JP2013175560A - Metal copper film obtained by forming into conductor at 140°c or less, metal copper pattern, and their manufacturing method - Google Patents
Metal copper film obtained by forming into conductor at 140°c or less, metal copper pattern, and their manufacturing method Download PDFInfo
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- JP2013175560A JP2013175560A JP2012038639A JP2012038639A JP2013175560A JP 2013175560 A JP2013175560 A JP 2013175560A JP 2012038639 A JP2012038639 A JP 2012038639A JP 2012038639 A JP2012038639 A JP 2012038639A JP 2013175560 A JP2013175560 A JP 2013175560A
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- Prior art keywords
- copper
- bipyridyl
- organic compound
- compound containing
- nitrogen
- Prior art date
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- 239000010949 copper Substances 0.000 title claims abstract description 162
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 161
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 64
- 239000002184 metal Substances 0.000 title claims abstract description 63
- 239000004020 conductor Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 81
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 74
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 53
- 239000002245 particle Substances 0.000 claims abstract description 49
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 40
- 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 abstract description 37
- 235000019253 formic acid Nutrition 0.000 claims abstract description 37
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 28
- 239000011574 phosphorus Substances 0.000 claims abstract description 28
- 230000008021 deposition Effects 0.000 claims abstract description 25
- 239000007789 gas Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 238000007639 printing Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 33
- 238000012545 processing Methods 0.000 claims description 27
- 238000000151 deposition Methods 0.000 claims description 23
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 20
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 18
- -1 4-fluoropyridine 2-bromopyridine Chemical compound 0.000 claims description 16
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 15
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 15
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 14
- 238000007641 inkjet printing Methods 0.000 claims description 13
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 claims description 10
- HJKGBRPNSJADMB-UHFFFAOYSA-N 3-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CN=C1 HJKGBRPNSJADMB-UHFFFAOYSA-N 0.000 claims description 10
- JVZRCNQLWOELDU-UHFFFAOYSA-N 4-Phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 claims description 10
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 10
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 10
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 claims description 10
- WZJYKHNJTSNBHV-UHFFFAOYSA-N benzo[h]quinoline Chemical compound C1=CN=C2C3=CC=CC=C3C=CC2=C1 WZJYKHNJTSNBHV-UHFFFAOYSA-N 0.000 claims description 10
- 229960004643 cupric oxide Drugs 0.000 claims description 10
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- 125000000623 heterocyclic group Chemical group 0.000 claims description 9
- JYYNAJVZFGKDEQ-UHFFFAOYSA-N 2,4-Dimethylpyridine Chemical compound CC1=CC=NC(C)=C1 JYYNAJVZFGKDEQ-UHFFFAOYSA-N 0.000 claims description 8
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 claims description 8
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- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical compound N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 claims description 5
- DRGAZIDRYFYHIJ-UHFFFAOYSA-N 2,2':6',2''-terpyridine Chemical compound N1=CC=CC=C1C1=CC=CC(C=2N=CC=CC=2)=N1 DRGAZIDRYFYHIJ-UHFFFAOYSA-N 0.000 claims description 5
- IBTGEEMBZJBBSH-UHFFFAOYSA-N 2,6-dimethoxypyridine Chemical compound COC1=CC=CC(OC)=N1 IBTGEEMBZJBBSH-UHFFFAOYSA-N 0.000 claims description 5
- NCRIDSGPLISUEU-UHFFFAOYSA-N 2-bromo-6-pyridin-2-ylpyridine Chemical group BrC1=CC=CC(C=2N=CC=CC=2)=N1 NCRIDSGPLISUEU-UHFFFAOYSA-N 0.000 claims description 5
- OKDGRDCXVWSXDC-UHFFFAOYSA-N 2-chloropyridine Chemical compound ClC1=CC=CC=N1 OKDGRDCXVWSXDC-UHFFFAOYSA-N 0.000 claims description 5
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- PVMNPAUTCMBOMO-UHFFFAOYSA-N 4-chloropyridine Chemical compound ClC1=CC=NC=C1 PVMNPAUTCMBOMO-UHFFFAOYSA-N 0.000 claims description 5
- IMEVSAIFJKKDAP-UHFFFAOYSA-N 4-methoxy-2-(4-methoxypyridin-2-yl)pyridine Chemical group COC1=CC=NC(C=2N=CC=C(OC)C=2)=C1 IMEVSAIFJKKDAP-UHFFFAOYSA-N 0.000 claims description 5
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- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 claims description 5
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- CMLWFCUAXGSMBB-UHFFFAOYSA-N tris(2,6-dimethoxyphenyl)phosphane Chemical compound COC1=CC=CC(OC)=C1P(C=1C(=CC=CC=1OC)OC)C1=C(OC)C=CC=C1OC CMLWFCUAXGSMBB-UHFFFAOYSA-N 0.000 claims description 5
- ITJHLZVYLDBFOJ-UHFFFAOYSA-N tris[3,5-bis(trifluoromethyl)phenyl]phosphane Chemical compound FC(F)(F)C1=CC(C(F)(F)F)=CC(P(C=2C=C(C=C(C=2)C(F)(F)F)C(F)(F)F)C=2C=C(C=C(C=2)C(F)(F)F)C(F)(F)F)=C1 ITJHLZVYLDBFOJ-UHFFFAOYSA-N 0.000 claims description 5
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 4
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Landscapes
- Manufacturing Of Printed Wiring (AREA)
Abstract
Description
本発明は、１４０℃以下の低温で銅系粒子堆積層を導体化して得られる金属銅膜及びその製造方法、金属銅パターン及びそれを用いた導体配線、金属銅バンプ、熱伝導路、接合材に関する。 The present invention relates to a metal copper film obtained by making a copper-based particle deposition layer into a conductor at a low temperature of 140 ° C. or less, a method for producing the same, a metal copper pattern, a conductor wiring using the same, a metal copper bump, a heat conduction path, and a bonding material About.
金属銅は高い電気伝導性と熱伝導性を有し、導体配線材料、熱伝達材料、熱交換材料、放熱材料として広く用いられている。これらの目的に用いられる銅のパターンを低コストで簡便に形成する手法として、銅インクを印刷により基板上に形成し、導体化処理により銅インクを銅に転換する方法が検討されている。
銅インクの導体化手法として、ギ酸ガス中での加熱処理が有効であることが報告されている（特許文献１）。本手法では２００℃以下の処理温度で、低抵抗の導体層を生成する特徴がある。本手法では１２０℃以上で導体化が進行するとされており、比較例１に示したように確かに１３０℃や１３０℃でも１２０分で銅インクの変色が生じ反応が生じていることが分かるが導通は得られず、１４０℃以下の低温で６０分以下の短時間での導体化処理に課題があった。なお、１４０℃以下、短時間での導体化が可能となれば、ポリエチレンテレフタレート（ＰＥＴ）などの耐熱性に乏しい廉価なフィルム上への銅インクの適用が可能となる。
Metallic copper has high electrical conductivity and thermal conductivity, and is widely used as a conductor wiring material, a heat transfer material, a heat exchange material, and a heat dissipation material. As a technique for easily and inexpensively forming a copper pattern used for these purposes, a method of forming a copper ink on a substrate by printing and converting the copper ink to copper by a conductor treatment has been studied.
It has been reported that heat treatment in formic acid gas is effective as a copper ink conductor method (Patent Document 1). This method is characterized by generating a low-resistance conductor layer at a processing temperature of 200 ° C. or lower. In this method, it is said that conductorization proceeds at 120 ° C. or higher, and as shown in Comparative Example 1, it can be seen that even at 130 ° C. or 130 ° C., the discoloration of the copper ink occurs and the reaction occurs in 120 minutes. There was no continuity, and there was a problem in the conductorization treatment in a short time of 60 minutes or less at a low temperature of 140 ° C. or less. If the conductor can be formed in a short time at 140 ° C. or less, the copper ink can be applied to an inexpensive film having poor heat resistance such as polyethylene terephthalate (PET).
本発明は、上記に鑑み、ＰＥＴなどの耐熱性に乏しい基板上に銅インクにより印刷された層を基板にダメージを与えない低温、短時間で処理して低抵抗の金属銅に転換する方法及びＰＥＴなどの耐熱性に乏しい基板上に印刷で形成された金属銅パターンを有する積層体を提供する。すなわち、１４０℃以下の低温で銅系粒子堆積層を導体化して得られる金属銅膜及びその製造方法、金属銅パターン及びそれを用いた導体配線、金属銅バンプ、熱伝導路、接合材を提供する。 In view of the above, the present invention is a method of converting a layer printed with copper ink on a substrate having poor heat resistance such as PET into copper metal having low resistance by treating the layer at a low temperature and in a short time without damaging the substrate, and Provided is a laminate having a metal copper pattern formed by printing on a substrate having poor heat resistance such as PET. That is, a metal copper film obtained by making a copper-based particle deposition layer into a conductor at a low temperature of 140 ° C. or less, a manufacturing method thereof, a metal copper pattern, a conductor wiring using the metal copper bump, a heat conduction path, and a bonding material are provided. To do.
発明者らは、銅インクのガス中での加熱による導体化処理において、１４０℃以下で導体化を可能とする活性の高いガス成分に関し鋭意検討をおこない、１４０℃以下で６０分以内に導体化できることを見出し本発明に達した。
本発明は、［１］ 銅系粒子堆積層を、リンを含有する有機化合物又は窒素を含有する有機化合物、及びギ酸をともに含む処理ガス中、１２０℃以上、１４０℃以下で処理してなることを特徴とする金属銅膜に関する。
また、本発明は、［２］ 窒素を含有する有機化合物が、窒素の複素環状構造を含む有機化合物であることを特徴とする上記［１］に記載の金属銅膜に関する。
また、本発明は、［３］ 窒素の複素環状構造を含む有機化合物が、２，２´−ビピリジル、２，３´−ビピリジル、ピリジン、６−メチル−２，２´−ビピリジル、６，６´−ジメチル−２，２´−ビピリジル、５，５´−ジメチル−２，２´−ビピリジル、４，４´−ジメチル−２，２´−ビピリジル、６−ブロモ−２，２´−ビピリジル、４，４´−ジメトキシ−２，２´-ビピリジル、４，５−ジアザフルオレン，２，２´：６´，２″−ターピリジン、２−（２−ピリジニル）キノリン、２−メチルピリジン、４−メチルピリジン、２−メトキシピリジン、３−メトキシピリジン、４−メトキシピリジン、２，６−ジメトキシピリジン、２−クロロピリジン、３−クロロピリジン、４−クロロピリジン、２−フロロピリジン、３−フロロピリジン、４−フロロピリジン、２−ブロモピリジン、３−ブロモピリジン、４−ブロモピリジン、２−フェニルピリジン、３−フェニルピリジン、４−フェニルピリジン、５−メチルピリジン−３−カルボニトリル、２，４−ルチジン、ピリダジン、ピリミジン、キナゾリン、２，２´−ビピリミジン、ピラジン、キノキサリン、フタラジン、シンノリン、キナゾリン、１，１０−フェナントロリン、４，７−フェナントロリン、１，７−フェナントロリン、キノリン、イソキノリン、ベンゾキノリン、アクリジン、ナフチリジンの群から選ばれる一つ以上である上記［２］に記載の金属銅膜に関する。
また、本発明は、［４］ リンを含有する有機化合物が、トリフェニルホスフィン、メチルジフェニルホスフィン、ジメチルフェニルホスフィン、トリストリメチルフェニルホスフィン、トリス（４−トリフルオロメチルフェニル）ホスフィン、トリス（２，６−ジメトキシフェニル）ホスフィン、トリス［３，５−ビス（トリフルオロメチル）フェニル］ホスフィン、２，４，６−トリ−t−ブチル−ホスフィニン、２，６−ジフェニルホスフィニン、フェニルホスフィン、ジフェニルホスフィンの群から選ばれる一つ以上である上記［１］から［３］のいずれかに記載の金属銅膜に関する。
また、本発明は、［５］ 前記銅系粒子堆積層を構成する銅系粒子が、酸化第二銅、酸化第一銅、又は金属銅のいずれか一つ以上である上記［１］から［４］のいずれかに記載の金属銅膜に関する。
The inventors have conducted intensive studies on highly active gas components that enable conductorization at 140 ° C. or lower in the conductor treatment by heating copper ink in gas, and made conductor within 60 minutes at 140 ° C. or lower. We have found that we have achieved the present invention.
In the present invention, [1] a copper-based particle deposition layer is processed at 120 ° C. or higher and 140 ° C. or lower in a processing gas containing an organic compound containing phosphorus or an organic compound containing nitrogen and formic acid. The present invention relates to a metal copper film characterized by
The present invention also relates to [2] the copper metal film according to the above [1], wherein the organic compound containing nitrogen is an organic compound containing a heterocyclic structure of nitrogen.
In the present invention, [3] the organic compound containing a heterocyclic structure of nitrogen is 2,2′-bipyridyl, 2,3′-bipyridyl, pyridine, 6-methyl-2,2′-bipyridyl, 6,6 '-Dimethyl-2,2'-bipyridyl, 5,5'-dimethyl-2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 6-bromo-2,2'-bipyridyl, 4,4'-dimethoxy-2,2'-bipyridyl, 4,5-diazafluorene, 2,2 ': 6', 2 "-terpyridine, 2- (2-pyridinyl) quinoline, 2-methylpyridine, 4 -Methylpyridine, 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, 2,6-dimethoxypyridine, 2-chloropyridine, 3-chloropyridine, 4-chloropyridine, 2-fluoropyridine, 3-fluoropyridi 4-fluoropyridine, 2-bromopyridine, 3-bromopyridine, 4-bromopyridine, 2-phenylpyridine, 3-phenylpyridine, 4-phenylpyridine, 5-methylpyridine-3-carbonitrile, 2,4- Lutidine, pyridazine, pyrimidine, quinazoline, 2,2′-bipyrimidine, pyrazine, quinoxaline, phthalazine, cinnoline, quinazoline, 1,10-phenanthroline, 4,7-phenanthroline, 1,7-phenanthroline, quinoline, isoquinoline, benzoquinoline, The metal copper film according to [2], which is one or more selected from the group of acridine and naphthyridine.
In the present invention, [4] the organic compound containing phosphorus is triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, tristrimethylphenylphosphine, tris (4-trifluoromethylphenyl) phosphine, tris (2,6 -Dimethoxyphenyl) phosphine, tris [3,5-bis (trifluoromethyl) phenyl] phosphine, 2,4,6-tri-t-butyl-phosphine, 2,6-diphenylphosphine, phenylphosphine, diphenylphosphine The metal copper film according to any one of [1] to [3], which is one or more selected from the group of
Moreover, this invention is [5] Said [1] to [1] whose copper type particles which constitute the above-mentioned copper type particle deposition layer are any one or more of cupric oxide, cuprous oxide, or metallic copper. 4]. The metal copper film according to any one of 4).
さらに、本発明は、［６］ 銅系粒子堆積層が、液状あるいはペースト状の銅インクの印刷によりパターニングされており、該パターニングされた層に対し、リンを含有する有機化合物又は窒素を含有する有機化合物、及びギ酸をともに含む処理ガス中、１２０℃以上、１４０℃以下で処理して得られる金属銅パターンに関する。
また、本発明は、［７］ 前記銅系粒子堆積層のパターニングに用いられる印刷法が、インクジェット印刷、スーパーインクジェット印刷、スクリーン印刷、転写印刷、オフセット印刷、ジェットプリンティング法、ディスペンサ、ニードルディスペンサ、カンマコータ、スリットコータ、ダイコータ、及びグラビアコータからなる群より選択されるいずれか１種である上記［６］に記載の金属銅パターンに関する。
Further, according to the present invention, [6] the copper-based particle deposition layer is patterned by printing a liquid or paste-like copper ink, and the patterned layer contains an organic compound containing nitrogen or nitrogen. The present invention relates to a metal copper pattern obtained by processing at 120 ° C. or higher and 140 ° C. or lower in a processing gas containing both an organic compound and formic acid.
The present invention also provides [7] The printing method used for patterning the copper-based particle deposition layer is ink jet printing, super ink jet printing, screen printing, transfer printing, offset printing, jet printing method, dispenser, needle dispenser, comma coater The metal copper pattern according to [6], which is any one selected from the group consisting of a slit coater, a die coater, and a gravure coater.
さらに、本発明は、［８］ 上記［６］又は［７］に記載の金属銅パターンを用いた導体配線に関する。
また、本発明は、［９］ 上記［６］又は［７］に記載の金属銅パターンを用いた金属銅バンプに関する。
また、本発明は、［１０］ 上記［６］又は［７］に記載の金属銅パターンを用いた熱伝導路に関する。
また、本発明は、［１１］ 上記［６］又は［７］に記載の金属銅パターンを用いた接合材に関する。
Furthermore, the present invention relates to [8] a conductor wiring using the metal copper pattern according to [6] or [7].
The present invention also relates to [9] a metal copper bump using the metal copper pattern according to [6] or [7].
[10] The present invention also relates to a heat conduction path using the metal copper pattern according to [6] or [7].
The present invention also relates to [11] a bonding material using the metal copper pattern according to [6] or [7].
さらに、本発明は、［１２］ 銅系粒子堆積層を、リンを含有する有機化合物又は窒素を含有する有機化合物、及びギ酸をともに含む処理ガス中、１２０℃以上、１４０℃以下で処理して金属銅膜とすることを特徴とする金属銅膜の製造方法に関する。
また、本発明は、［１３］ 窒素を含有する有機化合物が、窒素の複素環状構造を含む有機化合物である上記［１２］に記載の金属銅膜の製造方法に関する。
また、本発明は、［１４］ 窒素の複素環状構造を含む有機化合物が、２，２´−ビピリジル、２，３´−ビピリジル、ピリジン、６−メチル−２，２´−ビピリジル、６，６´−ジメチル−２，２´−ビピリジル、５，５´−ジメチル−２，２´-ビピリジル、４，４´−ジメチル−２，２´−ビピリジル、６−ブロモ−２，２´−ビピリジル、４，４´−ジメトキシ−２，２´-ビピリジル、４，５−ジアザフルオレン，２，２´：６´，２″−ターピリジン、２−（２−ピリジニル）キノリン、２−メチルピリジン、４−メチルピリジン、２−メトキシピリジン、３−メトキシピリジン、４−メトキシピリジン、２，６−ジメトキシピリジン、２−クロロピリジン、３−クロロピリジン、４−クロロピリジン、２−フロロピリジン、３−フロロピリジン、４−フロロピリジン、２−ブロモピリジン、３−ブロモピリジン、４−ブロモピリジン、２−フェニルピリジン、３−フェニルピリジン、４−フェニルピリジン、５−メチルピリジン−３−カルボニトリル、２，４−ルチジン、ピリダジン、ピリミジン、キナゾリン、２，２´−ビピリミジン、ピラジン、キノキサリン、フタラジン、シンノリン、キナゾリン、１，１０−フェナントロリン、４，７−フェナントロリン、１，７−フェナントロリン、キノリン、イソキノリン、ベンゾキノリン、アクリジン、ナフチリジンの群から選ばれる一つ以上である上記［１３］に記載の金属銅膜の製造方法に関する。
また、本発明は、［１５］ リンを含有する有機化合物が、トリフェニルホスフィン、メチルジフェニルホスフィン、ジメチルフェニルホスフィン、トリストリメチルフェニルホスフィン、トリス（４−トリフルオロメチルフェニル）ホスフィン、トリス（２，６−ジメトキシフェニル）ホスフィン、トリス［３，５−ビス（トリフルオロメチル）フェニル］ホスフィン、２，４，６−トリ−t−ブチル−ホスフィニン、２，６−ジフェニルホスフィニン、フェニルホスフィン、ジフェニルホスフィンの群から選ばれる一つ以上である上記［１２］から［１４］のいずれかに記載の金属銅膜の製造方法に関する。
また、本発明は、［１６］ 処理ガス中のリンを含有する有機化合物又は窒素を含有する有機化合物が、ギ酸に対し０．１ｍｏｌ％以上、４０ｍｏｌ％以下である上記［１２］から［１５］のいずれかに記載の金属銅膜の製造方法に関する。
Furthermore, the present invention provides [12] treating the copper-based particle deposition layer at a temperature of 120 ° C. or higher and 140 ° C. or lower in a processing gas containing an organic compound containing phosphorus or an organic compound containing nitrogen and formic acid. The present invention relates to a method for producing a metal copper film, characterized in that the metal copper film is used.
The present invention also relates to [13] the method for producing a metallic copper film according to [12], wherein the organic compound containing nitrogen is an organic compound containing a heterocyclic structure of nitrogen.
In the present invention, [14] the organic compound containing a heterocyclic structure of nitrogen is 2,2′-bipyridyl, 2,3′-bipyridyl, pyridine, 6-methyl-2,2′-bipyridyl, 6,6 '-Dimethyl-2,2'-bipyridyl, 5,5'-dimethyl-2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 6-bromo-2,2'-bipyridyl, 4,4'-dimethoxy-2,2'-bipyridyl, 4,5-diazafluorene, 2,2 ': 6', 2 "-terpyridine, 2- (2-pyridinyl) quinoline, 2-methylpyridine, 4 -Methylpyridine, 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, 2,6-dimethoxypyridine, 2-chloropyridine, 3-chloropyridine, 4-chloropyridine, 2-fluoropyridine, 3-fluoropyridi 4-fluoropyridine, 2-bromopyridine, 3-bromopyridine, 4-bromopyridine, 2-phenylpyridine, 3-phenylpyridine, 4-phenylpyridine, 5-methylpyridine-3-carbonitrile, 2,4 -Lutidine, pyridazine, pyrimidine, quinazoline, 2,2'-bipyrimidine, pyrazine, quinoxaline, phthalazine, cinnoline, quinazoline, 1,10-phenanthroline, 4,7-phenanthroline, 1,7-phenanthroline, quinoline, isoquinoline, benzoquinoline , A method for producing a metallic copper film according to the above [13], which is one or more selected from the group consisting of acridine and naphthyridine.
In the present invention, the organic compound containing [15] phosphorus is triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, tristrimethylphenylphosphine, tris (4-trifluoromethylphenyl) phosphine, tris (2,6 -Dimethoxyphenyl) phosphine, tris [3,5-bis (trifluoromethyl) phenyl] phosphine, 2,4,6-tri-t-butyl-phosphine, 2,6-diphenylphosphine, phenylphosphine, diphenylphosphine The method for producing a copper metal film according to any one of [12] to [14], which is at least one selected from the group of
The present invention also provides [16] The above [12] to [15], wherein the organic compound containing phosphorus or the organic compound containing nitrogen in the processing gas is 0.1 mol% or more and 40 mol% or less with respect to formic acid. The manufacturing method of the metal copper film | membrane in any one of.
本発明によれば、ＰＥＴ等の基板の耐熱性が１４０℃以下の汎用基板上に形成された銅インクを、基板のそり、収縮、白濁などの熱ダメージ無く導体化することができる。 According to the present invention, copper ink formed on a general-purpose substrate having a heat resistance of a substrate such as PET of 140 ° C. or less can be made into a conductor without thermal damage such as warpage, shrinkage, and cloudiness of the substrate.
本発明の金属銅膜は、基板上に印刷された銅インクを、リンを含有する有機化合物又は窒素を含有する有機化合物と、ギ酸をともに含む処理ガス雰囲気下１２０℃以上に加熱処理してなることを特徴としている。処理ガス中にリンを含有する有機化合物あるいは窒素を含有する有機化合物を、ギ酸と混合することにより、酸化銅から金属銅への還元反応の活性が向上し、反応時間の短縮、反応温度の１４０℃以下への低温化が可能になる。
以下に本発明の金属銅膜及びその製造方法についてそれぞれを交えて説明する。
The metal copper film of the present invention is obtained by heat-treating a copper ink printed on a substrate at 120 ° C. or higher in a processing gas atmosphere containing an organic compound containing phosphorus or an organic compound containing nitrogen and formic acid. It is characterized by that. By mixing an organic compound containing phosphorus or nitrogen in the process gas with formic acid, the activity of the reduction reaction from copper oxide to metallic copper is improved, the reaction time is shortened, and the reaction temperature is 140. The temperature can be lowered to below ℃.
The metal copper film of the present invention and the manufacturing method thereof will be described below together.
（導体化処理）
（処理ガス）
酸化銅から金属銅への還元反応を行う処理ガスとしては、ギ酸と、リンあるいは窒素を含有する有機化合物を共に含んだガスを用いる。
窒素を含有する有機化合物としては、窒素の複素環状構造を含む有機化合物が好ましく、中でも導体化処理温度で昇華等によりガス化するものが好ましい。このような化合物としては、２，２´−ビピリジル、６−メチル−２，２´−ビピリジル、６，６´−ジメチル−２，２´−ビピリジル、５，５´−ジメチル−２，２´−ビピリジル、４，４´−ジメチル−２，２´−ビピリジル、６−ブロモ−２，２´−ビピリジル、４，４´−ジメトキシ−２，２´−ビピリジル、２，３´−ビピリジル、４，５−ジアザフルオレン、２，２´：６´，２″−ターピリジン、２，２´−ビピリミジンなどのビピリジルやターピリジン類、ピリジン、２−メチルピリジン、４−メチルピリジン、２，４−ルチジン、２−メトキシピリジン、３−メトキシピリジン、４−メトキシピリジン、２，６−ジメトキシピリジン、２−クロロピリジン、３−クロロピリジン、４−クロロピリジン、２−フロロピリジン、３−フロロピリジン、４−フロロピリジン、２−ブロモピリジン、３−ブロモピリジン、４−ブロモピリジン、２−フェニルピリジン、３−フェニルピリジン、４−フェニルピリジン、２，６−ジフェニルピリジン、５−メチルピリジン−３−カルボニトリルなどのピリジン類；キノリン、イソキノリン、ベンゾキノリン、２−（２−ピリジニル）キノリンなどのキノリン類；ピリダジン、ピリミジン、ピラジンなどのジアジン類；キノキサリン、フタラジン、キナゾリン、シンノリンなどのキノキサリン類；１，１０−フェナントロリン、４，７−フェナントロリン、１，７−フェナントロリンなどのフェナントロリン類；トリアジン、アクリジン、ナフチリジン、ベンゾオキサゾール、ベンゾチアゾール、カルバゾール、ピロール、インドール、プリンが挙げられる。
(Conductor treatment)
(Processing gas)
As a processing gas for performing a reduction reaction from copper oxide to metallic copper, a gas containing both formic acid and an organic compound containing phosphorus or nitrogen is used.
As the organic compound containing nitrogen, an organic compound containing a heterocyclic structure of nitrogen is preferable, and those which are gasified by sublimation or the like at a conductorization temperature are preferable. Such compounds include 2,2'-bipyridyl, 6-methyl-2,2'-bipyridyl, 6,6'-dimethyl-2,2'-bipyridyl, 5,5'-dimethyl-2,2 '. -Bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 6-bromo-2,2'-bipyridyl, 4,4'-dimethoxy-2,2'-bipyridyl, 2,3'-bipyridyl, 4 , 5-diazafluorene, 2,2 ': 6', 2 "-terpyridine, bipyridyl and terpyridines such as 2,2'-bipyrimidine, pyridine, 2-methylpyridine, 4-methylpyridine, 2,4-lutidine 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, 2,6-dimethoxypyridine, 2-chloropyridine, 3-chloropyridine, 4-chloropyridine, 2-fluoropyridine, 3-fluoropyridine Pyridine, 4-fluoropyridine, 2-bromopyridine, 3-bromopyridine, 4-bromopyridine, 2-phenylpyridine, 3-phenylpyridine, 4-phenylpyridine, 2,6-diphenylpyridine, 5-methylpyridine-3 Pyridines such as carbonitrile; quinolines such as quinoline, isoquinoline, benzoquinoline, 2- (2-pyridinyl) quinoline; diazines such as pyridazine, pyrimidine, pyrazine; quinoxalines such as quinoxaline, phthalazine, quinazoline, cinnoline; Phenanthrolines such as 1,10-phenanthroline, 4,7-phenanthroline, 1,7-phenanthroline; triazine, acridine, naphthyridine, benzoxazole, benzothiazole, carbazole, pyrrole, indole, Phosphorus and the like.
リンを含有する有機化合物としては、導体化処理温度で昇華等によりガス化するものが好ましい。このような化合物としては、トリフェニルホスフィン、メチルジフェニルホスフィン、ジメチルフェニルホスフィン、トリストリメチルフェニルホスフィン、トリス（４−トリフルオロメチルフェニル）ホスフィン、トリス（２，６−ジメトキシフェニル）ホスフィン、トリス［３，５−ビス（トリフルオロメチル）フェニル］ホスフィン、２，４，６−トリ−t−ブチル−ホスフィニン、２，６−ジフェニルホスフィニン、フェニルホスフィン、ジフェニルホスフィンなどが挙げられる。 As the organic compound containing phosphorus, those which are gasified by sublimation or the like at a conductorization treatment temperature are preferable. Such compounds include triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, tristrimethylphenylphosphine, tris (4-trifluoromethylphenyl) phosphine, tris (2,6-dimethoxyphenyl) phosphine, tris [3, 5-bis (trifluoromethyl) phenyl] phosphine, 2,4,6-tri-t-butyl-phosphine, 2,6-diphenylphosphine, phenylphosphine, diphenylphosphine and the like.
ギ酸及び、含窒素有機化合物又はリンを含有する有機化合物の導入方法は、処理槽内の処理ガス濃度がそれぞれ所定の濃度となる方法であれば良い。ガスとして処理槽に導入する方法としては、ギ酸及び、含窒素有機化合物又はリンを含有する有機化合物をキャリヤガスに混合、加熱又は減圧によるガス化、あるいはこれらを組み合わせてガス状にした後、処理槽内に導入する方法がある。液体として処理槽に導入する方法としては、送液ポンプ、シリンジポンプ等流量の制御できる送液装置にて処理槽にギ酸及び、含窒素有機化合物又はリンを含有する有機化合物を導入し、加熱した処理槽内でガス化させても良い。なお、ギ酸と、含窒素有機化合物又はリンを含有する有機化合物をあらかじめ混合して導入しても良いし、別々に導入しても良い。ただし、ギ酸と、含窒素有機化合物又はリンを含有する有機化合物が反応し気化しにくくなる場合には別々に処理槽へ導入することが好ましい。
また、リンあるいは窒素を含有する有機化合物が常圧では気化しにくい場合には、ガス化の目的のため減圧下で処理しても良い。
The method for introducing the formic acid and the organic compound containing nitrogen-containing organic compound or phosphorus may be any method in which the processing gas concentration in the processing tank becomes a predetermined concentration. As a method of introducing the gas into the treatment tank, formic acid and a nitrogen-containing organic compound or phosphorus-containing organic compound are mixed with a carrier gas, gasified by heating or decompression, or combined to form a gas and then treated. There is a method to introduce into the tank. As a method of introducing into the treatment tank as a liquid, a formic acid and a nitrogen-containing organic compound or an organic compound containing phosphorus were introduced into the treatment tank and heated by a liquid feeding device capable of controlling the flow rate such as a liquid feeding pump and a syringe pump. You may gasify in a processing tank. Note that formic acid and a nitrogen-containing organic compound or an organic compound containing phosphorus may be mixed and introduced in advance, or may be introduced separately. However, when formic acid reacts with a nitrogen-containing organic compound or an organic compound containing phosphorus and is difficult to vaporize, it is preferably introduced separately into the treatment tank.
In addition, when an organic compound containing phosphorus or nitrogen is difficult to vaporize at normal pressure, it may be treated under reduced pressure for the purpose of gasification.
(処理条件)
リン又は窒素を含有する有機化合物の濃度の下限は、十分な導体化処理活性が得られる濃度以上であればよい。また、リン又は窒素を含有する有機化合物の濃度の上限は、導体化処理後の導体層への残留の観点から、十分な導体化処理活性が得られる濃度範囲で少ないほど良い。なお最適な濃度は、リン又は窒素を含有する有機化合物の種類、処理温度、ギ酸濃度、処理雰囲気の圧力、処理される銅インクの量に影響される。通常、処理雰囲気中のギ酸に対して０．１ｍｏｌ%以上、４０ｍｏｌ%以下が好ましく、０．５ｍｏｌ%以上、１０ｍｏｌ%以下がより好ましく、１ｍｏｌ%以上、５ｍｏｌ%以下がさらに好ましい。この範囲は、窒素を含有する有機化合物として、２，２´−ビピリジルを用いた場合に特に好ましい。
処理温度は、１２０℃以上が好ましく、十分な反応速度を得る点から１３０℃以上がより好ましい。処理温度の上限は基板の耐熱温度により規定され、１５０℃以下であればＰＥＴ基板への適用が可能となる。処理温度の上限は、耐熱性に乏しい基板上に銅インクにより金属銅膜や金属銅パターンを形成する観点から１４０℃以下とする。
処理時間は、処理される銅インクの量に依存するが、通常5分以上、６０分以下である。
(Processing conditions)
The minimum of the density | concentration of the organic compound containing phosphorus or nitrogen should just be more than the density | concentration from which sufficient conductorization process activity is obtained. Moreover, the upper limit of the density | concentration of the organic compound containing phosphorus or nitrogen is so good that it is small in the density | concentration range from which sufficient conductorization process activity is obtained from a viewpoint of the residual to the conductor layer after conductorization process. The optimum concentration is influenced by the type of organic compound containing phosphorus or nitrogen, the processing temperature, the formic acid concentration, the pressure of the processing atmosphere, and the amount of copper ink to be processed. Usually, 0.1 mol% or more and 40 mol% or less are preferable with respect to formic acid in the treatment atmosphere, 0.5 mol% or more and 10 mol% or less are more preferable, and 1 mol% or more and 5 mol% or less are more preferable. This range is particularly preferable when 2,2′-bipyridyl is used as the organic compound containing nitrogen.
The treatment temperature is preferably 120 ° C. or higher, and more preferably 130 ° C. or higher from the viewpoint of obtaining a sufficient reaction rate. The upper limit of the processing temperature is defined by the heat-resistant temperature of the substrate, and if it is 150 ° C. or lower, it can be applied to a PET substrate. The upper limit of the processing temperature is 140 ° C. or less from the viewpoint of forming a metal copper film or a metal copper pattern with a copper ink on a substrate having poor heat resistance.
The treatment time depends on the amount of copper ink to be treated, but is usually from 5 minutes to 60 minutes.
（銅系粒子堆積層）
銅系粒子堆積層は、銅酸化物と、金属状の遷移金属若しくは合金、又は金属元素を含む遷移金属錯体とを共に含有してなる層であり、本発明においては、ギ酸を含む有機化合物により処理する前に形成される層である。
すなわち、銅系粒子堆積層は、酸化第一銅、酸化第二銅、金属銅、金属銅合金のいずれか一つ以上からなる粒子の堆積層である。粒子堆積層に酸化銅（酸化第一銅、酸化第二銅、これらの混合物）と金属銅成分を含む場合、金属銅成分が銅の還元触媒として働き導体化処理にかかる時間を短縮することができる。
前記遷移金属、合金、又は金属錯体は、それぞれ、Ｃｕ、Ｐｄ、Ｐｔ、Ｎｉ、Ａｇ、Ａｕ、及びＲｈからなる群より選択される金属、これらの金属を含む合金、又はこれらの金属元素を含む遷移金属錯体である。
このような触媒作用を目的とした金属銅成分は、全銅系粒子中の１質量%以上であれば効果が期待でき、好ましくは３質量％以上、より好ましくは５質量％以上である。
本発明で使用される銅系粒子は、周囲が酸化物であるコアシェル金属粒子やそのほとんどすべてが酸化物である（例えば酸化銅）粒子であってもよく、１種を単独で又は２種以上を組み合わせて使用することができる。粒子形状は特に制限されず、略球状、扁平状、針状、ブロック状、板状、及び鱗片状等が挙げられる。中でも分散性の観点から、略球状、針状、及びブロック状の少なくとも１種であることが好ましい。粒子径は特に制限されないが、一次粒子の数平均粒子径が１ｎｍ〜５０μｍであることが好ましく、処理速度を速める観点から、１ｎｍ〜５μｍであることがより好ましく、基板との接着性の観点から、１０ｎｍ〜１μｍであることがさらに好ましい。なお、粒子径は、走査型電子顕微鏡を用いた観察により測定することができる。
銅系粒子を液状あるいはペースト状の銅インクとするため、銅系粒子を溶媒に分散して用いる。
銅系粒子の含有率は、例えば１〜９５質量％とすることができ、２０〜８０質量％であることがより好ましい。
(Copper particle deposition layer)
The copper-based particle deposition layer is a layer containing both a copper oxide and a metal-like transition metal or alloy, or a transition metal complex containing a metal element, and in the present invention, an organic compound containing formic acid is used. It is a layer formed before processing.
That is, the copper-based particle deposition layer is a particle deposition layer made of any one or more of cuprous oxide, cupric oxide, metallic copper, and metallic copper alloy. When the particle deposition layer contains copper oxide (cuprous oxide, cupric oxide, or a mixture thereof) and a metallic copper component, the metallic copper component can act as a copper reduction catalyst and reduce the time required for the conductor treatment. it can.
The transition metal, alloy, or metal complex includes a metal selected from the group consisting of Cu, Pd, Pt, Ni, Ag, Au, and Rh, an alloy containing these metals, or these metal elements, respectively. It is a transition metal complex.
The effect of such a metallic copper component for the purpose of catalysis can be expected if it is 1% by mass or more in the total copper-based particles, preferably 3% by mass or more, and more preferably 5% by mass or more.
The copper-based particles used in the present invention may be core-shell metal particles whose periphery is an oxide, or particles almost all of which are oxides (for example, copper oxide), and may be used alone or in combination of two or more. Can be used in combination. The particle shape is not particularly limited, and examples thereof include a substantially spherical shape, a flat shape, a needle shape, a block shape, a plate shape, and a scale shape. Among these, from the viewpoint of dispersibility, at least one of a substantially spherical shape, a needle shape, and a block shape is preferable. The particle diameter is not particularly limited, but the number average particle diameter of the primary particles is preferably 1 nm to 50 μm, more preferably 1 nm to 5 μm from the viewpoint of increasing the processing speed, and from the viewpoint of adhesiveness to the substrate. More preferably, it is 10 nm-1 micrometer. The particle diameter can be measured by observation using a scanning electron microscope.
In order to make the copper-based particles into a liquid or paste-like copper ink, the copper-based particles are dispersed in a solvent and used.
The content rate of copper-type particle | grains can be 1-95 mass%, for example, and it is more preferable that it is 20-80 mass%.
銅系粒子を溶媒に分散させることで、印刷法に適用可能なインクを得る場合、二次凝集体などを含めた平均体積粒径が５００ｎｍ以下であることが好ましい。平均体積粒径が５００ｎｍ以下であると、例えばインクジェット印刷法ではノズルの目詰まりなどの不具合が発生しにくく、より好ましい。体積粒径が５００ｎｍ以上の粒子があっても良いが、最大体積粒径は２μｍ以下であるとインクジェット印刷での目詰まりの発生等がなく好ましい。 When an ink applicable to a printing method is obtained by dispersing copper-based particles in a solvent, the average volume particle size including secondary aggregates is preferably 500 nm or less. When the average volume particle size is 500 nm or less, for example, in the ink jet printing method, problems such as nozzle clogging hardly occur, which is more preferable. Although particles having a volume particle diameter of 500 nm or more may be present, it is preferable that the maximum volume particle diameter is 2 μm or less because clogging does not occur in ink jet printing.
銅インクは、銅系粒子を分散媒に分散させ液状あるいはペースト状のインクとする。前記分散媒は少なくとも１種の溶媒を含むことが好ましい。前記溶媒としては２５℃における蒸気圧が１．３４×１０３Ｐａ未満であることが好ましく、１．０×１０３Ｐａ未満であることがより好ましい。
このような溶媒としては、例えば以下に示すものが挙げられる。すなわち、ノナン、デカン、ドデカン、テトラデカン等の脂肪族炭化水素系溶剤；エチルベンゼン、アニソール、メシチレン、ナフタレン、シクロヘキシルベンゼン、ジエチルベンゼン、フェニルアセトニトリル、ベンゾニトリル等の芳香族炭化水素系溶剤；酢酸イソブチル、プロピオン酸メチル、プロピオン酸エチル、γ−ブチロラクトン、グリコールスルファイト、乳酸エチル等のエステル系溶剤；１−ブタノール、シクロヘキサノール、α−テルピネオール、グリセリンなどのアルコ−ル系溶剤；シクロヘキサノン、２−ヘキサノン、２−ヘプタノン、２−オクタノン、１，３−ジオキソラン−２−オン、１，５，５−トリメチルシクロヘキセン−３−オン等のケトン系溶剤；ジエチレングリコールエチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテルアセテート、ジエチレングリコールエチルエーテルアセテート、ジエチレングリコールプロピルエーテルアセテート、ジエチレングリコールイソプロピルエーテルアセテート、ジエチレングリコールブチルエーテルアセテート、ジエチレングリコール−ｔ−ブチルエーテルアセテート、トリエチレングリコールメチルエーテルアセテート、トリエチレングリコールエチルエーテルアセテート、トリエチレングリコールプロピルエーテルアセテート、トリエチレングリコールイソプロピルエーテルアセテート、トリエチレングリコールブチルエーテルアセテート、トリエチレングリコール−ｔ−ブチルエーテルアセテート、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールモノブチルエーテル等のアルキレングリコール系溶剤；ジヘキシルエーテル、ブチルフェニルエーテル、ペンチルフェニルエーテル、メトキシトルエン、ベンジルエチルエーテル等のエーテル系溶剤；プロピレンカーボネート、エチレンカーボネート等のカーボネート系溶剤；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルピロリドンなどのアミド系溶剤；スルホラン等のスルホン系溶剤；マロノニトリルなどのニトリル系溶剤が例示できる。中でも、γ−ブチロラクトン、Ｎ−メチルピロリドン、グリコールスルファイト、プロピレンカーボネート、及びスルホランから選ばれる少なくとも１種が好ましい。これらの溶媒は、１種を単独で又は２種以上を組み合わせて使用することができる。
The copper ink is made into liquid or paste ink by dispersing copper-based particles in a dispersion medium. The dispersion medium preferably contains at least one solvent. The solvent preferably has a vapor pressure at 25 ° C. of less than 1.34 × 10 3 Pa, and more preferably less than 1.0 × 10 3 Pa.
Examples of such a solvent include those shown below. That is, aliphatic hydrocarbon solvents such as nonane, decane, dodecane, and tetradecane; aromatic hydrocarbon solvents such as ethylbenzene, anisole, mesitylene, naphthalene, cyclohexylbenzene, diethylbenzene, phenylacetonitrile, benzonitrile; isobutyl acetate, propionic acid Ester solvents such as methyl, ethyl propionate, γ-butyrolactone, glycol sulfite, ethyl lactate; alcohol solvents such as 1-butanol, cyclohexanol, α-terpineol, glycerin; cyclohexanone, 2-hexanone, 2- Ketone solvents such as heptanone, 2-octanone, 1,3-dioxolan-2-one, 1,5,5-trimethylcyclohexen-3-one; diethylene glycol ethyl ether, diethylene glycol Diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol isopropyl ether acetate, diethylene glycol butyl ether acetate , Diethylene glycol-t-butyl ether acetate, triethylene glycol methyl ether acetate, triethylene glycol ethyl ether acetate, triethylene glycol propyl ether acetate, triethylene glycol isopropyl ether acetate Alkylene glycol solvents such as tate, triethylene glycol butyl ether acetate, triethylene glycol-t-butyl ether acetate, dipropylene glycol dimethyl ether, dipropylene glycol monobutyl ether; dihexyl ether, butyl phenyl ether, pentyl phenyl ether, methoxy toluene, benzyl ethyl Ether solvents such as ether; carbonate solvents such as propylene carbonate and ethylene carbonate; amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; sulfone solvents such as sulfolane; malononitrile And nitrile solvents such as Among these, at least one selected from γ-butyrolactone, N-methylpyrrolidone, glycol sulfite, propylene carbonate, and sulfolane is preferable. These solvents can be used alone or in combination of two or more.
銅系インクの粘度及び表面張力は、適用する印刷法によって適正な範囲が異なる。
例えば、インクジェット印刷法に適用する場合の粘度は、２５℃で５０ｍＰａ・ｓ以下であることが好ましい。インクの粘度が５０ｍＰａ・ｓ以下であれば、インクジェット印刷時の不吐出ノズルの発生や、ノズルの目詰まりの発生を一層確実に防止することができる。また、インクの粘度は、２５℃で１〜３０ｍＰａ・ｓであることがより好ましい。インクの粘度を当該範囲とすることによって、液滴を小径化でき、インクの着弾径を一層小さくすることができる傾向がある。これにより、微細なパターンの形成が容易となる。
The appropriate range of the viscosity and surface tension of the copper-based ink varies depending on the printing method to be applied.
For example, the viscosity when applied to the inkjet printing method is preferably 50 mPa · s or less at 25 ° C. If the viscosity of the ink is 50 mPa · s or less, it is possible to more reliably prevent the occurrence of non-ejection nozzles during ink jet printing and the occurrence of nozzle clogging. Further, the viscosity of the ink is more preferably 1 to 30 mPa · s at 25 ° C. By setting the viscosity of the ink within this range, the diameter of the droplet can be reduced, and the landing diameter of the ink tends to be further reduced. Thereby, formation of a fine pattern becomes easy.
また、例えば、インクジェット印刷法に適用する場合の表面張力は、２５℃で２０ｍＮ／ｍ以上であることが好ましい。インクの表面張力が２０ｍＮ／ｍ未満の場合、インク液滴が基材上に着弾後に濡れ広がり、平坦な厚膜を形成できない傾向がある。インクの表面張力は、２０〜８０ｍＮ／ｍの範囲であることがより好ましい。これは、インクの表面張力が８０ｍＮ／ｍを超える場合、インクジェットノズル詰まりが発生し易くなる傾向があるためである。平坦な厚膜の形成性及び安定したインクジェット吐出性の観点から、２０〜５０ｍＮ／ｍであるとより好ましい。 For example, the surface tension when applied to the ink jet printing method is preferably 20 mN / m or more at 25 ° C. When the surface tension of the ink is less than 20 mN / m, the ink droplet tends to spread after landing on the substrate, and a flat thick film tends not to be formed. The surface tension of the ink is more preferably in the range of 20 to 80 mN / m. This is because when the surface tension of the ink exceeds 80 mN / m, the ink jet nozzles tend to be clogged. From the viewpoint of the formation of a flat thick film and stable inkjet discharge properties, it is more preferably 20 to 50 mN / m.
（パターニングされた金属銅パターン）
本発明のパターニングされた金属銅パターンは、銅系粒子堆積層が印刷によりパターニングされており、該パターニングされた層を前述の導体化処理により金属銅に転化して得られる。
すなわち、本発明のパターニングされた金属銅パターンは、銅系粒子堆積層形成用の液状あるいはペースト状の銅インクを配線パターン様に基板上に印刷して配線パターンとなる層を形成し、その配線パターンに対し、前述の導体化処理を施す。
(Patterned metal copper pattern)
The patterned metallic copper pattern of the present invention is obtained by converting a copper-based particle deposition layer into a metallic copper by printing, and the patterned layer is converted into metallic copper by the above-described conductive treatment.
That is, the patterned metal copper pattern of the present invention forms a layer to be a wiring pattern by printing a liquid or paste-like copper ink for forming a copper-based particle deposition layer on the substrate like a wiring pattern to form a wiring pattern layer. The pattern is subjected to the above-described conductor processing.
前記銅系粒子堆積層のパターニングに用いる印刷法は、銅系粒子堆積層を任意の場所に付着させられる手法であればよく、このような手法として、インクジェット印刷、スーパーインクジェット印刷、スクリーン印刷、転写印刷、オフセット印刷、ジェットプリンティング法、ディスペンサ、ジェットディスペンサ、ニードルディスペンサ、カンマコータ、スリットコータ、ダイコータ、グラビアコータ、凸版印刷、凹版印刷、グラビア印刷、ソフトリソグラフ、ディップペンリソグラフ、粒子堆積法、スプレーコータ、スピンコータ、アプリケータ、ディップコータ、電着塗装を用いることができ、中でも、インクジェット印刷、スーパーインクジェット印刷、スクリーン印刷、転写印刷、オフセット印刷、ジェットプリンティング法、ディスペンサ、ニードルディスペンサ、カンマコータ、スリットコータ、ダイコータ、及びグラビアコータからなる群より選択されるいずれか１種が好ましい。
以上のようにして銅系粒子堆積層パターンを描画した後は、前述の導体化処理により金属銅に転化してパターニングされた金属銅パターンが得られる。
基板としては、具体的には、ポリイミド、ポリエチレンナフレタート、ポリエーテルスルホン、ポリエチレンテレフタレート、ポリアミドイミド、ポリエーテルエーテルケトン、ポリカーボネート、液晶ポリマー、エポキシ樹脂、フェノール樹脂、シアネートエステル樹脂、ポリプロピレンなどのポリオレフィン、ポリアミド、ポリフェニレンスルフィド、架橋ポリビニル樹脂、さらに前記樹脂を使用した繊維強化樹脂、無機粒子充填樹脂やガラス、セラミックス等からなるフィルム、シート、板が挙げられる。
なお、本発明においては、比較的低温での処理を可能としているため、耐熱性が低い基板を使用することができるなど、使用する基板の制約が少ない。
The printing method used for the patterning of the copper-based particle deposition layer may be any method that allows the copper-based particle deposition layer to adhere to an arbitrary location. Examples of such a method include inkjet printing, super inkjet printing, screen printing, and transfer. Printing, offset printing, jet printing method, dispenser, jet dispenser, needle dispenser, comma coater, slit coater, die coater, gravure coater, letterpress printing, intaglio printing, gravure printing, soft lithography, dip pen lithography, particle deposition method, spray coater, Spin coaters, applicators, dip coaters, and electrodeposition coatings can be used. Among them, inkjet printing, super inkjet printing, screen printing, transfer printing, offset printing, jet printing, Supensa needle dispenser, Kanmakota, slit coater, die coater, and any one selected from the group consisting of a gravure coater are preferred.
After the copper-based particle deposition layer pattern is drawn as described above, a patterned copper metal pattern is obtained by converting to copper metal by the above-described conductive process.
Specifically, as the substrate, polyimide, polyethylene naphthalate, polyethersulfone, polyethylene terephthalate, polyamideimide, polyetheretherketone, polycarbonate, liquid crystal polymer, epoxy resin, phenol resin, cyanate ester resin, polyolefin such as polypropylene, Examples thereof include polyamide, polyphenylene sulfide, cross-linked polyvinyl resin, fiber reinforced resin using the resin, inorganic particle-filled resin, glass, ceramics, and other films, sheets, and plates.
In the present invention, since processing at a relatively low temperature is possible, there are few restrictions on the substrate to be used, for example, a substrate having low heat resistance can be used.
（導体配線、金属銅バンプ、熱伝導路、接合材）
本発明のパターニングされた金属銅パターンは、例えば、導体配線、金属銅バンプ、熱伝導路、接合材に適用することで、基板密着性に優れ、低体積抵抗率で、基板ダメージなく印刷形成することができ、好適に利用することが可能である。ここでいう、接合材とは、金属・金属間を接着剤やロウ付けのように力学的に接着するものである。
(Conductor wiring, metal copper bump, heat conduction path, bonding material)
The patterned metal copper pattern of the present invention is applied to, for example, a conductor wiring, a metal copper bump, a heat conduction path, and a bonding material, thereby being excellent in substrate adhesion, printed with low volume resistivity and without substrate damage. Can be used suitably. Here, the bonding material is a material that dynamically bonds metal to metal like an adhesive or brazing.
以下、本発明を実施例により具体的に説明するが、本発明はこれに制限されるものではない。
［実施例１］
(銅分散液１の調製)
２５０ｍＬのポリ容器に、炭酸プロピレン９０ｇを秤量し、ＣｕＯナノ粒子（平均粒径、７０ｎｍ）１１０ｇを加え、株式会社日本精機製作所製超音波ホモジナイザＵＳ−６００ＣＣＶＰの超音波端子を混合液中に約３ｃｍつかるようにポリ容器の高さを調製し、混合液の入ったポリ容器を冷却しながら、出力６００Ｗ、振動数１９．５ｋＨｚ、振幅２６．５μｍで５分間分散処理を行った。分散処理後、蓋付きのポリ瓶に内容物を移し、室温（２５℃）で冷却して固形分５５質量％の銅分散液１を得た。
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
[Example 1]
(Preparation of copper dispersion 1)
In a 250 mL plastic container, 90 g of propylene carbonate is weighed, 110 g of CuO nanoparticles (average particle size, 70 nm) are added, and an ultrasonic terminal of an ultrasonic homogenizer US-600CCVP manufactured by Nippon Seiki Seisakusho Co., Ltd. is about 3 cm in the liquid mixture. The height of the plastic container was adjusted so that it could be used, and a dispersion process was performed for 5 minutes at an output of 600 W, a frequency of 19.5 kHz, and an amplitude of 26.5 μm while cooling the plastic container containing the mixed solution. After the dispersion treatment, the contents were transferred to a plastic bottle with a lid and cooled at room temperature (25 ° C.) to obtain a copper dispersion 1 having a solid content of 55% by mass.
(銅分散液１を用いた塗布試験片の作製)
ガラス基板上に銅分散液１を滴下し、ギャップ７５μmに調整したベーカーアプリケータを用いて塗り広げた。その後、室温で１０時間放置し、１４０℃に設定した温風乾燥機で乾燥して銅分散液１塗布試験片を得た。
(Preparation of coated test piece using copper dispersion 1)
Copper dispersion 1 was dropped on a glass substrate and spread using a Baker applicator adjusted to a gap of 75 μm. Then, it was left to stand at room temperature for 10 hours, and dried with a warm air dryer set at 140 ° C. to obtain a copper dispersion 1 coating test piece.
(低温導体化処理)
ギ酸２７．１５ｇに、窒素を含有する有機化合物として２，２´−ビピリジル２．８５ｇを溶解して導体化処理液とした。銅分散液１塗布試験片は、オイルバスで加熱した平底のセパラブルフラスコの底に５ｍｍ厚のアルミ板を敷いた上にセットした。同アルミ板上にアルミカップを置き、シリンジポンプにより直径１mmのポリテトラフルオロエチレンチューブを通じて導体化処理液をアルミカップ内に０．０３６ｍｌ／ｍｉｎで送液して、加熱気化させた。銅分散液１塗布試験片に用いたガラス基板にクロメルアルメル熱電対をセットしアルミ板上にセットし試験片の温度を測定した。
銅分散液１塗布試験片をセットしたセパラブルフラスコに、窒素を０．３Ｌ／ｍｉｎで流しながら、１４６℃のオイルバスで加熱した。銅分散液１塗布試験片の温度が一定（１３０℃）になった後、上記の導体化処理液の送液を開始し、６０分間処理した。処理後、窒素のみを流しながら１３０℃、１０分保持し、その後セパラブルフラスコを放冷し、銅分散液１塗布試験片が５０℃以下になった後、銅分散液１塗布試験片を空気中に取り出した。銅分散液１塗布層は、塗布・乾燥後の黒色から銅色に変化していた。
(Low-temperature conductor treatment)
2.27 g of 2,2′-bipyridyl as an organic compound containing nitrogen was dissolved in 27.15 g of formic acid to prepare a conductor treatment solution. The copper dispersion 1 coating test piece was set on a flat bottom separable flask heated in an oil bath with a 5 mm thick aluminum plate laid on it. An aluminum cup was placed on the same aluminum plate, and the conductive treatment solution was fed into the aluminum cup at 0.036 ml / min through a polytetrafluoroethylene tube having a diameter of 1 mm by a syringe pump, and was vaporized by heating. A chromel alumel thermocouple was set on the glass substrate used for the copper dispersion 1 coating test piece and set on an aluminum plate, and the temperature of the test piece was measured.
The separable flask in which the copper dispersion 1 coating test piece was set was heated in an oil bath at 146 ° C. while flowing nitrogen at 0.3 L / min. After the temperature of the copper dispersion liquid 1 coating test piece became constant (130 ° C.), feeding of the above-mentioned conductor treatment liquid was started and processed for 60 minutes. After the treatment, hold nitrogen at 130 ° C. for 10 minutes, and then cool the separable flask. After the copper dispersion 1 coating test piece became 50 ° C. or less, the copper dispersion 1 coating test piece was air Removed inside. The copper dispersion 1 coating layer was changed from black after coating and drying to copper color.
導体化処理して得られた銅分散液１塗布試験片の金属銅膜を、四探針法低抵抗率計（ロレスタ−ＧＰ、三菱化学株式会社製)を用いて表面抵抗を測定した（０．０４６ Ω／□）。そして、銅分散液１塗布試験片の金属銅膜をＦＩＢ（Focused Ion Beam System (集束イオンビーム装置)）を用いて加工断面の観察から膜厚を求めた（膜厚２８．８μm）。表面抵抗と膜厚から算出した体積抵抗は、１．３×１０−６Ω・ｍであった。 The surface resistance of the metallic copper film of the copper dispersion 1 coating test piece obtained by conducting the conductor was measured using a four-probe method low resistivity meter (Loresta GP, manufactured by Mitsubishi Chemical Corporation) (0 .046 Ω / □). And the film thickness was calculated | required from the observation of the process cross section using the FIB (Focused Ion Beam System (focused ion beam apparatus)) for the metal copper film | membrane of the copper dispersion liquid 1 application | coating test piece (film thickness 28.8 micrometers). The volume resistance calculated from the surface resistance and the film thickness was 1.3 × 10 −6 Ω · m.
［実施例２］
(銅インク２の調製)
炭酸プロピレン１４６ｇ及びＣｕＯナノ粒子５４ｇを用いた以外は実施例１と同様にして２７質量%の銅分散液２を得た。
５０ｍＬの遠沈管に銅分散液２を約４０ｍＬ入れ、株式会社トミー精工製高速遠心機Ｓｕｐｒｅｍａ２５（ロータ：ＮＡ−８）を使用し、２５℃、１５００ｒｐｍで５分間遠心分離処理を行い沈降粒径０．９μｍ以上の粒子を除去した。遠心分離後、遠沈管を静かに取り出し、沈殿物を巻き上げないよう注意しながら上液をポリスポイトで回収して銅インク２を得た。
[Example 2]
(Preparation of copper ink 2)
A 27% by mass copper dispersion 2 was obtained in the same manner as in Example 1 except that 146 g of propylene carbonate and 54 g of CuO nanoparticles were used.
About 40 mL of the copper dispersion 2 is placed in a 50 mL centrifuge tube, and a high-speed centrifuge Suprema 25 (rotor: NA-8) manufactured by Tommy Seiko Co., Ltd. is used. Particles of 9 μm or more were removed. After centrifugation, the centrifuge tube was gently taken out, and the upper liquid was collected with a poly dropper while taking care not to wind up the precipitate, so that a copper ink 2 was obtained.
(銅インク２印刷試験片の作製)
ガラスプレパラートに５分間ＵＶ−Ｏ３照射し、この表面に銅インク２をインクジェット印刷し、銅インク２印刷試験片を得た。
(Preparation of copper ink 2 print test piece)
The glass preparation was irradiated with UV-O 3 for 5 minutes, and copper ink 2 was inkjet printed on the surface to obtain a copper ink 2 print test piece.
(低温導体化処理)
実施例１と同様にして銅インク２印刷試験片を処理した。
(Low-temperature conductor treatment)
The copper ink 2 print test piece was treated in the same manner as in Example 1.
［比較例１］
実施例１と同様に調製した銅分散液１塗布試験片を作製した。
(低温導体化処理)
銅分散液１塗布試験片をギ酸と２，２´−ビピリジルの混合液の代わりにギ酸のみを用い、処理時間を２時間とした以外は実施例１と同様に低温導体化処理した。その結果、銅分散液１塗布試験片の表面は、実施例１のような銅色にはならず、表面のみこげ茶色に変化した。表面抵抗を測定したところ測定上限以上、すなわち導電性はなかった。
[Comparative Example 1]
A copper dispersion 1 coating test piece prepared in the same manner as in Example 1 was prepared.
(Low-temperature conductor treatment)
The copper dispersion 1 coating test piece was subjected to low-temperature conductor treatment in the same manner as in Example 1 except that only formic acid was used instead of the mixed liquid of formic acid and 2,2′-bipyridyl, and the treatment time was 2 hours. As a result, the surface of the copper dispersion 1 coated test piece did not have a copper color as in Example 1, but changed to a dark brown surface. When the surface resistance was measured, it was above the upper limit of measurement, that is, there was no conductivity.
［実施例３］
基板にＰＥＴフィルム（東レ株式会社、ルミラー、５０μｍ）を用い、乾燥方法を常温減圧乾燥とした以外は、実施例１と同様に銅分散液１塗布試験片を作製した。
（低温導体化処理）
処理温度を１１０℃、１２０℃、１３０℃、１４０℃、１６０℃、１８０℃と変えた以外は実施例１と同様に低温導体化処理した。処理結果を表１にまとめて示した。この低温導体化手法では、１３０℃以上で導体化が可能であるが、１５０℃以上では基板のＰＥＴ樹脂が変形した。なお、１８０℃では基板の変形が激しく銅インクの状態は評価できなかった。
[Example 3]
A copper dispersion 1 coating test piece was prepared in the same manner as in Example 1 except that a PET film (Toray Industries, Lumirror, 50 μm) was used as the substrate and the drying method was room temperature vacuum drying.
(Low-temperature conductor treatment)
Low-temperature conductorization treatment was performed in the same manner as in Example 1 except that the treatment temperature was changed to 110 ° C, 120 ° C, 130 ° C, 140 ° C, 160 ° C, and 180 ° C. The processing results are summarized in Table 1. With this low-temperature conductorization method, conductorization is possible at 130 ° C. or higher, but the PET resin of the substrate was deformed at 150 ° C. or higher. At 180 ° C., the substrate was severely deformed, and the state of the copper ink could not be evaluated.
処理後の銅インク状態：○；銅色に変色、△；こげ茶色、×；黒色(銅インク色)
［実施例４］
実施例１と同様に銅分散液１塗布試験片を作製した。
（低温導体化処理）
ギ酸と２，２´−ビピリジルの混合処理液中の２，２´−ビピリジル濃度を、０．００３、０．３、２、３、５ｍｏｌ%と変えた以外は実施例１と同様に低温導体化処理した。処理結果をまとめて表２に示した。
[Example 4]
A copper dispersion 1 coating test piece was prepared in the same manner as in Example 1.
(Low-temperature conductor treatment)
Low-temperature conductor as in Example 1 except that the concentration of 2,2′-bipyridyl in the mixed treatment solution of formic acid and 2,2′-bipyridyl was changed to 0.003, 0.3, 2, 3, 5 mol%. Processed. The processing results are summarized in Table 2.
［実施例５］
実施例１と同様に銅分散液１塗布試験片を作製した。
（低温導体化処理）
ギ酸と２，２´−ビピリジルの混合処理液中の２，２´−ビピリジルを他の含窒素有機化合物と変えた以外は実施例１と同様に低温導体化処理した。処理結果を表３にまとめて示した。
[Example 5]
A copper dispersion 1 coating test piece was prepared in the same manner as in Example 1.
(Low-temperature conductor treatment)
The low-temperature conductorization treatment was performed in the same manner as in Example 1 except that 2,2′-bipyridyl in the mixed treatment solution of formic acid and 2,2′-bipyridyl was changed to other nitrogen-containing organic compounds. The processing results are summarized in Table 3.
［実施例６］
銅系粒子としてＣｕＯナノ粒子９９ｇと表面自然酸化Ｃｕナノ粒子（平均粒径６０ｎｍ、日清エンジニアリング株式会社製）１１ｇを用いた（銅分散液３とする）以外は実施例１と同様に銅分散液３塗布試験片を作製した。
（低温導体化処理）
実施例1と同様に銅分散液３塗布試験片を処理したところ、実施例１では銅分散液１塗布試験片表面の色が黒色から銅色に変色するのに５０分かかったところ、銅分散液３塗布試験片では３０分で銅色に変色し導体化時間が短縮した。
表面抵抗（０．０８７Ω／□）にＦＩＢ加工断面の観察から求めた膜厚１６μｍを乗算して求めた体積抵抗率は、１．４×１０−６Ω・ｍであった。
[Example 6]
Copper dispersion as in Example 1 except that 99 g of CuO nanoparticles and 11 g of surface natural oxidation Cu nanoparticles (average particle diameter 60 nm, manufactured by Nissin Engineering Co., Ltd.) were used as copper-based particles (referred to as “copper dispersion 3”). A liquid 3 coating test piece was prepared.
(Low-temperature conductor treatment)
When the copper dispersion 3 coating test piece was treated in the same manner as in Example 1, it took 50 minutes for the color of the surface of the copper dispersion 1 coating test piece to change from black to copper in Example 1. In the liquid 3 coating test piece, the color changed to copper color in 30 minutes and the conductorization time was shortened.
The volume resistivity obtained by multiplying the surface resistance (0.087Ω / □) by the film thickness of 16 μm obtained from the observation of the FIB processed cross section was 1.4 × 10 −6 Ω · m.
［実施例７］
実施例１と同様に銅分散液１塗布試験片を作製した。
（低温導体化処理）
銅分散液１塗布試験片は、オイルバスで加熱した平底のセパラブルフラスコの底に５ｍｍ厚のアルミ板を敷いた上にセットした。同アルミ板上にアルミカップを置き、２，２´−ビピリジル３ｇを入れた。銅分散液１塗布試験片に用いたガラス基板にクロメルアルメル熱電対をセットしアルミ板上にセットし試験片の温度を測定した。洗気瓶にギ酸を入れ窒素をバブリングしながら１１０℃のオイルバスで加熱してギ酸ガスの発生装置とした。
銅インク印刷パターン試験片をセットしたセパラブルフラスコに窒素を流しながら１４５℃のオイルバスで加熱し銅インク印刷パターン試験片の温度が一定（１３０℃）になった後、ギ酸ガスの発生装置で発生させたギ酸ガスを含む窒素ガスをこのセパラブルフラスコに通じ、６０分間処理した。処理後、ギ酸ガスの発生装置をはずし、窒素のみを流しながらセパラブルフラスコを放冷し、銅インク印刷パターン試験片が５０℃以下になった後、銅インク印刷パターン試験片を空気中に取り出した。
銅分散液１塗布層は、塗布・乾燥後の黒色から銅色に変化した。
表面抵抗は、０．０３３Ω／□であった。
[Example 7]
A copper dispersion 1 coating test piece was prepared in the same manner as in Example 1.
(Low-temperature conductor treatment)
The copper dispersion 1 coating test piece was set on a flat bottom separable flask heated in an oil bath with a 5 mm thick aluminum plate laid on it. An aluminum cup was placed on the same aluminum plate, and 3 g of 2,2′-bipyridyl was added. A chromel alumel thermocouple was set on the glass substrate used for the copper dispersion 1 coating test piece and set on an aluminum plate, and the temperature of the test piece was measured. A formic acid gas generator was prepared by putting formic acid into a washing bottle and heating it in an oil bath at 110 ° C. while bubbling nitrogen.
After flowing the nitrogen into the separable flask with the copper ink print pattern test piece set in an oil bath at 145 ° C and the temperature of the copper ink print pattern test piece becomes constant (130 ° C), use a formic acid gas generator. Nitrogen gas containing the generated formic acid gas was passed through the separable flask and treated for 60 minutes. After the treatment, remove the formic acid gas generator, allow the separable flask to cool while flowing only nitrogen, and after the copper ink print pattern test piece has reached 50 ° C or less, take out the copper ink print pattern test piece in the air. It was.
The copper dispersion 1 coating layer changed from black after coating and drying to copper.
The surface resistance was 0.033Ω / □.
［実施例８］
実施例１と同様に銅分散液１塗布試験片を作製した。
（低温導体化処理）
銅分散液１塗布試験片は、オイルバスで加熱した平底のセパラブルフラスコの底に５ｍｍ厚のアルミ板を敷いた上にセットした。同アルミ板上にアルミカップを置き、シリンジポンプと直径１ｍｍのポリテトラフルオロエチレンチューブを２組通じてギ酸とα−ピコリン（２−メチルピリジン）を別々にアルミカップ内に送液して加熱気化させた。ギ酸とα−ピコリンの送液速度はそれぞれ０．０３６ｍｌ／ｍｉｎ及び０．００６ｍｌ／ｍｉｎとした。銅分散液１塗布試験片に用いたガラス基板にクロメルアルメル熱電対をセットしアルミ板上にセットし試験片の温度を測定した。
銅分散液１塗布試験片をセットしたセパラブルフラスコに、ギ酸とα−ピコリンを送液せずに窒素を０．３Ｌ／ｍｉｎで流しながら、１４６℃のオイルバスで加熱した。銅分散液１塗布試験片の温度が一定（１３０℃）になった後、ギ酸とα−ピコリンの送液を開始し、６０分間処理した。処理後、窒素のみを流しながら１３０℃、１０分保持し、その後セパラブルフラスコを放冷し、銅分散液１塗布試験片が５０℃以下になった後、銅分散液１塗布試験片を空気中に取り出した。銅分散液１塗布層は、黒色から銅色に変化した。表面抵抗は、０．０６４Ω／□であった。
[Example 8]
A copper dispersion 1 coating test piece was prepared in the same manner as in Example 1.
(Low-temperature conductor treatment)
The copper dispersion 1 coating test piece was set on a flat bottom separable flask heated in an oil bath with a 5 mm thick aluminum plate laid on it. Place an aluminum cup on the same aluminum plate, and pass through two sets of syringe pump and 1mm diameter polytetrafluoroethylene tube to separate formic acid and α-picoline (2-methylpyridine) into the aluminum cup and heat to vaporize. I let you. The liquid feeding rates of formic acid and α-picoline were 0.036 ml / min and 0.006 ml / min, respectively. A chromel alumel thermocouple was set on the glass substrate used for the copper dispersion 1 coating test piece and set on an aluminum plate, and the temperature of the test piece was measured.
The separable flask in which the copper dispersion 1 coating test piece was set was heated in an oil bath at 146 ° C. while flowing formic acid and α-picoline at a rate of 0.3 L / min without feeding formic acid and α-picoline. After the temperature of the copper dispersion 1 coating test piece became constant (130 ° C.), the feeding of formic acid and α-picoline was started and treated for 60 minutes. After the treatment, hold nitrogen at 130 ° C. for 10 minutes, and then cool the separable flask. After the copper dispersion 1 coating test piece became 50 ° C. or less, the copper dispersion 1 coating test piece was air Removed inside. The copper dispersion 1 coating layer changed from black to copper. The surface resistance was 0.064Ω / □.
比較例１に示したように、還元剤としてキ酸を単独で用いた場合、１３０℃で２時間処理してもこげ茶色の状態で導電性は得られなかったが、本発明のギ酸に、リン又は窒素を含有する有機化合物を併用した処理とすることで１３０℃の低温でも酸化銅を還元し金属銅膜にすることができる。そのため、耐熱性に乏しい基板上に銅インクにより印刷された層を基板にダメージを与えない低温、短時間で処理して低抵抗の金属銅、金属銅パターンに転換することができる。 As shown in Comparative Example 1, when oxalic acid was used alone as a reducing agent, conductivity was not obtained in a dark brown state even when treated at 130 ° C. for 2 hours. By treating with an organic compound containing phosphorus or nitrogen, copper oxide can be reduced to a metal copper film even at a low temperature of 130 ° C. Therefore, a layer printed with copper ink on a substrate having poor heat resistance can be processed at a low temperature and in a short time without damaging the substrate, and converted into a low-resistance metal copper or metal copper pattern.
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|---|---|---|---|---|
| JP2016164225A (en) * | 2015-03-06 | 2016-09-08 | コニカミノルタ株式会社 | Electric conductive ink |
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