JP6263146B2 - Substrate with conductive film, method for producing the same, and conductive paste for polyimide substrate - Google Patents
Substrate with conductive film, method for producing the same, and conductive paste for polyimide substrate Download PDFInfo
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- 239000000758 substrate Substances 0.000 title claims description 102
- 239000004642 Polyimide Substances 0.000 title claims description 61
- 229920001721 polyimide Polymers 0.000 title claims description 61
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 121
- 229910052709 silver Inorganic materials 0.000 claims description 56
- 239000004332 silver Substances 0.000 claims description 56
- 239000011248 coating agent Substances 0.000 claims description 36
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- 229920005989 resin Polymers 0.000 claims description 32
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 21
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 21
- 239000011230 binding agent Substances 0.000 claims description 21
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 18
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
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- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
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- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- -1 aluminum compound Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
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- 239000008117 stearic acid Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
Description
本発明は、ポリイミド基板上に導電膜が備えられた導電膜付基板と、その製造方法、および、その導電膜の形成に好適に用いられる導電性ペーストに関する。 The present invention relates to a substrate with a conductive film provided with a conductive film on a polyimide substrate, a method for manufacturing the same, and a conductive paste suitably used for forming the conductive film.
例えば、回路基板の配線形成や、電子部品の電極形成等に用いられる導電性ペーストは、導電性粉末と、樹脂結合剤と、有機溶剤と、必要に応じて含まれるガラスフリット等の無機フィラーとから成るものである。この導電性ペーストは、概ね300(℃)以下の低温で熱処理を施すことによって基板上に導体膜を形成することができる熱硬化タイプと、400(℃)以上の温度で焼成処理を施すことによって導体膜を形成する焼成タイプとに大別される。 For example, the conductive paste used for circuit board wiring formation, electronic component electrode formation, and the like includes conductive powder, a resin binder, an organic solvent, and an inorganic filler such as glass frit that is included as necessary. It consists of This conductive paste is a thermosetting type that can form a conductor film on a substrate by performing a heat treatment at a low temperature of approximately 300 (° C.) or lower, and a baking treatment at a temperature of 400 (° C.) or higher. It is roughly classified into a firing type for forming a conductor film.
前者の熱硬化タイプは、樹脂結合剤として熱硬化樹脂が用いられたものであり、熱処理によってその熱硬化樹脂が硬化することで導電膜が形成される。このタイプは処理温度が低いことから基板の材質を選ばない利点があるが、導電性粉末は相互に接触した状態で樹脂結合剤によって固定されているだけであり、しかも、樹脂が残存することから、抵抗値が高めであり、また、耐熱性や長期的な信頼性が低いことが難点である。 The former thermosetting type uses a thermosetting resin as a resin binder, and a conductive film is formed by curing the thermosetting resin by heat treatment. This type has the advantage that the material of the substrate can be chosen because the processing temperature is low, but the conductive powder is only fixed by the resin binder in contact with each other, and the resin remains. The resistance value is high, and the heat resistance and long-term reliability are low.
一方、後者の焼成タイプでは、焼成処理によって導電性粉末自体が焼結し、或いは、これに加えてガラスフリットが焼結することで導電膜が形成される。このタイプは樹脂を焼失させると共に導電性粉末が焼結することから、抵抗値が低く、耐熱性や長期的な信頼性が高い利点があるが、高温の焼成処理が必要であることから、樹脂基板には適用できず、製造コストも高めになることが難点である。 On the other hand, in the latter firing type, the conductive powder itself is sintered by the firing treatment, or in addition to this, the glass frit is sintered to form the conductive film. This type burns the resin and sinters the conductive powder, so it has the advantages of low resistance, high heat resistance and long-term reliability. It is difficult to apply to a substrate and the manufacturing cost is high.
ところで、樹脂基板の一種であるポリイミド基板は、耐熱性が高く且つ可撓性に優れることから、携帯端末その他の電子機器の基板に広く用いられるようになっている。ポリイミド基板への配線形成は、銅を圧着してエッチング処理を施してパターン形成する方法が主流であるが、導体配線を低抵抗化するために、スクリーン印刷等により厚膜で形成することが検討されている。前述したように、樹脂基板には焼成タイプの導電性ペーストを使用できないことから、熱硬化タイプの導電性ペーストの改善が従来から試みられていたが、十分な導電性は得られていない。 By the way, a polyimide substrate, which is a kind of resin substrate, has high heat resistance and excellent flexibility, and is therefore widely used for substrates of portable terminals and other electronic devices. For wiring formation on polyimide substrates, the main method is to form a pattern by pressure-bonding copper and etching, but in order to reduce the resistance of conductor wiring, it is considered to form a thick film by screen printing etc. Has been. As described above, since baking type conductive paste cannot be used for the resin substrate, attempts have been made to improve thermosetting type conductive paste. However, sufficient conductivity has not been obtained.
例えば、導電性粉末と溶媒とバインダーとからなる導電性ペーストにおいて、そのバインダーが、アルミニウム化合物及びシランカップリング剤から選ばれる一種または二種以上を含むものが提案されている(特許文献１を参照。)。この導電性ペーストは、200(℃)で乾燥処理を施すことによって導電膜を形成するものであるが、比抵抗が2.9×10-5(Ω・cm)〜6.1×10-5(Ω・cm)程度と、比較的高い値に留まる。アルミニウム化合物及びシランカップリング剤が導電性を低下させているものと考えられる。 For example, a conductive paste composed of conductive powder, a solvent, and a binder has been proposed in which the binder includes one or more selected from an aluminum compound and a silane coupling agent (see Patent Document 1). .). This conductive paste forms a conductive film by performing a drying treatment at 200 (° C.), and has a specific resistance of 2.9 × 10 −5 (Ω · cm) to 6.1 × 10 −5 (Ω · cm ) Stays at a relatively high value. It is considered that the aluminum compound and the silane coupling agent are reducing the conductivity.
また、タップ密度が1.0〜10.0(g/cm3)、Ｄ５０粒子径が0.3〜5(μm)、ＢＥＴ比表面積0.3〜5.0(m2/g)の導電性粒子と、数平均分子量が10000〜300000であり、水酸基価2〜300(mgKOH/g)のエポキシ樹脂と、そのエポキシ樹脂中の水酸基とアルコール交換反応が可能であり、そのエポキシ樹脂100重量部に対して0.2〜20重量部の金属キレートとを含有する導電性インキが提案されている(特許文献２を参照。)。この導電性インキは、高精細な導電性パターンを印刷形成するためのもので、ポリイミド基板に対する密着性が優れることが記載されているが、上記ペーストと同様に熱硬化タイプであり、抵抗率が5.0×10-5(Ω・cm)程度と高く、導電性が不十分である。 Further, conductive particles having a tap density of 1.0 to 10.0 (g / cm 3 ), a D50 particle diameter of 0.3 to 5 (μm), a BET specific surface area of 0.3 to 5.0 (m 2 / g), and a number average molecular weight of 10,000 to 300,000, an epoxy resin having a hydroxyl value of 2 to 300 (mgKOH / g), and an alcohol exchange reaction with a hydroxyl group in the epoxy resin is possible, and 0.2 to 20 parts by weight of metal with respect to 100 parts by weight of the epoxy resin A conductive ink containing a chelate has been proposed (see Patent Document 2). This conductive ink is for printing and forming a high-definition conductive pattern, and it is described that it has excellent adhesion to a polyimide substrate, but it is a thermosetting type and has a resistivity similar to the above paste. It is as high as 5.0 × 10 -5 (Ω · cm) and conductivity is insufficient.
これらに対して、例えば、平均一次粒子径が50(nm)以下の金属粒子１の群と、平均一次粒子径が100(nm)以上の金属粒子２の群により構成される金属粉末成分、熱可塑性樹脂、分散媒からなり、金属と樹脂の合計質量に対する金属の質量の割合が94〜98(％)を示す焼成タイプの導電性ペーストが提案されている(特許文献３を参照。)。この導電性ペーストによれば、ポリイミド基板上にスクリーン印刷等で膜形成して、200(℃)程度の低温で焼成すると、導電性および密着性の両立した導電膜が得られるものとされている。 In contrast, for example, a metal powder component composed of a group of metal particles 1 having an average primary particle size of 50 (nm) or less and a group of metal particles 2 having an average primary particle size of 100 (nm) or more, heat There has been proposed a baked type conductive paste comprising a plastic resin and a dispersion medium and having a metal mass ratio of 94 to 98 (%) with respect to the total mass of the metal and resin (see Patent Document 3). According to this conductive paste, when a film is formed on a polyimide substrate by screen printing or the like and fired at a low temperature of about 200 (° C.), a conductive film having both conductivity and adhesion can be obtained. .
しかしながら、上記導電性ペーストは、未だ銅圧着配線に代わるものではなく、一層の改善が望まれていた。導電性はある程度改善しているものの十分ではなく、しかも、50(nm)以下の金属微粉末を必須とするものであることから、高コストで取扱性が悪いのである。上記特許文献３には、平均粒径が100(nm)以上の金属粒子のみを用いた導電性ペーストが導電性の低い比較例として記載されているが、これは金属粉末の焼結が十分に進んでいないためと考えられる。その焼結性を改善するために、50(nm)以下の微粉を混合しているのである。 However, the conductive paste has not yet replaced the copper crimped wiring, and further improvement has been desired. Although the conductivity is improved to some extent, it is not sufficient, and since it requires metal fine powder of 50 (nm) or less, it is expensive and poor in handling. In Patent Document 3 described above, a conductive paste using only metal particles having an average particle size of 100 (nm) or more is described as a comparative example with low conductivity. It is thought that it is not advanced. In order to improve the sinterability, fine powder of 50 nm or less is mixed.
本発明は、以上の事情を背景として為されたものであって、その目的は、導電性とポリイミド基板への密着性に優れた銀導電膜を備えた導電膜付基板、その製造方法、およびその導電膜付基板の製造に用い得るポリイミド基板用導電性ペーストを提供することにある。 The present invention has been made against the background of the above circumstances, and its purpose is to provide a conductive film-containing substrate comprising a silver conductive film excellent in conductivity and adhesion to a polyimide substrate, a method for producing the same, and An object of the present invention is to provide a conductive paste for a polyimide substrate that can be used for manufacturing the substrate with the conductive film.
斯かる目的を達成するため、第１発明の要旨とするところは、ポリイミド基板の一面に銀を導体成分として含む導電膜が備えられた導電膜付基板であって、前記導電膜および前記ポリイミド基板の構成成分がそれらの界面を越えてその導電膜の厚さ寸法以下の範囲で相互に他方に侵入することにより形成された凹凸面をその界面が成していることにある。 In order to achieve such an object, the gist of the first invention is a substrate with a conductive film provided with a conductive film containing silver as a conductor component on one surface of a polyimide substrate, the conductive film and the polyimide substrate. That is, the interface constitutes a concavo-convex surface formed by intruding into the other of the constituent components in the range of the conductive film beyond the thickness dimension of the conductive film.
また、前記目的を達成するための第２発明の要旨とするところは、銀を導体成分として含む導電膜をポリイミド基板上に形成する導電膜付基板の製造方法であって、(ａ)ロジン、脂肪酸、およびアミン類のうちの少なくとも１種から成る所定量のコート剤が表面に付着した銀粉末と、樹脂結合剤と、有機溶剤とを含む導電性ペーストを前記ポリイミド基板上に所定パターンで塗布するペースト塗布工程と、(ｂ)250〜300(℃)の最高温度で焼成処理を施すことにより銀を焼結させて前記導電性ペーストから導電膜を生成する焼成工程とを、含むことにある。 Moreover, the subject matter of the second invention for achieving the above object is a method for producing a substrate with a conductive film, wherein a conductive film containing silver as a conductive component is formed on a polyimide substrate, comprising: (a) rosin, A conductive paste including a silver powder having a predetermined amount of a coating agent composed of at least one of fatty acids and amines attached to the surface, a resin binder, and an organic solvent is applied on the polyimide substrate in a predetermined pattern. And (b) a baking step in which silver is sintered by performing baking treatment at a maximum temperature of 250 to 300 (° C.) to generate a conductive film from the conductive paste. .
また、前記目的を達成するための第３発明の要旨とするところは、銀粉末と、樹脂結合剤と、有機溶剤とを含み、ポリイミド基板上に導電膜を形成して導電膜付基板を製造するために用いられるポリイミド基板用導電性ペーストであって、前記銀粉末は、ロジン、脂肪酸、およびアミン類のうちの少なくとも１種から成るコート剤をその銀粉末に対する質量比で2.3(％)以下の量で表面に付着させたコート剤付着銀粉末であることにある。 The gist of the third invention for achieving the above object is to produce a substrate with a conductive film by forming a conductive film on a polyimide substrate containing silver powder, a resin binder, and an organic solvent. A conductive paste for a polyimide substrate used to form a coating agent comprising at least one of rosin, fatty acid, and amines in a weight ratio of 2.3 (%) or less with respect to the silver powder. That is, the coating agent-attached silver powder is attached to the surface in an amount of.
前記第１発明によれば、導電膜およびポリイミド基板は、それらの構成成分が導電膜の厚さ寸法以下の範囲で相互に他方に侵入しており、これにより形成された凹凸面をそれらの界面が成していることから、接触面積の増大に伴って導電性と密着性が高められる。そのため、高い導電性とポリイミド基板との高い密着性を有する導電膜が備えられた導電膜付基板が得られる。 According to the first aspect of the present invention, the conductive film and the polyimide substrate have their constituent components penetrating into the other in the range of the thickness dimension of the conductive film or less, and the uneven surface formed thereby is their interface. Therefore, the conductivity and adhesion are improved as the contact area increases. Therefore, the board | substrate with an electrically conductive film provided with the electrically conductive film which has high electroconductivity and the high adhesiveness with a polyimide substrate is obtained.
また、前記第２発明によれば、導電膜をポリイミド基板上に形成して導電膜付基板を製造するに際しては、ペースト塗布工程において、塗布される導電性ペーストが、銀粉末として、ロジン、脂肪酸、またはアミン類から成るコート剤が表面に付着したコート剤付着銀粉末が用いられていることから、焼成工程において、250〜300(℃)の範囲内の低温で焼成処理が施されても、十分に焼結が進むので、高い導電性とポリイミド基板への高い密着性を有する導電膜を備えた導電膜付基板が得られる。焼成温度が250(℃)未満では、焼結が十分に進まず、一方、300(℃)を超えても、導電性や密着性は特に向上しないので、ポリイミド基板に過剰な熱が与えられる不都合が生ずるに過ぎない。 According to the second aspect of the invention, when the conductive film is formed on the polyimide substrate to produce the conductive film-coated substrate, the conductive paste applied in the paste coating step is rosin, fatty acid as silver powder. In addition, since a coating agent-attached silver powder with a coating agent composed of amines attached to the surface is used, even if a baking treatment is performed at a low temperature in the range of 250 to 300 (° C.) in the baking step, Since the sintering proceeds sufficiently, a substrate with a conductive film provided with a conductive film having high conductivity and high adhesion to a polyimide substrate is obtained. If the firing temperature is less than 250 (° C), the sintering does not proceed sufficiently.On the other hand, if it exceeds 300 (° C), the conductivity and adhesion are not particularly improved, so that the polyimide substrate is given excessive heat. Only occurs.
なお、銀粉末を導体成分として含む導電性ペーストは、前述した50(nm)以下の微粉が用いられるような特殊なものでなければ、通常は、300(℃)以下の低温では焼結が進まない。そのため、ポリイミド基板等の樹脂基板に対しては、一般に熱硬化型ペーストが用いられていたが、これは銀粉末が相互に接触した状態で熱硬化樹脂で固定されているものに過ぎないので、高い導電性は得られない。しかしながら、本発明においては、熱硬化樹脂による固定ではなく、銀粉末自体が焼結する。このように焼結性が向上する理由は定かではないが、銀の焼結の進行に伴い、ポリイミド基板の表面と銀粉末を含む膜との接触面積が増大していき、銀粉末に付着させられたコート剤が接着剤或いは反応促進剤としてその接触界面に作用していることが考えられる。 Note that the conductive paste containing silver powder as a conductor component is normally not sintered at a low temperature of 300 (° C) or less unless it is a special powder that uses the fine powder of 50 (nm) or less. Absent. Therefore, for resin substrates such as polyimide substrates, thermosetting paste was generally used, but this is only what is fixed with thermosetting resin in a state where silver powder is in contact with each other, High conductivity cannot be obtained. However, in the present invention, silver powder itself is sintered, not fixed by thermosetting resin. The reason why the sinterability is improved is not clear, but as the sintering of silver progresses, the contact area between the surface of the polyimide substrate and the film containing silver powder increases and adheres to the silver powder. It is conceivable that the applied coating agent acts on the contact interface as an adhesive or a reaction accelerator.
また、前記第３発明によれば、ポリイミド基板用の導電性ペーストは、銀粉末が、ロジン、脂肪酸、またはアミン類から成るコート剤を、銀粉末に対する質量比で2.3(％)以下の範囲で付着させたコート剤付着銀粉末であることから、300(℃)以下、好ましくは270(℃)以下の低温で焼成処理を施しても、銀粉末の焼結が十分に進むので、高い導電性とポリイミド基板への高い密着性が得られる。なお、コート剤が僅かでも銀粉末に付着していれば、その量に応じて銀粉末の焼結性が高められるが、2.3(％)を超えて過剰になると焼成時に燃え抜け難くなって、膜密度を低下させ、導電性が低下する。 According to the third aspect of the invention, the conductive paste for the polyimide substrate includes a coating agent in which the silver powder is composed of rosin, fatty acid, or amines in a mass ratio of 2.3 (%) or less with respect to the silver powder. Since it is a silver powder coated with a coating agent, the silver powder is sufficiently sintered even when subjected to a baking treatment at a low temperature of 300 (° C.) or less, preferably 270 (° C.) or less. And high adhesion to the polyimide substrate. In addition, if the coating agent is attached to the silver powder even a little, the sinterability of the silver powder is enhanced according to the amount, but if it exceeds 2.3 (%), it becomes difficult to burn out during firing, The film density is lowered and the conductivity is lowered.
ここで、好適には、前記第１発明において、前記導電膜は銀が焼結しているものである。すなわち、第１発明の導電膜付基板は、焼成タイプの導電性ペーストを用いて、ポリイミド基板上に導電膜が形成されたものである。そのため、導電膜中の導体成分である銀が焼結していることから、高い導電性を有する。 Here, preferably, in the first invention, the conductive film is made of sintered silver. That is, the substrate with a conductive film of the first invention is obtained by forming a conductive film on a polyimide substrate using a baking type conductive paste. Therefore, since silver which is a conductor component in a conductive film is sintered, it has high conductivity.
また、好適には、前記第２発明において、前記銀粉末の表面に付着した前記コート剤は、その銀粉末に対する質量比で2.3(％)以下の量である。コート剤は僅かでも付着して入ればその量に応じて銀粉末の焼結性が改善されるが、2.3(％)を超えて過剰になると焼成時に燃え抜け難くなって、膜密度を低下させ、導電性が低下する。 Preferably, in the second invention, the coating agent attached to the surface of the silver powder is an amount of 2.3 (%) or less in terms of a mass ratio with respect to the silver powder. If even a small amount of coating agent adheres, the sinterability of the silver powder will be improved according to the amount, but if it exceeds 2.3 (%), it will be difficult to burn out during firing, and the film density will be reduced. , Conductivity decreases.
また、好適には、前記導電性ペーストにおいて、前記銀粉末は、平均粒径が0.5(μm)以下である。銀粒径が大きくなるほど焼結性が低下するが、1(μm)以上になると著しく焼結が進みにくくなり、抵抗値が増大する。 Preferably, in the conductive paste, the silver powder has an average particle size of 0.5 (μm) or less. As the silver particle size increases, the sinterability decreases. However, if the silver particle size is 1 (μm) or more, the sintering becomes extremely difficult to proceed and the resistance value increases.
また、好適には、前記導電性ペーストおよび前記導電膜は、実質的にガラスを含まないものである。なお、「実質的にガラスを含まない」とは、理想的にはガラスを全く含まないことを意味するが、焼結性等の特性に影響を与えない程度に含まれていることは許容される。 Preferably, the conductive paste and the conductive film do not substantially contain glass. Note that “substantially free of glass” means that it does not contain glass at all, but it is allowed to be contained to the extent that it does not affect properties such as sinterability. The
また、好適には、前記第２発明および前記第３発明において、前記樹脂結合剤は、分解温度が250(℃)以下のもの、すなわち、前記焼成温度よりも低温で燃え抜けるものである。このようにすれば、形成される導電膜中に有機物や炭化物が残存し難いことから、導電膜の導電性が一層高く且つポリイミド基板への密着性が一層高い導電膜付基板が得られる。印刷性や取扱性も考慮すると、アクリル樹脂が好ましい。例えば、メタクリル酸イソブチルの重合体で、平均分子量16万のものが挙げられる。なお、樹脂結合剤の分解温度が焼成温度よりも低いことは必須ではない。例えば、分解温度が300(℃)以上の樹脂結合剤が用いられてもよい。そのような場合にも、本願発明によれば銀粉末の焼結は十分に進むことから、導電膜に有機物や炭化物が残存しても、従来に比べて十分に高い導電性が得られる。 Preferably, in the second and third inventions, the resin binder has a decomposition temperature of 250 (° C.) or less, that is, burns out at a temperature lower than the firing temperature. In this way, since organic substances and carbides hardly remain in the conductive film to be formed, a conductive film-equipped substrate having higher conductivity of the conductive film and higher adhesion to the polyimide substrate can be obtained. In consideration of printability and handleability, an acrylic resin is preferable. For example, a polymer of isobutyl methacrylate having an average molecular weight of 160,000 can be mentioned. In addition, it is not essential that the decomposition temperature of the resin binder is lower than the firing temperature. For example, a resin binder having a decomposition temperature of 300 (° C.) or higher may be used. Even in such a case, according to the present invention, since the sintering of the silver powder proceeds sufficiently, even if organic matter or carbide remains in the conductive film, sufficiently high conductivity can be obtained compared to the conventional case.
以下、本発明の一実施例を図面を参照して詳細に説明する。なお、以下の実施例において図は適宜簡略化或いは変形されており、各部の寸法比および形状等は必ずしも正確に描かれていない。 Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings. In the following embodiments, the drawings are appropriately simplified or modified, and the dimensional ratios, shapes, and the like of the respective parts are not necessarily drawn accurately.
図１は、本発明の銀導電膜１０がポリイミド基板１２の一面に形成された導電膜付基板１４の断面を示す図である。この配線基板は、種々の電子機器等において、可撓性のある内部配線基板や、可動部分の端子と固定部分の端子とを接続するフレキシブル配線基板等として用いられるものである。銀導電膜１０は、例えば、1.0〜8.0(μm)程度の厚さ寸法を備えた銀のみから成るもので、ポリイミド基板１２が変形するときは、これに倣って変形する柔軟性を備えている。 FIG. 1 is a view showing a cross section of a conductive film-equipped substrate 14 in which a silver conductive film 10 of the present invention is formed on one surface of a polyimide substrate 12. This wiring board is used as a flexible internal wiring board, a flexible wiring board for connecting a terminal of a movable part and a terminal of a fixed part in various electronic devices. The silver conductive film 10 is made of only silver having a thickness dimension of about 1.0 to 8.0 (μm), for example, and has a flexibility to deform in accordance with the deformation of the polyimide substrate 12. .
上記導電膜付基板１４は、例えば、銀粉末と、樹脂結合剤と、有機溶剤とを含む導電性ペーストを用意し、ポリイミド基板１２上にスクリーン印刷、グラビア印刷、オフセット印刷、或いはインクジェット印刷等の適宜の印刷方法により膜形成して、焼成処理を施すことにより銀導電膜１０を生成して製造される。上記銀粉末は、表面に所定量のコート剤を付着させたコート剤付着銀粉末として添加する。コート剤は、ロジン、脂肪酸、アミン類の何れかである。脂肪酸としては、例えば、ステアリン酸、ラウリン酸、オレイン酸、リノール酸、デカン酸などが挙げられる。また、アミン類としては、例えば、ドデシルアミンが挙げられる。 The conductive film-attached substrate 14 is prepared, for example, by preparing a conductive paste containing silver powder, a resin binder, and an organic solvent, such as screen printing, gravure printing, offset printing, or inkjet printing on the polyimide substrate 12. A film is formed by an appropriate printing method, and a silver conductive film 10 is produced and manufactured by performing a baking treatment. The silver powder is added as a coating agent-attached silver powder having a predetermined amount of coating agent attached to the surface. The coating agent is any one of rosin, fatty acid, and amines. Examples of fatty acids include stearic acid, lauric acid, oleic acid, linoleic acid, decanoic acid and the like. Examples of amines include dodecylamine.
このようなコート剤付着銀粉末は、以下のようにして作成する。銀粉末としては、一般的な湿式法により調製された市販品を用いた。平均粒径0.07(μm)、0.10(μm)、0.5(μm)、0.8(μm)、0.9(μm)、1.0(μm)、1.4(μm)、3(μm)の球形状のものを用意した。これを例えばビーカーにそれぞれ約100(g)とり、さらにイソプロピルアルコール約1000(ml)を追加し十分に撹拌する。これを一晩放置し、次いで、上澄みを廃棄する。さらにイソプロピルアルコール約1000(ml)を投入し、撹拌後、一晩放置する。この洗浄操作を３〜５回繰り返す。これにより、これにより、銀粉末に付着している有機物を十分に除去する。 Such a coating agent-attached silver powder is prepared as follows. As the silver powder, a commercial product prepared by a general wet method was used. Spherical shapes with an average particle size of 0.07 (μm), 0.10 (μm), 0.5 (μm), 0.8 (μm), 0.9 (μm), 1.0 (μm), 1.4 (μm), 3 (μm) were prepared. . For example, about 100 (g) is added to each beaker, and about 1000 (ml) of isopropyl alcohol is further added and sufficiently stirred. This is left overnight and then the supernatant is discarded. Further, about 1000 (ml) of isopropyl alcohol is added, and after stirring, left overnight. This washing operation is repeated 3 to 5 times. Thereby, the organic substance adhering to the silver powder is sufficiently removed.
次いで、コート剤をイソプロピルアルコールに溶解させる。以下、コート剤としてロジンを用いる場合を例にとって説明する。ロジン原料としては、例えば、荒川化学工業製ガムロジンWWを用い、これを1.0〜2.5(g）とって、500(ml)のイソプロピルアルコールに添加し撹拌する。次いで、上記の洗浄操作を終えた銀粉の上澄み液を廃棄し、これにロジンを溶かしたイソプロピルアルコールを添加し十分に撹拌する。次いで、この混合物をナス型フラスコに移し替え、エバポレータを用いて55(℃)〜60(℃)の温水で加温しながら減圧させることで、イソプロピルアルコールを気化させる。このようにして得られた銀粉をトレイに載せ、一晩放置する。その後、200メッシュのスクリーンを用いてふるいを実施することで表面にロジンが付着した銀粉粒子を用意した。 Next, the coating agent is dissolved in isopropyl alcohol. Hereinafter, the case where rosin is used as a coating agent will be described as an example. As a rosin raw material, for example, gum rosin WW manufactured by Arakawa Chemical Industries, Ltd. is used, and 1.0 to 2.5 (g) is added to 500 (ml) of isopropyl alcohol and stirred. Next, the supernatant of the silver powder after the above washing operation is discarded, and isopropyl alcohol in which rosin is dissolved is added thereto and sufficiently stirred. Subsequently, this mixture is transferred to an eggplant type flask, and isopropyl alcohol is vaporized by reducing pressure while heating with warm water of 55 (° C.) to 60 (° C.) using an evaporator. The silver powder thus obtained is placed on a tray and left overnight. Thereafter, sieving was carried out using a 200-mesh screen to prepare silver powder particles having rosin adhered to the surface.
なお、付着したロジン量は、得られた銀粉をTG-DTAで昇温速度10(℃/min)で900(℃)まで測定して求めた。すなわち、TGの50(℃)の質量と400(℃)の質量との差を付着ロジン量とした。ロジン付着量は添加するガムロジンWWの量を変化させることで調整する。例えば、粒径0.1(μm)の銀粉の場合、ガムロジン量1.2(g)、1.7(g)、2.2(g)に対して、ロジン量は1.0(％)、1.6(％)、2.0(％)になる。 The amount of attached rosin was determined by measuring the obtained silver powder with TG-DTA at a temperature increase rate of 10 (° C./min) up to 900 (° C.). That is, the difference between the mass of TG of 50 (° C.) and the mass of 400 (° C.) was taken as the amount of adhered rosin. The amount of rosin adhesion is adjusted by changing the amount of gum rosin WW to be added. For example, in the case of silver powder with a particle size of 0.1 (μm), the amount of rosin is 1.0 (%), 1.6 (%), 2.0 (%) against the amount of gum rosin 1.2 (g), 1.7 (g), 2.2 (g) become.
上記のようにして、ロジン付着銀粉を用意し、樹脂結合剤および有機溶剤と攪拌機等で混合する。樹脂結合剤としては、例えばアクリル樹脂（三菱レーヨン製 ＥＭＢ−００２）、有機溶剤としては、例えばメンタノールを用いる。これらを所定量調合し、三本ロールミルを用いて分散処理を行ってペースト化することにより、導電性ペーストが得られる。上記アクリル樹脂は、250(℃)以下で燃え抜けるもので、スクリーン印刷性やハンドリング性を考慮した平均分子量16万程度のメタクリル酸イソブチルである。ペースト調製に際しては、印刷性を同等とするために、例えば、25(℃)−20(rpm)における粘度が180〜200(Pa・s)になるように調整する。 As described above, rosin-attached silver powder is prepared and mixed with a resin binder and an organic solvent with a stirrer or the like. For example, acrylic resin (EMB-002 manufactured by Mitsubishi Rayon) is used as the resin binder, and for example, mentanol is used as the organic solvent. A conductive paste is obtained by preparing a predetermined amount of these and carrying out dispersion treatment using a three-roll mill to form a paste. The acrylic resin burns out at 250 (° C.) or less, and is isobutyl methacrylate having an average molecular weight of about 160,000 considering screen printing properties and handling properties. In preparing the paste, for example, the viscosity at 25 (° C.)-20 (rpm) is adjusted to 180 to 200 (Pa · s) in order to make the printability equal.
このようにして用意した導電性ペーストを用いて、ポリイミド基板に厚膜スクリーン印刷を施す。印刷製版はSUS400製とした。また、印刷膜の幅寸法は500(μm)になるように印刷条件を設定した。乾燥後、250〜300(℃)の範囲内の温度で焼成処理を施すことにより、樹脂結合剤が燃え抜けると共に銀粉末が焼結し、前記銀導電膜１０が得られる。 Using the conductive paste thus prepared, thick film screen printing is performed on the polyimide substrate. The printing plate making was made of SUS400. Further, the printing conditions were set so that the width dimension of the printed film was 500 (μm). After drying, a baking treatment is performed at a temperature in the range of 250 to 300 (° C.), whereby the resin binder burns out and the silver powder is sintered, whereby the silver conductive film 10 is obtained.
本実施例によれば、上述したように銀粉末としてロジン、脂肪酸、或いはアミン類を付着させたコート剤付着銀粉末を用いていることから、上記のような250〜270(℃)の低温でも銀粉末の焼結が十分に進むので、例えば、シート抵抗値が2〜8(mΩ/□)程度の高い導電性と、高い密着性とを有する導電膜１０がポリイミド基板１２上に備えられた導電膜付基板１４が得られる。 According to this example, as described above, since the coating agent-attached silver powder to which rosin, fatty acid, or amines are attached is used as the silver powder, even at a low temperature of 250 to 270 (° C.) as described above. Since the sintering of the silver powder proceeds sufficiently, for example, a conductive film 10 having a high conductivity of about 2 to 8 (mΩ / □) and a high adhesion is provided on the polyimide substrate 12. A substrate 14 with a conductive film is obtained.
図２は、上記導電膜付基板１４の導電膜１０とポリイミド基板１２の界面近傍の断面のＳＥＭ像であり、図３は、その一部を更に拡大したＳＥＭ像である。図２の上半分程度を占める淡色部分が導電膜１０、その下側に位置する濃色部分がポリイミド基板１２である。このＳＥＭ像に現れている通り、導電膜１０は粒界が消失する程度まで十分に焼結している。しかも、導電膜１０と基板１２の界面には凹凸が形成されており、図３にその境界部分を拡大して示すように、銀とポリイミドが相互に他方の領域に侵入した状態となっている。 FIG. 2 is an SEM image of a cross section near the interface between the conductive film 10 and the polyimide substrate 12 of the substrate 14 with conductive film, and FIG. 3 is an enlarged SEM image of a part thereof. The light-colored portion occupying about the upper half of FIG. 2 is the conductive film 10, and the dark-colored portion positioned below the conductive film 10 is the polyimide substrate 12. As shown in the SEM image, the conductive film 10 is sufficiently sintered to such an extent that the grain boundary disappears. Moreover, irregularities are formed at the interface between the conductive film 10 and the substrate 12, and as shown in an enlarged view of the boundary portion in FIG. 3, silver and polyimide have entered the other region. .
ここで、ペースト組成や膜形成条件を種々変更して評価した試験結果を説明する。下記の表１は、コート剤の有無や種類、銀粒径を検討した結果をまとめたものである。表１において、No.1、No.2、No.6、No.13は比較例、他は実施例である。また、「組成」欄は、導電性ペーストの組成を質量百分率で示したもので、銀量を68〜75(％)、ガラス量を0〜2(％)、樹脂結合剤量を5〜6(％)、有機溶剤量を20〜24(％)の範囲とした。「樹脂/銀」は、銀に対する樹脂量の百分率である。また、「材料」欄において、「銀粒径」は、各ペーストに用いたコート剤付着前の銀粉末の粒径、「添加剤種」は、銀粉末のコート剤として用いた材料名、「付着量」は、付着させたコート剤量を前述したようにTG-DTAで測定した結果を銀粉末に対する百分率で示したものである。また、「ガラス」欄は、ペーストに添加したガラス粉末の組成系である。また、「試験条件・結果」欄において、「印刷版」はメッシュサイズ、「印刷厚み」は、印刷・乾燥後の膜厚である。また、「処理温度」は焼成処理の最高保持温度であり、各処理温度毎に、試験結果を示した。「焼成厚み」は、焼成後の膜厚、「抵抗値」は、焼成後にデジタルマルチメーターを用いて一般的な２端子法に基づいて端子間隔 10(cm)、ライン幅 500(μm)で測定した膜状導体の抵抗値である。また、「シート抵抗(mΩ/□)」は、上記抵抗値から次式より算出した焼成後のシート抵抗値である。なお、換算厚みは、10(μm)である。
シート抵抗値(mΩ/□) ＝ 測定抵抗値(Ω)×(導体幅(mm)/導体長さ(mm))×（導体厚み(μm)/換算厚み(μm))
Here, the test results evaluated by variously changing the paste composition and film forming conditions will be described. Table 1 below summarizes the results of examining the presence / absence and type of coating agent and the silver particle size. In Table 1, No. 1, No. 2, No. 6, No. 13 are comparative examples, and the others are examples. The “composition” column shows the composition of the conductive paste in mass percentage, the silver amount is 68 to 75 (%), the glass amount is 0 to 2 (%), and the resin binder amount is 5 to 6 (%), And the amount of organic solvent was in the range of 20 to 24 (%). “Resin / Silver” is the percentage of resin amount relative to silver. In the “Material” column, “Silver particle size” is the particle size of the silver powder before the coating agent used in each paste, “Additive type” is the name of the material used as the coating agent of the silver powder, “ The “adhesion amount” is the result of measuring the amount of the applied coating agent with TG-DTA as described above, expressed as a percentage of the silver powder. The “glass” column is a composition system of glass powder added to the paste. In the “Test conditions / results” column, “printing plate” is the mesh size, and “printing thickness” is the film thickness after printing and drying. The “treatment temperature” is the maximum holding temperature of the firing treatment, and the test results are shown for each treatment temperature. “Firing thickness” is the film thickness after firing, and “Resistance” is measured after firing using a digital multimeter at a terminal spacing of 10 (cm) and a line width of 500 (μm) based on the general two-terminal method. It is the resistance value of the film-like conductor. “Sheet resistance (mΩ / □)” is a sheet resistance value after firing calculated from the above resistance value by the following equation. The converted thickness is 10 (μm).
Sheet resistance value (mΩ / □) = measured resistance value (Ω) x (conductor width (mm) / conductor length (mm)) x (conductor thickness (μm) / converted thickness (μm))
また、「テープ強度」は、焼成後に、ポリイミド基板上に形成された銀導電膜の表面にセロハンテープ（ニチバン製 ＣＴ−１５１５３Ｐ）を指で押し付けて付着させ、テープを剥がして剥離したテープ面に付着する銀導電膜の様子を目視により観察して判定した。押しつけたテープのほぼ全面に銀導電膜がまったく付着しておらず、かつポリイミド基板上に形成された銀導電膜もそのまま残っているものを「○」、押しつけたテープに銀導電膜の一部が付着し、かつポリイミド基板上に形成された銀導電膜が一部残っていないものを「△」、押しつけたテープに銀導電膜の90(％)以上が付着し、かつポリイミド基板上に形成された銀導電膜の90(％)以上が残っていないものを「×」として３段階評価した。 In addition, the “tape strength” is obtained by applying a cellophane tape (CT-15153P manufactured by Nichiban) with a finger to the surface of the silver conductive film formed on the polyimide substrate after firing, and peeling off the tape to peel off the tape surface. The state of the attached silver conductive film was determined by visual observation. “○” indicates that the silver conductive film does not adhere to almost the entire surface of the pressed tape, and the silver conductive film formed on the polyimide substrate remains as it is, a part of the silver conductive film on the pressed tape. “△” indicates that the silver conductive film formed on the polyimide substrate does not remain, and 90% or more of the silver conductive film adheres to the pressed tape and is formed on the polyimide substrate. A silver conductive film in which 90% or more did not remain was evaluated as “x” and evaluated in three stages.
上記の表１において、比較例No.1、No.2のように、銀粉末をコート剤無しで用いたものは、ポリイミド基板上で焼結しないため、シート抵抗値が高く、テープ強度も低い結果であった。特に、粒径が1(μm)の銀粉末を用いたNo.1では、270(℃)で焼成してもシート抵抗値が32.3(mΩ/□)と著しく高い値に留まった。また、比較例No.13は、コート剤としてドデカンチオールを付着した銀粉末を用いたものであるが、焼結性の改善効果は得られず、270(℃)で焼成してもシート抵抗値が65.1(mΩ/□)と高い値に留まり、テープ強度も得られなかった。 In Table 1 above, as in Comparative Examples No. 1 and No. 2, those using silver powder without a coating agent do not sinter on the polyimide substrate, so the sheet resistance is high and the tape strength is also low. It was a result. In particular, in No. 1 using silver powder having a particle size of 1 (μm), the sheet resistance value remained at a remarkably high value of 32.3 (mΩ / □) even when fired at 270 (° C.). Comparative Example No. 13 uses silver powder with dodecanethiol attached as a coating agent, but the effect of improving the sinterability is not obtained, and the sheet resistance value even when fired at 270 (° C.) Remained at a high value of 65.1 (mΩ / □), and the tape strength was not obtained.
これらに対して、実施例No.3〜No.5、No.7〜No.12は、コート剤としてロジン、ステアリン酸、ラウリン酸、オレイン酸、リノール酸、デカン酸、ドデシルアミンを、それぞれ銀に対する質量比で0.16〜2.3(％)の範囲で付着したものであるが、何れも、250〜270(℃)で焼成処理を施すことにより、よく焼結し、シート抵抗値が2.4〜6.7(mΩ/□)と、高い導電性を得ることができた。また、テープ強度も全て「○」の結果となった。なお、No.3、No.4は、何れもロジンを用いて、銀粒径が0.1(μm)、0.07(μm)と異なる他は同様にして評価したものであるが、粒径の大きいNo.3の方が若干導電性に優れる結果であった。微粉の銀粉末は表面積が大きいため、コート剤量を多めに必要とするものと考えられる。なお、No.6は、ペースト中にガラス粉末を2(％)添加した他はNo.3と同様な条件であるが、導電性は十分に得られるものの、テープ強度が得られない結果となった。銀導電膜自体は焼結しているが、ガラスがポリイミド基板との密着性を阻害している可能性がある。 On the other hand, Examples No. 3 to No. 5, No. 7 to No. 12 are rosin, stearic acid, lauric acid, oleic acid, linoleic acid, decanoic acid, dodecylamine as the coating agent. Although it adheres in the range of 0.16-2.3 (%) by mass ratio with respect to each, it sinters well by giving a baking treatment at 250-270 (degreeC), and sheet resistance value is 2.4-6.7 ( mΩ / □) and high conductivity could be obtained. Also, all tape strengths were “◯”. No. 3 and No. 4 were evaluated in the same manner except that rosin was used and the silver particle diameter was different from 0.1 (μm) and 0.07 (μm). .3 was slightly better in conductivity. Since the fine silver powder has a large surface area, it is considered that a large amount of coating agent is required. No. 6 is the same conditions as No. 3 except that 2% glass powder was added to the paste. However, although sufficient conductivity was obtained, the tape strength could not be obtained. It was. Although the silver conductive film itself is sintered, there is a possibility that the glass has hindered adhesion to the polyimide substrate.
なお、図４、図５は、上記実施例No.7において、焼成温度が230(℃)の場合の断面写真であり、それぞれ前記図２、図３に対応するものである。焼成温度が230(℃)では低すぎるため、焼結が進まず、銀導電膜１０とポリイミド基板１２との界面も平坦な状態である。そのため、シート抵抗値が高く、且つテープ強度も得られないことになる。 4 and 5 are cross-sectional photographs when the firing temperature is 230 (° C.) in Example No. 7, and correspond to FIG. 2 and FIG. 3, respectively. Since the firing temperature is too low at 230 (° C.), sintering does not proceed and the interface between the silver conductive film 10 and the polyimide substrate 12 is also flat. Therefore, the sheet resistance value is high and the tape strength cannot be obtained.
また、下記の表２は、条件を更に変更して評価した結果をまとめたもので、No.14〜No.16は、銀粉末の粒径を検討した結果である。粒径が0.5〜1(μm)の銀粉末を用いたNo.14、No.15は、250〜270(℃)の焼成温度でシート抵抗値が3.5〜5.4(mΩ/□)と高い導電性が得られると共に、テープ強度も「○」であったが、粒径が3(μm)の銀粉末を用いたNo.16は、これらよりも導電性の劣る結果となった。特に、250(℃)の焼成温度ではシート抵抗値が10.5(mΩ/□)と大きく、テープ強度も「×」となった。但し、270(℃)で焼成すれば、テープ強度は十分に高くなると共に、シート抵抗値も7.1(mΩ/□)と、高めではあるが、使用可能な程度まで改善する。 In addition, Table 2 below summarizes the results of further evaluation and evaluation, and Nos. 14 to 16 are the results of studying the particle size of the silver powder. No.14 and No.15 using silver powder with a particle size of 0.5 to 1 (μm) have a high sheet resistance of 3.5 to 5.4 (mΩ / □) at a firing temperature of 250 to 270 (° C). No. 16 using silver powder with a particle size of 3 (μm) resulted in inferior conductivity compared to these. In particular, at a firing temperature of 250 (° C.), the sheet resistance value was as large as 10.5 (mΩ / □), and the tape strength was also “x”. However, firing at 270 (° C.) increases the tape strength sufficiently and also improves the sheet resistance to 7.1 (mΩ / □), albeit high, to a usable level.
また、No.17〜No.19は、ペースト中の樹脂結合剤量を銀に対する質量比で12.9〜4.3(％)の範囲で変化させたものである。何れの条件でも、250〜270(℃)の焼成でシート抵抗値が2.7〜5.4(mΩ/□)と高い導電性と、「○」評価の高いテープ強度とを得ることができた。ペースト中の樹脂量は、比較的広い範囲で許容される。 No. 17 to No. 19 are obtained by changing the amount of the resin binder in the paste in a range of 12.9 to 4.3 (%) in terms of mass ratio with respect to silver. Under any of the conditions, the sheet resistance value was as high as 2.7 to 5.4 (mΩ / □) by baking at 250 to 270 (° C.), and the tape strength with high “◯” evaluation could be obtained. The amount of resin in the paste is allowed in a relatively wide range.
また、No.20、No.21は、ペースト中の樹脂結合剤を変更して評価したもので、No.20は、分解温度の高いアクリル樹脂(例えば、分解温度が300(℃)程度の三菱レーヨン製 ＥＭＢ−３９８)を用いたもの、No.21は、エチルセルロース(例えば、分解温度が450(℃)程度のダウケミカル製 ＥＣ−４５)を用いたものであるが、何れも、250〜270(℃)の焼成温度でシート抵抗値が2.3〜2.8(mΩ/□)の高い導電性と、高いテープ強度とを得ることができた。なお、上記２種は、分解温度が高いことから、焼成後の銀導電膜１０内に有機物或いは炭化物として少なくとも一部が残存しているものと考えられるが、上記評価結果によれば、このような分解温度の高いものでも全く問題がなく、樹脂結合剤が完全に燃え抜けるものでなくとも差し支えないことが判る。 No. 20 and No. 21 were evaluated by changing the resin binder in the paste.No. 20 was an acrylic resin with a high decomposition temperature (for example, Mitsubishi with a decomposition temperature of about 300 (° C.). No. 21 using rayon EMB-398) is ethyl cellulose (for example, EC-45 made by Dow Chemical having a decomposition temperature of about 450 (° C.)). It was possible to obtain high electrical conductivity with a sheet resistance value of 2.3 to 2.8 (mΩ / □) and high tape strength at a firing temperature of (° C.). In addition, since the above two types have a high decomposition temperature, it is considered that at least a part of the organic conductive material or carbide remains in the fired silver conductive film 10, but according to the above evaluation results, It can be seen that there is no problem even if the decomposition temperature is high and the resin binder does not have to burn out completely.
また、No.22〜No.24は、ペースト中の樹脂結合剤と有機溶剤との割合を変化させると共に、印刷版を＃４００、＃２５０、＃１６５と変化させて、印刷厚みを3.2〜10.1(μm)の間で変化させたものである。印刷厚みが厚くなると、焼結性がやや悪くなる傾向があり、250〜270(℃)の焼成温度で、印刷厚みが3.2(μm)のNo.22、5.8(μm)のNo.23では、シート抵抗値が2.7〜3.7(mΩ/□)、テープ強度が「○」と良好な結果が得られたのに対し、印刷厚みが10.1(μm)のNo.24では、250(℃)でテープ強度が「×」となった。但し、No.24も270(℃)では十分に焼結し、シート抵抗値が4.8(mΩ/□)、テープ強度が「○」と、No.22、No.23にはやや劣るものの良好な結果が得られる。また、これらNo.22〜No.24の試料については、焼成温度300(℃)でも評価を行ったところ、シート抵抗値が2.4〜2.5(mΩ/□)、テープ強度が「○」と、何れも良好な結果が得られることが確認できた。 In No. 22 to No. 24, the ratio of the resin binder and the organic solvent in the paste was changed, and the printing plate was changed to # 400, # 250, and # 165, and the printing thickness was changed to 3.2 to 10.1. (μm). When the printed thickness is increased, the sinterability tends to be slightly worse, with a firing temperature of 250 to 270 (° C), a printed thickness of 3.2 (μm) No. 22, and a 5.8 (μm) No. 23, Good results were obtained with a sheet resistance value of 2.7 to 3.7 (mΩ / □) and tape strength of `` ○ '', whereas for No.24 with a printing thickness of 10.1 (μm), the tape was at 250 (° C). The strength was “x”. However, No.24 also sinters sufficiently at 270 (° C), sheet resistance value is 4.8 (mΩ / □), tape strength is `` ○ '', and although it is slightly inferior to No.22 and No.23, it is good Results are obtained. In addition, the samples No. 22 to No. 24 were evaluated even at a firing temperature of 300 (° C.). As a result, the sheet resistance value was 2.4 to 2.5 (mΩ / □) and the tape strength was “O”. It was confirmed that good results were obtained.
また、No.25は、コート剤を銀粉末に付着させず、ペースト中に添加したものであるが、250(℃)の焼成温度で、シート抵抗値が332(mΩ/□)と著しく大きく、導電性が得られず、テープ強度も「×」となった。ポリイミド基板上における銀粉末の焼結性を改善するためには、コート剤を銀粉末に付着させる処理が必須であることが確認できた。 In addition, No. 25 was added to the paste without causing the coating agent to adhere to the silver powder, but at a firing temperature of 250 (° C.), the sheet resistance value was 332 (mΩ / □) and was extremely large. Electrical conductivity could not be obtained, and the tape strength was “x”. In order to improve the sinterability of the silver powder on the polyimide substrate, it was confirmed that the treatment for attaching the coating agent to the silver powder was essential.
ここで、上述した実施例において、焼成後の銀導電膜１０の表面形状を評価した結果を説明する。図６は、銀導電膜１０の断面形状図である。この断面形状は、東京精密製 サーフコム４８０Ａを用いて、スキャンスピード 1.5(mm/sec)、倍率 10K、カットオフ 0.8(mm)として、形成した500(μm)幅の配線パターンをその幅方向に横断して測定した。図６において、縦方向は、銀導電膜１０の厚み方向、横方向はその幅方向であり、中央部の凹凸が生じている部分が銀導電膜１０，その両側の平坦な部分がポリイミド基板１２である。また、温度は、各評価試料の焼成温度で、250(℃)、270(℃)のものは、前記実施例No.3、300(℃)のものは、前記実施例No.22の試料を測定した。なお、325(℃)の試料は、これらと同様な導電性ペーストを用いたものであるが、この測定データは、前記表１、表２には掲載していない。 Here, in the Example mentioned above, the result of having evaluated the surface shape of the silver electrically conductive film 10 after baking is demonstrated. FIG. 6 is a cross-sectional view of the silver conductive film 10. This cross-sectional shape crossed the 500 (μm) wide wiring pattern in the width direction using a surfcom 480A manufactured by Tokyo Seimitsu, with a scan speed of 1.5 (mm / sec), a magnification of 10K, and a cutoff of 0.8 (mm). And measured. In FIG. 6, the vertical direction is the thickness direction of the silver conductive film 10, and the horizontal direction is the width direction. The central conductive film is uneven in the silver conductive film 10, and the flat portions on both sides thereof are the polyimide substrate 12. It is. Further, the temperature is the firing temperature of each evaluation sample, 250 (° C.), 270 (° C.) is the sample of Example No. 3, 300 (° C.) is the sample of Example No. 22. It was measured. The sample at 325 (° C.) uses a conductive paste similar to these, but this measurement data is not shown in Tables 1 and 2 above.
上記測定結果の断面形状に示されるように、250〜300(℃)の温度範囲で焼成処理を施して銀導電膜１０を形成することにより、前記図２、図３に示されるように、銀導電膜１０およびポリイミド基板１２の構成成分が相互に他方に侵入して凹凸形状の界面が形成されるが、その結果、銀導電膜１０の表面は、図６に示されるように、凹凸の激しい断面形状になる。この凹凸の大きさは、スケールに示されるように銀導電膜１０の厚さ寸法以下、すなわち2(μm)程度である。 As shown in the cross-sectional shape of the measurement result, the silver conductive film 10 is formed by performing a baking process in a temperature range of 250 to 300 (° C.). Constituent components of the conductive film 10 and the polyimide substrate 12 invade each other to form a concavo-convex shaped interface. As a result, the surface of the silver conductive film 10 has severe irregularities as shown in FIG. It becomes a cross-sectional shape. The size of the unevenness is not more than the thickness of the silver conductive film 10, that is, about 2 (μm) as shown in the scale.
これに対して、325(℃)で焼成した場合は、ポリイミド基板１２が銀導電膜１０に著しく浸食され銀導電膜１０の膜厚寸法以上の深さの凹所が形成される。このとき、銀導電膜１０側にも、ポリイミド基板１２の構成成分がおそらくは膜厚方向全体に亘って侵入しているものと推定され、シート抵抗値も高くなる。このように、焼成温度325(℃)ではポリイミド基板１２が破れるなど不都合が生じており、使用できないことが明らかであるため、前記表１、表２への掲載を省略した。 On the other hand, when baked at 325 (° C.), the polyimide substrate 12 is significantly eroded by the silver conductive film 10 to form a recess having a depth greater than the film thickness dimension of the silver conductive film 10. At this time, it is presumed that the constituent components of the polyimide substrate 12 have also invaded over the entire film thickness direction on the silver conductive film 10 side, and the sheet resistance value also increases. As described above, it is clear that the polyimide substrate 12 is broken at the firing temperature of 325 (° C.) and cannot be used. Therefore, the description in Tables 1 and 2 is omitted.
なお、図７は、銀導電膜１０の表面ＳＥＭ写真である。この写真に示すように、銀導電膜１０の表面には、多数の小さな穴が生じている。前記図６において現れる凹凸はこのような穴にも起因しているものと考えられるが、膜厚や構成成分の侵入深さを考える際には、この穴に起因する凹凸は無視している。 FIG. 7 is a surface SEM photograph of the silver conductive film 10. As shown in this photograph, many small holes are formed on the surface of the silver conductive film 10. The irregularities appearing in FIG. 6 are considered to be caused by such holes, but the irregularities caused by these holes are ignored when considering the film thickness and the penetration depth of the constituent components.
以上、説明したように、本実施例によれば、銀導電膜１０およびポリイミド基板１２は、それらの構成成分が銀導電膜１０の厚さ寸法以下の範囲で相互に他方に侵入しており、これにより形成された凹凸面をそれらの界面が成していることから、接触面積の増大に伴って導電性と密着性が高められる。そのため、高い導電性とポリイミド基板１２との高い密着性を有する銀導電膜１０が備えられた導電膜付基板１４が得られる。 As described above, according to the present embodiment, the silver conductive film 10 and the polyimide substrate 12 penetrate into the other in the range where their constituent components are equal to or less than the thickness dimension of the silver conductive film 10, Since the interface of the uneven surface formed thereby is formed, the conductivity and adhesion are improved as the contact area increases. Therefore, the board | substrate 14 with a electrically conductive film provided with the silver electrically conductive film 10 which has high electroconductivity and the high adhesiveness with the polyimide substrate 12 is obtained.
また、本実施例によれば、銀導電膜１０をポリイミド基板１２上に形成して導電膜付基板１４を製造するに際しては、ペースト塗布工程において、塗布される導電性ペーストが、銀粉末として、ロジン、脂肪酸、またはアミン類から成るコート剤が表面に付着したコート剤付着銀粉末が用いられていることから、焼成工程において、250〜300(℃)の範囲内の低温で焼成処理が施されても、十分に焼結が進むので、高い導電性とポリイミド基板１２への高い密着性を有する銀導電膜１０を備えた導電膜付基板１４が得られる。 In addition, according to the present embodiment, when the silver conductive film 10 is formed on the polyimide substrate 12 to produce the conductive film-coated substrate 14, the conductive paste applied in the paste application step is as silver powder. Since the coating agent-attached silver powder with the coating agent consisting of rosin, fatty acid, or amines attached to the surface is used, the firing process is performed at a low temperature in the range of 250 to 300 (° C) in the firing step. However, since sintering proceeds sufficiently, the conductive film-equipped substrate 14 including the silver conductive film 10 having high conductivity and high adhesion to the polyimide substrate 12 is obtained.
また、本実施例によれば、導電性ペーストは、銀粉末として、ロジン、脂肪酸、またはアミン類から成るコート剤が、銀粉末に対する質量比で2.3(％)以下の範囲で付着したコート剤付着銀粉末が用いられていることから、300(℃)以下の低温で焼成処理を施しても、銀粉末の焼結が十分に進むので、高い導電性とポリイミド基板１２への高い密着性が得られる。 Further, according to the present example, the conductive paste is a silver powder, and a coating agent composed of rosin, fatty acid, or amines adheres in a mass ratio of 2.3 (%) or less with respect to the silver powder. Since silver powder is used, the sintering of the silver powder is sufficiently advanced even if the baking treatment is performed at a low temperature of 300 (° C.) or less, so that high conductivity and high adhesion to the polyimide substrate 12 are obtained. It is done.
以上、本発明を図面を参照して詳細に説明したが、本発明は更に別の態様でも実施でき、その主旨を逸脱しない範囲で種々変更を加え得るものである。 As mentioned above, although this invention was demonstrated in detail with reference to drawings, this invention can be implemented also in another aspect, A various change can be added in the range which does not deviate from the main point.
１０：銀導電膜、１２：ポリイミド基板、１４：導電膜付基板 10: Silver conductive film, 12: Polyimide substrate, 14: Substrate with conductive film
Claims (6)
前記導電膜および前記ポリイミド基板の構成成分がそれらの界面を越えてその導電膜の厚さ寸法以下の範囲で相互に他方に侵入することにより形成された凹凸面をその界面が成していることを特徴とする導電膜付基板。 A conductive film-containing substrate provided with a conductive film containing silver as a conductor component on one surface of a polyimide substrate,
The interface forms an uneven surface formed by the constituent components of the conductive film and the polyimide substrate exceeding the interface and entering the other within the range of the thickness dimension of the conductive film. A substrate with a conductive film.
ロジン、脂肪酸、およびアミン類のうちの少なくとも１種から成る所定量のコート剤が表面に付着した銀粉末と、樹脂結合剤と、有機溶剤とを含む導電性ペーストを前記ポリイミド基板上に所定パターンで塗布するペースト塗布工程と、
250〜300(℃)の最高温度で焼成処理を施すことにより銀を焼結させて前記導電性ペーストから導電膜を生成する焼成工程と
を、含むことを特徴とする導電膜付基板の製造方法。 A method for manufacturing a substrate with a conductive film, wherein a conductive film containing silver as a conductor component is formed on a polyimide substrate,
A conductive paste containing a silver powder having a predetermined amount of a coating agent consisting of at least one of rosin, fatty acid, and amines attached to the surface, a resin binder, and an organic solvent is formed on the polyimide substrate in a predetermined pattern. Paste application process to apply in,
A method of producing a substrate with a conductive film, comprising: baking a silver by sintering at a maximum temperature of 250 to 300 (° C.) to form a conductive film from the conductive paste. .
前記銀粉末は、ロジン、脂肪酸、およびアミン類のうちの少なくとも１種から成るコート剤をその銀粉末に対する質量比で2.3(％)以下の量で表面に付着させたコート剤付着銀粉末であることを特徴とするポリイミド基板用導電性ペースト。 A conductive paste for a polyimide substrate, which contains silver powder, a resin binder, and an organic solvent, and is used for manufacturing a conductive film-coated substrate by forming a conductive film on a polyimide substrate,
The silver powder is a coating agent-attached silver powder in which a coating agent composed of at least one of rosin, fatty acid, and amines is attached to the surface in an amount of 2.3 (%) or less by mass ratio to the silver powder. A conductive paste for a polyimide substrate.
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| TW105104466A TWI687320B (en) | 2015-04-06 | 2016-02-16 | Substrate with conductive film, manufacturing method thereof, and conductive paste for polyimide substrate |
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| JP5164239B2 (en) * | 2006-09-26 | 2013-03-21 | Ｄｏｗａエレクトロニクス株式会社 | Silver particle powder, dispersion thereof, and method for producing silver fired film |
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