrodes, and address electrodes are arranged on the substrate. By applying an appropriate voltage between these electrodes, plasma discharge is generated in a desired cell and enclosed in each cell. The phosphor in the cell is excited by the ultraviolet rays generated by the discharge of the discharge gas such as Ne, Xe, and the like, and the visible light of the three primary colors is generated.
従来、こうしたバス電極やアドレス電極を得るには、有機バインダーにAgなどの金属粉末やガラスフリット等を分散、混練した導電ペーストを、電極に対応するパターンを備える印刷マスクを用いてガラス基板上に印刷し、その後の焼成工程において有機バインダーを飛散させる所謂スクリーン印刷法が知られている。しかしながら、スクリーン印刷法ではマスクパターン精度、ペーストの粘性、印刷速度、分散性などの最適化を図っても、工業的に安定して導電パターンの幅を100μm以下に細くするということができず、作成可能なファインパターンには限界があった。また、スクリーン印刷による方法では、印刷マスクの精度は、マスク製版の精度に依存するので、印刷マスクが大きくなるとマスクパターンの寸法誤差が大きくなってしまう。このため30インチ以上の大面積のPDPの場合に、高精細のPDPの生産はますます技術的に困難となっている。 Conventionally, in order to obtain such bus electrodes and address electrodes, a conductive paste in which a metal powder such as Ag or glass frit is dispersed and kneaded in an organic binder is applied to a glass substrate using a printing mask having a pattern corresponding to the electrodes. A so-called screen printing method in which an organic binder is scattered in a subsequent baking process is known. However, even if the screen printing method is optimized for mask pattern accuracy, paste viscosity, printing speed, dispersibility, etc., the width of the conductive pattern cannot be reduced to 100 μm or less in an industrially stable manner. There are limits to the fine patterns that can be created. Further, in the screen printing method, the accuracy of the printing mask depends on the accuracy of the mask plate making. Therefore, when the printing mask becomes large, the dimensional error of the mask pattern becomes large. For this reason, in the case of a PDP having a large area of 30 inches or more, the production of a high-definition PDP becomes increasingly technically difficult.
そこで、スクリーン印刷法よりも精細な導電パターンを得る方法として、感光性の樹脂組成物に金属粉末を混合した感光性導電ペーストを用いて導電パターンを生成する所謂フォトリソグラフィ法が知られている（特許文献１，２）。 Therefore, as a method for obtaining a finer conductive pattern than the screen printing method, a so-called photolithography method is known in which a conductive pattern is generated using a photosensitive conductive paste in which a metal powder is mixed with a photosensitive resin composition ( Patent Documents 1 and 2).
すなわち、フォトリソグラフィ法においては、ガラス基板上に感光性導電ペーストを塗布乾燥した後、形成すべき所定の導電パターンに対応するフォトマスクを介して光を照射し、塗膜の露光部分を硬化させ、現像液で現像して塗膜の非露光部分を除去した後、高温で焼成することにより導電パターンを作成する。このフォトリソグラフィ法によれば、スクリーン印刷法に比べて高精細な導電パターンを得ることができる。 That is, in the photolithography method, after applying and drying a photosensitive conductive paste on a glass substrate, light is irradiated through a photomask corresponding to a predetermined conductive pattern to be formed, and the exposed portion of the coating film is cured. Then, after developing with a developing solution to remove the non-exposed portion of the coating film, the conductive pattern is prepared by baking at a high temperature. According to this photolithography method, a high-definition conductive pattern can be obtained as compared with the screen printing method.
高導電性の導電パターンを得るためには、ペースト中の金属粉末の含有比率を高くする必要がある。ところが、前記のフォトリソグラフィ法の場合には、ペースト中の金属粉末の含有比率を上げると、塗膜の厚み方向への照射光の透過率が低くなるというジレンマがある。 In order to obtain a highly conductive pattern, it is necessary to increase the content ratio of the metal powder in the paste. However, in the case of the photolithography method, there is a dilemma that when the content ratio of the metal powder in the paste is increased, the transmittance of irradiation light in the thickness direction of the coating film is lowered.
すなわち、高導電性にするためにペースト中の金属粉末の含有比率を上げると、露光工程においてその金属粉末により塗膜の内部（深部）にまで十分な露光が行われにくくなり、その結果、膜厚方向の内部での硬化が不十分な部分が残ったまま現像が行われ、その結果、焼成後の導電パターンに欠けが生じたり、断線や亀裂等の構造欠陥が数多く生じて導電性及びファインライン性が共に悪くなるという問題が発生する。 That is, when the content ratio of the metal powder in the paste is increased in order to make it highly conductive, it becomes difficult for the metal powder to sufficiently expose the inside (deep part) of the coating film in the exposure process. Development is carried out with a portion that is insufficiently cured inside the thickness direction, resulting in chipping of the conductive pattern after firing, and numerous structural defects such as disconnection and cracks. There is a problem that both line properties deteriorate.
そこで塗膜内部を十分に硬化させるため、照射光を長時間照射すると、今度は反応で生成したラジカルや活性種の拡散が進んでしまい、導電パターンの解像度を下げる原因となっていた。 Therefore, when the irradiation light is irradiated for a long time in order to sufficiently cure the inside of the coating film, the diffusion of radicals and active species generated by the reaction proceeds, causing the resolution of the conductive pattern to be lowered.
これらの問題を解決すべく、例えば上述の特許文献１，２に記載された発明にあっては、感光性導電ペースト内に紫外線吸収剤を含有させたり、感光性の樹脂組成を調製したり、従来から様々な工夫が行われてきてはいるが、未だ十分な解決には至っていない。 In order to solve these problems, for example, in the inventions described in Patent Documents 1 and 2 described above, an ultraviolet absorber is contained in the photosensitive conductive paste, a photosensitive resin composition is prepared, Although various ideas have been made so far, it has not yet been solved sufficiently.
上述のように、導電パターンの高精細化に対する要求は高まる一方であり、昨今では、最小線幅20μm以下、最小線間隔が60μm以下のファインラインが求められるようになってきているが、その一方で、導電パターンの高導電性は達成しなければならない。 As described above, there is an increasing demand for higher definition conductive patterns. Recently, fine lines with a minimum line width of 20 μm or less and a minimum line spacing of 60 μm or less have been demanded. Therefore, high conductivity of the conductive pattern must be achieved.
そこで、本発明は、活性光に対する硬化性に優れ、高精細ながらも、低抵抗な導電パターンを得るのに好適な感光性導電ペーストを提供することを目的とする。 Accordingly, an object of the present invention is to provide a photosensitive conductive paste that is excellent in curability for active light and is suitable for obtaining a conductive pattern having a high resistance and a low resistance.
本発明の要旨は、少なくとも金属粉末と感光性有機成分を含有する感光性導電ペースト及びこの感光性導電ペーストに用いられる金属粉末に関し、この金属粉末は、Ag粉末、Agを主とした合金粉末、又は、その表面にAg若しくはAg合金を被覆した粉末から選択される何れか１種以上であって、JIS規格Z8722に従い測定されるＬ*ａ*ｂ*表色系の明度Ｌ*（以下単に「明度Ｌ*」と称する）が60以上であり、且つ、平均粒径が5μm以下であることを特徴とする。 The gist of the present invention relates to a photosensitive conductive paste containing at least a metal powder and a photosensitive organic component, and a metal powder used in the photosensitive conductive paste. The metal powder is an Ag powder, an alloy powder mainly composed of Ag, Alternatively, the lightness L * of the L * a * b * color system measured according to JIS standard Z8722 is one or more selected from powders coated with Ag or an Ag alloy on the surface (hereinafter simply referred to as “ Lightness L * ”) is 60 or more, and the average particle size is 5 μm or less.
また前記金属粉末は、明度Ｌ*が60以上の第１の金属粉末と、明度Ｌ*が60未満の第２の金属粉末を混合したものであっても良く、この場合、第２の金属粉末の明度Ｌ*は40以上であることが好ましく、更には、第１及び第２の金属粉末の総量に対する第２の金属粉末の含有比率が30重量％（wt％）以下であることが好ましい。 The metal powder may be a mixture of a first metal powder having a lightness L * of 60 or more and a second metal powder having a lightness L * of less than 60. In this case, the second metal powder The lightness L * is preferably 40 or more, and the content ratio of the second metal powder to the total amount of the first and second metal powders is preferably 30% by weight (wt%) or less.
更に好ましくは、金属粉末の明度Ｌ*は70以上である。 More preferably, the lightness L * of the metal powder is 70 or more.
本発明によれば、フォトリソグラフィ技術を用いて導電パターンを形成する材料としての感光性導電ペーストにおいて、ペースト中の導電成分としての金属粉末の特性の最適化を目指した結果、活性光に対する硬化性に優れ、高精細で高導電性の導電パターンを効率よく形成できる感光性導電ペーストが得られたものである。 According to the present invention, in a photosensitive conductive paste as a material for forming a conductive pattern using photolithography technology, the result of the optimization of the characteristics of the metal powder as the conductive component in the paste is the result In this way, a photosensitive conductive paste that can form a conductive pattern with excellent and high definition and high conductivity can be obtained.
より詳細には、本発明に係る金属粉末は、Ag粉末、Agを主とした合金粉末、又は、その表面にAg若しくはAg合金を被覆した粉末から選択される何れか１種以上であって、JIS規格Z8722に従い測定されるＬ*ａ*ｂ*表色系の明度Ｌ*が60以上で、且つ、平均粒径が5μm以下であり、この条件を満たす金属粉末を感光性導電ペースト中の導電成分として用いることにより光硬化性が向上し、その結果として、例えば当該条件範囲外の金属粉末を用いる感光性導電ペーストと比べた場合に同じ感光性有機成分や添加物を用いても2/3〜1/20程度の活性光照射量で光硬化させることができる。 More specifically, the metal powder according to the present invention is one or more selected from Ag powder, alloy powder mainly composed of Ag, or powder coated with Ag or Ag alloy on the surface thereof, The L * a * b * color system brightness L * measured according to JIS standard Z8722 is 60 or more and the average particle size is 5 μm or less. As a result, the photocurability is improved, and as a result, even if the same photosensitive organic components and additives are used as compared with a photosensitive conductive paste using a metal powder outside the range of the condition, for example, 2/3 It can be photocured with an active light irradiation amount of about 1/20.
それ故、従来の感光性導電ペーストと比べ、露光時間を大幅に短縮でき、ラジカル拡散を抑えることができるため、解像度の高い導電パターンを形成することが可能となった。 Therefore, compared with the conventional photosensitive conductive paste, the exposure time can be greatly shortened and radical diffusion can be suppressed, so that a conductive pattern with high resolution can be formed.
また、本発明に係る感光性導電ペーストは、露光工程において塗膜の内部にまで十分硬化されるため、焼成後の導電パターンに欠けが生じて断線や亀裂等の構造欠陥が発生するといった問題がないため、精細且つ導電性の優れた導電パターンを形成することが可能となった。 In addition, since the photosensitive conductive paste according to the present invention is sufficiently cured to the inside of the coating film in the exposure process, there is a problem that the conductive pattern after baking is chipped and structural defects such as disconnection and cracking occur. Therefore, it is possible to form a conductive pattern that is fine and has excellent conductivity.
更に、本発明に係る感光性導電ペーストは、露光時の硬化性に優れるため、従来よりも金属粉末の含有量を多くすることも可能であり、その結果、緻密で高導電性の導電パターンを得ることができるようになる。 Furthermore, since the photosensitive conductive paste according to the present invention is excellent in curability at the time of exposure, it is possible to increase the content of the metal powder as compared with the conventional case. As a result, a dense and highly conductive conductive pattern can be obtained. Be able to get.
また、本発明に用いられる金属粉末として、明度Ｌ*が60以上の第１の金属粉末と、明度Ｌ*が40以上60未満の第２の金属粉末を混合した場合には、上述した効果に加え、抵抗値や塗膜特性、焼成膜特性、ハンダ付性、等々といった導電パターンの特性をコントロールしやすくなり、導電ペーストの設計自由度を高めることも可能となる。 In addition, when the first metal powder having a lightness L * of 60 or more and the second metal powder having a lightness L * of 40 or more and less than 60 are mixed as the metal powder used in the present invention, the above-described effect is obtained. In addition, it becomes easy to control the characteristics of the conductive pattern such as resistance value, coating film characteristics, fired film characteristics, solderability, and the like, and it is possible to increase the degree of freedom in designing the conductive paste.
〔(1)金属粉末〕
本発明において使用される金属粉末は、導電性を有するものであり、例えば、Ag、Au、Pt、Pd、Cu、Ni、Alから選ばれる金属粉末又はこれらの金属を含む合金粉末であっても良い。また、金属や非金属の粉末表面に他の金属を被覆した被覆複合金属粉末であっても良く、更にはこれらの金属粉末の２種以上の混合粉であっても良い。
[(1) Metal powder]
The metal powder used in the present invention has conductivity, for example, a metal powder selected from Ag, Au, Pt, Pd, Cu, Ni, Al or an alloy powder containing these metals. good. Further, it may be a coated composite metal powder obtained by coating a metal or non-metal powder surface with another metal, and may be a mixed powder of two or more of these metal powders.
本発明において金属粉末としては、Ag、又はAgを主成分とする合金、若しくは、Ag又はAg合金の被覆金属粉が必須成分として用いられる。
In the present invention, as the metal powder, Ag or an alloy containing Ag as a main component, or a coated metal powder of Ag or an Ag alloy is used as an essential component .
また、金属粉末としては、上述したAg以外の金属粉末に対し、その表面にAg又はAg合金を被覆したものであっても良い。Agの被覆方法としては、粉末の明度Ｌ*が60以上という条件を満たす限り、従来公知の方法を用いることが可能である。本発明に係る金属粉末は、その明度Ｌ*はいずれも60以上である。 In addition, the metal powder may be a metal powder other than Ag described above, the surface of which is coated with Ag or an Ag alloy. As a method of coating Ag, a conventionally known method can be used as long as the lightness L * of the powder satisfies the condition of 60 or more. The lightness L * of the metal powder according to the present invention is 60 or more.
本発明では、明度Ｌ*が60以上の金属粉末（以下、第１の金属粉末）と、明度Ｌ*が60未満の金属粉末（第２の金属粉末）とを混合したものを用いても良い。 In the present invention, a mixture of a metal powder having a lightness L * of 60 or more (hereinafter referred to as a first metal powder) and a metal powder having a lightness L * of less than 60 (second metal powder) may be used. .
第１の金属粉末のみを単独で用いる場合と比べ、第２の金属粉末を混合させた方が、得られる導電パターンの特性、例えば、抵抗値や塗膜特性、焼成膜特性、ハンダ付性、等々に関してコントロールしやすくなり、導電ペーストとしての設計自由度が高まる。 Compared to the case where only the first metal powder is used alone, the mixture of the second metal powder has characteristics of the obtained conductive pattern, for example, resistance value, coating film characteristic, fired film characteristic, solderability, Etc., and the degree of freedom of design as a conductive paste increases.
なお、第２の金属粉末として明度Ｌ*が40よりも小さい金属粉末を使用することも可能ではあるが、その場合、金属粉末全体の明度Ｌ*を60以上にするために第１の金属粉末の含有比率を高くしなければならなくなり、混合粉とする効果が薄れる。その為、混合粉とする場合には、第２の金属粉末としては明度Ｌ*が40以上60未満のものを用いることが好ましい。 Although it is possible to use a metal powder having a lightness L * smaller than 40 as the second metal powder, in this case, in order to make the lightness L * of the entire metal powder 60 or more, the first metal powder Therefore, the effect of the mixed powder is reduced. Therefore, when the mixed powder is used, it is preferable to use the second metal powder having a lightness L * of 40 or more and less than 60.
なお、金属粉末全体に対する第２の金属粉末の比率が高くなると、金属粉末全体の明度Ｌ*が低くなって露光硬化しにくくなる他、焼成後のパターン精度が低下したり、比抵抗が高くなる場合がある。それ故、第１と第２の金属粉末を混合する場合には、第２の金属粉末が第１と第２の金属粉末の合計量の30重量％以下であることが望ましい。 Note that when the ratio of the second metal powder to the entire metal powder is increased, the brightness L * of the entire metal powder is decreased and exposure hardening is difficult, and the pattern accuracy after baking is decreased and the specific resistance is increased. There is a case. Therefore, when mixing the first and second metal powders, it is desirable that the second metal powder is 30% by weight or less of the total amount of the first and second metal powders.
本発明において、金属粉末の明度Ｌ*は、更に好ましくは70以上である。 In the present invention, the lightness L * of the metal powder is more preferably 70 or more.
本発明において、金属粉末の明度Ｌ*は、高ければ高いほど好ましい。金属粉末の明度Ｌ*を高くするためには、金属粉末の平均粒径は大きい方が有利であるが、本発明においては、金属粉末の平均粒径は5μm以下でなければならない。平均粒径が5μmを越えると印刷後の導電パターンの表面が粗くなり、パターン精度や寸法精度が低下する。 In the present invention, the lightness L * of the metal powder is preferably as high as possible. In order to increase the lightness L * of the metal powder, it is advantageous that the average particle size of the metal powder is large. However, in the present invention, the average particle size of the metal powder must be 5 μm or less. When the average particle diameter exceeds 5 μm, the surface of the conductive pattern after printing becomes rough, and the pattern accuracy and dimensional accuracy decrease.
また、金属粉末の平均粒径は0.1μm以上であることが好ましい。平均粒子径が0.1μm未満になると、凝集しやすくなるため、ペースト中での分散性や安定性が低下し、更にペーストとして保存中に参加が進行しやすくなり、ペーストの保存性も低下する他、粒子内や粒子間で照射光の複雑な反射を繰り返して反射率が小さくなるため、明度Ｌ*も低下する。 The average particle size of the metal powder is preferably 0.1 μm or more. If the average particle size is less than 0.1 μm, it tends to agglomerate, so the dispersibility and stability in the paste will be reduced, and further participation will be facilitated during storage as a paste, and the storage stability of the paste will also be reduced. The lightness L * is also reduced because the reflectance is reduced by repeating complicated reflection of the irradiation light within the particles or between the particles.
本発明に係る金属粉末の好ましい平均粒径は0.1μm以上5μm以下であり、より好ましくは0.5μm以上3μm以下、更に好ましくは1μm以上2μm以下である。 The preferred average particle size of the metal powder according to the present invention is 0.1 μm or more and 5 μm or less, more preferably 0.5 μm or more and 3 μm or less, and further preferably 1 μm or more and 2 μm or less.
金属粉末の形状としては、フレーク状や樹枝形状のものも使用できるが、本発明においては、凝集無く、表面の平滑な球状粒子であることが望ましい。 As the shape of the metal powder, flakes and dendrites can be used, but in the present invention, spherical particles having a smooth surface without aggregation are desirable.
こうした金属粉末は気相法や液相化学還元法によっても製造することは可能であるが、特公昭63-31522号公報等に記載されているような噴霧熱分解法や、もしくは、本出願人が先に出願した特願2001-108533（特開2002-20809号公報）や特願2002-264750に記載されている製造方法により製造されたものであることが特に好ましい。 Such a metal powder can be produced by a gas phase method or a liquid phase chemical reduction method, but the spray pyrolysis method described in Japanese Patent Publication No. 63-31522 or the present applicant Is preferably manufactured by the manufacturing method described in Japanese Patent Application No. 2001-108533 (Japanese Patent Laid-Open No. 2002-20809) or Japanese Patent Application No. 2002-264750 filed earlier.
特願2001-108533や特願2002-264750には、熱分解性の金属化合物粉末の１種又は２種以上を、キャリアガスを用いて反応容器に供給し、該金属化合物粉末を気相中に分散させた状態で、その分解温度より高く、且つ、該金属の融点をTm℃としたときに（Tm−200）℃以上の温度で加熱し、金属化合物粉末を熱分解させて金属粉末を製造する、金属粉末の製造方法が記載されている。 In Japanese Patent Application Nos. 2001-108533 and 2002-264750, one or more types of thermally decomposable metal compound powders are supplied to a reaction vessel using a carrier gas, and the metal compound powders are put into the gas phase. In a dispersed state, when the melting point of the metal is Tm ° C., the metal compound powder is heated to a temperature of (Tm−200) ° C. or higher to thermally decompose the metal compound powder to produce a metal powder. A method for producing a metal powder is described.
これらの製造方法で製造される金属粉末は、「極めて粒度分布が狭く、凝集のない球状の一次粒子である。」「表面が平滑で、高密度、高分散性である。」「結晶性が良好で粒子内部に欠陥が少なく、微粉末であるにも関わらず金属表面の活性が低いため酸化されにくく、それ故、ペーストとして保存中にも酸化されにくく、明度が劣化しない。」といった特徴を備える。 The metal powders produced by these production methods are “spherical primary particles with a very narrow particle size distribution and no aggregation.” “Smooth surface, high density and high dispersibility.” “Crystallinity” It is good and has few defects inside the particles, and although it is a fine powder, it is difficult to oxidize because of its low activity on the metal surface. Therefore, it is difficult to oxidize even during storage as a paste, and brightness does not deteriorate. ” Prepare.
それ故、これらの製造方法によれば、小粒径の球状粉で凝集がなく、しかも、明度Ｌ*が６０以上、特に７０以上の金属粉末を容易に得ることができるため、当該製造方法により得られる金属粉末は、本発明において特に好適に用いることができる。 Therefore, according to these production methods, a metal powder having a small particle size of spherical powder without aggregation and having a lightness L * of 60 or more, particularly 70 or more can be easily obtained. The obtained metal powder can be particularly preferably used in the present invention.
〔(2)感光性有機成分、添加剤等〕
本発明に係る感光性導電ペーストに用いられる感光性有機成分は、特に限定されることはなく、従来から感光性導電ペーストにおいて用いられてきた公知の光重合性または光変性化合物を用いることができ、例えば感光性のモノマー又はポリマーやオリゴマー等で構成される。
[(2) Photosensitive organic components, additives, etc.]
The photosensitive organic component used in the photosensitive conductive paste according to the present invention is not particularly limited, and a known photopolymerizable or photo-modifying compound conventionally used in photosensitive conductive paste can be used. For example, a photosensitive monomer or polymer or oligomer.
感光性モノマーの一例としては、不飽和基などの反応性官能基を有する光ラジカル重合性モノマーを含むものを用いることができ、例えば、アクリル基、メタアクリル基、アクリルアミド基、マレイン酸エステル、ビニル基、ビニルアミノ基、アリル基、アセチレン性不飽和基、等々の官能基を分子内に含有する化合物を挙げることができる。特に、重合性の観点からは、多官能性アクリレートまたは多官能性メタアクリレートモノマーが好ましい。 As an example of the photosensitive monomer, one containing a radically polymerizable monomer having a reactive functional group such as an unsaturated group can be used. For example, an acrylic group, a methacrylic group, an acrylamide group, a maleic acid ester, vinyl And compounds containing a functional group such as a group, vinylamino group, allyl group, acetylenically unsaturated group, etc. in the molecule. In particular, from the viewpoint of polymerizability, a polyfunctional acrylate or polyfunctional methacrylate monomer is preferable.
一例としては、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、テトラエチレングリコールジアクリレート等のポリエチレングリコールジアクリレート、あるいはポリウレタンジアクリレート類およびそれ等に対応するメタクリレート類；ペンタエリスリトールトリアクリレート、トリメチロールプロパントリアクリレート、トリメチロールメタントリアクリレート、エチレンオキシド変性トリメチロールプロパントリアクリレート、プロピレンオキシド変性トリメチロールプロパントリアクリレート、エピクロルヒドリン変性トリメチロールプロパントリアクリレート、ペンタエリスリトールテトラアクリレート、ペンタエリスリトールテトラメタアクリレート、テトラメチロールメタンテトラアクリレート、エチレンオキシド変性リン酸トリアクリレート、エピクロルヒドリン変性グリセロールトリアクリレート、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールモノヒドロキシペンタアクリレート、等々に代表される多官能アクリレートあるいはそれ等に対応するメタアクリレートモノマーを選択することができる。 Examples include polyethylene glycol diacrylates such as diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, or polyurethane diacrylates and corresponding methacrylates; pentaerythritol triacrylate, trimethylolpropane triacrylate , Trimethylol methane triacrylate, ethylene oxide modified trimethylol propane triacrylate, propylene oxide modified trimethylol propane triacrylate, epichlorohydrin modified trimethylol propane triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, tetramethylol methane tetraacrylate A polyfunctional acrylate represented by ethylene oxide-modified phosphoric acid triacrylate, epichlorohydrin-modified glycerol triacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, etc. or a methacrylate monomer corresponding to them. it can.
これら以外に、不飽和カルボン酸等の不飽和酸を加えることもでき、その場合には感光後の現像性を向上させることができる。不飽和カルボン酸の一例としては、アクリル酸、メタクリル酸、マレイン酸、フマル酸、ビニル酢酸、およびこれらの無水物が挙げられる。 In addition to these, an unsaturated acid such as an unsaturated carboxylic acid can also be added. In this case, the developability after exposure can be improved. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, vinyl acetic acid, and anhydrides thereof.
感光性ポリマーやオリゴマーの一例としては、上記したモノマーの少なくとも１種類を重合して得られたポリマーやオリゴマーの側鎖又は分子末端に官能基を付加させたものを用いることができる。 As an example of the photosensitive polymer or oligomer, a polymer or oligomer obtained by polymerizing at least one of the above-described monomers can be used in which a functional group is added to the side chain or molecular end of the polymer or oligomer.
更に感光性導電ペースト中には、必要に応じて、溶剤、光重合開始剤が加えられる。 Furthermore, a solvent and a photopolymerization initiator are added to the photosensitive conductive paste as necessary.
溶剤としては、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、エチレングリコール、プロピレングリコール等のアルコール類や、α−もしくはβ−テルピネオール等のテルペン類等、アセトン、メチルエチルケトン、シクロヘキサノン、Ｎ−メチル−２−ピロリドン、ジエチルケトン、２−ヘプタノン、４−ヘプタノン等のケトン類、トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類、等々を挙げることができ、これらの１種または２種以上を使用することができる。 Solvents include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, terpenes such as α- or β-terpineol, acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone , Ketones such as diethyl ketone, 2-heptanone, 4-heptanone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, and the like, and using one or more of these Can do.
光重合開始剤としては、例えば、ベンゾインとベンゾインアルキルエーテル類、アセトフェノン類、アミノアセトフェノン類、アントラキノン類、チオキサントン類、ケタール類、ベンゾフェノン類、キサントン類、フォスフィンオキサイド類、各種パーオキサイド類などが挙げられ、これら公知慣用の光重合開始剤を単独でまたは２種以上を組み合わせて用いることができる。 Examples of the photopolymerization initiator include benzoin and benzoin alkyl ethers, acetophenones, aminoacetophenones, anthraquinones, thioxanthones, ketals, benzophenones, xanthones, phosphine oxides, and various peroxides. These known and commonly used photopolymerization initiators can be used alone or in combination of two or more.
更に、感光性導電ペースト中には、必要に応じてガラスフリット等の無機成分を含有させてもよい。 Further, the photosensitive conductive paste may contain an inorganic component such as glass frit as necessary.
ガラスフリットとしては、ホウケイ酸系ガラス粉末等の公知のガラス粉末を使用することができ、例えばSiO2−PbO系、SiO2−ZnO系、SiO2−Bi2O3系、SiO2−K2O系、SiO2−Na2O系、SiO2−PbO−B2O3系、SiO2−ZnO−B2O3系、SiO2−Bi2O3−B2O3系、SiO2−K2O−B2O3系、SiO2−Na2O−B2O3系などのガラス粉末を用いることができる。 As the glass frit, known glass powders such as borosilicate glass powder can be used. For example, SiO 2 —PbO system, SiO 2 —ZnO system, SiO 2 —Bi 2 O 3 system, SiO 2 —K 2 O-based, SiO 2 -Na 2 O-based, SiO 2 -PbO-B 2 O 3 system, SiO 2 -ZnO-B 2 O 3 system, SiO 2 -Bi 2 O 3 -B 2 O 3 system, SiO 2 - Glass powders such as K 2 O—B 2 O 3 and SiO 2 —Na 2 O—B 2 O 3 can be used.
感光性導電ペースト中には、更に必要に応じて、その他、シリコーン系やアクリル系等の消泡剤、レベリング剤、密着性向上のためのカップリング剤、増感剤、重合禁止剤、増粘剤、沈殿防止剤、上記特許文献１に記載されているような紫外線吸収剤等々の添加剤を加えても良い。 In the photosensitive conductive paste, if necessary, other antifoaming agents such as silicones and acrylics, leveling agents, coupling agents for improving adhesion, sensitizers, polymerization inhibitors, thickeners. You may add additives, such as an agent, a precipitation inhibitor, and an ultraviolet absorber as described in the said patent document 1. FIG.
〔(3)感光性導電ペーストの製造、導電膜（導電パターン）の製造〕
上述した金属粉末、感光性有機成分及び必要に応じて添加される添加成分は、三本ロールミルやブレンダー等の機械を用いて混練分散させることによりペーストが得られる。得られた感光性導電ペーストは、スクリーン印刷法、バーコーター、ブレードコーターなど適宜の塗布方法でセラミックガラス基材、例えばPDPの背面ガラス基板上に塗布され、約60〜120℃で5〜60分程度乾燥される。
[(3) Production of photosensitive conductive paste, production of conductive film (conductive pattern)]
A paste can be obtained by kneading and dispersing the metal powder, the photosensitive organic component, and the additive component added as necessary using a machine such as a three-roll mill or a blender. The obtained photosensitive conductive paste is applied on a ceramic glass substrate, for example, a back glass substrate of PDP by an appropriate application method such as screen printing, bar coater, blade coater, and about 60 to 120 ° C. for 5 to 60 minutes. Dehydrated to a degree.
次に、形成すべき導電パターンに対応するフィルムやネガマスクを介して、上記塗布された塗膜に対して光を照射し、露光部分を光硬化させる。この際に使用される活性光としては、紫外線、電子線、Ｘ線などが挙げられるが、これらの中では紫外線が好ましく、その光源としては、ハロゲンランプ、低圧水銀灯、高圧水銀灯、殺菌灯等が使用される。 Next, light is irradiated to the applied coating film through a film or a negative mask corresponding to the conductive pattern to be formed, and the exposed portion is photocured. Examples of the active light used in this case include ultraviolet rays, electron beams, and X-rays. Among these, ultraviolet rays are preferable, and examples of the light source include halogen lamps, low-pressure mercury lamps, high-pressure mercury lamps, and germicidal lamps. used.
次に、現像液を用いて硬化されていない塗膜を除去する。現像は、浸漬法やスプレー法等で行う。現像液としては、前述の感光性有機成分が分解可能な有機溶媒を使用することができる。例えば、感光性有機成分中に、酸性基を持つ化合物が存在する場合、水酸化ナトリウムや炭酸ナトリウムなどの金属アルカリ水溶液の他、モノエタノールアミン、ジエタノールアミンなどの有機アルカリ水溶液を用いることができる。また、現像後に不要な現像液の除去のため、水洗や酸中和を行う。 Next, the uncured coating film is removed using a developer. Development is performed by an immersion method, a spray method, or the like. As the developer, an organic solvent capable of decomposing the photosensitive organic component described above can be used. For example, when a compound having an acidic group is present in the photosensitive organic component, an organic alkali aqueous solution such as monoethanolamine or diethanolamine can be used in addition to a metal alkali aqueous solution such as sodium hydroxide or sodium carbonate. In addition, washing and acid neutralization are performed to remove unnecessary developer after development.
そして、露光、現像後の塗膜を、約400〜900℃で5分〜１時間程度焼成し、感光性有機成分や光重合開始剤等々の有機物を完全に分解、飛散させて除去し、導電パターンを得ることができる。なお、焼成時の雰囲気は使用する金属粉末に応じて、酸化性雰囲気か非酸化性雰囲気中かが適宜選択される。 Then, the coated film after exposure and development is baked at about 400 to 900 ° C. for about 5 minutes to 1 hour, and organic substances such as the photosensitive organic component and the photopolymerization initiator are completely decomposed and scattered to remove the conductive film. A pattern can be obtained. Note that the atmosphere during firing is appropriately selected from an oxidizing atmosphere and a non-oxidizing atmosphere depending on the metal powder to be used.
なお、ここでは感光性導電ペーストを現像後に焼成しているが、本発明はこれに限定されるものではなく、露光、現像後に非焼成のまま導電性を呈するものも含まれる。 Here, although the photosensitive conductive paste is baked after development, the present invention is not limited to this, and includes those that exhibit conductivity without being baked after exposure and development.
以上のようにして本発明に係る感光性導電ペーストを用い導電パターンを形成した場合、焼成後の導電パターンの導体膜の厚みが15μm前後で、導体の最小線幅が20μm以下、導体間の最小線間隔60μm以下の高精細の導電パターンを得ることも可能となった。 When the conductive pattern is formed using the photosensitive conductive paste according to the present invention as described above, the thickness of the conductive film of the conductive pattern after baking is around 15 μm, the minimum line width of the conductor is 20 μm or less, and the minimum between conductors It was also possible to obtain a high-definition conductive pattern with a line spacing of 60 μm or less.
本発明を以下の実施例に基づいてより具体的に説明するが、これに限定されるものではない。 The present invention will be more specifically described based on the following examples, but is not limited thereto.
〔金属粉末〕
感光性導電ペースト用の金属粉末として、表１の４種類のAg粉末A〜Dを用意した。
[Metal powder]
Four types of Ag powders A to D shown in Table 1 were prepared as metal powders for the photosensitive conductive paste.
ここで、粉末Aは、特願2002-264750に記載された方法で製造されたものである。すなわち、炭酸銀粉末を気流式粉砕機で解砕して平均粒径約１μm、最大粒径約３μmの原料粉末を調製し、この粉末を、キャリヤガスとして流量200l／分の空気を随伴させ、５Kg／時間の供給速度で、開口部の断面積0.13cm2のノズルを通して、電気炉で約1000℃に加熱された反応管中に噴出させ、反応管内における気相中の原料粉末分散濃度を0.4g／lに保ったままで反応管を通過させて加熱し、生成した粉末をバグフィルターで捕集することにより、粉末Aを製造した。 Here, the powder A is produced by the method described in Japanese Patent Application No. 2002-264750. That is, a silver carbonate powder is crushed by an airflow type pulverizer to prepare a raw material powder having an average particle size of about 1 μm and a maximum particle size of about 3 μm. At a feed rate of 5 kg / hour, it is blown into a reaction tube heated to about 1000 ° C. in an electric furnace through a nozzle having a sectional area of 0.13 cm 2 , and the raw material powder dispersion concentration in the reaction tube is 0.4. The powder A was manufactured by passing the reaction tube through the reaction tube while maintaining it at g / l and heating, and collecting the produced powder with a bag filter.
また、粉末B〜Dは化学還元法により得られたものである。 Powders B to D were obtained by a chemical reduction method.
なお、ここで明度Ｌ*は、JIS規格Z8722（色の測定方法−反射及び透過物体色）に従い測定されるＬ*ａ*ｂ*表色系の明度Ｌ*を指し、以下においては、このJIS規格Z8722に準拠する測色色差計〔ND-1001PP：日本電色工業(株)製〕を用い測定して値を得た。 Here, the lightness L * is, JIS Standard Z8722 - refers to (color measuring method of reflection and transmission object color) is measured in accordance with L * a * b * color system of lightness L *, in the following, this JIS A colorimetric color difference meter [ND-1001PP: manufactured by Nippon Denshoku Industries Co., Ltd.] based on the standard Z8722 was used to obtain a value.
また、比表面積はBET法で測定し、平均粒径は粒度分布計で測定した。 The specific surface area was measured by the BET method, and the average particle size was measured by a particle size distribution meter.
〔硬化特性に関する評価〕
(1)導電パターンの作成
以下、含有する金属粉末のみが異なる８種類の感光性Agペーストを調製して評価を行った。
[Evaluation of curing characteristics]
(1) Preparation of conductive pattern Hereinafter, eight types of photosensitive Ag pastes differing only in the contained metal powder were prepared and evaluated.
先ず上記の粉末A〜Dの各100重量部に対して、それぞれ、紫外線硬化樹脂を30重量部、SiO2-Bi2O3-B2O3系の低融点ガラスフリットを1重量部、溶剤を5重量部、その他添加剤を4重量部加えて３本ロールミルで混練し、各粉末A〜Dをそれぞれ含む４種類の感光性Agペーストを調製した。 First, for each 100 parts by weight of the powders A to D, 30 parts by weight of an ultraviolet curable resin, 1 part by weight of a SiO 2 —Bi 2 O 3 —B 2 O 3 low melting point glass frit, and a solvent 5 parts by weight and 4 parts by weight of other additives were added and kneaded with a three-roll mill to prepare four types of photosensitive Ag pastes containing each of powders A to D.
次に上記の粉末Bと粉末Cとの混合比率を変えて４種類の混合粉を作り、上記と同様に、各混合粉100重量部に対して、それぞれ、紫外線硬化樹脂を30重量部、SiO2-Bi2O3-B2O3系の低融点ガラスフリットを1重量部、溶剤を5重量部、その他添加剤を4重量部加えて３本ロールミルで混練し、各混合粉をそれぞれ含む４種類の感光性Agペーストを調製した。 Next, four kinds of mixed powders were prepared by changing the mixing ratio of the above powder B and powder C. Similarly to the above, 30 parts by weight of UV curable resin and SiO2 were added to 100 parts by weight of each mixed powder. Add 1 part by weight of 2- Bi 2 O 3 -B 2 O 3 low melting point glass frit, 5 parts by weight of solvent and 4 parts by weight of other additives and knead them in a three-roll mill, including each mixed powder. Four types of photosensitive Ag paste were prepared.
そして、上記調製した計８種類の感光性Agペーストを、スクリーン印刷法によりガラス基板上全面に均一に塗布し、90℃で30分乾燥させて、塗布厚20μmの塗膜を得た。 Then, a total of eight types of photosensitive Ag pastes prepared as described above were uniformly applied on the entire surface of the glass substrate by a screen printing method and dried at 90 ° C. for 30 minutes to obtain a coating film having a coating thickness of 20 μm.
その後、露光装置〔マルチライトPM25C-75：超高圧水銀灯ランプUSH-250BY：ウシオ電機(株)製〕により、15μm、20μm、25μmの各線幅のパターンを有するネガマスクを介して、紫外線の平行度を視野角±2.8度の範囲で各塗膜を露光し、各塗膜毎に、その露光された領域のタック性が完全に無くなった状態になった時を硬化の終了点とし、それまでに要した紫外線の照射量（硬化露光量）を測定した。 After that, by using an exposure apparatus (Multilight PM25C-75: Ultra High Pressure Mercury Lamp Lamp USH-250BY: Ushio Electric Co., Ltd.), the parallelism of ultraviolet rays is measured through negative masks having line width patterns of 15 μm, 20 μm and 25 μm Each coating film is exposed within a viewing angle range of ± 2.8 degrees, and when the tackiness of the exposed area is completely eliminated for each coating film, the end point of curing is set as the end point of curing. The irradiated amount of ultraviolet light (cured exposure amount) was measured.
次に現像を行い、現像後の塗膜を空気中で550℃のピーク温度で10分間のサイクルで焼成して得られた導電パターンについて、それぞれの比抵抗値を測定した。 Next, development was performed, and the specific resistance values of the conductive patterns obtained by baking the developed coating film in air at a peak temperature of 550 ° C. in a cycle of 10 minutes were measured.
混合粉を含む上記８種類のAg粉末の各明度Ｌ*、各Ag粉末を用いたペーストの硬化露光量、比抵抗値、及び得られた導電パターンのファインライン性を目視にて評価した結果を表２に示す。 The lightness L * of the above eight types of Ag powder containing mixed powder, the cured exposure amount of the paste using each Ag powder, the specific resistance value, and the result of visual evaluation of the fine line property of the obtained conductive pattern It shows in Table 2.
但し、比較例２では、2000mJ/cm2以上の露光を行っても硬化しなかったため、硬化不十分のまま露光を終了し、そのまま焼成を行った。 However, in Comparative Example 2, since it was not cured even after exposure of 2000 mJ / cm 2 or more, the exposure was terminated with insufficient curing, and baking was performed as it was.
(2)結果
表２に示されるように、明度Ｌ*が60以上のAg粉末を使用した感光性導電ペースト（実施例１〜２）は、明度Ｌ*が60未満のAg粉末を使用した感光性導電ペースト（比較例１〜２）に比べ、少ない露光量で硬化が可能であり、焼成後の導電パターンに関しても、ファインライン性や導電性に優れていることが分かる。
(2) Results As shown in Table 2, the photosensitive conductive paste (Examples 1 and 2) using an Ag powder having a lightness L * of 60 or more is photosensitive using an Ag powder having a lightness L * of less than 60. As compared with the conductive conductive paste (Comparative Examples 1 and 2), it can be cured with a small amount of exposure, and the conductive pattern after firing is also excellent in fine line properties and conductivity.
特に粉末Aは平均粒径が2μm以下と小粒径であるにもかかわらず、その明度Ｌ*が70を越えており、この粉末Aを使用した感光性導電ペースト（実施例１）は25mJ/cm2で硬化させることができた。これは、従来市販されていた感光性導電ペーストが約300〜400mJ/cm2程度の露光量が必要であったことからすれば、粉末Aを用いた感光性ペーストは、従来の1/10以下の露光量で硬化させることが可能なものであり、ファインライン性に関しても特に優れた効果が得られた。 In particular, although the powder A has a small average particle diameter of 2 μm or less, the lightness L * exceeds 70, and the photosensitive conductive paste using this powder A (Example 1) is 25 mJ / It could be cured in cm 2. This is because the photosensitive conductive paste that has been marketed in the past required an exposure amount of about 300 to 400 mJ / cm 2. It was possible to cure at an exposure amount of 2 and a particularly excellent effect was obtained with respect to fine lineability.
また、明度Ｌ*が60以上の粉末Bと、明度Ｌ*が40以上60未満の粉末Cとを混合した混合粉であっても、混合粉の明度Ｌ*が60以上であれば（実施例３〜５）、硬化性、ファインライン性が共に良好で、比抵抗の更に低い導電パターンが得られた。 Further, even if the mixed powder is a powder obtained by mixing the powder B having a lightness L * of 60 or more and the powder C having a lightness L * of 40 or more and less than 60, if the lightness L * of the mixed powder is 60 or more (Example) 3-5), a curability and fine lineability were both good, and a conductive pattern with a lower specific resistance was obtained.
一方、明度Ｌ*が60未満のAg粉末を用いた導電ペースト（比較例１〜２）や、複数種のAg粉末を混合した状態で明度Ｌ*が60未満の混合粉を用いた導電ペースト（比較例３）は、硬化性、ファインライン性、比抵抗のいずれかに問題が発生していた。 On the other hand, a conductive paste using Ag powder having a lightness L * of less than 60 (Comparative Examples 1 and 2) or a conductive paste using a mixed powder having a lightness L * of less than 60 in a mixed state of plural types of Ag powder ( In Comparative Example 3), a problem occurred in any of curability, fine line property, and specific resistance.
例えば比較例２では、2000mJ/cm2以上の露光を行っても完全には硬化せず、また比較例１〜２では焼成後の導電パターンはファインライン性が十分なものではなく、しかもその表面にブリスタが発生し、比抵抗を測定することができなかった。 For example, in Comparative Example 2, it is not completely cured even after exposure of 2000 mJ / cm 2 or more, and in Comparative Examples 1 and 2, the conductive pattern after firing is not sufficiently fine-lined and its surface A blister occurred and the specific resistance could not be measured.
また比較例３も焼成後の導電パターンはファインライン性が十分なものではなく、しかもその比抵抗も十分満足できるレベルではなかった。 In Comparative Example 3, the conductive pattern after firing was not sufficiently fine-lined, and the specific resistance was not sufficiently satisfactory.
Claims (5)
前記金属粉末が、Ag粉末、Agを主とした合金粉末、又は、その表面にAg若しくはAg合金を被覆した粉末から選択される何れか１種以上であって、JIS規格Z8722に従い測定されるＬ*ａ*ｂ*表色系の明度Ｌ*が60以上であり、且つ、平均粒径が5μm以下であることを特徴とする感光性導電ペースト。 In a photosensitive conductive paste containing at least a metal powder and a photosensitive organic component,
The metal powder is at least one selected from Ag powder, alloy powder mainly composed of Ag, or powder having Ag or Ag alloy coated on its surface, and is measured according to JIS standard Z8722. * a * b * A photosensitive conductive paste having a color system lightness L * of 60 or more and an average particle size of 5 μm or less.
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