JP2009170277A - Conductive paste - Google Patents
Conductive paste Download PDFInfo
- Publication number
- JP2009170277A JP2009170277A JP2008007582A JP2008007582A JP2009170277A JP 2009170277 A JP2009170277 A JP 2009170277A JP 2008007582 A JP2008007582 A JP 2008007582A JP 2008007582 A JP2008007582 A JP 2008007582A JP 2009170277 A JP2009170277 A JP 2009170277A
- Authority
- JP
- Japan
- Prior art keywords
- conductive paste
- wiring
- silver particles
- substrate
- thickness
- 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.)
- Granted
Links
- 239000002245 particle Substances 0.000 claims abstract description 96
- 229910052709 silver Inorganic materials 0.000 claims abstract description 67
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000004332 silver Substances 0.000 claims abstract description 66
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 125000001424 substituent group Chemical group 0.000 claims abstract description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims description 66
- 238000000034 method Methods 0.000 claims description 42
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000000853 adhesive Substances 0.000 abstract description 24
- 230000001070 adhesive effect Effects 0.000 abstract description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 60
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 42
- 229910052751 metal Inorganic materials 0.000 description 36
- 239000002184 metal Substances 0.000 description 36
- 239000011888 foil Substances 0.000 description 19
- 239000011521 glass Substances 0.000 description 19
- 239000010931 gold Substances 0.000 description 16
- 238000007650 screen-printing Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000002923 metal particle Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 12
- -1 i-pentyl group Chemical group 0.000 description 10
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 6
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 5
- 229940093475 2-ethoxyethanol Drugs 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000005065 mining Methods 0.000 description 3
- 229910001923 silver oxide Inorganic materials 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 2
- IWTBVKIGCDZRPL-UHFFFAOYSA-N 3-methylpentanol Chemical compound CCC(C)CCO IWTBVKIGCDZRPL-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XRMVWAKMXZNZIL-UHFFFAOYSA-N 2,2-dimethyl-1-butanol Chemical compound CCC(C)(C)CO XRMVWAKMXZNZIL-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 description 1
- WFRBDWRZVBPBDO-UHFFFAOYSA-N 2-methyl-2-pentanol Chemical compound CCCC(C)(C)O WFRBDWRZVBPBDO-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- DUXCSEISVMREAX-UHFFFAOYSA-N 3,3-dimethylbutan-1-ol Chemical compound CC(C)(C)CCO DUXCSEISVMREAX-UHFFFAOYSA-N 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- PCWGTDULNUVNBN-UHFFFAOYSA-N 4-methylpentan-1-ol Chemical compound CC(C)CCCO PCWGTDULNUVNBN-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000004100 electronic packaging Methods 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
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 1
- ZOCHHNOQQHDWHG-UHFFFAOYSA-N hexan-3-ol Chemical compound CCCC(O)CC ZOCHHNOQQHDWHG-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VHWYCFISAQVCCP-UHFFFAOYSA-N methoxymethanol Chemical compound COCO VHWYCFISAQVCCP-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 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
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 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
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Abstract
Description
本発明は、導電性ペーストに関するものである。 The present invention relates to a conductive paste.
従来、銅箔を基板に張り合わせ、エッチングにより銅配線を製造する方法が主流である。しかしながら、この方法ではエッチングをするため、廃液、廃棄物等が大量に生じるという問題があった。 Conventionally, a method of manufacturing a copper wiring by attaching a copper foil to a substrate and etching is the mainstream. However, since this method performs etching, there is a problem that a large amount of waste liquid, waste, and the like are generated.
そこで、エッチングを用いない配線基板としては、粒径がミクロンオーダーの金属（例えば、銀、銅など）粒子と、接着剤（例えば、エポキシ系、アクリル系、シリコーン系など）とを含む導電性ペーストを基板の上に塗布し、１５０〜１８０℃で加熱して製造する方法が知られている（例えば、非特許文献１参照）。この製造方法によれば、加熱して接着剤が固化する際、導電性ペースト内の金属粒子の間隔が狭まり、その結果金属粒子が密集して電流が流れ、配線が製造される。ただし、この方法では、得られる電気抵抗値が１０-5Ωｃｍ-1オーダー程度と高めであり、さらに低い電気抵抗値が望まれていた。 Therefore, as a wiring board that does not use etching, a conductive paste containing metal (eg, silver, copper, etc.) particles having a particle size of micron order and an adhesive (eg, epoxy, acrylic, silicone, etc.). There is known a method of manufacturing by coating on a substrate and heating at 150 to 180 ° C. (see, for example, Non-Patent Document 1). According to this manufacturing method, when the adhesive is solidified by heating, the interval between the metal particles in the conductive paste is narrowed, and as a result, the metal particles are densely packed and a current flows to manufacture a wiring. However, with this method, the electrical resistance value obtained is as high as about 10 −5 Ωcm −1 , and a lower electrical resistance value has been desired.
また、粒径がミクロンオーダーの金属粒子と接着剤と酸化銀とを含む導電性ペーストを基板の上に塗布し、２００℃付近で加熱して配線を製造する方法も知られている（例えば、非特許文献２参照）。この製造方法によれば、前記ペーストを２００℃付近で加熱するとペースト中の酸化銀が銀に変化し、その結果、金属粒子が接続されて電流が流れ、配線が製造される。ただし、この製造方法では、形成された配線中に酸化銀由来の酸素が残存しやすく、その結果、配線が壊れやすいという問題点があった。 In addition, a method of manufacturing a wiring by applying a conductive paste containing metal particles having a particle size of micron order, an adhesive, and silver oxide on a substrate and heating at around 200 ° C. (for example, Non-patent document 2). According to this manufacturing method, when the paste is heated at around 200 ° C., the silver oxide in the paste is changed to silver, and as a result, the metal particles are connected, current flows, and the wiring is manufactured. However, this manufacturing method has a problem that oxygen derived from silver oxide tends to remain in the formed wiring, and as a result, the wiring is easily broken.
また、粒径がミクロンオーダーの金属粒子と接着剤と銀ナノ粒子とを含む導電性ペーストを基板の上に塗布し、２００℃付近で加熱して配線を製造する方法も知られている。この製造方法によれば、前記ペーストを２００℃付近で加熱すると銀ナノ粒子が金属粒子の間を接続させて電流が流れ、配線が製造される。ただしこの製造方法では、銀ナノ粒子の値段が高いという問題点があった。 There is also known a method of manufacturing a wiring by applying a conductive paste containing metal particles having a particle size of the order of microns, an adhesive, and silver nanoparticles on a substrate and heating at around 200 ° C. According to this manufacturing method, when the paste is heated at around 200 ° C., the silver nanoparticles connect the metal particles, current flows, and a wiring is manufactured. However, this production method has a problem that the price of silver nanoparticles is high.
前記の製造方法は、接着剤を含む導電性ペーストを用いる必要がある。しかしながら、粒径がミクロンオーダーの金属粒子と接着剤とを用いると、金属粒子間の密集が不十分であり、電気抵抗値が高いという問題があった。
そこで、本発明は、低電気抵抗値を生じるための、接着剤を必要としない導電性ペーストの提供を目的とする。 Accordingly, an object of the present invention is to provide a conductive paste that does not require an adhesive for producing a low electric resistance value.
本発明は、０．１μｍ〜１５μｍの平均粒径（メジアン径）を有する銀粒子と、アルコールとを含む導電性ペーストである。 The present invention is a conductive paste containing silver particles having an average particle diameter (median diameter) of 0.1 μm to 15 μm and alcohol.
本発明の導電性ペーストは接着剤を必要とせず、電気抵抗値が低いという利点がある。 The conductive paste of the present invention does not require an adhesive and has the advantage of low electrical resistance.
本発明の導電性ペーストに含まれる銀粒子とアルコールとの割合は、重量部で例えば銀粒子：アルコールが４：１〜１６：１、好ましくは６：１〜１２：１、より好ましくは８：１〜１０：１である。 The ratio of silver particles to alcohol contained in the conductive paste of the present invention is, for example, silver particles: alcohol 4: 1 to 16: 1, preferably 6: 1 to 12: 1, more preferably 8: by weight. 1-10: 1.
本発明の導電性ペーストに含まれる銀粒子は、平均粒径（メジアン径）が１種類のものであっても、２種類以上のものを混合して用いてもよい。前記銀粒子が１種類の場合、平均粒径（メジアン径）が０．１μｍ〜１５μｍであり、好ましくは０．１μｍ〜１０μｍであり、より好ましくは０．３μｍ〜５μｍである。前記銀粒子を２種類以上混合する場合には、平均粒径（メジアン径）が、例えば０．１μｍ〜１５μｍのものと、０．１μｍ〜１５μｍのものとの組み合わせ、好ましくは０．１μｍ〜１５μｍのものと、０．１μｍ〜１０μｍのものとの組み合わせ、より好ましくは０．１μｍ〜１５μｍのものと、０．３μｍ〜５μｍのものとの組み合わせである。前記銀粒子を２種類以上混合する場合には、平均粒径（メジアン径）が、０．１μｍ〜１５μｍのものの含有率は、例えば７０重量％以上、好ましくは８０重量％以上、よりこのましくは９０重量％以上である。 The silver particles contained in the conductive paste of the present invention may have one average particle diameter (median diameter) or a mixture of two or more kinds. When the silver particles are one kind, the average particle diameter (median diameter) is 0.1 μm to 15 μm, preferably 0.1 μm to 10 μm, more preferably 0.3 μm to 5 μm. When two or more kinds of silver particles are mixed, the average particle diameter (median diameter) is, for example, a combination of 0.1 μm to 15 μm and 0.1 μm to 15 μm, preferably 0.1 μm to 15 μm. And a combination of 0.1 μm to 10 μm, and more preferably a combination of 0.1 μm to 15 μm and 0.3 μm to 5 μm. When two or more kinds of the silver particles are mixed, the content of those having an average particle diameter (median diameter) of 0.1 μm to 15 μm is, for example, 70% by weight or more, preferably 80% by weight or more. Is 90% by weight or more.
本発明の導電性ペーストに含まれる銀粒子の平均粒径（メジアン径）は、レーザーの方法により測定することができる。 The average particle diameter (median diameter) of the silver particles contained in the conductive paste of the present invention can be measured by a laser method.
また、本発明の導電性ペーストに含まれる銀粒子は、比表面積が０．５ｍ2／ｇ〜３ｍ2／ｇであり、好ましくは０．６ｍ2／ｇ〜２．５ｍ2／ｇであり、より好ましくは０．６ｍ2／ｇ〜２ｍ2／ｇである。本発明の銅線製ペーストに含まれる銀粒子の比表面積は、ＢＥＴの方法により測定することができる。 Further, the silver particles contained in the conductive paste of the present invention has a specific surface area of 0.5m 2 / g~3m 2 / g, preferably 0.6m 2 /g~2.5m 2 / g, more preferably 0.6m 2 / g~2m 2 / g. The specific surface area of the silver particles contained in the copper wire paste of the present invention can be measured by the BET method.
本発明の導電性ペーストに含まれる銀粒子の形態は限定されないが、例えば、球状、扁平な形状、多面体等が挙げられる。前記銀粒子の形態は、平均粒径（メジアン径）が所定の範囲内の銀粒子に関して、均等であるのが好ましい。本発明の導電性ペーストに含まれる銀粒子は平均粒径（メジアン径）が２種類以上のものを混合する場合、それぞれの平均粒径（メジアン径）の銀粒子の形態は、同一であっても異なっていてもよい。例えば、平均粒径（メジアン径）が３μｍである銀粒子と平均粒径（メジアン径）が０．３μｍである銀粒子の２種類を混合する場合、平均粒径（メジアン径）が０．３μｍである銀粒子は球状であり、平均粒径（メジアン径）が３μｍである銀粒子は扁平な形状であってもよい。 Although the form of the silver particle contained in the electrically conductive paste of this invention is not limited, For example, spherical shape, a flat shape, a polyhedron etc. are mentioned. The form of the silver particles is preferably uniform with respect to silver particles having an average particle diameter (median diameter) within a predetermined range. When silver particles contained in the conductive paste of the present invention have two or more average particle diameters (median diameters) mixed, the form of the silver particles having the respective average particle diameters (median diameters) is the same. May be different. For example, when two types of silver particles having an average particle diameter (median diameter) of 3 μm and silver particles having an average particle diameter (median diameter) of 0.3 μm are mixed, the average particle diameter (median diameter) is 0.3 μm. The silver particles having a spherical shape and the average particle diameter (median diameter) of 3 μm may be flat.
本発明の導電性ペーストは、さらに銀以外の導電性金属の粒子を含んでもよい。前記導電性金属としては、例えば、パラジウム、白金、金、銅等が挙げられる。前記導電性金属の粒子は、平均粒径（メジアン径）が０．１μｍ〜１５μｍであり、好ましくは０．１μｍ〜１０μｍであり、より好ましくは０．３μｍ〜５μｍである。また、前記導電性金属の粒子は、比表面積が０．５ｍ2／ｇ〜３ｍ2／ｇであり、好ましくは０．６ｍ2／ｇ〜２．５ｍ2／ｇであり、より好ましくは０．６ｍ2／ｇ〜２ｍ2／ｇである。 The conductive paste of the present invention may further contain conductive metal particles other than silver. Examples of the conductive metal include palladium, platinum, gold, and copper. The conductive metal particles have an average particle diameter (median diameter) of 0.1 μm to 15 μm, preferably 0.1 μm to 10 μm, more preferably 0.3 μm to 5 μm. Further, the particles of the conductive metal has a specific surface area of 0.5m 2 / g~3m 2 / g, preferably 0.6m 2 /g~2.5m 2 / g, more preferably 0. It is 6 m 2 / g to 2 m 2 / g.
本発明の導電性ペーストにおいては、前記アルコールは、低級アルコールまたは、低級アルコキシ、アミノおよびハロゲンからなる群から選択される１以上の置換基を有する低級アルコールであるのが好ましい。前記低級アルコールは、例えば、炭素原子１〜６個を有するアルキル基と、水酸基１〜３個、好ましくは１〜２個を含むものが挙げられる。前記低級アルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｉ−ブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、ｉ−ペンチル基、ｓｅｃ−ペンチル基、ｔ−ペンチル基、２−メチルブチル基、ｎ−ヘキシル基、１−メチルペンチル基、２−メチルペンチル基、３−メチルペンチル基、４−メチルペンチル基、１−エチルブチル基、２−エチルブチル基、１，１−ジメチルブチル基、２，２−ジメチルブチル基、３，３−ジメチルブチル基、および１−エチル−１−メチルプロピル基などの直鎖状または分岐状のアルキル基が挙げられる。炭素原子１〜６個を有するアルキル基と水酸基１〜３個とを有する低級アルコールとしては、例えば、メタノール、エタノール、エチレングリコール、ｎ−プロパノール、ｉ−プロパノール、トリエチレングリコール、ｎ−ブタノール、ｉ−ブタノール、ｓｅｃ−ブタノール、ｔ−ブタノール、ｎ−ペンタノール、ｉ−ペンタノール、ｓｅｃ−ペンタノール、ｔ−ペンタノール、２−メチルブタノール、ｎ−ヘキサノール、１−メチルペンタノール、２−メチルペンタノール、３−メチルペンタノール、４−メチルペンタノール、１−エチルブタノール、２−エチルブタノール、１，１−ジメチルブタノール、２，２−ジメチルブタノール、３，３−ジメチルブタノール、および１−エチル−１−メチルプロパノール等が挙げられる。 In the conductive paste of the present invention, the alcohol is preferably a lower alcohol or a lower alcohol having one or more substituents selected from the group consisting of lower alkoxy, amino and halogen. Examples of the lower alcohol include those containing an alkyl group having 1 to 6 carbon atoms and 1 to 3 hydroxyl groups, preferably 1 to 2 hydroxyl groups. Examples of the lower alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, i-pentyl group, sec-pentyl group, t-pentyl group, 2-methylbutyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1 -Linear or branched such as ethylbutyl group, 2-ethylbutyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, and 1-ethyl-1-methylpropyl group -Like alkyl groups. Examples of the lower alcohol having an alkyl group having 1 to 6 carbon atoms and 1 to 3 hydroxyl groups include methanol, ethanol, ethylene glycol, n-propanol, i-propanol, triethylene glycol, n-butanol, i -Butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, sec-pentanol, t-pentanol, 2-methylbutanol, n-hexanol, 1-methylpentanol, 2-methylpen Tanol, 3-methylpentanol, 4-methylpentanol, 1-ethylbutanol, 2-ethylbutanol, 1,1-dimethylbutanol, 2,2-dimethylbutanol, 3,3-dimethylbutanol, and 1-ethyl- Examples include 1-methylpropanol.
低級アルコキシ、アミノおよびハロゲンからなる群から選択される１以上の置換基を有する前記低級アルコールにおいて、置換基については以下のとおりである。前記低級アルコキシとしては、前記低級アルキル基に−Ｏ−が置換された基が挙げられる。前記低級アルコキシとしては、メトキシ、エトキシ、ｎ−プロポキシ、ｉ−プロポキシ、ｎ−ブトキシ、ｉ−ブトキシ、ｓｅｃ−ブトキシ、ｔ−ブトキシ、ｎ−ペンチルオキシ等が挙げられる。前記ハロゲンとしては、フッ素、臭素、塩素およびヨウ素が挙げられる。 In the lower alcohol having one or more substituents selected from the group consisting of lower alkoxy, amino and halogen, the substituents are as follows. Examples of the lower alkoxy include groups in which —O— is substituted on the lower alkyl group. Examples of the lower alkoxy include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, sec-butoxy, t-butoxy, n-pentyloxy and the like. Examples of the halogen include fluorine, bromine, chlorine and iodine.
低級アルコキシ、アミノおよびハロゲンからなる群から選択される１以上の置換基を有する前記低級アルコールとしては、例えば、メトキシメタノール、２−メトキシエタノール、２−エトキシエタノール、２−クロロエタノール、エタノールアミン等が挙げられる。 Examples of the lower alcohol having one or more substituents selected from the group consisting of lower alkoxy, amino and halogen include methoxymethanol, 2-methoxyethanol, 2-ethoxyethanol, 2-chloroethanol, ethanolamine and the like. Can be mentioned.
また、本発明は、本発明の導電性ペーストを用いて配線を形成する方法であって、前記導電性ペーストを基板上に塗布し、塗布された前記基板を１５０〜３００℃で加熱し、配線を形成することを特徴とする。 Further, the present invention is a method for forming a wiring using the conductive paste of the present invention, wherein the conductive paste is applied onto a substrate, the applied substrate is heated at 150 to 300 ° C., and wiring is formed. It is characterized by forming.
前記方法において、基板としてはその表面に本発明の導電性ペーストを塗布することが可能であれば特に限定されないが、例えば半導体素子、酸化アルミニウム、窒化アルミニウム、酸化ジルコニウム、窒化ジルコニウム、酸化チタン、窒化チタンまたはこれらの混合物を含むセラミック基板、Ｃｕ、Ｆｅ、Ｎｉ、Ｃｒ、Ａｌ、Ａｇ、Ａｕ、Ｔｉまたはこれらの合金を含む金属基板、ガラスエポキシ基板、ＢＴレジン基板、ガラス基板、樹脂基板、紙等が挙げられる。前記方法は、加熱温度が低温であるため、熱可塑性樹脂のような加熱に弱いものも用いることができる。 In the above method, the substrate is not particularly limited as long as the conductive paste of the present invention can be applied to the surface thereof. For example, a semiconductor element, aluminum oxide, aluminum nitride, zirconium oxide, zirconium nitride, titanium oxide, nitride Ceramic substrate containing titanium or a mixture thereof, metal substrate containing Cu, Fe, Ni, Cr, Al, Ag, Au, Ti or alloys thereof, glass epoxy substrate, BT resin substrate, glass substrate, resin substrate, paper, etc. Is mentioned. Since the heating temperature is low in the method, a method that is vulnerable to heating, such as a thermoplastic resin, can be used.
前記方法において、導電性ペーストを基板上に塗布する工程は、基板表面に本発明の導電性ペーストを塗布することが可能であれば特に限定されないが、例えば、印刷法、コーティング法等により行ってもよい。前記印刷法としては、スクリーン印刷法、オフセット印刷法、インクジェット印刷法、フレキソ印刷法、グラビア印刷法、スタンピング、ディスペンス、スキ−ジ印刷、シルクスクリ−ン印刷、噴霧、刷毛塗り等が挙げられ、スクリーン印刷法、スタンピングおよびディスペンスが好ましい。前記塗布された導電性ペーストの厚さは、例えば、２０〜５００μｍ、好ましくは３０〜３００μｍ、より好ましくは５０〜２００μｍである。 In the above method, the step of applying the conductive paste on the substrate is not particularly limited as long as the conductive paste of the present invention can be applied to the substrate surface. For example, the method is performed by a printing method, a coating method, or the like. Also good. Examples of the printing method include screen printing method, offset printing method, ink jet printing method, flexographic printing method, gravure printing method, stamping, dispensing, squeegee printing, silk screen printing, spraying, brush coating, and the like. Screen printing, stamping and dispensing are preferred. The thickness of the applied conductive paste is, for example, 20 to 500 μm, preferably 30 to 300 μm, and more preferably 50 to 200 μm.
前記方法において、塗布された前記基板を加熱する工程は、非酸化性雰囲気下、大気下、真空雰囲気下、酸素もしくは混合ガス雰囲気下、気流中などの雰囲気下等で行ってもよい。大気雰囲気下で行えば、配線が低抵抗になり、配線形成が経済的なので好ましい。 In the method, the step of heating the coated substrate may be performed in a non-oxidizing atmosphere, in the air, in a vacuum atmosphere, in an oxygen or mixed gas atmosphere, in an atmosphere of air current, or the like. It is preferable to carry out in an air atmosphere since the wiring has low resistance and the wiring formation is economical.
前記方法において加熱して得られた配線の厚みは、例えば１５〜４００μｍ、好ましくは２０〜２５０μｍ、より好ましくは４０〜１８０μｍである。 The thickness of the wiring obtained by heating in the above method is, for example, 15 to 400 μm, preferably 20 to 250 μm, more preferably 40 to 180 μm.
前記方法は、さらに前記配線に接着剤を塗布する工程を含むのが好ましい。前記接着剤を塗布する工程により、前記基板と前記配線との接着性を高めることができる。また、接着剤を含む従来の導電性ペーストから形成された配線は、前記のように金属粒子間の密集が不十分であり、電気抵抗値が高いという問題があった。しかし、本発明の方法では、金属粒子間の密集は十分であり、その結果、電気抵抗値が低い配線が得られる。そのような本発明の方法に、前記配線に接着剤を塗布する工程をさらに含む場合、そのような配線を前記基板に強固に接着させることが可能であるので、電気抵抗値が低く、かつ、基板との接着性が高い配線を得ることができ、好ましい。 Preferably, the method further includes a step of applying an adhesive to the wiring. The adhesion between the substrate and the wiring can be enhanced by the step of applying the adhesive. Moreover, the wiring formed from the conventional conductive paste containing an adhesive has a problem that the density between the metal particles is insufficient as described above and the electric resistance value is high. However, in the method of the present invention, the metal particles are sufficiently dense, and as a result, a wiring having a low electric resistance value can be obtained. When such a method of the present invention further includes a step of applying an adhesive to the wiring, it is possible to firmly bond such wiring to the substrate, so that the electrical resistance value is low, and A wiring having high adhesion to the substrate can be obtained, which is preferable.
前記方法において用いることができる接着剤としては、エポキシ系、フェノール系、アクリル系、ポリイミド系、シリコン系、ウレタン系、熱可塑性系等が挙げられる。中でも前記接着剤としては、エポキシ系が好ましい。 Examples of the adhesive that can be used in the above method include epoxy, phenol, acrylic, polyimide, silicon, urethane, and thermoplastic. Among these, as the adhesive, an epoxy type is preferable.
以下において、平均粒径（メジアン径）はレーザー方法により、比表面積はＢＥＴ方法により測定した値である。
また、用いた銀粒子は、以下のとおりである。
福田金属箔粉工業株式会社製、製品名「ＡｇＣ−２３９」は、平均粒径（メジアン径）が２．０〜３．２μｍ、比表面積が０．６〜０．９ｍ2／ｇである。
三井金属鉱業株式会社製、製品名「ＦＨＤ」は、平均粒径（メジアン径）が０．３μｍ、比表面積が２．５４ｍ2／ｇである。
三井金属鉱業株式会社製、製品名「ＥＨＤ」は、平均粒径（メジアン径）が０．５μｍ、比表面積が１．７０ｍ2／ｇ、である。
In the following, the average particle diameter (median diameter) is a value measured by a laser method, and the specific surface area is a value measured by a BET method.
The silver particles used are as follows.
The product name “AgC-239” manufactured by Fukuda Metal Foil Industry Co., Ltd. has an average particle diameter (median diameter) of 2.0 to 3.2 μm and a specific surface area of 0.6 to 0.9 m 2 / g.
The product name “FHD” manufactured by Mitsui Metal Mining Co., Ltd. has an average particle diameter (median diameter) of 0.3 μm and a specific surface area of 2.54 m 2 / g.
The product name “EHD” manufactured by Mitsui Mining & Smelting Co., Ltd. has an average particle diameter (median diameter) of 0.5 μm and a specific surface area of 1.70 m 2 / g.
銀粒子（福田金属箔粉工業株式会社製、製品名「ＡｇＣ−２３９」、２．５ｇ）と、メタノール（０．３ｇ）とを２５℃で混合して導電性ペーストを得た。得られた導電性ペーストを、ガラス基板（厚み１ｍｍ）にスクリーン印刷法により厚み２００μｍに塗布した。前記導電性ペーストが塗布されたガラス基板を、２００℃で３０分間、大気雰囲気下で加熱した。得られた配線の厚みは、１７５〜１９５μｍである。前記得られた配線の電気抵抗値は７．１×１０-6Ω・ｃｍであった。 Silver particles (manufactured by Fukuda Metal Foil Industry Co., Ltd., product name “AgC-239”, 2.5 g) and methanol (0.3 g) were mixed at 25 ° C. to obtain a conductive paste. The obtained conductive paste was applied to a glass substrate (thickness 1 mm) to a thickness of 200 μm by screen printing. The glass substrate coated with the conductive paste was heated at 200 ° C. for 30 minutes in an air atmosphere. The thickness of the obtained wiring is 175 to 195 μm. The obtained wiring had an electric resistance of 7.1 × 10 −6 Ω · cm.
メタノールの代わりにエタノール（０．３ｇ）用いた以外は、実施例１と同様にして行った。得られた配線の電気抵抗値は、５．３×１０-6Ω・ｃｍであった。 The same procedure as in Example 1 was performed except that ethanol (0.3 g) was used instead of methanol. The obtained wiring had an electric resistance of 5.3 × 10 −6 Ω · cm.
メタノールの代わりにエチレングリコール（０．３ｇ）用いた以外は、実施例１と同様にして行った。得られた配線の電気抵抗値は１．０×１０-5Ω・ｃｍであった。 The same procedure as in Example 1 was performed except that ethylene glycol (0.3 g) was used instead of methanol. The obtained wiring had an electric resistance value of 1.0 × 10 −5 Ω · cm.
メタノールの代わりに２ーエトキシエタノール（０．３ｇ）用いた以外は、実施例１と同様にして行った。得られた配線の電気抵抗値は６．２×１０-6Ω・ｃｍであった。 The same procedure as in Example 1 was carried out except that 2-ethoxyethanol (0.3 g) was used instead of methanol. The obtained wiring had an electric resistance of 6.2 × 10 −6 Ω · cm.
［比較例１］
メタノールを用いない以外は、実施例１と同様にして行った。得られた配線の電気抵抗値は１．１×１０-5Ω・ｃｍであった。
[Comparative Example 1]
It carried out like Example 1 except not using methanol. The obtained wiring had an electric resistance value of 1.1 × 10 −5 Ω · cm.
［比較例２］
メタノールの代わりに水（０．３ｇ）用いた以外は、実施例１と同様にして行った。得られた配線に電気抵抗値は得られず、測定不能であった。
[Comparative Example 2]
The same procedure as in Example 1 was performed except that water (0.3 g) was used instead of methanol. An electrical resistance value could not be obtained for the obtained wiring, and measurement was impossible.
銀粒子（福田金属箔粉工業株式会社製、製品名「ＡｇＣ−２３９」、２ｇ）の代わりに、銀粒子（福田金属箔粉工業株式会社製、製品名「ＡｇＣ−２３９」、１ｇ）と銀粒子（三井金属鉱業株式会社製、製品名「ＦＨＤ」、１ｇ）との混合物を用いた以外は、実施例１と同様にして行った。得られた配線の電気抵抗値は６．７×１０-6Ω・ｃｍであった。 Instead of silver particles (Fukuda Metal Foil Powder Co., Ltd., product name “AgC-239”, 2 g), silver particles (Fukuda Metal Foil Powder Co., Ltd., product name “AgC-239”, 1 g) and silver are used. This was carried out in the same manner as in Example 1 except that a mixture with particles (Mitsui Metal Mining Co., Ltd., product name “FHD”, 1 g) was used. The obtained wiring had an electric resistance of 6.7 × 10 −6 Ω · cm.
メタノールの代わりにエタノール（０．４５ｇ）用いた以外は、実施例５と同様にして行った。得られた配線の電気抵抗値は、３．９×１０-6Ω・ｃｍであった。 The same procedure as in Example 5 was performed except that ethanol (0.45 g) was used instead of methanol. The obtained wiring had an electric resistance value of 3.9 × 10 −6 Ω · cm.
メタノールの代わりにエチレングリコール（０．２ｇ）用いた以外は、実施例５と同様にして行った。得られた配線の電気抵抗値は６．７×１０-6Ω・ｃｍであった。 The same procedure as in Example 5 was performed except that ethylene glycol (0.2 g) was used instead of methanol. The obtained wiring had an electric resistance of 6.7 × 10 −6 Ω · cm.
メタノールの代わりに２ーエトキシエタノール（０．２ｇ）用いた以外は、実施例５と同様にして行った。得られた配線の電気抵抗値は５．６×１０-6Ω・ｃｍであった。 The same procedure as in Example 5 was performed except that 2-ethoxyethanol (0.2 g) was used instead of methanol. The obtained wiring had an electric resistance of 5.6 × 10 −6 Ω · cm.
［比較例３］
メタノールを用いない以外は、実施例５と同様にして行った。得られた配線の電気抵抗値は２．０×１０-5Ω・ｃｍであった。
[Comparative Example 3]
It carried out like Example 5 except not using methanol. The obtained wiring had an electric resistance value of 2.0 × 10 −5 Ω · cm.
［比較例４］
メタノールの代わりに水（０．２ｇ）用いた以外は、実施例５と同様にして行った。得られた配線に電気抵抗値は得られず、測定不能であった。
[Comparative Example 4]
The same procedure as in Example 5 was performed except that water (0.2 g) was used instead of methanol. An electrical resistance value could not be obtained for the obtained wiring, and measurement was impossible.
銀粒子（福田金属箔粉工業株式会社製、製品名「ＡｇＣ−２３９」、２ｇ）の代わりに、銀粒子（福田金属箔粉工業株式会社製、製品名「ＡｇＣ−２３９」、１ｇ）と銀粒子（三井金属鉱業株式会社製、製品名「ＥＨＤ」、１ｇ）との混合物を用いた以外は、実施例１と同様にして行った。得られた配線の電気抵抗値は７．５×１０-6Ω・ｃｍであった。 Instead of silver particles (Fukuda Metal Foil Powder Co., Ltd., product name “AgC-239”, 2 g), silver particles (Fukuda Metal Foil Powder Co., Ltd., product name “AgC-239”, 1 g) and silver are used. The same procedure as in Example 1 was performed except that a mixture with particles (product name “EHD”, 1 g, manufactured by Mitsui Mining & Smelting Co., Ltd.) was used. The obtained wiring had an electric resistance of 7.5 × 10 −6 Ω · cm.
メタノールの代わりにエタノール（０．４５ｇ）用いた以外は、実施例９と同様にして行った。得られた配線の電気抵抗値は、４．９×１０-6Ω・ｃｍであった。 The same procedure as in Example 9 was performed except that ethanol (0.45 g) was used instead of methanol. The obtained wiring had an electric resistance value of 4.9 × 10 −6 Ω · cm.
メタノールの代わりにエチレングリコール（０．２ｇ）用いた以外は、実施例９と同様にして行った。得られた配線の電気抵抗値は７．８×１０-6Ω・ｃｍであった。 The same procedure as in Example 9 was performed except that ethylene glycol (0.2 g) was used instead of methanol. The obtained wiring had an electric resistance value of 7.8 × 10 −6 Ω · cm.
メタノールの代わりに２ーエトキシエタノール（０．２ｇ）用いた以外は、実施例９と同様にして行った。得られた配線の電気抵抗値は７．６×１０-6Ω・ｃｍであった。 The same procedure as in Example 9 was performed except that 2-ethoxyethanol (0.2 g) was used instead of methanol. The obtained wiring had an electric resistance of 7.6 × 10 −6 Ω · cm.
［比較例５］
メタノールを用いない以外は、実施例９と同様にして行った。得られた配線の電気抵抗値は２．１×１０-5Ω・ｃｍであった。
[Comparative Example 5]
It carried out like Example 9 except not using methanol. The obtained wiring had an electric resistance value of 2.1 × 10 −5 Ω · cm.
［比較例６］
メタノールの代わりに水（０．２ｇ）用いた以外は、実施例９と同様にして行った。得られた配線に電気抵抗値は得られず、測定不能であった。
[Comparative Example 6]
The same procedure as in Example 9 was performed except that water (0.2 g) was used instead of methanol. An electrical resistance value could not be obtained for the obtained wiring, and measurement was impossible.
前記実施例１〜１２および比較例１〜６で得られた電気抵抗値を表１および図１に示す。 The electrical resistance values obtained in Examples 1-12 and Comparative Examples 1-6 are shown in Table 1 and FIG.
前記表１および図１に示すように、実施例１〜１２の結果から、本発明の導電性ペーストを用いると、概ね１０-6オーダーの低い電気抵抗値が得られることが確認できた。また、本発明の導電性ペーストを用いると、加熱温度が低くても低電気抵抗値の配線が得られることを確認できた。 As shown in Table 1 and FIG. 1, from the results of Examples 1 to 12, it was confirmed that when the conductive paste of the present invention was used, a low electric resistance value of about 10 −6 order was obtained. Further, it was confirmed that when the conductive paste of the present invention was used, a wiring having a low electric resistance value was obtained even when the heating temperature was low.
銀粒子（福田金属箔粉工業株式会社製、製品名「ＡｇＣ−２３９」）と、銀粒子（三井金属鉱業株式会社製、製品名「ＥＨＤ」）とアルコール（０．２〜０．５ｇ）とを２５℃で混合して導電性ペーストを得た。アルコールとしては、メタノール（ＭｅＯＨ）、エタノール（ＥｔＯＨ）またはエチレングリコール（ＥＧ）を用いた。銀粒子全体における銀粒子（三井金属鉱業株式会社製、製品名「ＥＨＤ」）の含有率は、０重量％、３０重量％、５０重量％または１００重量％である。得られた導電性ペーストを、ガラス基板（厚み１ｍｍ）にスクリーン印刷法により厚み２００μｍに塗布した。前記導電性ペーストが塗布されたガラス基板を、２００℃で３０分間、大気雰囲気下で加熱した。得られた配線の厚みは、１７５〜１９５μｍである。得られた配線の電気抵抗値を表２および図２に示す。 Silver particles (Fukuda Metal Foil Powder Co., Ltd., product name “AgC-239”), silver particles (Mitsui Metal Mining Co., Ltd., product name “EHD”) and alcohol (0.2 to 0.5 g) Were mixed at 25 ° C. to obtain a conductive paste. As the alcohol, methanol (MeOH), ethanol (EtOH) or ethylene glycol (EG) was used. The content of silver particles (product name “EHD”, manufactured by Mitsui Mining & Smelting Co., Ltd.) in the entire silver particles is 0% by weight, 30% by weight, 50% by weight or 100% by weight. The obtained conductive paste was applied to a glass substrate (thickness 1 mm) to a thickness of 200 μm by screen printing. The glass substrate coated with the conductive paste was heated at 200 ° C. for 30 minutes in an air atmosphere. The thickness of the obtained wiring is 175 to 195 μm. The electric resistance values of the obtained wiring are shown in Table 2 and FIG.
銀粒子（三井金属鉱業株式会社製、製品名「ＥＨＤ」の代わりに銀粒子（三井金属鉱業株式会社製、製品名「ＦＨＤ」）を用いた以外は、実施例１３と同様にして行った。得られた配線の電気抵抗値を表２および図２に示す。 The same procedure as in Example 13 was performed except that silver particles (Mitsui Metal Mining Co., Ltd., product name “FHD”) were used instead of silver particles (Mitsui Metal Mining Co., Ltd., product name “EHD”). The electric resistance values of the obtained wiring are shown in Table 2 and FIG.
前記表２および図２に示すように、実施例１３および１４の結果から、粒径が０．３〜０．５μｍの範囲の銀粒子を３０〜５０％と、粒径が２．０〜３．２μｍの範囲の銀粒子を７０〜５０％とを含有する導電性ペーストを用いると、２．０〜３．２μｍの範囲の銀粒子のみを含有する導電性ペーストよりさらに低い電気抵抗率を達成できることが確認できた。 As shown in Table 2 and FIG. 2, from the results of Examples 13 and 14, 30 to 50% of silver particles having a particle size in the range of 0.3 to 0.5 μm and a particle size of 2.0 to 3 are obtained. Using a conductive paste containing 70 to 50% silver particles in the range of 2 μm achieves a lower electrical resistivity than a conductive paste containing only silver particles in the range of 2.0 to 3.2 μm I was able to confirm that it was possible.
銀粒子（福田金属箔粉工業株式会社製、製品名「ＡｇＣ−２３９」、１ｇ）と、銀粒子（三井金属鉱業株式会社製、製品名「ＥＨＤ」、１ｇ）とエチレングリコール（０．２ｇ）とを２５℃で混合して導電性ペーストを得た。得られた導電性ペーストを、ガラス基板（厚み１ｍｍ）にスクリーン印刷法により厚み２００μｍに塗布した。前記導電性ペーストが塗布されたガラス基板を、１８０℃、２００℃、２５０℃または３００℃で３０分間、大気雰囲気下で加熱した。得られた配線の厚みは、１７５〜１９５μｍである。得られた配線の電気抵抗値を表３および図３に示す。 Silver particles (manufactured by Fukuda Metal Foil Industry Co., Ltd., product name “AgC-239”, 1 g), silver particles (manufactured by Mitsui Metal Mining Co., Ltd., product name “EHD”, 1 g) and ethylene glycol (0.2 g) Were mixed at 25 ° C. to obtain a conductive paste. The obtained conductive paste was applied to a glass substrate (thickness 1 mm) to a thickness of 200 μm by screen printing. The glass substrate coated with the conductive paste was heated at 180 ° C., 200 ° C., 250 ° C. or 300 ° C. for 30 minutes in an air atmosphere. The thickness of the obtained wiring is 175 to 195 μm. The electrical resistance values of the obtained wiring are shown in Table 3 and FIG.
銀粒子（三井金属鉱業株式会社製、製品名「ＥＨＤ」の代わりに銀粒子（三井金属鉱業株式会社製、製品名「ＦＨＤ」、１ｇ）を用いた以外は、実施例１５と同様にして行った。得られた配線の電気抵抗値を表３および図３に示す。 Performed in the same manner as in Example 15 except that silver particles (Mitsui Metals Mining Co., Ltd., product name “FHD”, 1 g) were used instead of the product name “EHD”. The electrical resistance values of the obtained wiring are shown in Table 3 and FIG.
前記表３および図３に示すように、実施例１５および１６の結果から、粒径が０．３〜０．５μｍの範囲の銀粒子と、粒径が２．０〜３．２μｍの範囲の銀粒子とを含有する導電性ペーストを用いると、２００℃程度３０分間の加熱で、低い電気抵抗率を達成できることが確認できた。 As shown in Table 3 and FIG. 3, from the results of Examples 15 and 16, silver particles having a particle size in the range of 0.3 to 0.5 μm and particles having a particle size in the range of 2.0 to 3.2 μm. It was confirmed that when a conductive paste containing silver particles was used, a low electrical resistivity could be achieved by heating at about 200 ° C. for 30 minutes.
銀粒子（福田金属箔粉工業株式会社製、製品名「ＡｇＣ−２３９」、２．５ｇ）とエタノール（０．３ｇ）とを２５℃で混合して導電性ペーストを得た。得られた導電性ペーストを、ガラス基板（厚み１ｍｍ）にスクリーン印刷法により厚み２００μｍに塗布した。前記導電性ペーストが塗布されたガラス基板を、１５０℃、１６０℃、１７０℃、１８０℃、２００℃、２２０℃、２５０℃または３００℃で３０分間、大気雰囲気下で加熱した。得られた配線の厚みは、１７５〜１９５μｍである。得られた配線の電気抵抗値を表４および図４に示す。 Silver particles (made by Fukuda Metal Foil Powder Co., Ltd., product name “AgC-239”, 2.5 g) and ethanol (0.3 g) were mixed at 25 ° C. to obtain a conductive paste. The obtained conductive paste was applied to a glass substrate (thickness 1 mm) to a thickness of 200 μm by screen printing. The glass substrate coated with the conductive paste was heated at 150 ° C., 160 ° C., 170 ° C., 180 ° C., 200 ° C., 220 ° C., 250 ° C. or 300 ° C. for 30 minutes in an air atmosphere. The thickness of the obtained wiring is 175 to 195 μm. The electric resistance value of the obtained wiring is shown in Table 4 and FIG.
銀粒子（福田金属箔粉工業株式会社製、製品名「ＡｇＣ−２３９」、２．５ｇ）とエチレングリコール（０．９ｇ）とを２５℃で混合して導電性ペーストを得た。得られた導電性ペーストを、ガラス基板（厚み１ｍｍ）にスクリーン印刷法により厚み２００μｍに塗布した。前記導電性ペーストが塗布されたガラス基板を、１５０℃、１６０℃、１７０℃、１８０℃、２００℃、２２０℃、２５０℃または３００℃で３０分間、大気雰囲気下で加熱した。得られた配線の厚みは、１７５〜１９５μｍである。得られた配線の電気抵抗値を表４および図４に示す。 Silver particles (manufactured by Fukuda Metal Foil Powder Co., Ltd., product name “AgC-239”, 2.5 g) and ethylene glycol (0.9 g) were mixed at 25 ° C. to obtain a conductive paste. The obtained conductive paste was applied to a glass substrate (thickness 1 mm) to a thickness of 200 μm by screen printing. The glass substrate coated with the conductive paste was heated at 150 ° C., 160 ° C., 170 ° C., 180 ° C., 200 ° C., 220 ° C., 250 ° C. or 300 ° C. for 30 minutes in an air atmosphere. The thickness of the obtained wiring is 175 to 195 μm. The electric resistance value of the obtained wiring is shown in Table 4 and FIG.
前記エチレングリコールの量を、０．９ｇの代わりに０．３ｇ用いる以外は、実施例１８と同様にして行った。得られた配線の電気抵抗値を表４および図４に示す。 The same procedure as in Example 18 was performed except that 0.3 g of ethylene glycol was used instead of 0.9 g. The electric resistance value of the obtained wiring is shown in Table 4 and FIG.
前記表４および図４に示すように、実施例１７〜１９の結果から、粒径が０．３〜０．５μｍの範囲の銀粒子を含有する導電性ペーストを用いると、１８０℃程度３０分間の加熱で、低い電気抵抗率を達成できることが確認できた。 As shown in Table 4 and FIG. 4, from the results of Examples 17 to 19, when a conductive paste containing silver particles having a particle size in the range of 0.3 to 0.5 μm is used, approximately 180 ° C. for 30 minutes. It was confirmed that a low electrical resistivity can be achieved by heating of.
銀粒子（福田金属箔粉工業株式会社製、製品名「ＡｇＣ−２３９」、４ｇ）と、銀粒子（三井金属鉱業株式会社製、製品名「ＥＨＤ」、２ｇ）とエチレングリコール（０．６ｇ）とを２５℃で混合して導電性ペーストを得た。得られた導電性ペーストを、ガラス基板（厚み１ｍｍ）にスクリーン印刷法により厚み２００μｍに塗布した。前記導電性ペーストが塗布されたガラス基板を、２００℃で５分、１０分、２０分、３０分、または６０分間、大気雰囲気下で加熱した。得られた配線の厚みは、１７５〜１９５μｍである。得られた配線の電気抵抗値を表５および図５に示す。 Silver particles (Fukuda Metal Foil Powder Co., Ltd., product name “AgC-239”, 4 g), Silver particles (Mitsui Metal Mining Co., Ltd., product name “EHD”, 2 g) and ethylene glycol (0.6 g) Were mixed at 25 ° C. to obtain a conductive paste. The obtained conductive paste was applied to a glass substrate (thickness 1 mm) to a thickness of 200 μm by screen printing. The glass substrate coated with the conductive paste was heated at 200 ° C. for 5 minutes, 10 minutes, 20 minutes, 30 minutes, or 60 minutes in an air atmosphere. The thickness of the obtained wiring is 175 to 195 μm. The electrical resistance value of the obtained wiring is shown in Table 5 and FIG.
銀粒子（三井金属鉱業株式会社製、製品名「ＥＨＤ」の代わりに銀粒子（三井金属鉱業株式会社製、製品名「ＦＨＤ」、２ｇ）を用いた以外は、実施例２０と同様にして行った。得られた配線の電気抵抗値を表５および図５に示す。 Performed in the same manner as in Example 20 except that silver particles (Mitsui Metal Mining Co., Ltd., product name “FHD”, 2 g) were used instead of the product name “EHD”. The electrical resistance values of the obtained wiring are shown in Table 5 and FIG.
前記表５および図５に示すように、実施例２０および２１の結果から、粒径が０．３〜０．５μｍの範囲の銀粒子と、粒径が２．０〜３．２μｍの範囲の銀粒子とを含有する導電性ペーストを用いると、２００℃で３０分間程度の加熱で、低い電気抵抗率を達成できることが確認できた。 As shown in Table 5 and FIG. 5, from the results of Examples 20 and 21, the silver particles having a particle diameter in the range of 0.3 to 0.5 μm and the particle diameters in the range of 2.0 to 3.2 μm. It was confirmed that when a conductive paste containing silver particles was used, a low electrical resistivity could be achieved by heating at 200 ° C. for about 30 minutes.
銀粒子（福田金属箔粉工業株式会社製、製品名「ＡｇＣ−２３９」、１ｇ）と、銀粒子（三井金属鉱業株式会社製、製品名「ＦＨＤ」、１ｇ）とエタノール（０．４５ｇ）とを２５℃で混合して導電性ペーストを得た。得られた導電性ペーストを、ガラス基板（厚み１ｍｍ）にスクリーン印刷法により厚み２００μｍに塗布した。前記導電性ペーストが塗布されたガラス基板を、２００℃で３０分間、大気雰囲気下で加熱した。得られた配線の厚みは、１７５〜１９５μｍである。得られた配線の電気抵抗値は３．９×１０-6Ω・ｃｍであった。また、得られた配線の断面のＳＥＭ写真を図６（ａ）に示す。 Silver particles (Fukuda Metal Foil Powder Co., Ltd., product name “AgC-239”, 1 g), Silver particles (Mitsui Metal Mining Co., Ltd., product name “FHD”, 1 g) and ethanol (0.45 g) Were mixed at 25 ° C. to obtain a conductive paste. The obtained conductive paste was applied to a glass substrate (thickness 1 mm) to a thickness of 200 μm by screen printing. The glass substrate coated with the conductive paste was heated at 200 ° C. for 30 minutes in an air atmosphere. The thickness of the obtained wiring is 175 to 195 μm. The obtained wiring had an electric resistance value of 3.9 × 10 −6 Ω · cm. Moreover, the SEM photograph of the cross section of the obtained wiring is shown to Fig.6 (a).
［比較例７］
エタノールを用いない以外は、実施例２２と同様にして行った。得られた配線の電気抵抗値は２．０×１０-5Ω・ｃｍであった。また、得られた配線の断面のＳＥＭ写真を図６（ｂ）に示す。
[Comparative Example 7]
It carried out like Example 22 except not using ethanol. The obtained wiring had an electric resistance value of 2.0 × 10 −5 Ω · cm. Further, an SEM photograph of a cross section of the obtained wiring is shown in FIG.
前記図６に示すように、実施例２２および比較例７の結果から、本発明の導電性ペーストを用いると、２００℃で３０分間程度の加熱で、低い電気抵抗率を達成できることが確認できた。また、得られた配線において、金属粒子が密集していることを確認できた。 As shown in FIG. 6, from the results of Example 22 and Comparative Example 7, it was confirmed that when the conductive paste of the present invention was used, a low electrical resistivity could be achieved by heating at 200 ° C. for about 30 minutes. . Moreover, it was confirmed that the metal particles were dense in the obtained wiring.
銀粒子（福田金属箔粉工業株式会社製、製品名「ＡｇＣ−２３９」、２．５ｇ）と、エタノール（０．３ｇ）とを２５℃で混合して導電性ペーストを得た。得られた導電性ペーストを、ガラス基板（厚み１ｍｍ）にスクリーン印刷法により厚み２００μｍに塗布した。前記導電性ペーストが塗布されたガラス基板を、２００℃で３０分間、大気雰囲気下で加熱した。得られた配線の厚みは、１７５〜１９５μｍである。得られた配線の電気抵抗値は５．３×１０-6Ω・ｃｍであった。また、得られた配線の断面のＳＥＭ写真を図７（ａ）に示す。 Silver particles (manufactured by Fukuda Metal Foil Powder Co., Ltd., product name “AgC-239”, 2.5 g) and ethanol (0.3 g) were mixed at 25 ° C. to obtain a conductive paste. The obtained conductive paste was applied to a glass substrate (thickness 1 mm) to a thickness of 200 μm by screen printing. The glass substrate coated with the conductive paste was heated at 200 ° C. for 30 minutes in an air atmosphere. The thickness of the obtained wiring is 175 to 195 μm. The obtained wiring had an electric resistance of 5.3 × 10 −6 Ω · cm. Further, an SEM photograph of a cross section of the obtained wiring is shown in FIG.
［比較例８］
エタノールを用いない以外は、実施例２３と同様にして行った。得られた配線の電気抵抗値は１．１×１０-5Ω・ｃｍであった。また、得られた配線の断面のＳＥＭ写真を図７（ｂ）に示す。
[Comparative Example 8]
It carried out like Example 23 except not using ethanol. The obtained wiring had an electric resistance value of 1.1 × 10 −5 Ω · cm. Further, an SEM photograph of a cross section of the obtained wiring is shown in FIG.
前記図７に示すように、実施例２３および比較例８の結果から、本発明の導電性ペーストを用いると、２００℃で３０分間程度の加熱で、低い電気抵抗率を達成できることが確認できた。また、得られた配線において、金属粒子が密集していることを確認できた。 As shown in FIG. 7, from the results of Example 23 and Comparative Example 8, it was confirmed that when the conductive paste of the present invention was used, a low electrical resistivity could be achieved by heating at 200 ° C. for about 30 minutes. . Moreover, it was confirmed that the metal particles were dense in the obtained wiring.
［参考例１］
銀粒子（福田金属箔粉工業株式会社製、製品名「ＡｇＣ−２３９」、２ｇ）と、溶媒（０．２〜０．５ｇ）とを２５℃で混合して導電性ペーストを得た。得られた導電性ペーストを、ガラス基板（厚み１ｍｍ）にスクリーン印刷法により厚み２００μｍに塗布した。溶媒としては、水、メタノール、エタノール、エチレングリコールまたは２−エトキシエタノールを用いた。得られた前記導電性ペーストの塗布しやすさ（印刷性）を、表６に示す。表中の評価は、以下のとおりである。
[Reference Example 1]
Silver particles (made by Fukuda Metal Foil Powder Co., Ltd., product name “AgC-239”, 2 g) and a solvent (0.2 to 0.5 g) were mixed at 25 ° C. to obtain a conductive paste. The obtained conductive paste was applied to a glass substrate (thickness 1 mm) to a thickness of 200 μm by screen printing. As the solvent, water, methanol, ethanol, ethylene glycol or 2-ethoxyethanol was used. Table 6 shows the ease of application (printability) of the obtained conductive paste. The evaluation in the table is as follows.
［参考例２］
導電性ペーストを、銀粒子（福田金属箔粉工業株式会社製、製品名「ＡｇＣ−２３９」、１ｇ）と、銀粒子（三井金属鉱業株式会社製、製品名「ＦＨＤ」、１ｇ）とアルコール（０．２〜０．５ｇ）とを２５℃で混合して導電性ペーストを得た以外は、参考例１と同様にして行った。前記導電性ペーストの塗布しやすさ（印刷性）を、表６に示す。
[Reference Example 2]
The conductive paste is made of silver particles (Fukuda Metal Foil Powder Co., Ltd., product name “AgC-239”, 1 g), silver particles (Mitsui Metal Mining Co., Ltd., product name “FHD”, 1 g) and alcohol ( 0.2 to 0.5 g) was performed at 25 ° C. in the same manner as in Reference Example 1 except that a conductive paste was obtained. Table 6 shows the ease of application of the conductive paste (printability).
［参考例３］
導電性ペーストを、銀粒子（福田金属箔粉工業株式会社製、製品名「ＡｇＣ−２３９」、１ｇ）と、銀粒子（三井金属鉱業株式会社製、製品名「ＥＨＤ」、１ｇ）とアルコール（０．２〜０．５ｇ）とを２５℃で混合して導電性ペーストを得た以外は、参考例１と同様にして行った。前記導電性ペーストの塗布しやすさ（印刷性）を、表６に示す。
[Reference Example 3]
The conductive paste is made of silver particles (Fukuda Metal Foil Industry Co., Ltd., product name “AgC-239”, 1 g), silver particles (Mitsui Metal Mining Co., Ltd., product name “EHD”, 1 g) and alcohol ( 0.2 to 0.5 g) was performed at 25 ° C. in the same manner as in Reference Example 1 except that a conductive paste was obtained. Table 6 shows the ease of application of the conductive paste (printability).
表６に示すように、参考例１〜３の結果から、本発明の導電性ペーストを用いると、印刷性に優れることが確認できた。また、アルコールとしてエチレングリコールを用いる場合、導電性ペーストが安定したペーストであった。 As shown in Table 6, from the results of Reference Examples 1 to 3, it was confirmed that when the conductive paste of the present invention was used, the printability was excellent. Further, when ethylene glycol was used as the alcohol, the conductive paste was a stable paste.
銀粒子（福田金属箔粉工業株式会社製、製品名「ＡｇＣ−２３９」、４ｇ）とエチレングリコール（０．４ｇ）とを２５℃で混合して導電性ペーストを得た。得られた導電性ペーストを、Ａｕ／Ｎｉ基板（Ｎｉ厚み１ｍｍ。Ａｕ基板にＮｉでメッキした基板。）にスクリーン印刷法により厚み１００μｍに塗布した。次にその導電性ペーストの上にＡｕ／Ｎｉ基板（寸法４ｍｍ×４ｍｍ。Ｎｉ厚み１ｍｍ。Ａｕ基板にＮｉでメッキした基板。）を載せた。前記導電性ペーストが塗布された基板を、２２０℃で４０分間、大気雰囲気下で加熱した。得られた配線の厚みは、７５〜９５μｍである。 Silver particles (manufactured by Fukuda Metal Foil Industry Co., Ltd., product name “AgC-239”, 4 g) and ethylene glycol (0.4 g) were mixed at 25 ° C. to obtain a conductive paste. The obtained conductive paste was applied to an Au / Ni substrate (Ni thickness: 1 mm. Au substrate plated with Ni) to a thickness of 100 μm by screen printing. Next, an Au / Ni substrate (size 4 mm × 4 mm, Ni thickness 1 mm, a substrate plated with Ni on an Au substrate) was placed on the conductive paste. The substrate coated with the conductive paste was heated at 220 ° C. for 40 minutes in an air atmosphere. The obtained wiring has a thickness of 75 to 95 μm.
得られたドット状に形成した配線の基板への接合強度を測定した。測定方法は、ＪＩＳＺ３１９８−７に準じる方法に従い行った。 The bonding strength to the substrate of the wiring formed in the dot shape was measured. The measuring method was performed according to a method according to JISZ3198-7.
その後、基板と配線の上に配置された基板との間に存在する配線に、導電性接着剤（藤倉化成株式会社製、製品名「ＸＢ−５１２７」）を塗布した。１５０℃で３０分間加熱して前記接着剤を硬化させた。その後、得られた配線の基板への接合強度を前記と同様にして測定した。得られた接合強度を表７に示す。 Thereafter, a conductive adhesive (product name “XB-5127”, manufactured by Fujikura Kasei Co., Ltd.) was applied to the wiring existing between the substrate and the substrate disposed on the wiring. The adhesive was cured by heating at 150 ° C. for 30 minutes. Thereafter, the bonding strength of the obtained wiring to the substrate was measured in the same manner as described above. Table 7 shows the obtained bonding strength.
導電性ペーストを、銀粒子（福田金属箔粉工業株式会社製、製品名「ＡｇＣ−２３９」、２ｇ）と、銀粒子（三井金属鉱業株式会社製、製品名「ＦＨＤ」、２ｇ）エチレングリコール（０．４ｇ）とを２５℃で混合して導電性ペーストを得た以外は、実施例２４と同様にして行った。得られた配線の厚みは、７５〜９５μｍである。得られた接合強度を表７に示す。 The conductive paste is made of silver particles (Fukuda Metal Foil Powder Co., Ltd., product name “AgC-239”, 2 g) and silver particles (Mitsui Metal Mining Co., Ltd., product name “FHD”, 2 g) ethylene glycol ( 0.4 g) at 25 ° C., except that a conductive paste was obtained. The obtained wiring has a thickness of 75 to 95 μm. Table 7 shows the obtained bonding strength.
［参考例４］
銀粒子（福田金属箔粉工業株式会社製、製品名「ＡｇＣ−Ａ」、４ｇ）と、エタノール（０．４ｇ）とを２５℃で混合して導電性ペーストを得た。次にその導電性ペーストの上にＡｕ／Ｎｉ基板（寸法４ｍｍ×４ｍｍ。Ｎｉ厚み１ｍｍ。Ａｕ基板にＮｉでメッキした基板。）を載せた。前記導電性ペーストが塗布された基板を、４３０℃で３０分間、大気雰囲気下で加熱した。得られた配線の厚みは、７５〜９５μｍである。得られた接合強度を表７に示す。
[Reference Example 4]
Silver particles (made by Fukuda Metal Foil Powder Co., Ltd., product name “AgC-A”, 4 g) and ethanol (0.4 g) were mixed at 25 ° C. to obtain a conductive paste. Next, an Au / Ni substrate (size 4 mm × 4 mm, Ni thickness 1 mm, a substrate plated with Ni on an Au substrate) was placed on the conductive paste. The substrate coated with the conductive paste was heated at 430 ° C. for 30 minutes in an air atmosphere. The obtained wiring has a thickness of 75 to 95 μm. Table 7 shows the obtained bonding strength.
［参考例５］
導電性接着剤（藤倉化成株式会社製、製品名「ＸＡ−５５５４」）を、Ａｕ／Ｎｉ基板（Ｎｉ厚み1ｍｍ。Ａｕ基板にＮｉでメッキした基板。）にスクリーン印刷法により厚み１００μｍに塗布した。次にその接着剤の上にＡｕ／Ｎｉ基板（寸法４ｍｍ×４ｍｍ。Ｎｉ厚み１ｍｍ。Ａｕ基板にＮｉでメッキした基板。）を載せた。前記接着剤が塗布された基板を、１５０℃で３０分間加熱して前記接着剤を硬化させた。その後、得られた基板への接合強度を実施例２４と同様にして測定した。得られた接合強度を表７に示す。
[Reference Example 5]
A conductive adhesive (product name “XA-5554”, manufactured by Fujikura Kasei Co., Ltd.) was applied to an Au / Ni substrate (Ni thickness: 1 mm. Au substrate plated with Ni) to a thickness of 100 μm by screen printing. . Next, an Au / Ni substrate (size: 4 mm × 4 mm, Ni thickness: 1 mm, a substrate plated with Ni on an Au substrate) was placed on the adhesive. The substrate coated with the adhesive was heated at 150 ° C. for 30 minutes to cure the adhesive. Thereafter, the bonding strength to the obtained substrate was measured in the same manner as in Example 24. Table 7 shows the obtained bonding strength.
［参考例７］
銀ナノペースト（ハリマ化成株式会社製、製品名「ＮＰＳ−ＨＴＢ」、４ｇ）を、Ａｕ／Ｎｉ基板（Ｎｉ厚み１ｍｍ。Ａｕ基板にＮｉでメッキした基板。）にスクリーン印刷法により厚み１００μｍに塗布した。次にその導電性ペーストの上にＡｕ／Ｎｉ基板（寸法４ｍｍ×４ｍｍ。Ｎｉ厚み１ｍｍ。Ａｕ基板にＮｉでメッキした基板。）を載せた。前記導電性ペーストが塗布された基板を、４３０℃で３０分間、大気雰囲気下で加熱した。得られた配線の厚みは、７５〜９５μｍである。その後、得られた基板への接合強度を実施例２４と同様にして測定した。得られた接合強度を表７に示す。
[Reference Example 7]
Silver nano paste (manufactured by Harima Kasei Co., Ltd., product name “NPS-HTB”, 4 g) is applied to an Au / Ni substrate (Ni thickness: 1 mm. Au substrate plated with Ni) to a thickness of 100 μm by screen printing. did. Next, an Au / Ni substrate (size 4 mm × 4 mm, Ni thickness 1 mm, a substrate plated with Ni on an Au substrate) was placed on the conductive paste. The substrate coated with the conductive paste was heated at 430 ° C. for 30 minutes in an air atmosphere. The obtained wiring has a thickness of 75 to 95 μm. Thereafter, the bonding strength to the obtained substrate was measured in the same manner as in Example 24. Table 7 shows the obtained bonding strength.
表７に示すように、実施例２４および２５の結果から、本発明の導電性ペーストを用い、配線を形成後に導電性接着剤を用いると、低い電気抵抗率と高い接合強度を両立できることが確認できた。 As shown in Table 7, from the results of Examples 24 and 25, it was confirmed that the use of the conductive paste of the present invention and the use of the conductive adhesive after forming the wiring can achieve both low electrical resistivity and high bonding strength. did it.
本発明の導電性ペーストは、耐熱パワー配線、部品電極、ダイアタッチ、微細バンプ、フラットパネル、ソーラ配線等の製造用途およびウエハ接続等の用途にも適用できる。 The conductive paste of the present invention can be applied to manufacturing applications such as heat resistant power wiring, component electrodes, die attach, fine bumps, flat panels, solar wiring, and wafer connection.
Claims (3)
アルコールとを含む導電性ペースト。 Silver particles having an average particle diameter (median diameter) of 0.1 μm to 15 μm;
A conductive paste containing alcohol.
塗布された前記基板を１５０〜３００℃で加熱し、配線を形成する方法。 A method for forming a wiring using the conductive paste according to claim 1, wherein the conductive paste is applied on a substrate,
A method of heating the coated substrate at 150 to 300 ° C. to form a wiring.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008007582A JP5207281B2 (en) | 2008-01-17 | 2008-01-17 | Conductive paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008007582A JP5207281B2 (en) | 2008-01-17 | 2008-01-17 | Conductive paste |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2009170277A true JP2009170277A (en) | 2009-07-30 |
| JP5207281B2 JP5207281B2 (en) | 2013-06-12 |
Family
ID=40971222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008007582A Active JP5207281B2 (en) | 2008-01-17 | 2008-01-17 | Conductive paste |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5207281B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012102275A1 (en) * | 2011-01-28 | 2012-08-02 | 日立化成工業株式会社 | Adhesive composition and semiconductor device using same |
| WO2015194536A1 (en) * | 2014-06-16 | 2015-12-23 | 国立大学法人大阪大学 | Method for synthesizing silver particles, silver particles, method for manufacturing electroconductive paste, and electroconductive paste |
| JP2016225100A (en) * | 2015-05-29 | 2016-12-28 | 株式会社ダイセル | Joint conductive paste |
| WO2017188446A1 (en) * | 2016-04-28 | 2017-11-02 | シャープ株式会社 | Conductive paste, electrode connection structure, and electrode connection structure production method |
| WO2020008689A1 (en) | 2018-07-06 | 2020-01-09 | 千住金属工業株式会社 | Conductive paste and sintered body |
| WO2021025003A1 (en) | 2019-08-07 | 2021-02-11 | 株式会社ダイセル | Adhesive conductive paste |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015115665A1 (en) | 2014-02-03 | 2015-08-06 | 国立大学法人大阪大学 | Bonded structure and method for producing bonded structure |
| JP6628351B2 (en) | 2015-07-24 | 2020-01-08 | 国立大学法人大阪大学 | Silver particle production method |
| JP6795307B2 (en) | 2016-02-12 | 2020-12-02 | 国立大学法人大阪大学 | Joining material, manufacturing method of joining material, manufacturing method of joining structure |
| JP6706818B2 (en) * | 2016-06-30 | 2020-06-10 | 国立大学法人大阪大学 | Semiconductor device |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004265901A (en) * | 2003-01-23 | 2004-09-24 | Matsushita Electric Ind Co Ltd | Conductive paste, circuit forming substrate using the same, and its manufacturing method |
| JP2004362950A (en) * | 2003-06-05 | 2004-12-24 | Noritake Co Ltd | Conductive paste mainly composed of silver powder, and its manufacturing method |
| JP2005093380A (en) * | 2003-09-19 | 2005-04-07 | Mitsui Mining & Smelting Co Ltd | Silver ink and manufacturing method of silver ink |
| JP2006066235A (en) * | 2004-08-27 | 2006-03-09 | Kinugawa Rubber Ind Co Ltd | Conductive elastic body composition |
| JP2006202604A (en) * | 2005-01-20 | 2006-08-03 | Matsushita Electric Ind Co Ltd | Conductive paste, wiring board using the same, and manufacturing method of multilayered board and electronic parts mounted body |
| WO2006126614A1 (en) * | 2005-05-25 | 2006-11-30 | Nihon Handa Co., Ltd. | Paste-like silver composition, method for producing same, method for producing solid silver, solid silver, bonding method, and method for manufacturing circuit board |
| JP2007042301A (en) * | 2005-07-29 | 2007-02-15 | Toda Kogyo Corp | Conductive composition, conductive paste, and conductive film |
| WO2007034833A1 (en) * | 2005-09-21 | 2007-03-29 | Nihon Handa Co., Ltd. | Pasty silver particle composition, process for producing solid silver, solid silver, joining method, and process for producing printed wiring board |
-
2008
- 2008-01-17 JP JP2008007582A patent/JP5207281B2/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004265901A (en) * | 2003-01-23 | 2004-09-24 | Matsushita Electric Ind Co Ltd | Conductive paste, circuit forming substrate using the same, and its manufacturing method |
| JP2004362950A (en) * | 2003-06-05 | 2004-12-24 | Noritake Co Ltd | Conductive paste mainly composed of silver powder, and its manufacturing method |
| JP2005093380A (en) * | 2003-09-19 | 2005-04-07 | Mitsui Mining & Smelting Co Ltd | Silver ink and manufacturing method of silver ink |
| JP2006066235A (en) * | 2004-08-27 | 2006-03-09 | Kinugawa Rubber Ind Co Ltd | Conductive elastic body composition |
| JP2006202604A (en) * | 2005-01-20 | 2006-08-03 | Matsushita Electric Ind Co Ltd | Conductive paste, wiring board using the same, and manufacturing method of multilayered board and electronic parts mounted body |
| WO2006126614A1 (en) * | 2005-05-25 | 2006-11-30 | Nihon Handa Co., Ltd. | Paste-like silver composition, method for producing same, method for producing solid silver, solid silver, bonding method, and method for manufacturing circuit board |
| JP2007042301A (en) * | 2005-07-29 | 2007-02-15 | Toda Kogyo Corp | Conductive composition, conductive paste, and conductive film |
| WO2007034833A1 (en) * | 2005-09-21 | 2007-03-29 | Nihon Handa Co., Ltd. | Pasty silver particle composition, process for producing solid silver, solid silver, joining method, and process for producing printed wiring board |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012102275A1 (en) * | 2011-01-28 | 2012-08-02 | 日立化成工業株式会社 | Adhesive composition and semiconductor device using same |
| TWI653347B (en) | 2014-06-16 | 2019-03-11 | 國立大學法人大阪大學 | Silver particle synthesizing method, silver particle, conductive paste manufacturing method, and conductive paste |
| CN106660131B (en) * | 2014-06-16 | 2019-03-19 | 国立大学法人大阪大学 | Argent grain synthetic method, Argent grain, electrocondution slurry manufacturing method and electrocondution slurry |
| US10201852B2 (en) | 2014-06-16 | 2019-02-12 | Osaka University | Silver particle synthesizing method, silver particles, conductive paste producing method, and conductive paste |
| CN106660131A (en) * | 2014-06-16 | 2017-05-10 | 国立大学法人大阪大学 | Method for synthesizing silver particles, silver particles, method for manufacturing electroconductive paste, and electroconductive paste |
| JPWO2015194536A1 (en) * | 2014-06-16 | 2017-05-18 | 国立大学法人大阪大学 | Method for synthesizing silver particles, silver particles, method for producing conductive paste, and conductive paste |
| WO2015194536A1 (en) * | 2014-06-16 | 2015-12-23 | 国立大学法人大阪大学 | Method for synthesizing silver particles, silver particles, method for manufacturing electroconductive paste, and electroconductive paste |
| EP3156157A4 (en) * | 2014-06-16 | 2018-02-21 | Osaka University | Method for synthesizing silver particles, silver particles, method for manufacturing electroconductive paste, and electroconductive paste |
| KR102153165B1 (en) | 2014-06-16 | 2020-09-07 | 오사카 유니버시티 | Method for synthesizing silver particles, silver particles, method for manufacturing electroconductive paste, and electroconductive paste |
| KR20170018897A (en) | 2014-06-16 | 2017-02-20 | 오사카 유니버시티 | Method for synthesizing silver particles, silver particles, method for manufacturing electroconductive paste, and electroconductive paste |
| JP2016225100A (en) * | 2015-05-29 | 2016-12-28 | 株式会社ダイセル | Joint conductive paste |
| CN109313955B (en) * | 2016-04-28 | 2020-06-09 | 夏普株式会社 | Conductive paste, electrode connection structure, and method for manufacturing electrode connection structure |
| JPWO2017188446A1 (en) * | 2016-04-28 | 2019-04-04 | シャープ株式会社 | Conductive paste, electrode connection structure, and method of manufacturing electrode connection structure |
| CN109313955A (en) * | 2016-04-28 | 2019-02-05 | 夏普株式会社 | The manufacturing method of conductive paste, electrode connecting structure and electrode connecting structure |
| WO2017188446A1 (en) * | 2016-04-28 | 2017-11-02 | シャープ株式会社 | Conductive paste, electrode connection structure, and electrode connection structure production method |
| WO2020008689A1 (en) | 2018-07-06 | 2020-01-09 | 千住金属工業株式会社 | Conductive paste and sintered body |
| US11710580B2 (en) | 2018-07-06 | 2023-07-25 | Senju Metal Industry Co., Ltd. | Electrically conductive paste and sintered body |
| EP4148748A1 (en) | 2018-07-06 | 2023-03-15 | Senju Metal Industry Co., Ltd. | Electrically conductive paste and sintered body |
| WO2021025003A1 (en) | 2019-08-07 | 2021-02-11 | 株式会社ダイセル | Adhesive conductive paste |
| KR20220042428A (en) | 2019-08-07 | 2022-04-05 | 주식회사 다이셀 | Bonding Conductor Paste |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5207281B2 (en) | 2013-06-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5207281B2 (en) | Conductive paste | |
| JP4362742B2 (en) | Method for solidifying paste-like metal particle composition, method for joining metal members, and method for producing printed wiring board | |
| JP5611537B2 (en) | Conductive bonding material, bonding method using the same, and semiconductor device bonded thereby | |
| JP4353380B2 (en) | Paste-like silver particle composition, method for producing solid silver, solid silver, joining method, and method for producing printed wiring board | |
| JP4347381B2 (en) | Paste silver composition for adhesion of metal-based adherend, method for producing the same, and method for bonding metal-based adherend | |
| TW487742B (en) | Electrode for PTC thermistor, manufacture thereof, and PTC thermistor | |
| JP5670924B2 (en) | Conductive bonding material, method of bonding ceramic electronic material using the same, and ceramic electronic device | |
| TW201011088A (en) | Conductive adhesive and LED substrate using it | |
| JP5011225B2 (en) | Metal member bonding agent, metal member bonded body manufacturing method, metal member bonded body, and electric circuit connecting bump manufacturing method | |
| JP6766160B2 (en) | Composition for metal bonding | |
| KR20180059490A (en) | Conductive paste and conductive film | |
| JP2007184153A (en) | Conductive paste composition for low-temperature calcination and method of forming wiring pattern using the paste composition | |
| EP3806111B1 (en) | Electrically conductive paste and sintered body | |
| TWI609381B (en) | Method of fabricating high-conductivity thick-film copper paste coated with nano-silver for being sintered in the air | |
| JP3879749B2 (en) | Conductive powder and method for producing the same | |
| WO2018030173A1 (en) | Bonding composition and method for preparing same | |
| JP7317397B2 (en) | COPPER OXIDE PASTE AND METHOD FOR MANUFACTURING ELECTRONIC COMPONENT | |
| JP2017179428A (en) | Conductive material, forming method of conducive film, circuit board, semiconductor device, and manufacturing method of semiconductor device | |
| JP6408695B2 (en) | Copper-containing conductive paste and electrode made from copper-containing conductive paste | |
| JP7269565B2 (en) | Conductive ink composition and conductive laminate | |
| JP6564024B2 (en) | Method for manufacturing a solar cell having a copper electrode | |
| JP7132591B2 (en) | Conductive paste and sintered body | |
| JP2014181164A (en) | Metal paste composition for ceramic material | |
| JPS59103204A (en) | Thick film gold metallized composition | |
| JP6323587B1 (en) | Bonding paste, and article bonded with the bonding paste |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20110112 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20120203 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120214 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120413 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120816 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20121012 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20121211 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130118 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130207 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130213 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160301 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5207281 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |