JP2009181946A - Electrically conductive board, and manufacturing method thereof - Google Patents
Electrically conductive board, and manufacturing method thereof Download PDFInfo
- Publication number
- JP2009181946A JP2009181946A JP2008022766A JP2008022766A JP2009181946A JP 2009181946 A JP2009181946 A JP 2009181946A JP 2008022766 A JP2008022766 A JP 2008022766A JP 2008022766 A JP2008022766 A JP 2008022766A JP 2009181946 A JP2009181946 A JP 2009181946A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- fine particles
- base material
- substrate
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Manufacturing Of Printed Wiring (AREA)
- Manufacturing Of Electric Cables (AREA)
- General Induction Heating (AREA)
Abstract
Description
本発明は導電性基板及びその製造方法に関し、さらに詳しくは、基材上にパターニングされた導電性薄膜を有する導電性基板及びその製造方法に関する。 The present invention relates to a conductive substrate and a manufacturing method thereof, and more particularly to a conductive substrate having a conductive thin film patterned on a base material and a manufacturing method thereof.
従来、基材上に導電性の配線を施した回路基板を製造するためには、金属箔を貼り合せた基材上にフォトレジスト等を塗布し、所望の回路パターン露光し、ケミカルエッチングによりパターンを形成する方法が用いられてきた。この方法では、導電性の配線として金属箔を用いることができるため、体積抵抗率が小さく、高性能の導電性基板を製造することができるが、該方法は工程数が多く、煩雑であるとともに、フォトレジスト材料を要するなどの欠点がある。 Conventionally, in order to manufacture a circuit board with conductive wiring on a base material, a photoresist or the like is applied onto the base material bonded with a metal foil, a desired circuit pattern is exposed, and a pattern is formed by chemical etching. The method of forming has been used. In this method, since a metal foil can be used as the conductive wiring, a volume resistivity is small and a high-performance conductive substrate can be manufactured. However, this method has many steps and is complicated. However, there are drawbacks such as requiring a photoresist material.
これに対し、金属微粒子を分散させた塗料でパターンを直接基材に印刷する方法が注目されている。このような基材に直接パターンを印刷する方法は、フォトレジスト等を用いる必要がなく、きわめて生産性の高い方法である。
しかしながら、この方法では導電性材料として金属微粒子を用いるために、粒子間の界面での電気抵抗が問題であり、金属箔なみの導電性を達成するためには、金属微粒子を数百度の温度で焼結させることが必要である。ところが、数百度の温度での焼結を必要とすると、金属微粒子を分散させた塗料を塗布する基材が制限され、例えば、歪点が６００℃程度の通常のガラスやＰＥＴ（ポリエチレンテレフタレート）等のプラスチックフィルムからなる基材を用いることは困難となる。
On the other hand, a method of directly printing a pattern on a base material with a paint in which metal fine particles are dispersed has attracted attention. Such a method for printing a pattern directly on a substrate does not require the use of a photoresist or the like, and is a highly productive method.
However, in this method, since metal fine particles are used as the conductive material, the electrical resistance at the interface between the particles is a problem. To achieve conductivity similar to that of metal foil, the metal fine particles are heated at a temperature of several hundred degrees. It is necessary to sinter. However, if sintering at a temperature of several hundred degrees is required, the base material on which the coating material in which the metal fine particles are dispersed is limited. For example, ordinary glass having a strain point of about 600 ° C., PET (polyethylene terephthalate), etc. It is difficult to use a substrate made of a plastic film.
ところで、金属微粒子は十分にその粒子径を小さくすると、低温で焼結することが知られている。例えば、銀粒子の場合には、平均粒子径数ｎｍ〜数１０ｎｍ程度の超微粒子である場合に、２００℃以下でも焼結することが知られている。
このような、金属が超微粒子化するとその金属の融点よりも格段に低い温度で焼結する性質を利用して、金属微粒子の平均粒子径を１〜１００ｎｍに制御した低温焼結型導電性金属ペーストが提案されている（特許文献１参照）。
特許文献１で提案される低温焼結型導電性金属ペーストは、該金属ペーストを構成する導電性媒体としての金属超微粒子に加えて、より粒子径の大きな金属フィラーを用いたものであり、基板上に塗布、焼成した際、密着力が良く、比較的厚さを増した際にも、表面形状がなめらかで、また、低抵抗かつ微細な回路を形成できるとされている。
しかしながら、特許文献１で提案される低温焼結型導電性金属ペーストを用いた場合であっても、焼成処理を通常１８０〜２３０℃の温度で６０分程度は行っており、必ずしも基材への損傷を完全に抑制することはできず、また、導電性についても必ずしも満足できるものではなかった。
By the way, it is known that metal fine particles are sintered at a low temperature when the particle diameter is sufficiently reduced. For example, in the case of silver particles, it is known that sintering is performed even at 200 ° C. or lower when the particles are ultrafine particles having an average particle diameter of several nanometers to several tens of nanometers.
Such a low-temperature sintered conductive metal in which the average particle size of metal fine particles is controlled to 1 to 100 nm by utilizing the property of sintering at a temperature much lower than the melting point of the metal when the metal becomes ultrafine particles. A paste has been proposed (see Patent Document 1).
The low-temperature sintering type conductive metal paste proposed in
However, even when the low-temperature sintered type conductive metal paste proposed in
一方、基材に損傷を与えず、基材上の微粒子を焼結させる方法として、マイクロ波を利用する技術が近年注目を集めている。例えば、高分子フィルム表面に酸化チタンなどの半導体微粒子の分散液を塗装し、これに２８ＧＨｚのマイクロ波を照射して焼結することを特徴とする焼結方法が提案されている（特許文献２参照）。
しかしながら、一般に金属にマイクロ波を照射した場合には、金属がマイクロ波を反射してしまうため、金属の焼結にマイクロ波を使用することはできないとされてきた。これに対し、最近、金属が微粒子である場合には、マイクロ波が内部にまで浸透することが明らかとなり、粉末冶金などに利用され始めている。
On the other hand, as a method for sintering fine particles on a base material without damaging the base material, a technique using microwaves has recently attracted attention. For example, there has been proposed a sintering method characterized in that a dispersion of semiconductor fine particles such as titanium oxide is coated on the surface of a polymer film, and is irradiated with 28 GHz microwave for sintering (Patent Document 2). reference).
However, in general, when a metal is irradiated with microwaves, the metal reflects the microwaves, and thus it has been considered that microwaves cannot be used for metal sintering. On the other hand, recently, when the metal is fine particles, it has been clarified that the microwave penetrates into the inside, and has started to be used for powder metallurgy and the like.
このような技術背景の下、金属を要素として含む薄膜形成方法であって、基板上の少なくとも一部に金属と有機物とを含むペーストを形成し、これに上方から１ＧＨｚ〜１００ＧＨｚの電磁波を照射する薄膜形成方法が提案されている（特許文献３参照）。
しかしながら、特許文献３に開示される薄膜形成方法においては、金属の粒子径についての制御がなされていず、導電性についてはやはり不十分なものであった。また、均一な加熱を行うためには、周波数の大きなマイクロ波電源や特殊な反応炉が必要となり、大がかりな装置が必要であった。
Under such a technical background, a thin film forming method including a metal as an element, a paste including a metal and an organic substance is formed on at least a part of a substrate, and an electromagnetic wave of 1 GHz to 100 GHz is irradiated on the paste from above. A thin film forming method has been proposed (see Patent Document 3).
However, in the thin film forming method disclosed in Patent Document 3, the metal particle diameter is not controlled, and the conductivity is still insufficient. Moreover, in order to perform uniform heating, a microwave power source having a high frequency and a special reaction furnace are required, and a large-scale apparatus is required.
本発明は、このような状況下、基材として耐熱性の低い材料を用いることができ、かつ実用上十分な導電性を有する導電性基板及び該導電性基板を高い生産性で製造する方法を提供することを目的とするものである。 Under such circumstances, the present invention provides a conductive substrate that can use a material having low heat resistance as a base material and has sufficient conductivity in practice, and a method for manufacturing the conductive substrate with high productivity. It is intended to provide.
本発明者は、前記目的を達成するために鋭意研究を重ねた結果、基材上に導電性薄膜を形成するに際し、特定の平均粒子径を有する金属又は金属化合物の微粒子を分散させた分散液を用い、該金属微粒子を焼結させるための焼成方法として、電磁誘導加熱を用いることで上記課題を解決し得ることを見出した。本発明は、かかる知見に基づいて完成したものである。
すなわち、本発明は、基材上に金属又は金属化合物の微粒子の分散液を印刷し、焼成してなる導電性基板の製造方法であって、金属又は金属化合物の微粒子の平均一次粒子径が１〜１００ｎｍであり、焼成を電磁誘導加熱により行うことを特徴とする導電性基板の製造方法、及び該製造方法により得られる導電性基板を提供するものである。
As a result of intensive studies to achieve the above object, the present inventor has dispersed a fine particle of a metal or a metal compound having a specific average particle diameter when forming a conductive thin film on a substrate. As a firing method for sintering the fine metal particles, it has been found that the above problem can be solved by using electromagnetic induction heating. The present invention has been completed based on such findings.
That is, the present invention is a method for producing a conductive substrate obtained by printing a dispersion liquid of metal or metal compound fine particles on a substrate and firing the dispersion, wherein the average primary particle diameter of the metal or metal compound fine particles is 1. The present invention provides a method for producing a conductive substrate having a thickness of 100 nm and firing by electromagnetic induction heating, and a conductive substrate obtained by the production method.
本発明によれば、金属微粒子層が電磁誘導加熱により選択的に加熱されるため、基材として耐熱性の低い材料を用いても、基材に損傷を与えずに導電性薄膜を形成することができ、実用上十分な導電性を有する導電性基板を高い生産性で製造することができる。 According to the present invention, since the metal fine particle layer is selectively heated by electromagnetic induction heating, the conductive thin film can be formed without damaging the substrate even when a material having low heat resistance is used as the substrate. Thus, a conductive substrate having practically sufficient conductivity can be manufactured with high productivity.
本発明の導電性基板の製造方法は、基材上に金属又は金属化合物の微粒子の分散液を印刷し、焼成してなるものであって、分散液中の金属又は金属化合物の微粒子の平均一次粒子径が１〜１００ｎｍであり、焼成を電磁誘導加熱により行うことを特徴とする。
本発明において用いる基材としては、金属微粒子層のみを選択的に加熱するために、絶縁性であることが好ましい。例えば、ソーダライムガラス、無アルカリガラス、ホウケイ酸ガラス、高歪点ガラス、石英ガラス等のガラス、アルミナ、シリカ、などの無機材料を用いることができ、さらに高分子材料、紙などを用いることもできる。本発明においては、基材に直接、金属微粒子分散液又は金属化合物微粒子分散液を印刷するので、従来のフォトレジスト等による方法では使用できなかった紙基材を用いることもできる。また、本発明では後に詳述するように、金属又は金属化合物の微粒子の焼結が低温で行われ、基材に損傷を与えることがないため、高歪点ガラスなど耐熱性の高い特殊なガラスを使わなくてもよく、耐熱性の低い通常のソーダライムガラス等であっても使用することができる。さらには、プラスチックなどの高分子材料も基材とすることができる。
The method for producing a conductive substrate of the present invention is obtained by printing a dispersion of metal or metal compound fine particles on a base material and firing the dispersion. The average primary of the metal or metal compound fine particles in the dispersion The particle diameter is 1 to 100 nm, and firing is performed by electromagnetic induction heating.
The substrate used in the present invention is preferably insulative in order to selectively heat only the metal fine particle layer. For example, inorganic materials such as soda lime glass, alkali-free glass, borosilicate glass, high strain point glass, quartz glass, alumina, silica, etc. can be used, and polymer materials, paper, etc. can also be used. it can. In the present invention, since the metal fine particle dispersion or the metal compound fine particle dispersion is directly printed on the base material, a paper base material that could not be used by a conventional method using a photoresist or the like can also be used. In addition, as described in detail later in the present invention, since the fine particles of metal or metal compound are sintered at a low temperature and do not damage the base material, a special glass having high heat resistance such as a high strain point glass. May be used, and even ordinary soda lime glass having low heat resistance can be used. Furthermore, a polymer material such as plastic can be used as the base material.
基材として用い得る高分子材料としては、用途に応じて種々のものを挙げることができ、例えば、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリスチレン、トリアセチルセルロース、ポリカーボネート、ポリイミド、ポリアミドイミド、ポリエーテルスルホン、ポリエーテルイミド、エポキシ樹脂、ガラス−エポキシ樹脂、ポリフェニレンエーテルなどを使用することができる。特に、本発明では融点が３００℃以下のプラスチックを基材として用いることができるので、基材に対する制約がなく好ましい。
基材の厚さについては特に制限はないが、通常１０〜３００μｍの範囲である。１０μｍ以上であると、導電性薄膜を形成するに際して、基材が変形することがなく、印刷配線の形状安定性の点で好適である。一方、３００μｍ以下であると連続の巻き取り加工を行う場合に、柔軟性の点で好適である。
Examples of the polymer material that can be used as the substrate include various materials depending on the application, such as polyethylene terephthalate, polyethylene naphthalate, polystyrene, triacetyl cellulose, polycarbonate, polyimide, polyamideimide, polyethersulfone, Polyetherimide, epoxy resin, glass-epoxy resin, polyphenylene ether, and the like can be used. In particular, in the present invention, a plastic having a melting point of 300 ° C. or lower can be used as the base material, which is preferable because there is no restriction on the base material.
Although there is no restriction | limiting in particular about the thickness of a base material, Usually, it is the range of 10-300 micrometers. When the thickness is 10 μm or more, the substrate is not deformed when the conductive thin film is formed, which is preferable in terms of the shape stability of the printed wiring. On the other hand, when it is 300 μm or less, it is preferable in terms of flexibility when performing continuous winding.
また、基材と導電性薄膜との密着性を向上させるために、基材の表面に易接着成分を成膜することができる。但し、易接着成分を成膜する方法は、塗布又は印刷のプロセスが必要であること、製造コストが増大することなどから、このような密着層は設けないことが好ましい。また、基材はコロナ処理、乾式ＵＶ照射処理、エキシマランプ照射処理、大気圧プラズマ処理等による易接着処理がなされていてもよい。これらの方法は、乾式であり、大気圧下で行うことができ、導電性基板を作製する工程において、その工程の一部として連続的に行えるため好ましい。 Moreover, in order to improve the adhesiveness of a base material and an electroconductive thin film, an easily bonding component can be formed into a film on the surface of a base material. However, it is preferable not to provide such an adhesion layer in the method of forming the easy-adhesive component because an application or printing process is required and the manufacturing cost increases. The base material may be subjected to easy adhesion treatment by corona treatment, dry UV irradiation treatment, excimer lamp irradiation treatment, atmospheric pressure plasma treatment or the like. These methods are preferable because they are dry, can be performed under atmospheric pressure, and can be continuously performed as part of the process in the process of manufacturing the conductive substrate.
本発明の製造方法で用いる分散液中には、平均一次粒子径１〜１００ｎｍの金属又は金属化合物の微粒子が分散状態で存在する。金属の種類としては、導電性を有するものであれば特に制限されるものではないが、高い導電性を有し、かつ微粒子を容易に維持できる点から、金、銀、銅、ニッケル、スズ、及びアルミニウムが好ましく、さらには金、銀、及び銅が好ましく、導電性及び経済性を加味すると、銅及び銀が好ましい。これらの金属は１種を単独で用いてもよいし、２種以上を混合して、又は合金化して使用してもよい。また、スズドープ酸化インジウム（ＩＴＯ）、酸化亜鉛、酸化チタンなどの導電性を有する金属酸化物などの金属化合物や、一部が金属状態であって導電性を有する酸化銅、酸化銀等の金属化合物であれば、電磁誘導により加熱することができる。 In the dispersion used in the production method of the present invention, fine particles of metal or metal compound having an average primary particle diameter of 1 to 100 nm are present in a dispersed state. The type of metal is not particularly limited as long as it has conductivity, but from the viewpoint of having high conductivity and easily maintaining fine particles, gold, silver, copper, nickel, tin, And aluminum are preferable, and gold, silver, and copper are preferable, and copper and silver are preferable in consideration of conductivity and economy. One kind of these metals may be used alone, or two or more kinds may be mixed or alloyed. In addition, metal compounds such as tin-doped indium oxide (ITO), zinc oxide, titanium oxide and other conductive metal oxides, and metal compounds such as copper oxide and silver oxide which are partly in a metal state and have conductivity If so, it can be heated by electromagnetic induction.
また、分散液の分散安定性を高めるために、微粒子の表面処理を行ったり、高分子、イオン性化合物、界面活性剤等からなる分散剤を添加してもよい。
なお、以後、本明細書においては、金属状態の微粒子を「金属微粒子」といい、金属の微粒子又は金属化合物の微粒子は単に「微粒子」と表現する。
In addition, in order to improve the dispersion stability of the dispersion, surface treatment of the fine particles may be performed, or a dispersant composed of a polymer, an ionic compound, a surfactant, or the like may be added.
Hereinafter, in this specification, fine particles in a metal state are referred to as “metal fine particles”, and metal fine particles or metal compound fine particles are simply referred to as “fine particles”.
上記金属微粒子の調製方法としては種々の方法があるが、メカノケミカル法などによる金属粉を粉砕して得る物理的な方法；ＣＶＤ法や蒸着法、スパッタ法、熱プラズマ法、レーザー法のような化学的な乾式法；熱分解法、化学還元法、電気分解法、超音波法、レーザーアブレーション法、超臨界流体法、マイクロ波合成法等による化学的な湿式法と呼ばれる方法で作製できる。
得られた微粒子は、分散液とするために、微粒子にポリビニルピロリドンなどの水溶性高分子やグラフト共重合高分子のような保護剤、界面活性剤、金属と相互作用するようなチオール基やアミノ基、水酸基、カルボキシル基を有する化合物で被覆することが好ましい。また、合成法によっては、原料の熱分解物や金属酸化物が粒子表面を保護し、分散性に寄与する場合もある。熱分解法や化学還元法などの湿式法で作製した場合は、還元剤などがそのまま微粒子の保護剤として作用することがある。
There are various methods for preparing the metal fine particles, but a physical method obtained by pulverizing metal powder by a mechanochemical method, such as a CVD method, a vapor deposition method, a sputtering method, a thermal plasma method, or a laser method. It can be produced by a chemical dry method; a method called a chemical wet method such as a thermal decomposition method, a chemical reduction method, an electrolysis method, an ultrasonic method, a laser ablation method, a supercritical fluid method, or a microwave synthesis method.
In order to make the obtained fine particles into a dispersion liquid, the fine particles are protected with a water-soluble polymer such as polyvinyl pyrrolidone, a protective agent such as a graft copolymer, a surfactant, a thiol group or an amino acid that interacts with a metal. It is preferable to coat with a compound having a group, a hydroxyl group and a carboxyl group. Depending on the synthesis method, the pyrolyzate or metal oxide of the raw material may protect the particle surface and contribute to dispersibility. When produced by a wet method such as a thermal decomposition method or a chemical reduction method, the reducing agent or the like may act as a protective agent for the fine particles as it is.
本発明で用いる微粒子の平均一次粒子径は１〜１００ｎｍの範囲であることが肝要である。平均一次粒子径が１ｎｍ未満であると分散液の分散安定性、導電性の点で不都合があり、平均一次粒子径が１００ｎｍを超えると、融点が高く、十分な焼結が困難となり、高い導電性が得られない。以上の観点から、微粒子の平均一次粒子径は１〜７０ｎｍの範囲が好ましく、さらに２〜５０ｎｍの範囲がより好ましい。ここで、分散液中の微粒子の平均一次粒子径は、透過型電子顕微鏡による観察像から測定される。 It is important that the average primary particle diameter of the fine particles used in the present invention is in the range of 1 to 100 nm. If the average primary particle size is less than 1 nm, there are disadvantages in terms of dispersion stability and conductivity of the dispersion, and if the average primary particle size exceeds 100 nm, the melting point is high and sufficient sintering becomes difficult, resulting in high conductivity. Sex cannot be obtained. From the above viewpoint, the average primary particle diameter of the fine particles is preferably in the range of 1 to 70 nm, and more preferably in the range of 2 to 50 nm. Here, the average primary particle diameter of the fine particles in the dispersion is measured from an image observed with a transmission electron microscope.
微粒子分散液を構成し、上記微粒子を分散させる分散媒としては、水及び／又は有機溶媒を用いることができる。有機溶媒としては、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、グリセリンなどのアルコール類；トルエン、キシレンなどの芳香族炭化水素；アセトン、メチルエチルケトン、メチルイソブチルケトンなどのケトン類；酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル、酢酸イソブチルなどのエステル類；テトラヒドロフラン、ジオキサン、エチレングリコールモノメチルエーテル（メチルセロソルブ）、エチレングリコールモノエチルエーテル（エチルセロソルブ）、エチレングリコールモノブチルエーテル（ブチルセロソルブ）などのエーテル類、ヘキサン等の脂肪族炭化水素、シクロヘキサン等の脂環式炭化水素などが挙げられる。
これらのうち、取り扱いの容易さ、環境性能などの観点から水、アルコール類、エーテル類の分散媒が好ましい。
As a dispersion medium constituting the fine particle dispersion and dispersing the fine particles, water and / or an organic solvent can be used. Organic solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and glycerin; aromatic hydrocarbons such as toluene and xylene; acetone, methyl ethyl ketone Ketones such as methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, and isobutyl acetate; tetrahydrofuran, dioxane, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve) , Ethers such as ethylene glycol monobutyl ether (butyl cellosolve), aliphatic hydrocarbons such as hexane, cyclohexane Such alicyclic hydrocarbons.
Of these, water, alcohols, and ether dispersion media are preferred from the viewpoint of easy handling and environmental performance.
さらに基材への密着性を高めること、造膜性を高めること、印刷適性を付与すること、及び分散性を高めることを目的として、例えばポリエステル樹脂、アクリル樹脂、あるいはウレタン樹脂等を樹脂バインダーとして分散液に添加してもよい。また、高温で焼成した後の基材との密着性あるいは造膜性を維持するために、エチルシリケート及びシリケートオリゴマー等の無機バインダーを使用してもよい。また、必要に応じて、粘度調整剤、表面張力調整剤、あるいは安定剤等を添加してもよい。 Further, for example, polyester resin, acrylic resin, or urethane resin is used as a resin binder for the purpose of enhancing adhesion to a substrate, enhancing film-forming properties, imparting printability, and enhancing dispersibility. It may be added to the dispersion. In addition, an inorganic binder such as ethyl silicate and silicate oligomer may be used in order to maintain adhesion or film-forming property with the base material after firing at a high temperature. Moreover, you may add a viscosity modifier, a surface tension modifier, a stabilizer, etc. as needed.
本発明の微粒子分散液は、固形分濃度が５〜６０質量％の範囲が好ましい。固形分濃度が５質量％以上であると十分な導電性が得られ、６０質量％以下であると、粘度が十分に低く、基材への微粒子分散液の印刷が容易である。以上の観点から、微粒子分散液中の固形分濃度は１０〜５０質量％の範囲がより好ましい。 The fine particle dispersion of the present invention preferably has a solid concentration of 5 to 60% by mass. When the solid content concentration is 5% by mass or more, sufficient conductivity is obtained, and when it is 60% by mass or less, the viscosity is sufficiently low and the fine particle dispersion can be easily printed on the substrate. From the above viewpoint, the solid content concentration in the fine particle dispersion is more preferably in the range of 10 to 50% by mass.
基材上に微粒子分散液を印刷する方法としては特に制限されず、グラビア印刷、スクリーン印刷、スプレーコート、スピンコート、コンマコート、バーコート、ナイフコート、オフセット印刷、フレキソ印刷、インクジェット印刷、ディスペンサ印刷などの方法を用いることができる。これらのうち、微細なパターニングを行うことができるという観点から、グラビア印刷、フレキソ印刷、インクジェット印刷が好ましい。
また、本発明では、基材上に微粒子分散液を所望のパターンに直接印刷することができるため、従来のフォトレジストを用いた手法に比較して、著しく生産性を向上させることができる。
The method for printing the fine particle dispersion on the substrate is not particularly limited, and gravure printing, screen printing, spray coating, spin coating, comma coating, bar coating, knife coating, offset printing, flexographic printing, inkjet printing, dispenser printing. Such a method can be used. Of these, gravure printing, flexographic printing, and inkjet printing are preferable from the viewpoint that fine patterning can be performed.
Further, in the present invention, since the fine particle dispersion can be directly printed on the base material in a desired pattern, productivity can be remarkably improved as compared with a conventional method using a photoresist.
基材上の微粒子分散液は印刷後、通常の方法で乾燥を行ってもよい。具体的には、例えば、通常のオーブン等を用いて、８０〜１８０℃程度の温度で、０．１〜６０分程度加熱して乾燥させることが好ましい。基材が損傷しない範囲であらかじめ加熱乾燥することにより粒子の一部が焼結され、電磁誘導加熱がより進行する。なお、乾燥の温度及び時間については、使用する基材の耐熱性に合わせて適宜変更することができる。
また、乾燥後の印刷部分の膜厚は用途等に応じ、適宜塗布量や微粒子の平均一次粒子径等を変化させて制御することができるが、通常、０．０１〜１００μｍの範囲、好ましくは０．１〜５０μｍの範囲である。
The fine particle dispersion on the substrate may be dried by a usual method after printing. Specifically, for example, it is preferable to dry by heating for about 0.1 to 60 minutes at a temperature of about 80 to 180 ° C. using an ordinary oven or the like. Part of the particles are sintered by heating and drying in advance as long as the substrate is not damaged, and electromagnetic induction heating further proceeds. In addition, about the temperature and time of drying, it can change suitably according to the heat resistance of the base material to be used.
Further, the thickness of the printed portion after drying can be controlled by appropriately changing the coating amount and the average primary particle diameter of the fine particles according to the use etc., but is usually in the range of 0.01 to 100 μm, preferably It is in the range of 0.1 to 50 μm.
次に、本発明における焼成は、微粒子分散液を塗布した基材を電磁誘導加熱により行うものであり、この焼成によって金属微粒子を焼結させる。電磁誘導加熱の具体的方法としては、従来公知の方法を用いることができ、誘導加熱コイルにより発生する磁力線によって、微粒子により形成された膜に誘導電流が生じ、膜の抵抗によって加熱するものである。絶縁性基材には誘導電流が流れないため、基材は加熱されない。基材は加熱コイルに接触させる必要はなく、非接触でも加熱することができる。電磁誘導加熱の条件としては、特に限定されるものではなく、出力０．１〜１０００ｋＷ、周波数５〜１００ｋＨｚの範囲であれば本発明の効果を奏する。また、電磁誘導加熱は、コイル形状に合わせて加熱がなされるため、基板は一定速度で移動させながら加熱することが好ましく、その速度は例えば０．０１〜１００ｍ／minとすることができる。そのため、Ｒｏｌｌ to Ｒｏｌｌの加工装置に設置するのが容易である。
電磁波誘導加熱の条件が上記範囲内であると、微粒子が選択的に加熱され、基材に損傷を与えることがない。また、通常行われる加熱炉や赤外線を利用した加熱において、基材に損傷を与えない条件を選んで焼成した場合に不十分な導電性しか得られない材料に対しても、良好な導電性の膜を形成することができる。
電磁誘導加熱を行う反応炉は、酸化しやすい金属微粒子を焼結させる場合は、酸素が存在すると酸化反応が進行して導電性が低くなるため、窒素ガス、アルゴンガス等を導入するなどして、酸素濃度を低くすることにより、酸化を抑えることが好ましい。
Next, the firing in the present invention is performed by electromagnetic induction heating on the substrate coated with the fine particle dispersion, and the fine metal particles are sintered by this firing. As a specific method of electromagnetic induction heating, a conventionally known method can be used. Inductive current is generated in the film formed of the fine particles by the magnetic lines generated by the induction heating coil, and the film is heated by the resistance of the film. . Since no induced current flows through the insulating substrate, the substrate is not heated. The substrate need not be in contact with the heating coil and can be heated even without contact. The conditions for electromagnetic induction heating are not particularly limited, and the effects of the present invention can be achieved as long as the output is in the range of 0.1 to 1000 kW and the frequency is 5 to 100 kHz. Moreover, since electromagnetic induction heating is performed according to the coil shape, the substrate is preferably heated while being moved at a constant speed, and the speed can be set to 0.01 to 100 m / min, for example. Therefore, it is easy to install in a Roll to Roll processing apparatus.
When the electromagnetic induction heating conditions are within the above range, the fine particles are selectively heated and the substrate is not damaged. In addition, in a heating furnace or infrared heating that is usually performed, even for materials that have insufficient conductivity when fired under conditions that do not damage the substrate, good conductivity A film can be formed.
In a reactor that performs electromagnetic induction heating, when sintering fine metal particles that easily oxidize, if oxygen is present, the oxidation reaction proceeds and the conductivity decreases, so nitrogen gas, argon gas, etc. are introduced. It is preferable to suppress oxidation by lowering the oxygen concentration.
本発明の導電性基板は上述の方法により得ることができるものであり、基材上にパターニングされた導電性薄膜を有する導電性基板であって、導電性薄膜が平均一次粒子径１〜１００ｎｍの金属微粒子が融着した構造を有し、かつ該金属微粒子の密度が該導電性薄膜の厚さ方向に均一である。ここで、微粒子の融着とは、微粒子どうしが焼結、溶融などにより連続の膜を形成している状態のことをいう。全面が金属箔状になっていてもよいし、一部が結合している形状でもよい。
また、微粒子の融着は平面方向及び深さ方向のいずれにも進行し、金属微粒子の密度は導電性薄膜の厚さ方向に均一である。従って、導電性が良好であり、電気的に信頼性の高い配線が得られる。
The conductive substrate of the present invention can be obtained by the above-described method, and is a conductive substrate having a conductive thin film patterned on a base material, and the conductive thin film has an average primary particle diameter of 1 to 100 nm. The metal fine particles have a fused structure, and the density of the metal fine particles is uniform in the thickness direction of the conductive thin film. Here, the fusion of the fine particles refers to a state in which the fine particles form a continuous film by sintering or melting. The whole surface may be in the form of a metal foil, or a shape in which a part is bonded.
Further, the fusion of the fine particles proceeds in both the plane direction and the depth direction, and the density of the metal fine particles is uniform in the thickness direction of the conductive thin film. Therefore, it is possible to obtain a wiring having good conductivity and high electrical reliability.
本発明の導電性基板は、ＪＩＳＫ７１９４規格に準拠して測定した表面抵抗と、導電性薄膜の厚みより算出した体積抵抗率が２．０×１０-6〜２．０×１０-4Ω・cmであり、良好な導電性を示す。特に、金属として平均粒子径１〜３０ｎｍ程度の銀微粒子を用い、金属微粒子分散液の固形分濃度を１０〜２５質量％の範囲に制御し、電磁誘導加熱を行うことにより、２．０×１０-5Ω・cm以下の体積抵抗率を示す。 The conductive substrate of the present invention has a volume resistivity calculated from the surface resistance measured in accordance with the JISK7194 standard and the thickness of the conductive thin film of 2.0 × 10 −6 to 2.0 × 10 −4 Ω · cm. It shows good conductivity. In particular, silver fine particles having an average particle diameter of about 1 to 30 nm are used as the metal, and the solid content concentration of the metal fine particle dispersion is controlled to be in the range of 10 to 25% by mass, and electromagnetic induction heating is performed. It shows a volume resistivity of -5 Ω · cm or less.
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、この例によってなんら限定されるものではない。
（評価方法）
各実施例及び比較例で得られた導電性基板について、体積抵抗率によって評価した。評価方法は以下のとおりである。また、微粒子の平均一次粒子径及び構造観察は以下の方法により行った。
（体積抵抗率の測定方法）
ダイアインスツルメンツ社製の低抵抗率計（商品名、ロレスタＧＰ）を使用し、ＪＩＳＫ７１９４規格に準拠して、体積抵抗率を測定した。
（微粒子の平均一次粒子径）
透過型電子顕微鏡により測定した。
（構造観察）
（株）日立ハイテクノロジー製の走査型電子顕微鏡Ｓ−４５００を用いて、実施例１〜３、比較例１及び２で作製した導電性基板について、膜の表面を観察した。また、実施例３及び比較例２で作製した導電性基板については、基板をミクロトームにより切断し、断面も併せて観察した。表面の観察は倍率５万倍、断面の観察は倍率１０万倍で行った。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.
(Evaluation methods)
About the electroconductive board | substrate obtained by each Example and the comparative example, it evaluated by the volume resistivity. The evaluation method is as follows. Moreover, the average primary particle diameter and structure observation of fine particles were performed by the following method.
(Measurement method of volume resistivity)
Volume resistivity was measured using a low resistivity meter (trade name, Loresta GP) manufactured by Dia Instruments Co., Ltd. in accordance with JISK7194 standard.
(Average primary particle size of fine particles)
It was measured with a transmission electron microscope.
(Structure observation)
Using the scanning electron microscope S-4500 manufactured by Hitachi High-Technology Co., Ltd., the surface of the film was observed for the conductive substrates prepared in Examples 1 to 3 and Comparative Examples 1 and 2. Moreover, about the electroconductive board | substrate produced in Example 3 and Comparative Example 2, the board | substrate was cut | disconnected with the microtome and the cross section was also observed collectively. The surface was observed at a magnification of 50,000, and the cross section was observed at a magnification of 100,000.
実施例１
銀微粒子のアルコール分散液（商品名：ＡＧ−ＩＪ−Ｇ−１００−Ｓ１、キャボット社製、平均一次粒子径４０ｎｍ）を、固形分１５質量％に調整した。続いて、１０ｃｍ角、厚み５０μｍのポリエチレンナフタレートフィルム（商品名：テオネックスＱ８１、帝人デュポンフィルム（株）製）をガラス基板に粘着テープで固定し、スピンコート法により銀微粒子をフィルム上に塗布し、１２０℃のオーブンで３０分間乾燥させた。乾燥膜厚は０．６μｍであり、体積抵抗率は１．０×１０-4Ω・cmであった。続いて、直径１５ｃｍの加熱コイル上から５ｍｍのギャップでセラミックス板を設置した加熱装置にこの基板を設置し、コイルに高周波電源（周波数３０ｋＨｚ）から１０Ａの電流を流し、基板を１ｍ／minの速度でコイル上を非接触で通過させ、電磁誘導加熱した。形成した銀塗膜の体積抵抗率は、９．０×１０-6Ω・ｃｍとなった。基板の表面を走査型電子顕微鏡により観察したところ、図１に示すように、微粒子どうしが溶融・焼結して融着した構造が観察された。また、基材については変形がなく、ダメージを受けていないことが確認された。
Example 1
An alcohol dispersion of silver fine particles (trade name: AG-IJ-G-100-S1, manufactured by Cabot Corporation, average primary particle size 40 nm) was adjusted to a solid content of 15% by mass. Subsequently, a polyethylene naphthalate film (trade name: Teonex Q81, manufactured by Teijin DuPont Films Co., Ltd.) having a 10 cm square and a thickness of 50 μm is fixed to the glass substrate with an adhesive tape, and silver fine particles are applied onto the film by a spin coating method. And dried in an oven at 120 ° C. for 30 minutes. The dry film thickness was 0.6 μm, and the volume resistivity was 1.0 × 10 −4 Ω · cm. Subsequently, this substrate is placed on a heating device in which a ceramic plate is placed with a gap of 5 mm from a heating coil having a diameter of 15 cm. A current of 10 A is supplied to the coil from a high frequency power source (frequency 30 kHz), and the substrate is moved at a speed of 1 m / min. And passed on the coil in a non-contact manner and heated by electromagnetic induction. The volume resistivity of the formed silver coating film was 9.0 × 10 −6 Ω · cm. When the surface of the substrate was observed with a scanning electron microscope, as shown in FIG. 1, a structure in which fine particles were melted and sintered and fused was observed. Further, it was confirmed that the base material was not deformed and was not damaged.
実施例２
実施例１において、ポリエチレンナフタレートフィルムに代えて、ポリエチレンテレフタレートフィルム（商品名：ルミラーＴ６０、東レ（株）製）を用い、実施例１と同様に塗布し、１００℃のオーブンで３０分間乾燥させた。乾燥膜厚は０．６μｍであった。体積抵抗率は７．４×１０-3Ω・cmであった。続いて、実施例１と同様に電磁誘導加熱を行った。形成した銀塗膜の体積抵抗率は、１．５×１０-5Ω・ｃｍとなった。基板の表面を走査型電子顕微鏡により観察したところ、図２に示すように、微粒子どうしが溶融・焼結して融着した構造が観察された。また、基材については変形がなく、ダメージを受けていないことが確認された。
Example 2
In Example 1, instead of the polyethylene naphthalate film, a polyethylene terephthalate film (trade name: Lumirror T60, manufactured by Toray Industries, Inc.) was used and applied in the same manner as in Example 1 and dried in an oven at 100 ° C. for 30 minutes. It was. The dry film thickness was 0.6 μm. The volume resistivity was 7.4 × 10 −3 Ω · cm. Subsequently, electromagnetic induction heating was performed in the same manner as in Example 1. The volume resistivity of the formed silver coating film was 1.5 × 10 −5 Ω · cm. When the surface of the substrate was observed with a scanning electron microscope, as shown in FIG. 2, a structure in which fine particles were melted and sintered and fused was observed. Further, it was confirmed that the base material was not deformed and was not damaged.
比較例１
実施例２において、電磁誘導加熱を加えなかった試料の基板の表面を走査型電子顕微鏡により観察したところ、図３に示すように、微粒子どうしの溶融・焼結は確認できなかった。更に、１５０℃のオーブンで６０分間の加熱を行ったところ、体積抵抗率は９．０×１０-6Ω・ｃｍとなったが、フィルムが熱収縮して変形した。
Comparative Example 1
In Example 2, when the surface of the substrate of the sample to which electromagnetic induction heating was not applied was observed with a scanning electron microscope, melting / sintering between the fine particles could not be confirmed as shown in FIG. Furthermore, heating for 60 minutes in an oven at 150 ° C. resulted in a volume resistivity of 9.0 × 10 −6 Ω · cm, but the film was deformed by heat shrinkage.
実施例３
濃度４０質量％に調整したクエン酸ナトリウム水溶液５００ｍｌに、濃度３０質量％に調整した硫酸第一鉄水溶液２００ｍｌを混合した。この混合液に、濃度１０質量％に調整した硝酸銀水溶液２００ｍｌを添加し、混合攪拌して反応させ、銀微粒子水分散液を得た。続いて、銀微粒子水分散液を、遠心分離機によって分離して、銀微粒子固形物を得た。銀微粒子固形物を水に分散させて洗浄し、再び遠心分離機によって分離して、銀微粒子固形物を得た。銀微粒子固形物を、水、エタノール、１−ブタノールを２：７：１の割合で混合した溶媒に分散し、固形分を１０質量％に調整した。得られた銀微粒子の平均一次粒子径は１５ｎｍであった。続いて、１０ｃｍ角、厚み５０μｍのポリエチレンテレフタレートフィルム（商品名：ルミラーＴ６０、東レ（株）製）をガラス基板に粘着テープで固定し、スピンコート法により銀微粒子をフィルム上に塗布し、１００℃のオーブンで３０分間乾燥させた。乾燥膜厚は０．２μｍであり、体積抵抗率は１．７×１０-3Ω・cmであった。続いて、実施例１と同様に電磁誘導加熱を行った。形成した銀塗膜の体積抵抗率は、８．１×１０-6Ω・ｃｍとなった。基板の表面及び断面を走査型電子顕微鏡により観察したところ、図４に示すように、微粒子どうしが溶融・焼結して融着した構造が観察された。また、基材については変形がなく、ダメージを受けていないことが確認された。
Example 3
To 500 ml of an aqueous sodium citrate solution adjusted to a concentration of 40% by mass, 200 ml of an aqueous ferrous sulfate solution adjusted to a concentration of 30% by mass was mixed. To this mixed solution, 200 ml of an aqueous silver nitrate solution adjusted to a concentration of 10% by mass was added, and the mixture was stirred and reacted to obtain a silver fine particle aqueous dispersion. Subsequently, the silver fine particle aqueous dispersion was separated by a centrifugal separator to obtain a silver fine particle solid. The silver fine particle solid was dispersed in water, washed, and again separated by a centrifuge to obtain a silver fine particle solid. The silver fine particle solid was dispersed in a solvent in which water, ethanol, and 1-butanol were mixed at a ratio of 2: 7: 1, and the solid content was adjusted to 10% by mass. The average primary particle diameter of the obtained silver fine particles was 15 nm. Subsequently, a polyethylene terephthalate film (trade name: Lumirror T60, manufactured by Toray Industries, Inc.) having a 10 cm square and a thickness of 50 μm was fixed to the glass substrate with an adhesive tape, and silver fine particles were applied on the film by a spin coating method. In the oven for 30 minutes. The dry film thickness was 0.2 μm, and the volume resistivity was 1.7 × 10 −3 Ω · cm. Subsequently, electromagnetic induction heating was performed in the same manner as in Example 1. The volume resistivity of the formed silver coating film was 8.1 × 10 −6 Ω · cm. When the surface and cross section of the substrate were observed with a scanning electron microscope, as shown in FIG. 4, a structure in which fine particles were melted and sintered and fused was observed. Further, it was confirmed that the substrate was not deformed and not damaged.
比較例２
実施例３において、電磁誘導加熱を加えなかった試料の基板の表面及び断面を走査型電子顕微鏡により観察したところ、図５に示すように、微粒子どうしの溶融・焼結は確認できなかった。更に、１５０℃のオーブンで６０分間の加熱を行ったところ、体積抵抗率は１．３×１０-5Ω・ｃｍとなったが、フィルムが熱収縮して変形した。
Comparative Example 2
In Example 3, when the surface and cross section of the substrate of the sample to which electromagnetic induction heating was not applied were observed with a scanning electron microscope, melting / sintering between the fine particles could not be confirmed as shown in FIG. Furthermore, when heating was performed in an oven at 150 ° C. for 60 minutes, the volume resistivity became 1.3 × 10 −5 Ω · cm, but the film was deformed by heat shrinkage.
実施例４
銅微粒子の分散液（商品名：Ｃｕメタルインク、アルバックマテリアル（株）製、平均一次粒子径５ｎｍ）を、固形分３０質量％に調整した。続いて、１０ｃｍ角、厚み５０μｍのポリエチレンナフタレートフィルム（商品名：テオネックスＱ８１、帝人デュポンフィルム（株）製）をガラス基板に粘着テープで固定し、スピンコート法により銅微粒子をフィルム上に塗布し、１５０℃のオーブンで３０分間乾燥させた。乾燥膜厚は１．０μｍであった。乾燥した膜に導電性は確認されなかった。続いて、実施例１と同様の電磁誘導加熱装置を真空炉内に設置して、ロータリーポンプで減圧した後、窒素ガスを大気圧まで導入した。その後、電磁誘導加熱を行った。形成した銅塗膜の体積抵抗率は、２．０×１０-5Ω・ｃｍとなった。基材については変形がなく、ダメージを受けていないことが確認された。
Example 4
A dispersion of copper fine particles (trade name: Cu metal ink, manufactured by ULVAC Material Co., Ltd., average primary particle size of 5 nm) was adjusted to a solid content of 30% by mass. Subsequently, a polyethylene naphthalate film (trade name: Teonex Q81, manufactured by Teijin DuPont Films Co., Ltd.) having a 10 cm square and a thickness of 50 μm is fixed to the glass substrate with an adhesive tape, and copper fine particles are applied onto the film by a spin coating method. And dried in an oven at 150 ° C. for 30 minutes. The dry film thickness was 1.0 μm. No conductivity was confirmed in the dried film. Subsequently, an electromagnetic induction heating device similar to that in Example 1 was installed in a vacuum furnace, and after reducing the pressure with a rotary pump, nitrogen gas was introduced to atmospheric pressure. Thereafter, electromagnetic induction heating was performed. The volume resistivity of the formed copper coating film was 2.0 × 10 −5 Ω · cm. It was confirmed that the substrate was not deformed and not damaged.
比較例３
実施例４において、電磁誘導加熱を行う前の試料を、窒素ガス雰囲気に置換したオーブンにて、２００℃で１８０分間の加熱を行ったところ、体積抵抗率は８．０×１０-4Ω・ｃｍまで低下したが、１０-5Ω・ｃｍ台とすることはできなかった。また、フィルムは熱収縮して変形した。
Comparative Example 3
In Example 4, when the sample before electromagnetic induction heating was heated at 200 ° C. for 180 minutes in an oven substituted with a nitrogen gas atmosphere, the volume resistivity was 8.0 × 10 −4 Ω · Although it decreased to cm, it could not be in the 10 −5 Ω · cm range. Further, the film was deformed by heat shrinkage.
実施例５
ＩＴＯ微粒子のアルコール分散液（三菱マテリアル（株）製、平均一次粒子径２０ｎｍ、固形分１５質量％）を、スピンコート法により、ガラス基板に粘着テープで固定した１０ｃｍ角、厚み５０μｍのポリエチレンテレフタレートフィルム（商品名：ルミラーＴ６０、東レ（株）製）に塗布し、１２０℃のオーブンで３０分間乾燥させた。乾燥膜厚は０．４μｍであり、体積抵抗率は４０Ω・cmであった。続いて、基板の移動速度を１ｍ／minから０．１ｍ／minの速度に変更したこと以外は実施例１と同様にして、電磁誘導加熱を行った。形成したＩＴＯ塗膜の体積抵抗率は２Ω・cmとなった。また、フィルムの変形などのダメージはなかった。
Example 5
Polyethylene terephthalate film of 10 cm square and 50 μm thickness, in which an alcohol dispersion of ITO fine particles (Mitsubishi Materials Co., Ltd., average primary particle size 20 nm, solid content 15% by mass) is fixed to a glass substrate with an adhesive tape by spin coating. (Product name: Lumirror T60, manufactured by Toray Industries, Inc.) and dried in an oven at 120 ° C. for 30 minutes. The dry film thickness was 0.4 μm and the volume resistivity was 40 Ω · cm. Subsequently, electromagnetic induction heating was performed in the same manner as in Example 1 except that the moving speed of the substrate was changed from 1 m / min to 0.1 m / min. The volume resistivity of the formed ITO coating film was 2 Ω · cm. Also, there was no damage such as film deformation.
比較例４
実施例５において、電磁誘導加熱に代えて、１５０℃のオーブンで１８０分間の加熱を行ったが、体積抵抗率は４０Ω・cmと変化がみられなかった。また、フィルムは熱収縮して変形した。
Comparative Example 4
In Example 5, instead of electromagnetic induction heating, heating was performed in an oven at 150 ° C. for 180 minutes, but the volume resistivity did not change as 40 Ω · cm. Further, the film was deformed by heat shrinkage.
上記実施例及び比較例の結果を第１表にまとめる。本発明の方法によれば、基材として耐熱性の低い材料を用いても、基材に損傷を与えずに導電性薄膜を形成することができ、実用上十分な導電性を有する導電性基板を高い生産性で製造し得ることがわかる。 The results of the above examples and comparative examples are summarized in Table 1. According to the method of the present invention, it is possible to form a conductive thin film without damaging the base material even if a material having low heat resistance is used as the base material, and a conductive substrate having practically sufficient conductivity. It can be seen that can be manufactured with high productivity.
＊表中「ＰＥＮ」は「ポリエチレンナフタレートフィルム」、「ＰＥＴ」は「ポリエチレンテレフタレートフィルム」、「ＩＴＯ」は「スズドープ酸化インジウム」を表わす。 * In the table, “PEN” represents “polyethylene naphthalate film”, “PET” represents “polyethylene terephthalate film”, and “ITO” represents “tin-doped indium oxide”.
本発明によれば、基材として耐熱性の低い材料を用いることができ、かつ実用上十分な導電性を有する導電性基板及び該導電性基板を高い生産性で製造する方法を提供することができる。本発明の導電性基板は、金属微粒子又は金属化合物の微粒子を分散させた塗料で回路パターン等を直接基材に印刷することができるので、フォトレジスト等を用いる従来の方法に比較して生産性がきわめて高い。また、微粒子を分散させた塗料を塗布する基材が制限されず、例えば、汎用のガラスやＰＥＴ等のプラスチックフィルムを基材として用いることができ、フレキシブルプリント配線板、ＲＦＩＤタグアンテナ、メンブレンスイッチ、電磁波遮蔽材、フラットパネルディスプレイ用の電極及び配線材料など種々の用途に応用展開することができる。 According to the present invention, it is possible to provide a conductive substrate that can use a material having low heat resistance as a base material and that has practically sufficient conductivity, and a method for manufacturing the conductive substrate with high productivity. it can. Since the conductive substrate of the present invention can directly print a circuit pattern or the like on a base material with a paint in which metal fine particles or metal compound fine particles are dispersed, productivity is higher than conventional methods using a photoresist or the like. Is extremely high. Moreover, the base material to which the coating material in which the fine particles are dispersed is not limited, and for example, a plastic film such as general-purpose glass or PET can be used as the base material. The present invention can be applied to various applications such as electromagnetic shielding materials, electrodes for flat panel displays, and wiring materials.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008022766A JP5446097B2 (en) | 2008-02-01 | 2008-02-01 | Conductive substrate and method for manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008022766A JP5446097B2 (en) | 2008-02-01 | 2008-02-01 | Conductive substrate and method for manufacturing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2009181946A true JP2009181946A (en) | 2009-08-13 |
| JP5446097B2 JP5446097B2 (en) | 2014-03-19 |
Family
ID=41035729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008022766A Expired - Fee Related JP5446097B2 (en) | 2008-02-01 | 2008-02-01 | Conductive substrate and method for manufacturing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5446097B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011083813A1 (en) * | 2010-01-08 | 2011-07-14 | 東洋紡績株式会社 | Electrically conductive paste and metal thin film |
| JP2013016428A (en) * | 2011-07-06 | 2013-01-24 | Shin Etsu Polymer Co Ltd | Method for forming insulating part and method for manufacturing conductive pattern formation substrate |
| JP2013522026A (en) * | 2010-03-19 | 2013-06-13 | オウェンス ブロックウェイ グラス コンテナー インコーポレイテッド | Hardened coating on glass container |
| JP2015076611A (en) * | 2013-10-07 | 2015-04-20 | ザ・ボーイング・カンパニーＴｈｅＢｏｅｉｎｇ Ｃｏｍｐａｎｙ | Ecological method for constructing circuit boards |
| JP2016025257A (en) * | 2014-07-23 | 2016-02-08 | コニカミノルタ株式会社 | Conductive pattern manufacturing device |
| JPWO2016111133A1 (en) * | 2015-01-06 | 2017-08-17 | 株式会社フジクラ | Conductor layer manufacturing method and wiring board |
| KR101786722B1 (en) | 2010-07-13 | 2017-10-18 | 소에이 가가쿠 고교 가부시키가이샤 | Conductive paste |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10301415A (en) * | 1997-04-25 | 1998-11-13 | Canon Inc | Heating device and image forming device |
| JP2006269984A (en) * | 2005-03-25 | 2006-10-05 | Furukawa Electric Co Ltd:The | Method for baking metallic particle for mutually fusing metallic particle by high-frequency electromagnetic-wave irradiation and electronic part and material for baking metallic particle manufactured by using its method |
| JP2007027487A (en) * | 2005-07-19 | 2007-02-01 | Dowa Holdings Co Ltd | Method for forming conductive film or wiring |
| JP2007134239A (en) * | 2005-11-11 | 2007-05-31 | Daiken Kagaku Kogyo Kk | Conductive paste and electrode structure |
| JP2008243946A (en) * | 2007-03-26 | 2008-10-09 | Dainippon Printing Co Ltd | Conductive substrate and its manufacturing method |
-
2008
- 2008-02-01 JP JP2008022766A patent/JP5446097B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10301415A (en) * | 1997-04-25 | 1998-11-13 | Canon Inc | Heating device and image forming device |
| JP2006269984A (en) * | 2005-03-25 | 2006-10-05 | Furukawa Electric Co Ltd:The | Method for baking metallic particle for mutually fusing metallic particle by high-frequency electromagnetic-wave irradiation and electronic part and material for baking metallic particle manufactured by using its method |
| JP2007027487A (en) * | 2005-07-19 | 2007-02-01 | Dowa Holdings Co Ltd | Method for forming conductive film or wiring |
| JP2007134239A (en) * | 2005-11-11 | 2007-05-31 | Daiken Kagaku Kogyo Kk | Conductive paste and electrode structure |
| JP2008243946A (en) * | 2007-03-26 | 2008-10-09 | Dainippon Printing Co Ltd | Conductive substrate and its manufacturing method |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011083813A1 (en) * | 2010-01-08 | 2011-07-14 | 東洋紡績株式会社 | Electrically conductive paste and metal thin film |
| CN102696075A (en) * | 2010-01-08 | 2012-09-26 | 东洋纺织株式会社 | Electrically conductive paste and metal thin film |
| JP5692066B2 (en) * | 2010-01-08 | 2015-04-01 | 東洋紡株式会社 | Conductive paste and metal thin film |
| CN102696075B (en) * | 2010-01-08 | 2015-11-25 | 东洋纺织株式会社 | Conductive paste and metallic film |
| KR101774069B1 (en) | 2010-01-08 | 2017-09-01 | 도요보 가부시키가이샤 | Electrically conductive paste and metal thin film |
| JP2013522026A (en) * | 2010-03-19 | 2013-06-13 | オウェンス ブロックウェイ グラス コンテナー インコーポレイテッド | Hardened coating on glass container |
| JP2016137489A (en) * | 2010-03-19 | 2016-08-04 | オウェンス ブロックウェイ グラス コンテナー インコーポレイテッド | Hardening coating on glass vessel |
| KR101786722B1 (en) | 2010-07-13 | 2017-10-18 | 소에이 가가쿠 고교 가부시키가이샤 | Conductive paste |
| JP2013016428A (en) * | 2011-07-06 | 2013-01-24 | Shin Etsu Polymer Co Ltd | Method for forming insulating part and method for manufacturing conductive pattern formation substrate |
| JP2015076611A (en) * | 2013-10-07 | 2015-04-20 | ザ・ボーイング・カンパニーＴｈｅＢｏｅｉｎｇ Ｃｏｍｐａｎｙ | Ecological method for constructing circuit boards |
| JP2016025257A (en) * | 2014-07-23 | 2016-02-08 | コニカミノルタ株式会社 | Conductive pattern manufacturing device |
| JPWO2016111133A1 (en) * | 2015-01-06 | 2017-08-17 | 株式会社フジクラ | Conductor layer manufacturing method and wiring board |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5446097B2 (en) | 2014-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5982033B2 (en) | Metal fine particle dispersion, copper fine particle dispersion, method for producing copper fine particle dispersion, and method for producing conductive substrate | |
| JP5446097B2 (en) | Conductive substrate and method for manufacturing the same | |
| JP5387034B2 (en) | Conductive substrate | |
| KR101157854B1 (en) | Method for forming transparent conductive film and transparent electrode | |
| JP2008243946A (en) | Conductive substrate and its manufacturing method | |
| JP5067426B2 (en) | Copper wiring pattern forming method and copper oxide particle dispersion used therefor | |
| JP5332759B2 (en) | Method for manufacturing conductive substrate and conductive substrate | |
| JP2005531679A (en) | Low temperature sintered conductive nano ink and method for producing the same | |
| JP2012214898A (en) | Silver-coated copper powder and method for producing the same, and conductive paste, conductive adhesive agent, conductive film, and electric circuit containing the silver-coated copper powder | |
| TWI364402B (en) | ||
| WO2014054618A1 (en) | Silver hybrid copper powder, method for producing same, conductive paste containing silver hybrid copper powder, conductive adhesive, conductive film and electrical circuit | |
| JP5849426B2 (en) | Metal oxide fine particle dispersion, conductive substrate and method for producing the same | |
| JP2012174374A (en) | Method for producing conductive coating film and conductive coating film | |
| JP2009088122A (en) | Conductive substrate | |
| JP2015214722A (en) | Method for manufacturing copper fine particle sintered body and conductive substrate | |
| JP2009278045A (en) | Workpiece and method for producing the same | |
| JP5354037B2 (en) | Method for manufacturing conductive substrate | |
| JP5151622B2 (en) | Method for manufacturing conductive substrate and conductive substrate | |
| KR20160056861A (en) | digitizer flexible printed circuits board using light sintering and method for manufacturing thereof | |
| JP2010277974A (en) | Conductive thin film substrate, and method of manufacturing the same | |
| JP5402139B2 (en) | Antenna pattern and method of manufacturing antenna pattern | |
| JP2016135562A (en) | Laminate, production method of conductive substrate using the same, production method of electronic device, and transfer tool | |
| JP5531394B2 (en) | Semiconductor substrate manufacturing method and semiconductor substrate obtained by the method | |
| JP5338235B2 (en) | Manufacturing method of conductive substrate and conductive substrate obtained by the method | |
| JP2012174375A (en) | Method for producing conductive coating film and conductive coating film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20101206 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20121218 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130214 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20130903 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20131008 |
|
| A911 | Transfer of reconsideration by examiner before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20131113 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20131203 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20131216 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |