JP5660368B2 - Manufacturing method of substrate with Cu pattern and substrate with Cu pattern obtained thereby - Google Patents
Manufacturing method of substrate with Cu pattern and substrate with Cu pattern obtained thereby Download PDFInfo
- Publication number
- JP5660368B2 JP5660368B2 JP2010153608A JP2010153608A JP5660368B2 JP 5660368 B2 JP5660368 B2 JP 5660368B2 JP 2010153608 A JP2010153608 A JP 2010153608A JP 2010153608 A JP2010153608 A JP 2010153608A JP 5660368 B2 JP5660368 B2 JP 5660368B2
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- JP
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- Prior art keywords
- substrate
- resin
- pattern
- printing
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000758 substrate Substances 0.000 title claims description 107
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000010949 copper Substances 0.000 claims description 92
- 229920005989 resin Polymers 0.000 claims description 74
- 239000011347 resin Substances 0.000 claims description 74
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 42
- 239000002245 particle Substances 0.000 claims description 40
- 239000007864 aqueous solution Substances 0.000 claims description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 29
- 229910052802 copper Inorganic materials 0.000 claims description 25
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 22
- 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 21
- 235000019253 formic acid Nutrition 0.000 claims description 21
- 238000007639 printing Methods 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 14
- 238000007641 inkjet printing Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000005751 Copper oxide Substances 0.000 claims description 9
- 229910000431 copper oxide Inorganic materials 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 7
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- 239000011248 coating agent Substances 0.000 claims description 6
- 230000035515 penetration Effects 0.000 claims description 6
- 150000004703 alkoxides Chemical class 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000007645 offset printing Methods 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 4
- 239000004645 polyester resin Substances 0.000 claims description 4
- 229920001225 polyester resin Polymers 0.000 claims description 4
- 239000009719 polyimide resin Substances 0.000 claims description 4
- 238000007650 screen-printing Methods 0.000 claims description 4
- 238000010023 transfer printing Methods 0.000 claims description 4
- 239000004962 Polyamide-imide Substances 0.000 claims description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- 238000005259 measurement Methods 0.000 claims description 3
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- 229920005668 polycarbonate resin Polymers 0.000 claims description 3
- 239000004431 polycarbonate resin Substances 0.000 claims description 3
- 229920005749 polyurethane resin Polymers 0.000 claims description 3
- 229920003987 resole Polymers 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
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- 238000000034 method Methods 0.000 description 27
- 239000010410 layer Substances 0.000 description 20
- 239000004020 conductor Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 11
- 238000012545 processing Methods 0.000 description 10
- 229960004643 cupric oxide Drugs 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 7
- 239000004744 fabric Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
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- 150000002500 ions Chemical class 0.000 description 4
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- 239000012498 ultrapure water Substances 0.000 description 4
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- HPUOAJPGWQQRNT-UHFFFAOYSA-N pentoxybenzene Chemical compound CCCCCOC1=CC=CC=C1 HPUOAJPGWQQRNT-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- CUQOHAYJWVTKDE-UHFFFAOYSA-N potassium;butan-1-olate Chemical compound [K+].CCCC[O-] CUQOHAYJWVTKDE-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 238000002174 soft lithography Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Images
Description
本発明は、基板に塗布法または印刷法によりＣｕパターンを形成するＣｕパターン付基板の製造方法とその製造方法を用いて得られるＣｕパターン付基板に関する。 The present invention relates to a method for manufacturing a substrate with a Cu pattern for forming a Cu pattern on a substrate by a coating method or a printing method, and a substrate with a Cu pattern obtained by using the manufacturing method.
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。
一方、インクジェット、ジェットディスペンサ、ニードルディスペンサ、ディスペンサ、有版印刷はフォトレジスト工程を用いることなく任意の形状に液状の材料を塗布できるため、オンデマンド生産、省力化、省材料化、低コスト化の点から注目されている。特に、非接触で成形可能なインクジェット、ジェットディスペンサでは、段差や曲面、小面積への印刷が可能であり、有版印刷では不可能なパターン形成が可能である。
従来、このような目的としては銅ナノ粒子の分散液が提案されているが、生成した導体層の低接着性および処理印刷層の剥離、脆弱性に問題があり、当該印刷インクを導体配線材料、熱伝達材料、熱交換材料、放熱材料に適用できなかった。
低接着性および処理印刷層の剥離の原因は、印刷インク中の金属元素含有粒子が焼結した多孔質な焼結体であり、その多孔質焼結体の脆弱性と、印刷層と基板間の空隙の発生や印刷層と基板間に結合が生じず接着性が得られないためである。このような課題に対し、従来は下地樹脂にポリイミドの前駆体を用いその上に導体インクを印刷する(例えば、特許文献１参照)、あるいは半硬化のエポキシ樹脂上に導体インクを印刷し(特願２００８−２６７４００号)、下地となる樹脂に流動性を持たせて導体層に追従させ接着性を得る方法が提案されているが、下地樹脂材料や製造方法に制約が生じる。
また、このような印刷により金属銅パターンを形成する印刷インクとしては、金属銅ナノ粒子の分散液や金属錯体の溶液あるいは分散液が提案されている。しかし、銅は室温（２５℃）で酸化状態が安定であり必ず酸化状態の銅原子を含むため、金属銅として導体、導熱性を発現するには酸化状態の銅原子を還元し、さらに金属銅の連続体とする必要がある。
その還元手法として、ギ酸ガスを用いた還元手法が知られている。ギ酸ガスを用いた還元手法としてギ酸リフロー炉が、銅およびハンダ表面の酸化皮膜の除去に効果があることが報告されている(例えば、特許文献２参照)。また、このギ酸の還元力を導体インクの導体化手法として適用する手法が近年、報告されている（例えば、特許文献３、４、５参照）。
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.
On the other hand, since inkjet, jet dispenser, needle dispenser, dispenser, and plate printing can apply liquid materials in any shape without using a photoresist process, on-demand production, labor saving, material saving, and cost reduction It is attracting attention from a point. In particular, inkjet and jet dispensers that can be formed in a non-contact manner can print on steps, curved surfaces, and small areas, and can form patterns that are impossible with plate printing.
Conventionally, a dispersion of copper nanoparticles has been proposed for such a purpose, but there are problems with the low adhesion of the produced conductor layer and the peeling and brittleness of the treated printed layer. It could not be applied to heat transfer materials, heat exchange materials, and heat dissipation materials.
The cause of low adhesion and peeling of the treated printed layer is the porous sintered body in which the metal element-containing particles in the printing ink are sintered. The vulnerability of the porous sintered body and the gap between the printed layer and the substrate This is because the generation of voids and the bonding between the printed layer and the substrate do not occur, and the adhesiveness cannot be obtained. To deal with such problems, conventionally, a polyimide precursor is used as a base resin and a conductor ink is printed thereon (see, for example, Patent Document 1), or a conductor ink is printed on a semi-cured epoxy resin (special feature). (Application No. 2008-267400), a method has been proposed in which a resin as a base is made to have fluidity so as to follow the conductor layer to obtain adhesion, but there are restrictions on the base resin material and the manufacturing method.
Moreover, as a printing ink for forming a metallic copper pattern by such printing, a dispersion of metallic copper nanoparticles or a solution or dispersion of a metal complex has been proposed. However, copper has a stable oxidation state at room temperature (25 ° C.) and always contains copper atoms in the oxidation state. Therefore, copper atoms in the oxidation state are reduced in order to exhibit conductor and heat conductivity as metal copper, and further, copper metal It is necessary to make it a continuum.
As a reduction technique, a reduction technique using formic acid gas is known. As a reduction method using formic acid gas, it has been reported that a formic acid reflow furnace is effective in removing an oxide film on the surface of copper and solder (for example, see Patent Document 2). In recent years, a method of applying this reducing power of formic acid as a method for making a conductor ink into a conductor has been reported (see, for example,
本発明者らは、銅酸化物粒子のギ酸ガス処理が、昇華性のギ酸銅を経由して進行することを指摘している（特願２００９−２１５００３号）。酸化銅はギ酸と反応しギ酸銅が生成し、ギ酸銅はその昇華性によりガス状となり拡散し、ギ酸銅の熱分解により金属Ｃｕが生成する。この際、ギ酸銅がガス状を経ることで基板と追随した形状の緻密な金属Ｃｕ層が形成可能である（図２）。しかし、樹脂基板上で単なる基板と追随した形状を形成した場合、樹脂と金属Ｃｕ層の間に十分な相互作用は得られず、接着性は得られていなかった。
本発明は、樹脂と金属Ｃｕ層の接着性が良好であるＣｕパターン付基板の製造方法及びそれにより得られるＣｕパターン付基板を提供することを目的とする。
The present inventors have pointed out that formic acid gas treatment of copper oxide particles proceeds via sublimable copper formate (Japanese Patent Application No. 2009-215033). Copper oxide reacts with formic acid to produce copper formate, and copper formate diffuses into a gaseous state due to its sublimation property, and metal Cu is produced by thermal decomposition of copper formate. At this time, a dense metal Cu layer having a shape following the substrate can be formed by the copper formate passing through the gaseous state (FIG. 2). However, when a shape following a simple substrate was formed on the resin substrate, sufficient interaction was not obtained between the resin and the metal Cu layer, and adhesion was not obtained.
An object of this invention is to provide the manufacturing method of the board | substrate with Cu pattern in which the adhesiveness of resin and a metal Cu layer is favorable, and the board | substrate with Cu pattern obtained by it.
本発明者らは、上記課題の検討の結果、有機基板の表面を強アルカリ水溶液で処理することにより、接着力が得られることがわかった。得られた樹脂基板の断面を観察すると、基板を処理していない場合（図２）では見られない、樹脂基板表面から１００ｎｍ程度の銅の貫入が見られた（図１）。これは、樹脂基板表面を強アルカリ水溶液で処理することにより、表面の樹脂の主鎖の切断による架橋密度低下と水酸基やカルボキシル基、カルボニル基のような親水性置換基が導入され、昇華したギ酸銅がこの層に浸透後、熱分解して樹脂表面層内に金属銅が形成され、これが接着性のアンカーとして働き接着力が向上したと考える。
すなわち、前記課題を解決する本発明は以下の通りである。
（１）樹脂基板を強アルカリ水溶液中に浸漬処理し、樹脂基板をイオン交換水あるいは蒸留水で洗浄、乾燥した後、酸化銅（Ｉ）または酸化銅（ＩＩ）からなる粒子を全粒子中９５質量％以上含み、２５℃における蒸気圧が１．３４×１０ ３ Ｐａ未満である溶剤を含む導体インクを塗布あるいは印刷により成形した後、ギ酸を含むガス雰囲気中で１２０℃以上に加熱することを特徴とするＣｕパターン付基板の製造方法。
樹脂基板を強アルカリ水溶液で処理した後は、処理し樹脂基板を乾燥することが好ましい。
（２）強アルカリ水溶液が、アルカリ金属の水酸化物、アルカリ土類金属の水酸化物または金属アルコキシドのいずれかである上記（１）に記載のＣｕパターン付基板の製造方法。
（３）塗布あるいは印刷が、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種以上である上記（１）または（２）に記載のＣｕパターン付基板の製造方法。
（４）樹脂基板が強アルカリ水溶液中で加水分解反応をする有機樹脂材料からなる基板である上記（１）ないし（３）のいずれかに記載のＣｕパターン付基板の製造方法。
（５） 樹脂基板が有機樹脂材料からなり、前記有機樹脂材料が、エポキシ樹脂、イソシアナート樹脂、ポリイミド樹脂、フェノール樹脂、レゾール樹脂、ポリアミド樹脂、ポリアミドイミド樹脂、ポリウレタン樹脂、ポリカーボネート樹脂、ポリエステル樹脂、尿素樹脂のいずれかである上記（１）ないし（４）のいずれかに記載のＣｕパターン付基板の製造方法。
（６）上記（１）ないし（５）のいずれかに記載のＣｕパターン付基板の製造方法により得られるＣｕパターン付基板。
（７）上記（６）に記載のＣｕパターン付基板であって、得られたＣｕパターン付基板の断面観察において、サイカス（ＳＡＩＣＡＳ（Surface And Interfacial Cutting AnalysisSystem））測定によりＣｕパターンと樹脂基板の密着性が０．３ｋN／ｍ以上で樹脂基板中にＣｕパターンとの界面から５ｎｍ以上、３００ｎｍ以下の深さで銅の貫入が観察されることを特徴とするＣｕパターン付基板。
As a result of studying the above problems, the present inventors have found that an adhesive force can be obtained by treating the surface of the organic substrate with a strong alkaline aqueous solution. When the cross section of the obtained resin substrate was observed, copper penetration of about 100 nm from the surface of the resin substrate, which was not observed when the substrate was not processed (FIG. 2), was observed (FIG. 1). This is because the surface of the resin substrate is treated with a strong alkaline aqueous solution to reduce the crosslinking density due to cleavage of the resin main chain on the surface and introduce a hydrophilic substituent such as a hydroxyl group, a carboxyl group or a carbonyl group, and sublimate formic acid. After copper penetrates into this layer, it is thermally decomposed to form metallic copper in the resin surface layer, which acts as an adhesive anchor and is considered to have improved adhesive strength.
That is, the present invention for solving the above problems is as follows.
(1) The resin substrate is dipped in a strong alkaline aqueous solution , and the resin substrate is washed with ion-exchanged water or distilled water and dried, and then particles of copper (I) oxide or copper (II) oxide are contained in 95 of all particles. After forming a conductor ink containing a solvent containing a mass% and having a vapor pressure of less than 1.34 × 10 3 Pa at 25 ° C. by coating or printing, heating to 120 ° C. or more in a gas atmosphere containing formic acid A method for manufacturing a substrate with a Cu pattern, which is characterized.
After the resin substrate is treated with a strong alkaline aqueous solution, it is preferable to treat and dry the resin substrate.
(2) The manufacturing method of the board | substrate with Cu pattern as described in said (1) whose strong alkali aqueous solution is either an alkali metal hydroxide, an alkaline earth metal hydroxide, or a metal alkoxide .
(3 ) Coating or printing is selected from the group consisting of inkjet printing, super inkjet printing, screen printing, transfer printing, offset printing, jet printing, dispenser, needle dispenser, comma coater, slit coater, die coater, and gravure coater. The manufacturing method of the board | substrate with Cu pattern as described in said (1) or ( 2 ) which is any 1 type or more.
( 4 ) The method for producing a substrate with a Cu pattern according to any one of (1) to ( 3 ), wherein the resin substrate is a substrate made of an organic resin material that undergoes a hydrolysis reaction in a strong alkaline aqueous solution.
( 5 ) The resin substrate is made of an organic resin material, and the organic resin material is an epoxy resin, an isocyanate resin, a polyimide resin, a phenol resin, a resole resin, a polyamide resin, a polyamideimide resin, a polyurethane resin, a polycarbonate resin, a polyester resin, The manufacturing method of the board | substrate with Cu pattern in any one of said (1) thru | or (4) which is either urea resin .
( 6) A substrate with a Cu pattern obtained by the method for producing a substrate with a Cu pattern according to any one of (1) to ( 5 ).
(7) The Cu pattern-attached substrate as described in ( 6 ) above, wherein in the cross-sectional observation of the obtained Cu pattern-provided substrate, the adhesion between the Cu pattern and the resin substrate is measured by CYCAS (SAICAS (Surface And Interfacial Cutting Analysis System)) measurement. A Cu-patterned substrate characterized in that the penetration of copper is observed at a depth of 5 nm or more and 300 nm or less from the interface with the Cu pattern in the resin substrate with a property of 0.3 kN / m or more.
本発明のＣｕパターン付基板の製造方法で得られたＣｕパターン付基板は、樹脂と金属Ｃｕ層の接着性が良好である基板が得られ、導体インクを塗布あるいは印刷で形成することができる。 A substrate with a Cu pattern obtained by the method for producing a substrate with a Cu pattern of the present invention provides a substrate with good adhesion between a resin and a metal Cu layer, and can be formed by applying or printing a conductive ink.
＜強アルカリ水溶液中への浸漬処理＞
本発明のＣｕパターン付基板の製造方法で用いる強アルカリ水溶液で処理する方法として、強アルカリ水溶液中への浸漬処理が好ましい。本発明のＣｕパターン付基板の製造方法は、樹脂基板を強アルカリ水溶液中へ浸漬処理することにより樹脂基板表面を部分的に加水分解し、その上に銅元素含有粒子を含む導体インク（銅酸化物粒子を主成分とする粒子堆積層）を塗布あるいは印刷によりパターニングし、この粒子堆積層を、１２０℃以上において加熱したガス状のギ酸により処理してなることを特徴としている。
本発明で用いる樹脂基板の強アルカリ水溶液処理では、樹脂基板表面を構成する樹脂の主鎖を部分的に加水分解することにより、架橋密度や分子間パッキングが疎で、親金属イオン性の置換基が導入された表面層が形成される。続く、ガス状のギ酸処理において、昇華してガス化したギ酸銅が強アルカリ水溶液処理で形成された樹脂表面層中に浸透・分解して、樹脂表面層中に金属銅が析出し樹脂に銅が貫入した層が形成されて、その上部に形成されたＣｕ膜の接着性が発現する。
この要件を満たす基板、強アルカリ水溶液、処理条件、洗浄（イオン交換水、蒸留水洗浄工程）、基板の乾燥について、それぞれを交えて説明する。
<Immersion treatment in strong alkaline aqueous solution>
As a method of treating with a strong alkaline aqueous solution used in the method for producing a substrate with a Cu pattern of the present invention, an immersion treatment in a strong alkaline aqueous solution is preferable. In the method for producing a substrate with a Cu pattern according to the present invention, the resin substrate surface is partially hydrolyzed by immersing the resin substrate in a strong alkaline aqueous solution, and a conductive ink containing copper element-containing particles thereon (copper oxidation) It is characterized in that a particle deposition layer (mainly composed of physical particles) is patterned by coating or printing, and the particle deposition layer is treated with gaseous formic acid heated at 120 ° C. or higher.
In the strong alkaline aqueous solution treatment of the resin substrate used in the present invention, the main chain of the resin constituting the resin substrate surface is partially hydrolyzed so that the crosslink density and intermolecular packing are sparse, and the parent metal ionic substituent A surface layer into which is introduced is formed. In the subsequent gaseous formic acid treatment, the sublimated and gasified copper formate permeates and decomposes into the resin surface layer formed by the strong alkaline aqueous solution treatment, and metallic copper is deposited in the resin surface layer, and copper is added to the resin. Is formed, and the adhesion of the Cu film formed thereon is developed.
The substrate that satisfies this requirement, the strong alkaline aqueous solution, the processing conditions, the cleaning (ion-exchange water and distilled water cleaning step), and the drying of the substrate will be described together.
（樹脂基板）
本発明で用いられる樹脂基板は、強アルカリ水溶液処理して樹脂基板表面を改質するため有機樹脂材料からなる基板であることが好ましい。有機樹脂材料は、強アルカリ水溶液との接触により加水分解性を有する有機樹脂材料が適用でき、例えばこのような有機樹脂材料として、エポキシ樹脂、イソシアナート樹脂、フェノール樹脂、レゾール樹脂、ポリイミド樹脂、ポリアミド樹脂、ポリアミドイミド樹脂、ポリウレタン樹脂、ポリカーボネート樹脂、ポリエステル樹脂、尿素樹脂が好ましいものとして挙げられる。樹脂基板としては、これら単体の有機樹脂材料基板以外に、無機フィラの充填や、クロスへの含浸したエポキシ樹脂／ガラスクロス、ポリエステル樹脂／ガラスクロス・ガラス布織布、ポリイミド樹脂／ガラスクロス等の有機・無機コンポジットの樹脂基板でもよい。
(Resin substrate)
The resin substrate used in the present invention is preferably a substrate made of an organic resin material in order to modify the resin substrate surface by treating with a strong alkaline aqueous solution. As the organic resin material, an organic resin material having hydrolyzability by contact with a strong alkaline aqueous solution can be applied. For example, as such an organic resin material, epoxy resin, isocyanate resin, phenol resin, resol resin, polyimide resin, polyamide Preferred examples include resins, polyamideimide resins, polyurethane resins, polycarbonate resins, polyester resins, and urea resins. In addition to these single organic resin material substrates, resin substrates include inorganic filler filling, cloth impregnated epoxy resin / glass cloth, polyester resin / glass cloth / glass cloth, polyimide resin / glass cloth, etc. Organic / inorganic composite resin substrates may also be used.
（強アルカリ水溶液）
本発明で用いる強アルカリ水溶液の強アルカリの種類としては、水溶液として強アルカリ性を示す物質を用いることができ、例えば、アルカリ金属やアルカリ土類金属の水酸化物、金属アルコキシド等が好ましいものとして挙げられる。アルカリ金属の水酸化物として、水酸化リチウム、水酸化ナトリウム、水酸化カリウムなどが例示され、アルカリ土類金属の水酸化物として、水酸化カルシウム、水酸化ストロンチウム、水酸化バリウムなどが例示される。また、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウムのようなテトラアルキルアンモニウムを単独で、または併用して用いることができる。金属アルコキシドとしては、ナトリウムメトキシド、ナトリウムエトキシド、カリウムブトキシド等が挙げられる。
(Strong alkaline aqueous solution)
As the type of strong alkali in the strong alkaline aqueous solution used in the present invention, a substance exhibiting strong alkalinity can be used as the aqueous solution. For example, alkali metal and alkaline earth metal hydroxides, metal alkoxides and the like are preferable. It is done. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide and potassium hydroxide, and examples of the alkaline earth metal hydroxide include calcium hydroxide, strontium hydroxide and barium hydroxide. . Further, tetraalkylammonium hydroxide such as tetramethylammonium hydroxide and tetraethylammonium hydroxide can be used alone or in combination. Examples of the metal alkoxide include sodium methoxide, sodium ethoxide, potassium butoxide and the like.
（処理条件）
強アルカリ水溶液の濃度は樹脂基板の表面処理層の形成度合いから調整することが望ましい。表面処理層の形成度合いは、強アルカリ水溶液の濃度だけでなく、基板の種類、アルカリの種類、処理温度、処理時間にも影響されるため、各々の系に対して最適濃度は異なる。基板の種類にあわせて、アルカリの種類、強アルカリ水溶液の濃度、処理温度、処理時間を調整することが望ましい。なお、処理強度が強すぎる場合には、樹脂の腐食に伴い樹脂の減量や樹脂脆弱層が形成され、樹脂基板の変形、マイグレーション特性の悪化や、Ｃｕ膜の接着力の低下が生じる。逆に、処理強度が低い場合には、接着力の発現は得られない。強アルカリ水溶液とは、樹脂基板の表面処理を行った場合、接着力が発現できる濃度のアルカリ水溶液を意味する。この接着力は、指でこすっても取れない程度であり、好ましくは、Ｃｕパターンと樹脂基板の密着性が０．３ｋN／ｍ以上である。また、金属アルコキシドの場合、水溶液である必要はない。
(Processing conditions)
The concentration of the strong alkaline aqueous solution is desirably adjusted based on the degree of formation of the surface treatment layer of the resin substrate. The degree of formation of the surface treatment layer is affected not only by the concentration of the strong alkaline aqueous solution, but also by the type of substrate, the type of alkali, the treatment temperature, and the treatment time, so the optimum concentration differs for each system. It is desirable to adjust the type of alkali, the concentration of the strong alkaline aqueous solution, the processing temperature, and the processing time in accordance with the type of substrate. When the processing strength is too strong, the resin is reduced and a resin fragile layer is formed due to the corrosion of the resin, which causes deformation of the resin substrate, deterioration of migration characteristics, and reduction of the adhesive strength of the Cu film. On the contrary, when the processing strength is low, the expression of adhesive force cannot be obtained. The strong alkaline aqueous solution means an alkaline aqueous solution having a concentration capable of exhibiting an adhesive force when the surface treatment of the resin substrate is performed. This adhesive strength is such that it cannot be removed by rubbing with a finger, and preferably the adhesion between the Cu pattern and the resin substrate is 0.3 kN / m or more. In the case of metal alkoxide, it is not necessary to be an aqueous solution.
水洗（イオン交換水、蒸留水洗浄工程）
強アルカリ水溶液中への浸漬処理で用いたアルカリ金属イオンやアルカリ土類金属イオンが基板上に残存すると、Ｃｕ膜の腐食の原因となるだけでなく、配線として用いた場合には少量でもエレクトロマイグレーションの原因となる。そこで、強アルカリ水溶液中への浸漬処理後にイオン交換水や蒸留水のようなイオン性不純物の少ない水を用いて洗浄を行うことが好ましい。洗浄方法としては、溜水洗、流水洗浄、超音波洗浄、流水式超音波洗浄、煮沸、ジェット洗浄、混合噴流洗浄を用いることができる。また、酸性溶液で中和してから水洗を行ってもよい。
Water washing (ion exchange water, distilled water washing process)
If the alkali metal ions or alkaline earth metal ions used in the immersion treatment in a strong alkaline aqueous solution remain on the substrate, it will not only cause corrosion of the Cu film, but also electromigration even when used in small quantities. Cause. Therefore, it is preferable to perform washing using water with less ionic impurities such as ion-exchanged water or distilled water after the immersion treatment in the strong alkaline aqueous solution. As washing methods, water washing, running water washing, ultrasonic washing, running water type ultrasonic washing, boiling, jet washing, and mixed jet washing can be used. Moreover, you may wash with water, after neutralizing with an acidic solution.
（基板の乾燥）
強アルカリ水溶液で処理した樹脂基板は、水洗した後、乾燥することが好ましい。乾燥は、風乾、ホットプレート、温風乾燥機、恒温槽、乾燥窒素気流、乾燥空気気流、赤外線加熱、電磁波加熱等により乾燥する。
(Dry substrate)
The resin substrate treated with the strong alkaline aqueous solution is preferably dried after being washed with water. Drying is performed by air drying, hot plate, hot air dryer, thermostatic bath, dry nitrogen stream, dry air stream, infrared heating, electromagnetic wave heating, or the like.
＜銅元素含有粒子を含む導体インクの塗布あるいは印刷＞
（銅元素含有粒子を含む導体インク）
本発明で用いる銅元素含有粒子を含む導体インクは、後述のギ酸ガス処理においてギ酸と反応して昇華性のあるギ酸銅を生成する必要があるため、銅酸化物粒子を必須成分とする。また、印刷性の観点から２５℃における蒸気圧が１．３４×１０３Ｐａ未満である溶剤を含むことが好ましい。
なお、インクジェット印刷用のＣｕインクでは、平均分散粒径が５００ｎｍ以下で、最大分散粒径が２μｍ以下となるように分散している必要がある。
<Application or printing of conductor ink containing copper element-containing particles>
(Conductor ink containing copper element-containing particles)
The conductor ink containing the copper element-containing particles used in the present invention needs to react with formic acid in the formic acid gas treatment described later to produce sublimable copper formate, and therefore contains copper oxide particles as an essential component. Moreover, it is preferable to include the solvent whose vapor pressure in 25 degreeC is less than 1.34 * 10 < 3 > Pa from a printable viewpoint.
The Cu ink for inkjet printing needs to be dispersed so that the average dispersed particle size is 500 nm or less and the maximum dispersed particle size is 2 μm or less.
（銅酸化物粒子）
銅酸化物粒子は、酸化銅（Ｉ）［酸化第一銅］又は酸化銅（ＩＩ）［酸化第二銅］からなる粒子を全粒子中９５質量％以上含んでいることが好ましい。本発明において使用される銅酸化物粒子は、一次粒子の数平均粒子径が１〜１，０００ｎｍであることが好ましく、１〜５００ｎｍであることがより好ましく、１０〜１００ｎｍであることがさらに好ましい。例えば、シーアイ化成株式会社製の気相蒸発法により作製された酸化銅ナノ粒子や日清エンジニアリング株式会社製のプラズマ炎法により合成された酸化銅ナノ粒子のような市販品として入手可能なものを用いてもよい。
(Copper oxide particles)
It is preferable that the copper oxide particles contain 95% by mass or more of particles made of copper (I) oxide [cuprous oxide] or copper (II) oxide [cupric oxide] in all particles. The copper oxide particles used in the present invention preferably have a primary particle number average particle size of 1 to 1,000 nm, more preferably 1 to 500 nm, and even more preferably 10 to 100 nm. . For example, commercially available products such as copper oxide nanoparticles produced by the vapor phase evaporation method manufactured by CI Kasei Co., Ltd. and copper oxide nanoparticles synthesized by the plasma flame method produced by Nissin Engineering Co., Ltd. It may be used.
（分散）
分散は、超音波分散機、ビーズミルなどのメディア分散機、ホモミキサーやシルバーソン攪拌機などのキャビテーション攪拌装置、アルテマイザーなどの対向衝突法、クレアＳＳ５（エムテクニック株式会社）などの超薄膜高速回転式分散機、自転公転式ミキサなどを用いて行うことができる。
(dispersion)
Dispersion includes ultrasonic dispersers, media dispersers such as bead mills, cavitation stirrers such as homomixers and silverson stirrers, opposed collision methods such as artemizers, and ultra-thin high-speed rotating systems such as Claire SS5 (M Technique Co., Ltd.) It can be carried out using a disperser, a rotating / revolving mixer, or the like.
（溶剤）
溶剤としては、２５℃における蒸気圧が１．３４×１０３Ｐａ未満、好ましくは、１．０×１０３Ｐａ・ｓ未満である溶剤を用いることが好ましい。
このような溶剤としては、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、フェニルシクロヘキサン、ベンゾニトリル、メシチレン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、乳酸メ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；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。
(solvent)
As the solvent, it is preferable to use a solvent having a vapor pressure at 25 ° C. of less than 1.34 × 10 3 Pa, preferably less than 1.0 × 10 3 Pa · s.
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, phenylcyclohexane, benzonitrile, and mesitylene; Ester solvents such as isobutyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, glycol sulfite, ethyl lactate, methyl lactate; alcohol solvents such as 1-butanol, cyclohexanol, α-terpineol, glycerin; Ketone solvents such as cyclohexanone, 2-hexanone, 2-heptanone, 2-octanone, 1,3-dioxolan-2-one, 1,5,5-trimethylcyclohexen-3-one; 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, Alkylene glycol solvents such as reethylene glycol isopropyl ether acetate, 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 Ether solvents such as toluene and benzyl ethyl ether; carbonate solvents such as propylene carbonate and ethylene carbonate; amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; nitriles such as malononitrile Examples of the solvent are: Among these, γ-butyrolactone, N-methylpyrrolidone, glycol sulfite, and propylene carbonate are preferable. These solvents can be used alone or in combination of two or more.
また、本発明のインクジェット印刷用のＣｕインクにおいては、その平均分散粒径が５００ｎｍ以下で、最大分散粒径が２μｍ以下となるように分散して用いることが好ましい。平均分散粒径が５００ｎｍを超えると、印刷性や抵抗の発現安定性が十分でなくなる。例えば、インクジェット印刷法で吐出する際に、インクジェットヘッドノズルの目詰まり等が発生し、安定して印刷することができなくなる。また、オフセット印刷法などにＣｕインクを使用したときに、印刷物にかすれ等が発生する。印刷性や抵抗の発現安定性をより改善するため、該粒子の平均分散粒径は３００ｎｍ以下であることが好ましい。この平均分散粒径は小さいことが好ましいが、通常その下限は５ｎｍ程度である。さらに、同様の観点から、該粒子の最大分散粒径は２μｍ以下であることが好ましく、１μｍ以下であることがより好ましい。
ここで、平均分散粒径及び最大分散粒径は、粒子のブラウン運動による動的光散乱法に基づいて、光子相関法により測定される。平均分散粒径及び最大分散粒径の測定は、例えば、ベックマンコールタ社製「サブミクロン粒子アナライザーＮ５型」（商品名）を用いて行うことができる。
In addition, in the Cu ink for ink jet printing of the present invention, it is preferable to use it dispersed so that the average dispersed particle diameter is 500 nm or less and the maximum dispersed particle diameter is 2 μm or less. When the average dispersed particle size exceeds 500 nm, the printability and the resistance expression stability are not sufficient. For example, when ejecting by the ink jet printing method, clogging of the ink jet head nozzle or the like occurs, and it becomes impossible to print stably. In addition, when Cu ink is used in an offset printing method or the like, the printed matter is blurred. In order to further improve the printability and the stability of resistance development, the average dispersed particle size of the particles is preferably 300 nm or less. The average dispersed particle size is preferably small, but the lower limit is usually about 5 nm. Furthermore, from the same viewpoint, the maximum dispersed particle size of the particles is preferably 2 μm or less, and more preferably 1 μm or less.
Here, the average dispersed particle size and the maximum dispersed particle size are measured by a photon correlation method based on a dynamic light scattering method using Brownian motion of particles. The average dispersed particle size and the maximum dispersed particle size can be measured using, for example, “Submicron Particle Analyzer N5 Type” (trade name) manufactured by Beckman Coulter.
本発明で用いるインクジェット印刷用のＣｕインクは、２５℃における動的粘度が５ｍＰａ・ｓ以上であり、１００ｍＰａ・ｓ以下であることが好ましく、５０ｍＰａ・ｓ以下であることがより好ましい。５ｍＰａ・ｓ未満であると、インクジェットノズルからの吐出時に霧状に吐出したり、基板に着液後に流動して印字形状を保てなくなったりする。また、１００ｍＰａ・ｓを超えると吐出が不可能となる。なお、「２５℃における動的粘度」とは、別言すると、測定温度２５℃、せん断速度１０ｓ−１でのせん断粘度である。 The Cu ink for ink jet printing used in the present invention has a dynamic viscosity at 25 ° C. of 5 mPa · s or more, preferably 100 mPa · s or less, and more preferably 50 mPa · s or less. If it is less than 5 mPa · s, it may be ejected in the form of a mist at the time of ejection from an inkjet nozzle, or it may flow after being deposited on the substrate and keep the printed shape. Moreover, when it exceeds 100 mPa * s, discharge becomes impossible. The “dynamic viscosity at 25 ° C.” is, in other words, the shear viscosity at a measurement temperature of 25 ° C. and a shear rate of 10 s −1 .
（印刷あるいは塗布手法）
前記導体インク（Ｃｕインク）のパターニングに用いる印刷法は、Ｃｕインク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、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種以上が好ましい。
(Printing or coating method)
The printing method used for the patterning of the conductor ink (Cu ink) may be any method that allows Cu ink to adhere to an arbitrary place. Examples of such methods include inkjet printing, super inkjet printing, screen printing, transfer printing, Offset printing, jet printing method, dispenser, jet dispenser, needle dispenser, comma coater, slit coater, die coater, gravure coater, relief printing, intaglio printing, gravure printing, soft lithography, dip pen lithography, particle deposition method, spray coater, spin coater, Dip coater and electrodeposition coating can be used. Among them, inkjet printing, super inkjet printing, screen printing, transfer printing, offset printing, jet printing method, dispensing Needle dispenser Kanmakota, slit coater, die coater, and any one or more selected from the group consisting of a gravure coater are preferred.
＜Ｃｕパターン付基板評価手法＞
（接着性）
Ｃｕパターン付基板のＣｕパターンと樹脂基板の接着性は、簡易的にはテープ剥離試験、クロスカット試験を用いることができる。より好ましくはサイカス（ＳＩＣＡＳ（Surface And Interfacial Cutting Analysis System）により界面の接着強度を測定する。良好な界面が形成されていれば０．３ｋN／ｍ以上の測定値が得られる。
サイカス（SAICAS）と呼ばれる微少部切削装置は、表面から深さ位置を制御しつつ微細で鋭利な切り刃による切削を行い、刃にかかる応力と各構成単膜の物性を関連付ける手法である。この手法は基板状態のままの付着力を定量評価できることが利点である。これは市販の、例えば、ダイプラ・ウィンテス株式会社製ＮＮ−０３等を用いて測定することができる。
<Cu substrate evaluation method with Cu pattern>
(Adhesiveness)
For the adhesion between the Cu pattern of the substrate with a Cu pattern and the resin substrate, a tape peeling test or a cross-cut test can be used simply. More preferably, the adhesive strength of the interface is measured by SICAS (Surface And Interfacial Cutting Analysis System. If a good interface is formed, a measured value of 0.3 kN / m or more can be obtained.
A micro cutting device called SAICAS is a technique for performing cutting with a fine and sharp cutting blade while controlling the depth position from the surface, and associating the stress applied to the blade with the physical properties of each constituent single film. This method has the advantage that the adhesion force in the substrate state can be quantitatively evaluated. This can be measured using commercially available, for example, NN-03 manufactured by Daipura Wintes Co., Ltd.
（Ｃｕパターン付基板の断面観察）
金属Ｃｕ膜の貫入構造は断面加工し走査型イオン顕微鏡（ＳＩＭ）、走査型電子顕微鏡（ＳＥＭ）あるいは透過型電子顕微鏡（ＴＥＭ）観察することで確認できる。断面加工方法としては集束イオンビーム（ＦＩＢ）加工、クロスセクションポリッシャ法（ＣＰ）加工が好ましい。
(Cross-section observation of substrate with Cu pattern)
The penetration structure of the metal Cu film can be confirmed by processing a cross section and observing with a scanning ion microscope (SIM), a scanning electron microscope (SEM), or a transmission electron microscope (TEM). As the cross-section processing method, focused ion beam (FIB) processing and cross-section polisher method (CP) processing are preferable.
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）
（樹脂基板）
低粗化銅箔（Ｆ０−ＷＳ、古河電気工業株式会社製）付きエポキシ基板（Ｅ６７９ＦＢ、日立化成工業株式会社製）の銅箔をペルオキソ二硫酸アンモニウム（純正化学株式会社製、過流酸アンモニウム）水溶液で全面エッチングし、水洗、乾燥し樹脂基板とした。
（基板の強アルカリ水溶液処理）
水酸化ナトリウム（和光純薬工業株式会社製）４ｇを超純水（超純水製造装置ＰＲＯ−０２５０、ＦＰＣ−０５００、オルガノ株式会社製）１００ｇに溶かし１ｍｏｌ／Lの水溶液を調製した。水酸化ナトリウムを２００ｍLビーカーに注ぎウォーターバスで液温７０℃に調整した。前述の樹脂基板を１０分間この水酸化ナトリウム水溶液に浸漬した。その後、１Lの超純水に１０分ずつ、超純水を新しいものに換えて３回浸漬して洗浄した。洗浄後、１１０℃の温風乾燥機（セーフティオーブンＳＰＨ−２０１、エスペック株式会社製）で３０分乾燥して強アルカリ水溶液処理した基板とした。
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
Example 1
(Resin substrate)
Copper foil of epoxy board (E679FB, manufactured by Hitachi Chemical Co., Ltd.) with low roughened copper foil (F0-WS, manufactured by Furukawa Electric Co., Ltd.) in aqueous solution of ammonium peroxodisulfate (manufactured by Junsei Chemical Co., Ltd., ammonium persulfate) The whole surface was etched, washed with water and dried to obtain a resin substrate.
(Strong alkaline aqueous solution treatment of substrates)
4 g of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 100 g of ultrapure water (ultra pure water production apparatus PRO-0250, FPC-0500, manufactured by Organo Corporation) to prepare a 1 mol / L aqueous solution. Sodium hydroxide was poured into a 200 mL beaker and adjusted to a liquid temperature of 70 ° C. with a water bath. The aforementioned resin substrate was immersed in this aqueous sodium hydroxide solution for 10 minutes. Then, the ultrapure water was replaced with a new one for 10 minutes in 1 L of ultrapure water and washed by immersing 3 times. After cleaning, the substrate was dried with a hot air dryer (safety oven SPH-201, manufactured by Espec Co., Ltd.) at 110 ° C. for 30 minutes to give a substrate treated with a strong alkaline aqueous solution.
（Ｃｕインクの調製）
Ｃｕインクは、ＣｕＯナノ粒子（平均粒径７０ｎｍ、シーアイ化成株式会社製）４０ｇをポリ瓶に秤量し、分散媒として４−メチル−１，３−ジオキソラン−２−オン（和光純薬工業株式会社製）を６０ｇ加え、超音波ホモジナイザー（ＵＳ−６００、日本精機株式会社製）により１９．６ｋＨｚ、６００Ｗ、５分間処理して調製した。
(Preparation of Cu ink)
For Cu ink, 40 g of CuO nanoparticles (average particle size 70 nm, manufactured by C-I Kasei Co., Ltd.) were weighed into a plastic bottle, and 4-methyl-1,3-dioxolan-2-one (Wako Pure Chemical Industries, Ltd.) was used as a dispersion medium. 60 g) and 19.6 kHz, 600 W for 5 minutes using an ultrasonic homogenizer (US-600, manufactured by Nippon Seiki Co., Ltd.).
（Ｃｕインク塗布サンプルの作製）
前記強アルカリ水溶液処理した基板上に前記Ｃｕインクを滴下し、ギャップ１００μｍに調整したベーカーアプリケータ（ＹＢＡ型、ヨシミツ精機株式会社製）により塗布した。その後、６時間自然乾燥した後、１６０℃に加熱したホットプレート上に置き３０分間乾燥し銅系粒子堆積層を形成したＣｕインク塗布サンプルを得た。
(Preparation of Cu ink application sample)
The Cu ink was dropped onto the substrate treated with the strong alkaline aqueous solution, and applied with a Baker applicator (YBA type, manufactured by Yoshimitsu Seiki Co., Ltd.) adjusted to a gap of 100 μm. Then, after naturally drying for 6 hours, it placed on the hotplate heated at 160 degreeC, and it dried for 30 minutes, and obtained the Cu ink application | coating sample which formed the copper-type particle deposition layer.
（ギ酸ガス処理）
洗気瓶にギ酸を入れ窒素をバブリングしてギ酸ガスの発生装置とした。前記塗布サンプル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厚さ５ｍｍのガラス板を敷いた上にセットした。サンプルと同じガラス基板上にクロメルアルメル熱電対をセットし処理温度を測定した。このサンプルをセットしたセパラブルフラスコに窒素を流しながら１９５℃のオイルバスで加熱しガラス基板の温度が一定（１７０℃）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０．３Ｌ／ｍｉｎでこのセパラブルフラスコに通じ、銅系粒子堆積層を６０分間処理した。処理後、ギ酸ガスの発生装置をはずし、窒素を流しながらセパラブルフラスコを放冷し、サンプルが５０℃以下になった後、サンプルを空気中に取り出した。以上のようにしてＣｕパターン付基板を作製した。
(Formic acid treatment)
A formic acid gas generator was prepared by putting formic acid into a washing bottle and bubbling nitrogen. The coated sample was set on a flat bottom separable flask heated in an oil bath with a 5 mm thick glass plate on it. A chromel alumel thermocouple was set on the same glass substrate as the sample, and the processing temperature was measured. Nitrogen containing formic acid gas generated by a formic acid gas generator after the temperature of the glass substrate becomes constant (170 ° C.) by heating in a separable flask in which this sample is set while flowing nitrogen in a 195 ° C. oil bath. Gas was passed through the separable flask at 0.3 L / min, and the copper-based particle deposition layer was treated for 60 minutes. After the treatment, the formic acid gas generator was removed, and the separable flask was allowed to cool while flowing nitrogen, and after the sample became 50 ° C. or lower, the sample was taken out into the air. A substrate with a Cu pattern was produced as described above.
（特性評価）
Ｃｕパターン付基板の接着力は、Ｃｕパターン表面の脆弱層をクロスで擦り取ったあと、テープ剥離テストを行った結果、下部の緻密層の密着性は良好であった。また、サイカス（ＳＡＩＣＡＳ）装置（ＤＮ−２０、ダイプラ・ウィンテス株式会社）を用いて、切削速度１μｍ／秒、切削幅５００μｍ、深さはＣｕパターンと基板の界面になる条件で、樹脂基板とＣｕパターン界面の接着力を測定した結果、その値は０．３２ｋN／ｍであった。
集束イオンビーム（ＦＩＢ）加工断面の走査イオン顕微鏡像（ＳＩＭ像）観察を行い、基板表面から１００ｎｍの銅の貫入を確認した（図１）。
(Characteristic evaluation)
As for the adhesive force of the substrate with Cu pattern, after the fragile layer on the surface of the Cu pattern was scraped with a cloth, a tape peeling test was performed. As a result, the adhesion of the dense layer at the bottom was good. Further, using a SAICAS device (DN-20, Daipura Wintes Co., Ltd.), the cutting speed is 1 μm / second, the cutting width is 500 μm, and the depth is a condition that becomes an interface between the Cu pattern and the substrate. As a result of measuring the adhesive force at the pattern interface, the value was 0.32 kN / m.
Scanning ion microscope image (SIM image) observation of a focused ion beam (FIB) processed cross section was performed, and 100 nm copper penetration from the substrate surface was confirmed (FIG. 1).
（比較例１）
基板のアルカリ水溶液処理を行わなかった以外は、（実施例１と同様に（樹脂基板）、（Ｃｕインクの調製）、（Ｃｕインク塗布サンプルの作製）、（ギ酸ガス処理）を行った。
(特性評価)
Ｃｕパターン付基板の接着力は、Ｃｕパターン表面の脆弱層をクロスで擦り取ったところすべて剥離した。
ＦＩＢ加工断面の走査イオン顕微鏡（ＳＩＭ）像観察を上記実施例１と同様に行ったが、基板表面からの銅の貫入はまったく見られなかった（図２）。
(Comparative Example 1)
(Resin substrate), (Preparation of Cu ink), (Preparation of Cu ink-coated sample), and (Formic acid gas treatment) were performed in the same manner as in Example 1 except that the substrate was not subjected to the alkaline aqueous solution treatment.
(Characteristic evaluation)
The adhesive strength of the substrate with the Cu pattern was peeled off when the fragile layer on the surface of the Cu pattern was scraped with a cloth.
Observation of the scanning ion microscope (SIM) image of the FIB processed cross section was carried out in the same manner as in Example 1, but no penetration of copper from the substrate surface was observed (FIG. 2).
１．ＦＩＢ加工保護層（タングステン）
２．ギ酸ガス処理されたＣｕインク層
３．Ｃｕの貫入したエポキシ樹脂基板表面層
４．エポキシ樹脂基板
1. FIB protective layer (tungsten)
2. 2. Cu ink layer treated with
Claims (7)
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