JP2015063712A - Organic gold compound, manufacturing method thereof, and conductive paste - Google Patents
Organic gold compound, manufacturing method thereof, and conductive paste Download PDFInfo
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- JP2015063712A JP2015063712A JP2013196741A JP2013196741A JP2015063712A JP 2015063712 A JP2015063712 A JP 2015063712A JP 2013196741 A JP2013196741 A JP 2013196741A JP 2013196741 A JP2013196741 A JP 2013196741A JP 2015063712 A JP2015063712 A JP 2015063712A
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- organic gold
- alkanethiols
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- 150000002344 gold compounds Chemical class 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000010931 gold Substances 0.000 claims abstract description 53
- 229910052737 gold Inorganic materials 0.000 claims abstract description 43
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 39
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 25
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 11
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 claims abstract description 11
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- ZRKMQKLGEQPLNS-UHFFFAOYSA-N 1-Pentanethiol Chemical compound CCCCCS ZRKMQKLGEQPLNS-UHFFFAOYSA-N 0.000 claims abstract description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 claims abstract description 6
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical group O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 claims abstract description 6
- 229910052788 barium Inorganic materials 0.000 claims abstract description 5
- 150000001414 amino alcohols Chemical class 0.000 claims abstract description 4
- 235000001727 glucose Nutrition 0.000 claims abstract description 4
- 150000002304 glucoses Chemical class 0.000 claims abstract description 4
- -1 gold ion Chemical class 0.000 claims abstract description 4
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract 4
- 150000003839 salts Chemical class 0.000 claims abstract 2
- 235000002639 sodium chloride Nutrition 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000011230 binding agent Substances 0.000 claims description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- OQMBBFQZGJFLBU-UHFFFAOYSA-N Oxyfluorfen Chemical compound C1=C([N+]([O-])=O)C(OCC)=CC(OC=2C(=CC(=CC=2)C(F)(F)F)Cl)=C1 OQMBBFQZGJFLBU-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229920003002 synthetic resin Polymers 0.000 claims description 2
- 239000000057 synthetic resin Substances 0.000 claims description 2
- 238000010304 firing Methods 0.000 abstract description 11
- 238000007650 screen-printing Methods 0.000 abstract description 7
- 239000004952 Polyamide Substances 0.000 abstract description 4
- 229920002647 polyamide Polymers 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 229910001873 dinitrogen Inorganic materials 0.000 description 13
- 230000005587 bubbling Effects 0.000 description 12
- 239000010408 film Substances 0.000 description 12
- 229920001721 polyimide Polymers 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 239000010409 thin film Substances 0.000 description 10
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 9
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 9
- 229940116411 terpineol Drugs 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000005070 ripening Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000001856 Ethyl cellulose Substances 0.000 description 5
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 5
- 229920001249 ethyl cellulose Polymers 0.000 description 5
- 235000019325 ethyl cellulose Nutrition 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 150000002429 hydrazines Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 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
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- VVBXIYWYQPFUKL-UHFFFAOYSA-K 2-ethylhexanoate gold(3+) Chemical compound [Au+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O VVBXIYWYQPFUKL-UHFFFAOYSA-K 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920000896 Ethulose Polymers 0.000 description 1
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- DJXRYKXIIQBVBJ-UHFFFAOYSA-K [Au+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O Chemical compound [Au+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O DJXRYKXIIQBVBJ-UHFFFAOYSA-K 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229920000180 alkyd Polymers 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
- 229940088601 alpha-terpineol Drugs 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- ZUDYPQRUOYEARG-UHFFFAOYSA-L barium(2+);dihydroxide;octahydrate Chemical compound O.O.O.O.O.O.O.O.[OH-].[OH-].[Ba+2] ZUDYPQRUOYEARG-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- MXZVHYUSLJAVOE-UHFFFAOYSA-N gold(3+);tricyanide Chemical compound [Au+3].N#[C-].N#[C-].N#[C-] MXZVHYUSLJAVOE-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Parts Printed On Printed Circuit Boards (AREA)
- Chemically Coating (AREA)
- Conductive Materials (AREA)
Abstract
Description
本発明は、有機金化合物、その製造方法及び導電性ペーストに関し、さらに詳しくは、ポリアミドフイルム、プリント配線基板、セラミックICパッケージ、ウエハ等の電子部品へ金膜導電回路形成用などの導電性ペーストに用いられる有機金化合物、その製造方法及び導電性ペーストに関する。 The present invention relates to an organic gold compound, a method for producing the same, and a conductive paste. More specifically, the present invention relates to a conductive paste for forming a gold film conductive circuit on an electronic component such as a polyamide film, a printed wiring board, a ceramic IC package, or a wafer. The present invention relates to an organic gold compound used, a method for producing the same, and a conductive paste.
従来、基板上に膜状電極等の導電性パターンを形成するため導電性ペーストとして有機金ペーストが知られている。
このような有機金ペーストの代表的な用途としては、ファクシミリー等のプリンターヘッドとして使用されているサーマルプリンターヘッドの電極作成が挙げられる。
Conventionally, an organic gold paste is known as a conductive paste for forming a conductive pattern such as a film electrode on a substrate.
A typical application of such an organic gold paste is the production of electrodes for thermal printer heads used as printer heads for facsimiles and the like.
この出願に関連する先行技術としては、金化合物として、α―ピネン、α―ターピネオール、イソボルネオールのメルカプタン金、またはサルフィド金、アベチエン酸金、ネオデカン酸金、２−エチルヘキサン酸金、ナフテン酸金等の１種又は２種以上を用い、これにロジウム化合物、ビスマス化合物、クロム化合物、鉛化合物、ケイ素化合物、有機樹脂、有機溶媒を配合した有機金ペーストを用い、セラミック基板にスクリーン印刷した後、８００〜８５０℃で焼成し、金薄膜を得ることが知られている（例えば、特許文献１）。
このような従来の有機金ペーストは、８００℃以上の高温で焼成するため基板としてセラミックス等の高温に耐える材料しか使用することができず。耐熱性フィルムとして知られるポリアミドフイルム等の機能性樹脂のフィルムおよび基板へ適用することは不可能であった。また焼成炉として高温対応の物を使用しているためエネルギーコストがかかる問題もあった。
Prior art related to this application includes gold compounds such as α-pinene, α-terpineol, gold isocaptane, or sulfide gold, gold abetienoate, gold neodecanoate, gold 2-ethylhexanoate, gold naphthenate. After using one or two or more of the above, an organic gold paste containing a rhodium compound, a bismuth compound, a chromium compound, a lead compound, a silicon compound, an organic resin, an organic solvent, and screen printing on a ceramic substrate, It is known that a gold thin film is obtained by baking at 800 to 850 ° C. (for example, Patent Document 1).
Since such a conventional organic gold paste is fired at a high temperature of 800 ° C. or higher, only a material that can withstand high temperatures such as ceramics can be used as a substrate. It was impossible to apply to functional resin films such as polyamide films and substrates known as heat resistant films. Moreover, since the thing corresponding to high temperature is used as a baking furnace, there also existed a problem which requires energy cost.
本発明は、このような従来の有機金ペーストの高温焼成という難点を改良して２５０℃以下の低温焼成によってもシート抵抗を有する金皮膜を形成できる有機金化合物及びそれを用いた有機金ペーストを提供することを目的とする。 The present invention provides an organic gold compound capable of forming a gold film having a sheet resistance even by low-temperature baking at 250 ° C. or less by improving the difficulty of high-temperature baking of such a conventional organic gold paste, and an organic gold paste using the same The purpose is to provide.
本発明者は、上記課題を解決するため、低温で焼成することによりシート抵抗を有する金皮膜がえられる有機金化合物について鋭意検討した結果、金塩とアルカンチオール類とを不活性ガスの存在下に還元剤を含有する水溶液中で温度０℃〜７５℃で反応させ、反応終了後、反応溶液を濃縮、晶析することにより得られた有機金化合物は有機金ペーストとし、ポリアミドフイルムにスクリーン印刷、２５０℃で焼成した結果、シート抵抗に優れた金成膜が得られることを知見して本発明に到達した。 In order to solve the above-mentioned problems, the present inventor has intensively studied an organic gold compound capable of obtaining a gold film having a sheet resistance by baking at a low temperature. As a result, the gold salt and alkanethiols are obtained in the presence of an inert gas. Is reacted in an aqueous solution containing a reducing agent at a temperature of 0 ° C. to 75 ° C. After completion of the reaction, the organic gold compound obtained by concentrating and crystallizing the reaction solution is used as an organic gold paste, and screen printing is performed on a polyamide film. As a result of firing at 250 ° C., it was found that a gold film excellent in sheet resistance was obtained, and the present invention was achieved.
すなわち、本発明は、以下の内容をその発明の要旨とするものである。
（１）金塩とアルカンチオール類とを不活性ガスの存在下に還元剤を含有する水溶液中で反応させることにより金イオンにアルカンチオール類を配位させてなる一般式（１）で表される有機金化合物。
一般式（１）
（化１）
ＣＨ３−（ＣＨ２）ｎ−Ｓ−Ａｕ （１）
（式中、ｎは１〜５である）
（２）金塩は、水酸化金、金酸バリウム、雷金から選ばれる一種又は二種以上である請求項１に記載の有機金化合物。
（３）アルカンチオール類が１−プロパンチオール、１−ブタンチオールおよび１−ペンタンチオールのうちいずれかである請求項１又は請求項２に記載の有機金化合物。
（４）還元剤がヒドラジン系塩類、亜硫酸ナトリウム、シュウ酸、蟻酸、グルコース類およびアミノアルコール類から選ばれる一種又は二種以上である一般式（１）で表される請求項１〜３のいずれかに記載の有機金化合物。
（５）金塩とアルカンチオール類とを不活性ガスの存在下に還元剤を含有する水溶液中で温度０℃〜７５℃で反応させ、反応終了後、反応溶液を濃縮、晶析することを特徴とする請求項１〜４のいずれかに記載の有機金化合物の製造方法。
（６）請求項１、２、３または４のいずれかに記載の有機金化合物に、合成樹脂バインダーを配合することを特徴とする導電性ペースト。
That is, this invention makes the following content the summary of the invention.
(1) It is represented by the general formula (1) in which an alkanethiol is coordinated to a gold ion by reacting a gold salt and an alkanethiol in an aqueous solution containing a reducing agent in the presence of an inert gas. Organic gold compounds.
General formula (1)
(Chemical formula 1)
CH 3 - (CH 2) n -S-Au (1)
(Where n is 1 to 5)
(2) The organic gold compound according to claim 1, wherein the gold salt is one or more selected from gold hydroxide, barium goldate, and thunder gold.
(3) The organogold compound according to claim 1 or 2, wherein the alkanethiol is any one of 1-propanethiol, 1-butanethiol and 1-pentanethiol.
(4) Any one of claims 1 to 3 represented by the general formula (1), wherein the reducing agent is one or more selected from hydrazine salts, sodium sulfite, oxalic acid, formic acid, glucoses and amino alcohols. An organic gold compound as described above.
(5) Reacting gold salt and alkanethiols in an aqueous solution containing a reducing agent in the presence of an inert gas at a temperature of 0 ° C to 75 ° C, and concentrating and crystallizing the reaction solution after completion of the reaction. The method for producing an organic gold compound according to any one of claims 1 to 4.
(6) A conductive paste comprising a synthetic resin binder in the organic gold compound according to any one of claims 1, 2, 3 and 4.
本発明の有機金化合物の提供、製造方法及び導電性ペーストによれば一般式（１）で表される有機金化合物は、有機樹脂バインダーに配合してペースト化し、これをセラミック基板、ソーダーライム基板のみならずポリイミドフイルムに印刷し、２５０℃以下の低温で焼成することにより基板との密着性が良好でシート抵抗値の低い金パターンを形成することができるのでプラスチックフイルムにも適用性が有る。また、本発明にて提供される有機金化合物は、ノンシアン金の化合物である為、金めっき用金塩の材料とする事により、環境負荷の少ない金めっき液の作製が可能であり、その金源となり得る材料であるのでその工業的利用価値大である。 According to the provision of the organic gold compound of the present invention, the production method and the conductive paste, the organic gold compound represented by the general formula (1) is blended into an organic resin binder to form a paste, and this is formed into a ceramic substrate and a soda lime substrate. In addition to printing on a polyimide film and baking at a low temperature of 250 ° C. or lower, a gold pattern with good adhesion to the substrate and a low sheet resistance value can be formed, so that it has applicability to a plastic film. In addition, since the organic gold compound provided in the present invention is a non-cyanide gold compound, it is possible to produce a gold plating solution with less environmental impact by using a gold salt material for gold plating. Since it is a material that can be a source, its industrial utility value is great.
以下、本発明の有機金化合物、その製造方法及びそれを用いた導電性ペーストについて詳細に説明する。
本発明にかかる有機金化合物の製造方法は、電子部品の電極形成などの導電性ペーストに用いられる分散性、導電皮膜形成性に優れた有機金化合物の製造方法であり、また、導電性ペーストは、この製造方法で得られた有機金化合物を用いたものである。
Hereinafter, the organic gold compound of the present invention, the production method thereof, and the conductive paste using the same will be described in detail.
The method for producing an organic gold compound according to the present invention is a method for producing an organic gold compound that is excellent in dispersibility and conductive film-forming properties used in conductive pastes such as electrode formation of electronic components. The organic gold compound obtained by this production method is used.
１ 有機金化合物の製造方法
本発明の有機金化合物の製造方法は、水酸化金、金酸バリウム、雷金等から選ばれる金塩と、アルカンチオール類、例えば、１−プロパンチオール、１−ブタンチオールおよび１−ペンタチオールから選ばれるいずれかと窒素ガスおよびアルゴンガスなどの不活性ガスの存在下、還元剤を含有する水溶液中で温度０℃〜７５℃で反応させる。反応終了後、不活性ガスの存在下、反応溶液を３０℃以下に冷却し結晶を析出させ１２０℃以下で乾燥することにより有機金化合物の結晶粉末を得る。
1 Method for Producing Organogold Compound The method for producing an organogold compound of the present invention comprises a gold salt selected from gold hydroxide, barium goldate, thunder metal, and alkanethiols such as 1-propanethiol and 1-butane. The reaction is carried out at a temperature of 0 ° C. to 75 ° C. in an aqueous solution containing a reducing agent in the presence of any one selected from thiol and 1-pentathiol and an inert gas such as nitrogen gas and argon gas. After completion of the reaction, in the presence of an inert gas, the reaction solution is cooled to 30 ° C. or lower to precipitate crystals and dried at 120 ° C. or lower to obtain an organic gold compound crystal powder.
還元剤としてはヒドラジン系塩類、亜硫酸ナトリウム、シュウ酸、蟻酸、グルコース類およびアミノアルコール類から選ばれる一種又は二種以上が使用される。
得られた有機金化合物の結晶粉末は、導電性ペーストに適した粉末とするため衝撃式、摩砕式などの粉砕方式で平均粒径０．１μｍ〜２μｍの微分末とするのが好ましい。
As the reducing agent, one or more selected from hydrazine salts, sodium sulfite, oxalic acid, formic acid, glucoses and amino alcohols are used.
The obtained organic gold compound crystal powder is preferably a powder having an average particle size of 0.1 μm to 2 μm by a pulverization method such as an impact method or a grinding method in order to obtain a powder suitable for a conductive paste.
上記の方法でアルカンチオール類が１−プロパンチオールで合成して得られた結晶を成分分析した結果、理論値と略一致するＡｕ７２．２％（計算値：７２．４％）、Ｓ１１．７％（計算値：１１．８％）であった。したがって、本発明の有機金化合物は、上記一般式（１）で表される結晶であることを確認した。 As a result of component analysis of crystals obtained by synthesizing alkanethiols with 1-propanethiol by the above method, Au 72.2% (calculated value: 72.4%), S11.7%, which almost agrees with the theoretical value. (Calculated value: 11.8%). Therefore, it was confirmed that the organogold compound of the present invention was a crystal represented by the general formula (1).
２ 導電性ペースト
本発明の導電性ペーストは、本発明の有機金化合物と、有機樹脂バインダー、有機溶媒を主成分とするものである。
有機樹脂バインダーとしては、従来の導電性ペーストに用いるものを使用することができる。例えば、エチルセルロース、ヒドロキシエチルセルロース等のセルロース系高分子、ポリブチルメタアクリレート、ポリメチルメタアクリレート、ポリエチルメタアクリレート等のアクリル系樹脂、エポキシ系樹脂、ポリウレタン系樹脂、フエノール樹脂、アルキッド樹脂、ポリビニルブチラール等をブチルカルビトール、ブチルカルビトールアセテート、ターピネオールなどの溶媒に溶解した有機樹脂バインダーに本発明の有機金化合物を混合し、必要に応じて界面活性剤、可塑剤、分散剤等を添加し、三本ロールミルその他の混練機を用いて混練・分散してペースト化することによって得られる。
2 Conductive Paste The conductive paste of the present invention contains the organic gold compound of the present invention, an organic resin binder, and an organic solvent as main components.
As an organic resin binder, what is used for the conventional conductive paste can be used. For example, cellulose polymers such as ethyl cellulose and hydroxyethyl cellulose, acrylic resins such as polybutyl methacrylate, polymethyl methacrylate, and polyethyl methacrylate, epoxy resins, polyurethane resins, phenol resins, alkyd resins, polyvinyl butyral, etc. The organic gold compound of the present invention is mixed with an organic resin binder dissolved in a solvent such as butyl carbitol, butyl carbitol acetate, or terpineol, and a surfactant, plasticizer, dispersant, etc. are added as necessary. It can be obtained by kneading and dispersing into a paste using this roll mill or other kneader.
以下、実施例により本発明を具体的に説明する。 Hereinafter, the present invention will be described specifically by way of examples.
（１）有機金化合物の製造
塩化金酸５０.０ｇを純水５００ｍｌに溶解し、これに５％炭酸水素ナトリウムをｐＨ９．０になるまで、添加・攪拌する。析出した水酸化金を濾別後純水にて洗浄する。
次に、洗浄後の水酸化金を純水８００ｍｌに分散した後、窒素ガスをバブリングしながら加熱・攪拌をして液温を６０℃にする。そのまま１時間放置する。
次いで、この懸濁溶液に亜硫酸ナトリウム４８．２ｇの少量（一部）をゆっくり添加する。反応の様子を確認しながら、１−プロパンチオール１３．９ｇの少量（一部）をゆっくり添加する。残りの亜硫酸ナトリウムを反応の様子を確認しながら添加する。窒素ガスのバブリングはそのまま継続しながら反応溶液の温度を６０〜６５℃に保温して３時間熟成を行う。
更に、反応溶液へ残りの１−プロパンチオールを徐々に添加する。１−プロパンチオールの添加終了後、反応溶液の温度を７０℃に保ち窒素ガスのバブリングをそのまま５時間継続し、再熟成を行う。その際、還流の要領で溶媒が減らない様にする。
再熟成終了後の反応溶液は、そのまま窒素ガスのバブリング及び、攪拌を継続しながら３０℃以下に冷却し結晶を析出させる。次いで、結晶を濾過、エタノールで洗浄した後、７０℃で乾燥する事により、２２．４ｇの淡黄色粉末状の結晶を得た。（収率：６７．８％）
（２）導電性ペーストの調製
実施例１で得た有機金化合物２０重量部、有機樹脂ダインダー（エチルセルロース６重量％ターピネオール溶液）２０重量部、ターピネオール１０重量部を予備混練した後、これを３本ロールミルにより混練して導電性ペーストを調製した。
この導電性ペーストを用いて５０ｍｍ×６０ｍｍ×０．１ｍｍのポリイミドフイルム上に３２５メッシュのスクリーンでスクリーン印刷後、乾燥機で１２０℃１５分間乾燥し、コンベア炉にてピーク温度２５０℃、ピーク焼成時間１０分間、入口から出口まで６０分間かけて焼成し、ポリイミドフイルム上に２ｍｍ×２０ｍｍの金薄膜パターンを設けた。
このようにして得られた金薄膜のシート抵抗値を測定した結果を表１に示す。
(1) Production of organic gold compound 50.0 g of chloroauric acid is dissolved in 500 ml of pure water, and 5% sodium hydrogen carbonate is added to this and stirred until the pH is 9.0. The precipitated gold hydroxide is filtered off and washed with pure water.
Next, after the gold hydroxide after washing is dispersed in 800 ml of pure water, the liquid temperature is set to 60 ° C. by heating and stirring while bubbling nitrogen gas. Leave for 1 hour.
Then, a small amount (part) of 48.2 g of sodium sulfite is slowly added to this suspension solution. While confirming the state of the reaction, a small amount (part) of 13.9 g of 1-propanethiol is slowly added. Add the remaining sodium sulfite while confirming the reaction. While the bubbling of nitrogen gas is continued as it is, the temperature of the reaction solution is kept at 60 to 65 ° C. and aged for 3 hours.
Further, the remaining 1-propanethiol is gradually added to the reaction solution. After completion of the addition of 1-propanethiol, the temperature of the reaction solution is kept at 70 ° C., and bubbling of nitrogen gas is continued for 5 hours as it is, followed by ripening. At this time, the solvent should not be reduced in the manner of reflux.
The reaction solution after completion of ripening is cooled to 30 ° C. or lower while continuing bubbling of nitrogen gas and stirring as it is to precipitate crystals. Next, the crystals were filtered, washed with ethanol, and then dried at 70 ° C. to obtain 22.4 g of pale yellow powdery crystals. (Yield: 67.8%)
(2) Preparation of conductive paste 20 parts by weight of the organic gold compound obtained in Example 1, 20 parts by weight of an organic resin dinder (ethyl cellulose 6% by weight terpineol solution) and 10 parts by weight of terpineol were pre-kneaded, and then three of these were mixed. A conductive paste was prepared by kneading with a roll mill.
Using this conductive paste, screen printing on a 325 mesh screen on a polyimide film of 50 mm x 60 mm x 0.1 mm, followed by drying at 120 ° C for 15 minutes with a dryer, peak temperature at 250 ° C in a conveyor furnace, peak firing time Baking was performed for 10 minutes from the inlet to the outlet over 60 minutes, and a gold thin film pattern of 2 mm × 20 mm was provided on the polyimide film.
The results of measuring the sheet resistance value of the gold thin film thus obtained are shown in Table 1.
（１）有機金化合物の製造
塩化金酸５０.０ｇを純水５００ｍｌに溶解し、これに１０％アンモニア水をｐＨ１０．０になるまで、添加・攪拌する。析出した雷金を濾別後純水にて洗浄する。
次に、洗浄後の雷金を純水８００ｍｌに分散した後、窒素ガスをバブリングしながら加熱・攪拌をして液温を６０℃にする。そのまま１時間放置する。
次いで、この懸濁溶液に亜硫酸ナトリウム４８．２ｇの少量（一部）をゆっくり添加する。反応の様子を確認しながら、１−プロパンチオール１３．９ｇの少量（一部）をゆっくり添加する。残りの亜硫酸ナトリウムを反応の様子を確認しながら添加する。窒素ガスのバブリングはそのまま継続しながら反応溶液の温度を６０〜６５℃に保温して３時間熟成を行う。
更に、反応溶液へ残りの１−プロパンチオールを徐々に添加する。１−プロパンチオールの添加終了後、反応溶液の温度を７０℃に保ち窒素ガスのバブリングをそのまま５時間継続し、再熟成を行う。その際、還流の要領で溶媒が減らない様にする。
再熟成終了後の反応溶液は、そのまま窒素ガスのバブリング及び、攪拌を継続しながら３０℃以下に冷却し結晶を析出させる。次いで、結晶を濾過、エタノールで洗浄した後、７０℃で乾燥する事により、２０．３ｇの淡黄色粉末状の結晶を得た。（収率：６１．５％）
（２）導電性ペーストの調製
実施例２で得た有機金化合物２０重量部、有機樹脂バインダー（エチルセルロース６重量％ターピネオール溶液）２０重量部、ターピネオール１０重量部を予備混練した後、これを３本ロールミルにより混練して導電性ペーストを調製した。
この導電性ペーストを用いて５０ｍｍ×６０ｍｍ×０．１ｍｍのポリイミドフイルム上に３２５メッシュのスクリーンでスクリーン印刷後、乾燥機で１２０℃１５分間乾燥し、コンベア炉にてピーク温度２５０℃、ピーク焼成時間１０分間、入口から出口まで６０分間かけて焼成し、ポリイミドフイルム上に２ｍｍ×２０ｍｍの金薄膜パターンを設けた。このようにして得られた金薄膜のシート抵抗値を測定した結果を表１に示す。
(1) Production of organic gold compound 50.0 g of chloroauric acid is dissolved in 500 ml of pure water, and 10% aqueous ammonia is added and stirred therein until the pH reaches 10.0. The deposited thunder gold is separated by filtration and washed with pure water.
Next, after the washed thunder gold is dispersed in 800 ml of pure water, the liquid temperature is set to 60 ° C. by heating and stirring while bubbling nitrogen gas. Leave for 1 hour.
Then, a small amount (part) of 48.2 g of sodium sulfite is slowly added to this suspension solution. While confirming the state of the reaction, a small amount (part) of 13.9 g of 1-propanethiol is slowly added. Add the remaining sodium sulfite while confirming the reaction. While the bubbling of nitrogen gas is continued as it is, the temperature of the reaction solution is kept at 60 to 65 ° C. and aged for 3 hours.
Further, the remaining 1-propanethiol is gradually added to the reaction solution. After completion of the addition of 1-propanethiol, the temperature of the reaction solution is kept at 70 ° C., and bubbling of nitrogen gas is continued for 5 hours as it is, followed by ripening. At this time, the solvent should not be reduced in the manner of reflux.
The reaction solution after completion of ripening is cooled to 30 ° C. or lower while continuing bubbling of nitrogen gas and stirring as it is to precipitate crystals. Next, the crystals were filtered, washed with ethanol, and dried at 70 ° C. to obtain 20.3 g of a pale yellow powdery crystal. (Yield: 61.5%)
(2) Preparation of conductive paste 20 parts by weight of the organic gold compound obtained in Example 2, 20 parts by weight of an organic resin binder (ethylcellulose 6% by weight terpineol solution) and 10 parts by weight of terpineol were pre-kneaded, and then three of these were mixed. A conductive paste was prepared by kneading with a roll mill.
Using this conductive paste, screen printing on a 325 mesh screen on a polyimide film of 50 mm x 60 mm x 0.1 mm, followed by drying at 120 ° C for 15 minutes with a dryer, peak temperature at 250 ° C in a conveyor furnace, peak firing time Baking was performed for 10 minutes from the inlet to the outlet over 60 minutes, and a gold thin film pattern of 2 mm × 20 mm was provided on the polyimide film. The results of measuring the sheet resistance value of the gold thin film thus obtained are shown in Table 1.
（１）有機金化合物の製造
塩化金酸５０.０ｇを純水５００ｍｌに溶解し、これに水酸化バリウム八水和物１１４．８ｇを添加・攪拌する。析出した金酸バリウムを濾別後純水にて洗浄する。
次に、洗浄後の金酸バリウムを純水８００ｍｌに分散した後、窒素ガスをバブリングしながら加熱・攪拌をして液温を６０℃にする。そのまま１時間放置する。
次いで、この懸濁溶液に亜硫酸ナトリウム４８．２ｇの少量（一部）をゆっくり添加する。反応の様子を確認しながら、１−プロパンチオール１３．９ｇの少量（一部）をゆっくり添加する。残りの亜硫酸ナトリウムを反応の様子を確認しながら添加する。窒素ガスのバブリングはそのまま継続しながら反応溶液の温度を６０〜６５℃に保温して３時間熟成を行う。
更に、反応溶液へ残りの１−プロパンチオールを徐々に添加する。１−プロパンチオールの添加終了後、反応溶液の温度を７０℃に保ち窒素ガスのバブリングをそのまま５時間継続し、再熟成を行う。その際、還流の要領で溶媒が減らない様にする。
再熟成終了後の反応溶液は、そのまま窒素ガスのバブリング及び、攪拌を継続しながら３０℃以下に冷却し結晶を析出させる。次いで、結晶を濾過、エタノールで洗浄した後、７０℃で乾燥する事により、１７．８ｇの淡黄色粉末状の結晶を得た。（収率：５３．９％）
（２）導電性ペーストの調製
実施例３で得た有機金化合物２０重量部、有機樹脂バインダー（エチルセルロース６重量％ターピネオール溶液）２０重量部、ターピネオール１０重量部を予備混練した後、これを３本ロールミルにより混練して導電性ペーストを調製した。
この導電性ペーストを用いて５０ｍｍ×６０ｍｍ×０．１ｍｍのポリイミドフイルム上に３２５メッシュのスクリーンでスクリーン印刷後、乾燥機で１２０℃１５分間乾燥し、コンベア炉にてピーク温度２５０℃、ピーク焼成時間１０分間、入口から出口まで６０分間かけて焼成し、ポリイミドフイルム上に２ｍｍ×２０ｍｍの金薄膜パターンを設けた。このようにして得られた金薄膜のシート抵抗値を測定した結果を表１に示す。
(1) Production of organic gold compound 50.0 g of chloroauric acid is dissolved in 500 ml of pure water, and 114.8 g of barium hydroxide octahydrate is added and stirred therein. The precipitated barium metal oxide is filtered off and washed with pure water.
Next, after the washed barium aurate is dispersed in 800 ml of pure water, the liquid temperature is set to 60 ° C. by heating and stirring while bubbling nitrogen gas. Leave for 1 hour.
Then, a small amount (part) of 48.2 g of sodium sulfite is slowly added to this suspension solution. While confirming the state of the reaction, a small amount (part) of 13.9 g of 1-propanethiol is slowly added. Add the remaining sodium sulfite while confirming the reaction. While the bubbling of nitrogen gas is continued as it is, the temperature of the reaction solution is kept at 60 to 65 ° C. and aged for 3 hours.
Further, the remaining 1-propanethiol is gradually added to the reaction solution. After completion of the addition of 1-propanethiol, the temperature of the reaction solution is kept at 70 ° C., and bubbling of nitrogen gas is continued for 5 hours as it is, followed by ripening. At this time, the solvent should not be reduced in the manner of reflux.
The reaction solution after completion of ripening is cooled to 30 ° C. or lower while continuing bubbling of nitrogen gas and stirring as it is to precipitate crystals. Next, the crystals were filtered, washed with ethanol, and then dried at 70 ° C. to obtain 17.8 g of pale yellow powdery crystals. (Yield: 53.9%)
(2) Preparation of conductive paste 20 parts by weight of the organic gold compound obtained in Example 3, 20 parts by weight of an organic resin binder (ethylcellulose 6% by weight terpineol solution) and 10 parts by weight of terpineol were pre-kneaded, and then three of these were mixed. A conductive paste was prepared by kneading with a roll mill.
Using this conductive paste, screen printing on a 325 mesh screen on a polyimide film of 50 mm x 60 mm x 0.1 mm, followed by drying at 120 ° C for 15 minutes with a dryer, peak temperature at 250 ° C in a conveyor furnace, peak firing time Baking was performed for 10 minutes from the inlet to the outlet over 60 minutes, and a gold thin film pattern of 2 mm × 20 mm was provided on the polyimide film. The results of measuring the sheet resistance value of the gold thin film thus obtained are shown in Table 1.
導電性ペーストの調製
α―ピネンサルファイド金化合物２０重量部、有機樹脂バインダー（エチルセルロース６重量％ターピネオール溶液）２０重量部、ターピネオール１０重量部を予備混練した後、これを３本ロールミルにより混練して導電性ペーストを調製した。
この導電性ペーストを用いて５０ｍｍ×６０ｍｍ×０．１ｍｍのポリイミドフイルム上に３２５メッシュのスクリーンでスクリーン印刷後、乾燥機で１２０℃１５分間乾燥し、コンベア炉にてピーク温度２５０℃、ピーク焼成時間１０分間、入口から出口まで６０分間かけて焼成し、ポリイミドフイルム上に２ｍｍ×２０ｍｍの金薄膜パターンを設けた。このようにして得られた金薄膜のシート抵抗値を測定した結果を表１に示す。
Preparation of conductive paste 20 parts by weight of α-pinene sulfide gold compound, 20 parts by weight of an organic resin binder (6% by weight of ethylcellulose terpineol solution) and 10 parts by weight of terpineol were pre-kneaded and then kneaded by a three-roll mill. An adhesive paste was prepared.
Using this conductive paste, screen printing on a 325 mesh screen on a polyimide film of 50 mm x 60 mm x 0.1 mm, followed by drying at 120 ° C for 15 minutes with a dryer, peak temperature at 250 ° C in a conveyor furnace, peak firing time Baking was performed for 10 minutes from the inlet to the outlet over 60 minutes, and a gold thin film pattern of 2 mm × 20 mm was provided on the polyimide film. The results of measuring the sheet resistance value of the gold thin film thus obtained are shown in Table 1.
表１から、本発明の有機金化合物によるペーストにより形成された薄膜は、ポリイミドフイルム上において低温焼成を実施した場合においても緻密な皮膜となっているため導電性が極めて良好であることが確認された。
一方、比較例の有機金ペーストにより形成された膜は、低温での焼結性がよくないため導電性が測定できなかった。
本発明の有機金属化合物は、図１に示すように示差熱分析結果からも明らかなように低温焼成においても金属Ａｕ析出が有効である。
ＴＧ−ＤＴＡの測定結果より、ＴＧ曲線から、１９５℃付近から分解が始まり、一気に金属Ａｕになっている事が確認出来る。更に、２３０℃付近で反応が終結しており、低温焼成にて金属Ａｕ析出が可能である事を示している。
また、ＤＴＡ曲線から、金属Ａｕになる際、吸熱反応である事が確認出来る。通常、有機成分が燃焼する為、発熱反応を示す事が多いが、本熱分解機構は、配位子の燃焼による金属Ａｕの析出では無く、金−配位子間での電子授受反応による配位子脱離−金属Ａｕの析出である。
Table 1 confirms that the thin film formed from the paste of the organic gold compound of the present invention has a very good conductivity because it is a dense film even when subjected to low-temperature firing on a polyimide film. It was.
On the other hand, the film formed of the organic gold paste of the comparative example was not good in sinterability at low temperatures, and therefore the conductivity could not be measured.
In the organometallic compound of the present invention, metal Au precipitation is effective even in low-temperature firing, as is apparent from the differential thermal analysis results as shown in FIG.
From the measurement result of TG-DTA, it can be confirmed from the TG curve that the decomposition started at around 195 ° C., and it became metal Au at a stretch. Furthermore, the reaction is terminated at around 230 ° C., indicating that metal Au can be deposited by low-temperature firing.
Moreover, it can confirm that it is an endothermic reaction when it becomes metal Au from a DTA curve. Usually, the organic component burns and often exhibits an exothermic reaction, but this thermal decomposition mechanism is not the deposition of metal Au due to the combustion of the ligand, but the distribution by the electron transfer reaction between the gold and the ligand. Ligand elimination-metal Au precipitation.
Claims (6)
一般式（１）
（化１）
ＣＨ３−（ＣＨ２）ｎ−Ｓ−Ａｕ （１）
（式中、ｎは１〜５である）
An organic gold represented by the general formula (1) obtained by reacting a gold salt with an alkanethiol in an aqueous solution containing a reducing agent in the presence of an inert gas to coordinate the alkanethiol to the gold ion. Compound.
General formula (1)
(Chemical formula 1)
CH 3 - (CH 2) n -S-Au (1)
(Where n is 1 to 5)
A conductive paste comprising a synthetic resin binder in the organic gold compound according to any one of claims 1, 2, 3 and 4.
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| JP2013196741A JP5526272B1 (en) | 2013-09-24 | 2013-09-24 | ORGANIC GOLD COMPOUND, PROCESS FOR PRODUCING THE SAME, AND CONDUCTIVE PASTE |
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| JP2013196741A JP5526272B1 (en) | 2013-09-24 | 2013-09-24 | ORGANIC GOLD COMPOUND, PROCESS FOR PRODUCING THE SAME, AND CONDUCTIVE PASTE |
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