JPH06157945A - Electrically conductive paint curable with electron ray - Google Patents
Electrically conductive paint curable with electron rayInfo
- Publication number
- JPH06157945A JPH06157945A JP30697292A JP30697292A JPH06157945A JP H06157945 A JPH06157945 A JP H06157945A JP 30697292 A JP30697292 A JP 30697292A JP 30697292 A JP30697292 A JP 30697292A JP H06157945 A JPH06157945 A JP H06157945A
- Authority
- JP
- Japan
- Prior art keywords
- electron beam
- electron ray
- electrically conductive
- meth
- polymerizable compound
- 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.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
- H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は電子線硬化型樹脂組成物
をバインダ−とし電子線のみで硬化することを特徴とす
る電子線硬化型導電性ペ−ストに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electron beam curable conductive paste which comprises an electron beam curable resin composition as a binder and is cured only by an electron beam.
【０００２】[0002]
【従来の技術及び問題点】従来、導体を形成する導電性
ペ−ストとしては金、銀、白金、パラジウムなどの貴金
属微粉末と熱硬化型樹脂組成物あるいは熱可塑性樹脂を
バインダ−とした（ポリマ−シックフィルム、以下ＰＴ
Ｆ）ペ−スト、あるいはガラス粉をバインダ−とし焼成
する（サ−メットシックフィルム、以下ＣＴＦ）ペ−ス
トがあり両者とも硬化に熱を要するため加熱、冷却など
の熱履歴によるプリント基板の反り、変形、収縮などの
大きな問題点を抱えているのが現状である。そこで室温
付近の温度で導電性ペ−ストを硬化させる電子線硬化型
導電性ペ−ストの出現が所望されているが、まだ工業的
な利用に至っていない。電子線硬化型樹脂組成物をバイ
ンダ−とし銀粉のごとき導電性粉末を混合した組成物を
用いる方法が研究されているが、同組成物を適当な方法
で被着体に塗膜として塗布して電子線照射しても見かけ
上硬化はするものの、初期導電性あるいは、成膜時の接
着性、塗膜の劣化による長期信頼性の欠如などの問題点
を有していた。例えば、特開昭５７−１８７９９３号公
報に、電子線硬化型の導電性塗料による導電路形成方法
が示されている。これは、導電性樹脂組成物の絶縁基板
に対する接着性不良や、耐久性の悪さの問題があり、未
だ実用になっていない。2. Description of the Related Art Conventionally, as a conductive paste for forming a conductor, fine powder of precious metal such as gold, silver, platinum, palladium and a thermosetting resin composition or a thermoplastic resin has been used as a binder ( Polymer-thick film, hereinafter PT
F) There is a paste or baking using glass powder as a binder (cermet thick film, hereinafter CTF), and both require heat to cure, so the warpage of the printed circuit board due to heat history such as heating and cooling. Currently, there are major problems such as deformation and shrinkage. Therefore, the emergence of an electron beam curable conductive paste which cures the conductive paste at a temperature near room temperature is desired, but it has not yet been industrially utilized. A method of using a composition in which an electron beam curable resin composition is used as a binder and conductive powder such as silver powder is studied, but the composition is applied to an adherend as a coating film by an appropriate method. Although it is apparently cured by electron beam irradiation, it has problems such as initial conductivity, adhesiveness during film formation, and lack of long-term reliability due to deterioration of the coating film. For example, Japanese Patent Application Laid-Open No. 57-187993 discloses a method for forming a conductive path using an electron beam curable conductive coating material. This has not been put to practical use yet because of problems such as poor adhesion of the conductive resin composition to the insulating substrate and poor durability.
【０００３】[0003]
【発明が解決しようとする課題】しかるに本発明は、こ
の様な現状を顧みて行われたものであり電子線で硬化
し、初期の導電性、接着性も良好であり、長期信頼性を
も有する電子線硬化型導電性ペ−ストを提供するもので
ある。すなわち、電子線による硬化は紫外線による硬化
の場合に必要である光開始剤や増感剤を多量に使用しな
くてもよいため硬化後の物性を損なうことがない。However, the present invention has been made in consideration of such a situation as described above, and it is cured by an electron beam and has good initial conductivity and adhesiveness, and long-term reliability. The present invention provides an electron beam curable conductive paste. That is, the curing by electron beam does not impair the physical properties after curing because it is not necessary to use a large amount of photoinitiator or sensitizer, which is necessary in the case of curing by ultraviolet rays.
【０００４】[0004]
【課題を解決するための手段】本発明者らは鋭意研究し
た結果、分子内に少なくとも１個以上の（メタ）アクリ
ルアミド基を有する電子線重合性化合物（Ｂ１）を必須
成分とする電子線硬化型樹脂組成物（Ｂ）をバインダ−
として用いれば導電性微粉末（Ａ）との分散性も良好で
あり電子線照射により内部まで均一に硬化し、硬化後の
物性も優れた電子線硬化型導電性ペ−ストが得られるこ
とを見いだし、この知見に基づいて本発明をなすに至っ
た。Means for Solving the Problems As a result of intensive studies by the present inventors, electron beam curing containing an electron beam polymerizable compound (B1) having at least one (meth) acrylamide group in the molecule as an essential component. Binder of the resin composition (B)
When used as the above, it is possible to obtain an electron beam-curable conductive paste which has good dispersibility with the conductive fine powder (A), is uniformly cured to the inside by electron beam irradiation, and has excellent physical properties after curing. The present invention has been found out, and the present invention has been completed based on this finding.
【０００５】本発明で使用する導電性微粉末（Ａ）と
は、金、銀、銅、白金、パラジウム、ニッケルなどの金
属粉のほかに無機物、プラスチック、セラミックスなど
の表面を上記金属で被覆したものなどを挙げることがで
きる。その含有率は本発明における電子線硬化型導電性
ペ−ストの４０〜９５重量％であることが好ましく、更
に好ましくは５０〜９０重量％である。含有率が４０重
量％未満の場合は、硬化物の導電性が低下し、一方、９
５重量％を越える場合は電子線硬化型導電性ペ−ストの
粘度が著しく高くなり取扱いが困難となるとともに電子
線の透過性が悪くなるため硬化物の物性が低下する。The conductive fine powder (A) used in the present invention includes metal powders such as gold, silver, copper, platinum, palladium and nickel, as well as the surfaces of inorganic materials, plastics, ceramics and the like coated with the above metals. You can list things such as things. The content thereof is preferably 40 to 95% by weight, more preferably 50 to 90% by weight of the electron beam-curable conductive paste in the present invention. If the content is less than 40% by weight, the conductivity of the cured product will decrease, while
If it exceeds 5% by weight, the viscosity of the electron beam-curable conductive paste becomes extremely high, making it difficult to handle and impairing the electron beam permeability, so that the physical properties of the cured product deteriorate.
【０００６】本発明でいう分子内に少なくとも１個以上
の（メタ）アクリルアミド基を有する電子線重合性化合
物（Ｂ１）については特に制限はない。例えば、分子内
に少なくとも１個以上の１級または２級のアミノ基を有
するアミン化合物のアミノ基を（メタ）アクリロイル化
することで容易に得ることができる。これらアミン化合
物の例を挙げるとエチレンジアミン、ジエチレントリア
ミン、トリエチレンテトラミン、テトラエチレンペンタ
ミン、ペンタエチレンヘキサミンなどのエチレンアミン
類、ピペリジン、２−メチルピペリジン、４−アミノメ
チルピペリジン、Ｎ−アミノプロピル−４−ピペコリン
などのピペリジン誘導体、ピペラジン、２−メチルピペ
ラジンなどのピペラジン誘導体、モルフォリン、Ｎ−ア
ミノプロピルモルフォリンなどのモルフォリン誘導体、
アンモニア、モノメチルアミン、ジメチルアミン、ジエ
チルアミン、３−エトキシプロピルアミン、ピロリジ
ン、シクロヘキシルアミン、プロピレンジアミン、ヘキ
サメチレンジアミン、１，４−シクロヘキサンジアミ
ン、ｏ−フェニレンジアミン、ｐ−フェニレンジアミ
ン、トルエン−２，４−ジアミン、４，４’−ジフェニ
ルメタンジアミン、ポリオキシプロピレンジアミン、
Ｎ，Ｎ−ジメチルエチレンジアミン、Ｎ，Ｎ−ジメチル
−１，３−プロパンジアミン、イソホロンジアミン、イ
ミノビスプロピルアミン、１，２−シクロヘキサンジア
ミン、１級または２級のアミノ基を有するポリシロキサ
ン、ポリブタジエン化合物などのアミン化合物、さらに
は両末端がアミンなどのプレポリマ−などである。さら
には（メタ）アクリルアミド基を有する反応性モノマ−
を用いて電子線重合性化合物（Ｂ１）を得ることもでき
る。例えば、Ｎ−メチロ−ルアクリルアミドとポリエチ
レングリコ−ルから脱水反応で得られる反応縮合物、Ｎ
−メチロ−ルアクリルアミドとヘキサメチレンジイソシ
アネ−トとの付加反応で得られる反応付加物などが挙げ
られる。これら電子線重合性化合物（Ｂ１）は単独また
は２種以上併用して使用される。（但し、（メタ）アク
リルアミド基はメタクリルアミド基およびアクリルアミ
ド基を示す。）The electron beam polymerizable compound (B1) having at least one or more (meth) acrylamide group in the molecule referred to in the present invention is not particularly limited. For example, it can be easily obtained by (meth) acryloylating an amino group of an amine compound having at least one primary or secondary amino group in the molecule. Examples of these amine compounds include ethyleneamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine, piperidine, 2-methylpiperidine, 4-aminomethylpiperidine, N-aminopropyl-4-. Piperidine derivatives such as pipecoline, piperazine, piperazine derivatives such as 2-methylpiperazine, morpholine, morpholine derivatives such as N-aminopropylmorpholine,
Ammonia, monomethylamine, dimethylamine, diethylamine, 3-ethoxypropylamine, pyrrolidine, cyclohexylamine, propylenediamine, hexamethylenediamine, 1,4-cyclohexanediamine, o-phenylenediamine, p-phenylenediamine, toluene-2,4 -Diamine, 4,4'-diphenylmethanediamine, polyoxypropylenediamine,
N, N-dimethylethylenediamine, N, N-dimethyl-1,3-propanediamine, isophoronediamine, iminobispropylamine, 1,2-cyclohexanediamine, polysiloxane having a primary or secondary amino group, polybutadiene compound And a prepolymer having amines at both ends. Furthermore, a reactive monomer having a (meth) acrylamide group
Can also be used to obtain the electron beam polymerizable compound (B1). For example, a reaction condensate obtained by dehydration reaction from N-methylolacrylamide and polyethylene glycol, N
-Reaction adducts obtained by addition reaction of methylol acrylamide and hexamethylene diisocyanate, etc. may be mentioned. These electron beam polymerizable compounds (B1) are used alone or in combination of two or more. (However, the (meth) acrylamide group represents a methacrylamide group and an acrylamide group.)
【０００７】本発明でいう電子線重合性化合物（Ｂ２）
については特に制限はない。例えば、（１）スチレン、
α−メチルスチレンなどのスチレン系化合物、（２）メ
チル（メタ）アクリレ−ト、エチル（メタ）アクリレ−
ト、テトラヒドロフルフリル（メタ）アクリレ−トなど
のモノ（メタ）アクリレ−ト化合物、（３）エチレング
リコ−ルジ（メタ）アクリレ−ト、１，６−ヘキサンジ
オ−ル（メタ）アクリレ−トなどのアルキレングリコ−
ルジ（メタ）アクリレ−ト化合物、（４）トリメチロ−
ルプロパントリ（メタ）アクリレ−ト、ペンタエリスリ
ト−ルテトラ（メタ）アクリレ−トなどの多価（メタ）
アクリレ−ト化合物などが挙げられ、単独または２種以
上併用して使用される。（但し、（メタ）アクリレ−ト
はメタクリレ−トおよびアクリレ−トを示す。）The electron beam polymerizable compound (B2) referred to in the present invention
There is no particular limitation. For example, (1) styrene,
Styrene compounds such as α-methylstyrene, (2) methyl (meth) acrylate, ethyl (meth) acrylate
, Mono (meth) acrylate compounds such as tetrahydrofurfuryl (meth) acrylate, (3) ethylene glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate, etc. Alkylene glyco-
Luge (meth) acrylate compound, (4) trimethylo-
Polypropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, etc.
Examples thereof include acrylate compounds, which may be used alone or in combination of two or more. (However, (meth) acrylate represents methacrylate and acrylate.)
【０００８】本発明で使用する電子線硬化型樹脂組成物
（Ｂ）中電子線重合性化合物（Ｂ１）と電子線重合性化
合物（Ｂ２）との混合比は電子線重合性化合物（Ｂ
１）：電子線重合性化合物（Ｂ２）＝１００：０〜１
０：９０（重量比）であることが好ましく、更に好まし
くは電子線重合性化合物（Ｂ２）が７５重量％以下であ
ることが好ましい。電子線重合性化合物（Ｂ２）が９０
重量％を超えると電子線硬化型樹脂組成物（Ｂ）が十分
重合することができず硬化後の物性が低下する。なお、
電子線重合性化合物（Ｂ１）または（Ｂ２）が固体の場
合には他の液体である電子線重合性化合物（Ｂ１）また
は（Ｂ２）を混合することで電子線硬化型樹脂組成物
（Ｂ）の成分として用いることができるのでなんら問題
はない。In the electron beam curable resin composition (B) used in the present invention, the mixing ratio of the electron beam polymerizable compound (B1) and the electron beam polymerizable compound (B2) is such that the electron beam polymerizable compound (B
1): electron beam polymerizable compound (B2) = 100: 0-1
It is preferably 0:90 (weight ratio), and more preferably 75% by weight or less of the electron beam polymerizable compound (B2). 90 electron beam polymerizable compound (B2)
If the content exceeds 5% by weight, the electron beam curable resin composition (B) cannot be sufficiently polymerized and the physical properties after curing deteriorate. In addition,
When the electron beam polymerizable compound (B1) or (B2) is a solid, the electron beam polymerizable compound (B1) or (B2) which is another liquid is mixed to obtain an electron beam curable resin composition (B). Since it can be used as a component of, there is no problem.
【０００９】電子線照射の条件については特に制限はな
く、２〜３０Ｍｒａｄの条件が一般的である。There are no particular restrictions on the electron beam irradiation conditions, and conditions of 2 to 30 Mrad are common.
【００１０】被着体の材質としては、紙フェノ−ル、ガ
ラスエポキシ、アルミナ、ホ−ロ、ベリリア、窒化アル
ミニウム、炭化珪素、ＰＥＴ、プラスチックなどがあり
これらも特別な制限はない。Materials for the adherend include paper phenol, glass epoxy, alumina, hollow, beryllia, aluminum nitride, silicon carbide, PET, and plastic, and there is no particular limitation.
【００１１】[0011]
【作用】本発明における電子線硬化型樹脂組成物の重合
速度は市販の電子線硬化型樹脂の中で重合速度が速いと
されているアクリレ−ト系樹脂のそれより格段に速い。
よって、本発明による電子線硬化型導電性組成物を用い
れば塗膜内部まで均一に硬化し、硬化後の物性も優れた
導電性硬化物が得られる。The rate of polymerization of the electron beam curable resin composition of the present invention is significantly higher than that of the acrylate resin, which is said to have a higher polymerization rate among commercially available electron beam curable resins.
Therefore, when the electron beam curable conductive composition according to the present invention is used, a conductive cured product can be obtained which is cured evenly inside the coating film and has excellent physical properties after curing.
【００１２】[0012]
【実施例】以下、実施例により本発明を更に詳しく説明
するが、もちろん、本発明はこれらの実施例によってな
んら限定されるものではない。なお、実施例中に部とあ
るのは重量部を意味する。EXAMPLES The present invention will be described in more detail below with reference to examples, but of course the present invention is not limited to these examples. In the examples, "parts" means "parts by weight".
【００１３】[0013]
【製造例１】メチルイミノビスプロピルアミン（広栄化
学工業（株）製）のアミノ基をアクリロイル化し２官能
のアクリルアミド樹脂を調製した。上記アクリルアミド
樹脂７０部、エポキシアクリレ−ト（昭和高分子
（株）、SP-4010）２０部、２−ヒドロキシエチルアク
リレ−ト１０部、Ａｇｃ−Ｂ（福田金属箔粉工業（株）
製、鱗片状銀粉）３００部を３本ロ−ルでよく混錬し電
子線硬化型導電性ペ−スト（Ｉ）を得た。Production Example 1 A bifunctional acrylamide resin was prepared by acryloylating the amino group of methyliminobispropylamine (manufactured by Koei Chemical Industry Co., Ltd.). 70 parts of the above acrylamide resin, 20 parts of epoxy acrylate (Showa Polymer Co., Ltd., SP-4010), 10 parts of 2-hydroxyethyl acrylate, Agc-B (Fukuda Metal Foil & Powder Co., Ltd.)
300 parts of scaly silver powder) was well kneaded with 3 rolls to obtain an electron beam-curable conductive paste (I).
【００１４】[0014]
【製造例２】ジエチレントリアミン（関東電化工業
（株）製）のアミノ基をアクリロイル化し３官能のアク
リルアミド樹脂を調製した。上記アクリルアミド樹脂７
０部、ペンタエリスリト−ルテトラアクリレ−ト２０
部、２−ヒドロキシエチルアクリレ−ト１０部、Ａｇｃ
−Ｂ（福田金属箔粉工業（株）製、鱗片状銀粉）３００
部を３本ロ−ルでよく混錬し電子線硬化型導電性ペ−ス
ト（ＩＩ）を得た。[Production Example 2] A trifunctional acrylamide resin was prepared by acryloylating the amino group of diethylenetriamine (produced by Kanto Denka Kogyo Co., Ltd.). Acrylamide resin 7
0 parts, pentaerythritol tetraacrylate 20
Part, 2-hydroxyethyl acrylate 10 parts, Agc
-B (scaly silver powder manufactured by Fukuda Metal Foil & Powder Co., Ltd.) 300
The parts were well kneaded with 3 rolls to obtain an electron beam-curable conductive paste (II).
【００１５】[0015]
【製造例３】イミノビスプロピルアミン（広栄化学工業
（株）製）のアミノ基をアクリロイル化し３官能のアク
リルアミド樹脂を調製した。上記アクリルアミド樹脂７
０部、エポキシアクリレ−ト（昭和高分子（株）、SP-4
010）２０部、２−ヒドロキシエチルアクリレ−ト１０
部、Ａｇｃ−Ｂ（福田金属箔粉工業（株）製、鱗片状銀
粉）３００部を３本ロ−ルでよく混錬し電子線硬化型導
電性ペ−スト（ＩＩＩ）を得た。[Production Example 3] An amino group of iminobispropylamine (manufactured by Koei Chemical Industry Co., Ltd.) was acryloylated to prepare a trifunctional acrylamide resin. Acrylamide resin 7
0 parts, epoxy acrylate (Showa High Polymer Co., SP-4
010) 20 parts, 2-hydroxyethyl acrylate 10
And Agc-B (Fukuda Metal Foil & Powder Co., Ltd. product, scaly silver powder) 300 parts were well kneaded with 3 rolls to obtain an electron beam-curable conductive paste (III).
【００１６】[0016]
【製造例４】トリエチレンテトラミン（関東電化工業
（株）製）のアミノ基をアクリロイル化し４官能のアク
リルアミド樹脂を調製した。上記アクリルアミド樹脂７
０部、ペンタエリスリト−ルテトラアクリレ−ト３０
部、Ａｇｃ−Ｂ（福田金属箔粉工業（株）製、鱗片状銀
粉）３００部を３本ロ−ルでよく混錬し電子線硬化型導
電性ペ−スト（ＩＶ）を得た。[Production Example 4] A tetrafunctional acrylamide resin was prepared by acryloylating the amino group of triethylenetetramine (manufactured by Kanto Denka Kogyo Co., Ltd.). Acrylamide resin 7
0 parts, pentaerythritol tetraacrylate 30
And Agc-B (manufactured by Fukuda Metal Foil & Powder Co., Ltd., scale-like silver powder) (300 parts) were well kneaded with 3 rolls to obtain an electron beam-curable conductive paste (IV).
【００１７】[0017]
【製造例５】テトラエチレンペンタミン（関東電化工業
（株）製）のアミノ基をアクリロイル化し５官能のアク
リルアミド樹脂を調製した。上記アクリルアミド樹脂７
０部、ペンタエリスリト−ルテトラアクリレ−ト３０
部、Ａｇｃ−Ｂ（福田金属箔粉工業（株）製、鱗片状銀
粉）３００部を３本ロ−ルでよく混錬し電子線硬化型導
電性ペ−スト（Ｖ）を得た。[Production Example 5] Amino group of tetraethylenepentamine (manufactured by Kanto Denka Kogyo Co., Ltd.) was acryloylated to prepare a pentafunctional acrylamide resin. Acrylamide resin 7
0 parts, pentaerythritol tetraacrylate 30
Part, Agc-B (manufactured by Fukuda Metal Foil & Powder Co., Ltd., flaky silver powder) 300 parts were well kneaded with 3 rolls to obtain an electron beam curable conductive paste (V).
【００１８】[0018]
【製造参考例１】両末端がアクリレ−トの電子線硬化型
樹脂 ＮＫ ＥＳＴＥＲ Ａ６００（新中村化学工業
（株）製）１００部、Ａｇｃ−Ｂ（福田金属箔粉工業
（株）製、鱗片状銀粉）３００部を３本ロ−ルでよく混
錬してペ−スト（ＶＩ）を得た。[Production Reference Example 1] 100 parts of electron beam curable resin NK ESTER A600 (manufactured by Shin-Nakamura Chemical Co., Ltd.) with acrylate at both ends, Agc-B (manufactured by Fukuda Metal Foil & Powder Co., Ltd., scale-shaped) 300 parts of silver powder) was well kneaded with 3 rolls to obtain a paste (VI).
【００１９】[0019]
【実施例１】銅張りガラスエポキシ基板上に、電子線硬
化型導電性ペ−スト（Ｉ）を印刷し、電子線を照射し
た。電子線の照射は日新ハイボルテ−ジ（株）製エリア
ビ−ム型電子線照射装置を用いて１０Ｍｒａｄの照射線
量で照射した。得られた硬化物の表面を指先でこすった
が擦りあとはつかなかった。得られた硬化物の性能を表
１に示す。また、基板との接着性をＪＩＳ Ｋ５４００
に従って調べたところ、１００／１００であり、良好な
接着性を示した。Example 1 An electron beam curable conductive paste (I) was printed on a copper-clad glass epoxy substrate and irradiated with an electron beam. The electron beam was irradiated with an irradiation dose of 10 Mrad using an area beam type electron beam irradiation device manufactured by Nisshin High Voltage Co., Ltd. The surface of the obtained cured product was rubbed with a fingertip but was not rubbed. The performance of the obtained cured product is shown in Table 1. In addition, the adhesiveness to the substrate is JIS K5400
It was 100/100 and showed good adhesiveness.
【００２０】[0020]
【表１】 [Table 1]
【００２１】[0021]
【実施例２〜５】電子線硬化型導電性ペ−スト（Ｉ）の
代わりに電子線硬化型導電性ペ−スト（ＩＩ〜Ｖ）を用
いた他は実施例１と同様にして評価を行い、その結果を
表１に示した。また、基板との接着性をＪＩＳ Ｋ５４
００に従って調べたところ、すべて １００／１００で
あり、良好な接着性を示した。Examples 2 to 5 Evaluations were made in the same manner as in Example 1 except that electron beam curable conductive pastes (II to V) were used instead of electron beam curable conductive pastes (I). The results are shown in Table 1. In addition, the adhesiveness with the substrate can be measured according to JIS K54.
When examined according to No. 00, all were 100/100, indicating good adhesion.
【００２２】[0022]
【比較例１】実施例１〜５における電子線硬化型導電性
ペ−スト（Ｉ〜Ｖ）の代わりに製造参考例１のペ−スト
（ＶＩ）を用いた他は実施例１〜５と同様にして評価を
行い、その結果を表１に示した。Comparative Example 1 Examples 1 to 5 except that the paste (VI) of Production Reference Example 1 was used in place of the electron beam curable conductive paste (IV) in Examples 1 to 5. The evaluation was performed in the same manner, and the results are shown in Table 1.
【００２３】[0023]
【比較例２】製造例１の導電性ペースト４００部に光重
合開始剤として、１−ヒドロキシシクロヘキシルフェニ
ルケトン６部を加え、３本ロ−ルでよく混練して紫外線
硬化型導電性ペースト（ＶＩＩ）とした。銅張りガラス
エポキシ基板上にペースト（ＶＩＩ）を印刷し、６０秒
紫外線照射して硬化を行った。硬化物の初期物性は優れ
ていたが耐久性に難点が見られた。得られた硬化物の性
能を表１に示す。[Comparative Example 2] To 400 parts of the conductive paste of Production Example 1 was added 6 parts of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator, and the mixture was kneaded well with three rolls to obtain an ultraviolet-curable conductive paste (VII). ). The paste (VII) was printed on a copper-clad glass epoxy substrate and irradiated with ultraviolet rays for 60 seconds to cure. Although the initial physical properties of the cured product were excellent, there were some problems in durability. The performance of the obtained cured product is shown in Table 1.
【００２４】[0024]
【本発明の効果】本発明による電子線硬化型導電性ペ−
ストの優れた効果として次の点が挙げられる。 （１）電子線照射、数秒で導電性ペ−ストを完全に硬化
させることができる。よって従来の熱硬化型導電性ペ−
ストに比べ、製造ラインの大幅なスピ−ドアップが可能
であり、紫外線硬化型導電性組成物と比較しても、工程
の合理化が図れる。 （２）電子線による硬化は、紫外線による硬化の場合に
必要である光開始剤や増感剤を多量に使用しなくてもよ
いため硬化後の物性を損なうことがない。 （３）加熱、冷却などの熱履歴によるプリント基板の反
り、変形、収縮などの問題がないので従来、耐熱性が十
分でないためプリント基板の被着体としては好ましくな
かったプラスチック、ＰＥＴなども被着体として用いる
ことができる。 （４）溶剤を含まないため、スクリ−ン印刷中あるいは
塗布中に溶剤の揮発が起こらず、スクリ−ン版の目詰ま
りが起きない。また、作業環境性に優れている。 （５）得られた最終硬化物は被着体との接着性、可撓性
に優れている。 本発明の電子線硬化型導電性ペ−ストは上記した長所を
生かして、プリント基板への導電回路の形成、ハイブリ
ッドＩＣの導体部、抵抗体の電極端子部品など多種多様
な用途に使用できる。EFFECT OF THE INVENTION Electron beam curable conductive sheet according to the present invention
The following points can be mentioned as the excellent effects of the strike. (1) The conductive paste can be completely cured by electron beam irradiation for a few seconds. Therefore, the conventional thermosetting conductive paper
Compared with the strike, the production line can be greatly speeded up, and the process can be rationalized even when compared with the ultraviolet curable conductive composition. (2) Curing by electron beam does not impair the physical properties after curing because it is not necessary to use a large amount of photoinitiator and sensitizer required for curing by ultraviolet rays. (3) Since there is no problem of warpage, deformation, shrinkage, etc. of the printed circuit board due to heat history of heating, cooling, etc., plastic, PET, etc., which has been conventionally unfavorable as an adherend of the printed circuit board due to insufficient heat resistance, are also covered. It can be used as a body. (4) Since the solvent is not contained, the solvent does not volatilize during screen printing or application, and the screen plate does not clog. It also has excellent work environment. (5) The obtained final cured product has excellent adhesiveness to an adherend and flexibility. The electron beam curable conductive paste of the present invention can be used for various purposes such as formation of a conductive circuit on a printed circuit board, a conductor part of a hybrid IC, and electrode terminal parts of a resistor, by utilizing the above advantages.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｆ 2/54 ＭＤＴ 7442−4Ｊ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location C08F 2/54 MDT 7442-4J
Claims (3)
くとも１個以上の（メタ）アクリルアミド基を有する電
子線重合性化合物（Ｂ１）または、該化合物（Ｂ１）と
分子内に（メタ）アクリルアミド基を有さない電子線重
合性化合物（Ｂ２）との混合物を含む電子線硬化型樹脂
組成物を必須成分とすることを特徴とする電子線硬化型
導電性ペ−スト。1. An electron beam polymerizable compound (B1) having (A) a conductive fine powder and (B) at least one or more (meth) acrylamide group in the molecule, or the compound (B1) in the molecule. An electron beam curable conductive paste comprising an electron beam curable resin composition containing a mixture with an electron beam polymerizable compound (B2) having no (meth) acrylamide group as an essential component.
樹脂組成物を電子線照射で硬化させた硬化物。2. A cured product obtained by curing the electron beam curable resin composition according to claim 1 by electron beam irradiation.
樹脂組成物を電子線照射で硬化させた硬化物を基板面上
に配してなるプリント基板。3. A printed circuit board comprising a cured product obtained by curing the electron beam curable resin composition according to claim 1 by electron beam irradiation and arranging the cured product on the substrate surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30697292A JPH06157945A (en) | 1992-11-17 | 1992-11-17 | Electrically conductive paint curable with electron ray |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30697292A JPH06157945A (en) | 1992-11-17 | 1992-11-17 | Electrically conductive paint curable with electron ray |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06157945A true JPH06157945A (en) | 1994-06-07 |
Family
ID=17963485
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30697292A Pending JPH06157945A (en) | 1992-11-17 | 1992-11-17 | Electrically conductive paint curable with electron ray |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06157945A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002197435A (en) * | 2000-12-27 | 2002-07-12 | Toppan Forms Co Ltd | Method for forming antenna circuit for non-contacting ic medium using electron beam and the medium provided with the circuit |
| JP2002197921A (en) * | 2000-12-26 | 2002-07-12 | Toppan Forms Co Ltd | Electron beam curing conductive paste, conductor circuit using it, and ic media having antenna part formed with electron beam curing conductive paste |
| WO2006053783A1 (en) * | 2004-11-19 | 2006-05-26 | Glaxo Group Limited | Amide and peptide derivatives of tetraalkylenepentamines as transfection agents |
| WO2011090103A1 (en) | 2010-01-21 | 2011-07-28 | 株式会社フジクラ | Electron-beam-curable electrically conductive paste and process for production of circuit board using same |
| WO2012098951A1 (en) * | 2011-01-19 | 2012-07-26 | 株式会社ダイセル | Electron-beam-curable composition, and cured product thereof |
| JP2013116927A (en) * | 2011-10-31 | 2013-06-13 | Kohjin Holdings Co Ltd | Active energy ray-curable coating composition and coating agent |
-
1992
- 1992-11-17 JP JP30697292A patent/JPH06157945A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002197921A (en) * | 2000-12-26 | 2002-07-12 | Toppan Forms Co Ltd | Electron beam curing conductive paste, conductor circuit using it, and ic media having antenna part formed with electron beam curing conductive paste |
| JP2002197435A (en) * | 2000-12-27 | 2002-07-12 | Toppan Forms Co Ltd | Method for forming antenna circuit for non-contacting ic medium using electron beam and the medium provided with the circuit |
| WO2006053783A1 (en) * | 2004-11-19 | 2006-05-26 | Glaxo Group Limited | Amide and peptide derivatives of tetraalkylenepentamines as transfection agents |
| JP2008520610A (en) * | 2004-11-19 | 2008-06-19 | グラクソ グループ リミテッド | Amide and peptide derivatives of tetraalkylenepentamine as transfection agents |
| WO2011090103A1 (en) | 2010-01-21 | 2011-07-28 | 株式会社フジクラ | Electron-beam-curable electrically conductive paste and process for production of circuit board using same |
| JP2011150897A (en) * | 2010-01-21 | 2011-08-04 | Fujikura Ltd | Electron beam curing conductive paste and method of manufacturing circuit board using the conductive paste |
| US8734910B2 (en) | 2010-01-21 | 2014-05-27 | Fujikura Ltd. | Electroconductive paste for electron beam curing and circuit board production method using same |
| WO2012098951A1 (en) * | 2011-01-19 | 2012-07-26 | 株式会社ダイセル | Electron-beam-curable composition, and cured product thereof |
| JP2013116927A (en) * | 2011-10-31 | 2013-06-13 | Kohjin Holdings Co Ltd | Active energy ray-curable coating composition and coating agent |
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