JPS62135580A - Conductive bonded structure and production thereof - Google Patents

Conductive bonded structure and production thereof

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Publication number
JPS62135580A
JPS62135580A JP27880085A JP27880085A JPS62135580A JP S62135580 A JPS62135580 A JP S62135580A JP 27880085 A JP27880085 A JP 27880085A JP 27880085 A JP27880085 A JP 27880085A JP S62135580 A JPS62135580 A JP S62135580A
Authority
JP
Japan
Prior art keywords
acid
conductive adhesive
mixture
crosslinking agent
aromatic
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
Application number
JP27880085A
Other languages
Japanese (ja)
Other versions
JPH0623348B2 (en
Inventor
Sugiro Otani
大谷　杉郎
Hiroya Kakegawa
宏弥 掛川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ibiden Co Ltd
Original Assignee
Ibiden Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ibiden Co Ltd filed Critical Ibiden Co Ltd
Priority to JP27880085A priority Critical patent/JPH0623348B2/en
Priority to US06/938,253 priority patent/US4911983A/en
Priority to EP19860309562 priority patent/EP0225802B1/en
Priority to DE19863686561 priority patent/DE3686561T2/en
Publication of JPS62135580A publication Critical patent/JPS62135580A/en
Priority to US07/460,620 priority patent/US5017431A/en
Publication of JPH0623348B2 publication Critical patent/JPH0623348B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacturing Of Electrical Connectors (AREA)
  • Connections Effected By Soldering, Adhesion, Or Permanent Deformation (AREA)

Abstract

PURPOSE:To obtain the titled bonded structure free from conductive aggregates and having excellent heat resistance and strength, by bonding an adherend with an adhesive comprised of a thermosetting compsn. comprising a condensed arom. polycyclic compd., an arom. crosslinking agent, and an acid catalyst. CONSTITUTION:A mixture of a condensed arom. polycyclic compd. (a) and an arom. crosslinking agent (b) in a molar ratio of (b) to (a) of 0.5-4.0 is reacted with an acid catalyst (c) in an amt. of 0.1-10wt% based on the mixture at 60-300 deg.C to obtain an adhesive (B) comprised of a thermosetting compsn. An adherend (A) which is electrically conductive and has H, halogen, OH group, epoxy or acid anhydride structure, etc., on its surface is bonded to the component B via an arom. crosslinking agent (C) which is a mono- or polycyclic arom. compd. having at least two groups of at least one member selected from hydroxymethyl groups and halomethyl group, a surface treating agent which is a mixture of components (b) and (c) or an additive, in the presence of a catalyst for promoting the conductivity impartment, thereby curing the component B at 100-400 deg.C for 10-30hr and imparting conductivity by virtue of the org. conjugation.

Description

【発明の詳細な説明】 （産業上の利用分野） 未発［Ｊｌは特に導電性骨材を必要としない導電性接着
構造物及びその製造方法に関し、特に本発明は新規な熱
硬化性樹脂を接着剤とする導電性接着構造物及びその製
造方法に関するものである。Detailed Description of the Invention (Field of Industrial Application) Undeveloped [Jl particularly relates to a conductive adhesive structure that does not require a conductive aggregate and a method for manufacturing the same. The present invention relates to a conductive adhesive structure used as an adhesive and a method for manufacturing the same.

（従来の技術） 従来、熱硬化性樹脂を接着剤とする導電性接着構造物と
しては導電性の骨材を添加せずに導電性か発現した例を
見ない。(Prior Art) Conventionally, there has been no example of a conductive adhesive structure using a thermosetting resin as an adhesive that exhibits conductivity without adding conductive aggregate.

（発明が解決しようとする問題点） 従来の導電性接着剤はすべて銀、銅、黒鉛、炭素等の導
電性骨材の存在なしに導電性を賦享させることがてきな
い欠点を有していた。(Problems to be Solved by the Invention) All conventional conductive adhesives have the disadvantage that they cannot provide conductivity without the presence of conductive aggregates such as silver, copper, graphite, and carbon. Ta.

（問題点を解決するための「段） 本発明は、銀、銅、！！Ａ鉛、炭素等の導電性骨材の存
在なしに導−［性を賦１ＦさせることがｒＩ丁能な導電
性接着剤から成る導電性接着構造物及びその製造方υ、
を提供することを［１的とするものである。(Steps to Solve the Problems) The present invention provides a conductive material that is capable of imparting conductive properties without the presence of conductive aggregates such as silver, copper, lead, and carbon. Conductive adhesive structure made of adhesive and method for producing the same υ,
The first objective is to provide the following.

未発明者らは昭和６０年１０　Ｊｌ　４　Ｆ＋に金沢市
において開仔された日本化学会第５１秋季年会においで
、主として二環以上の縮合多環芳香族化合物と、ヒドロ
キシメチル基１（、へロメチル基のいずれか少なくとも
一種の基を二個以上有する一環または二環以ヒの刀香環
から成る芳香族架橋剤と、酸触媒とを組み合わせて成る
熱硬化性組成物（以下Ｃ０ＰＮＡ樹脂組成物と略記）に
ついて発表を行った。（シンポジウム講演了・稿集１．
ｐ５３９−本発明は、前記本発明者らか発表した、Ｃ０
ＰＮＡ樹脂組成のうち縮合多環芳香族化合物としてナフ
タレン、アシドラセン、フェナントレン、ビレン、クリ
セン、ナフタセン、アセナフテン、アセナフチレン、ペ
リレン、コロネン、及びこれらをＦ骨格とする誘導体の
中から選ばれる一種又は二種以上の混合物或いは、石炭
系若しくは石油系の改質油、タール、ピッチ及びこれら
の誘導体を用いた場合、導電性化促進触媒の存在下で、
このＣ０ＰＮＡ樹脂組成物か硬化した後に芳香族共役系
に基づく導゛屯性を示すことに着１１　Ｌ　、これを４
電性接着剤として適用し、特に６種の表面η′７七ノモ
ノ有し若しくは導入された被着材と１１１ｊ記接１１剤
とを表面処理剤若しくは添加剤を介してより強国に結合
させ、かつ実質的に導電性を示す導電外接ｒＩ構造物を
提供することを目的とするものであり、特許請求の範囲
記載の導電性接着構造物とその製造方法を提供すること
によって１１ｆ１記目的をＩｉ！成することがてきる。At the 51st Autumn Annual Meeting of the Chemical Society of Japan held in Kanazawa City on 10 Jl 4 F+ in 1985, the uninventors discovered that fused polycyclic aromatic compounds of two or more rings and hydroxymethyl group 1 (, A thermosetting composition (hereinafter referred to as C0PNA resin composition) consisting of a combination of an aromatic crosslinking agent consisting of one or two or more aromatic rings having two or more of at least one type of heromethyl group, and an acid catalyst. I gave a presentation on (Symposium lecture completed, Manuscript 1.
p539-The present invention is based on the C0
One or more types selected from naphthalene, acidoracene, phenanthrene, birene, chrysene, naphthacene, acenaphthene, acenaphthylene, perylene, coronene, and derivatives having these as F skeletons as condensed polycyclic aromatic compounds in the PNA resin composition. or a coal-based or petroleum-based reformed oil, tar, pitch, and their derivatives, in the presence of a conductivity-promoting catalyst,
After this C0PNA resin composition was cured, it was found that it exhibited toughness based on the aromatic conjugated system.
Applied as an electrically conductive adhesive, in particular, bonding an adherend having or introducing six types of surface η'7 and an adhesive described in 111j more strongly via a surface treatment agent or an additive, The object of the present invention is to provide a conductive circumscribed rI structure that is substantially conductive, and by providing the conductive adhesive structure and the manufacturing method thereof described in the claims, the object 11f1 can be achieved. ! It is possible to achieve.

次に本発明の詳細な説明する。Next, the present invention will be explained in detail.

即ち、この第一の発明はＣ０ＰＮＡ樹脂組成物接着剤と
、表面に水素、ハロゲン、ヒ１〜ロキシル基、カルボニ
ル基、カルボキシル基、アルデヒドＸ　、エポキシ構造
、ラクトン構造、エーテル構造、酸無水物構造から選ば
れる少なくとも一種を有し若しくは導入された被着材と
が、前記被着材と接着剤の界面においで、前記表面処理
剤若しくは前記添加剤を介して結合しかつ、導電性化側
進触媒の存在下てこのＣ０ＰＮＡ樹脂組成物の硬化体か
芳香族共役系に基づく導電性を示す、耐熱性。That is, the first invention is a C0PNA resin composition adhesive and a surface containing hydrogen, halogen, H-1-roxyl group, carbonyl group, carboxyl group, aldehyde X, epoxy structure, lactone structure, ether structure, and acid anhydride structure. The adherend material having or introduced at least one selected from the following is bonded via the surface treatment agent or the additive at the interface between the adherend material and the adhesive, and the conductivity side progresses. The cured product of the C0PNA resin composition exhibits conductivity based on an aromatic conjugated system in the presence of a catalyst and is heat resistant.

耐水性、寸法安定性、強度、熱伝導性等に富んだ導電性
接着構造物である。It is a conductive adhesive structure with excellent water resistance, dimensional stability, strength, and thermal conductivity.

また、第二、第三の発明はＣ０ＰＮＡ樹脂組成物接着剤
と１表面官ず上貼を有し若しくは導入された被着材とを
芳香族架橋剤を主体とする表面処理剤若しくは添加剤に
よって化学的に結合させ、かつ導電性化促進触媒の存在
ドでこのＣ０ＰＮＡ樹脂組成物か硬化した後に芳香族共
役系に基づく導電性を賦午させて成る耐熱性、耐水性、
寸法安定性、強度、熱伝導性等に富んだ導電性接ノー構
造物を製造する方法である。In addition, the second and third inventions provide a C0PNA resin composition adhesive and an adherend having or having a surface-free top layer, by using a surface treatment agent or additive mainly containing an aromatic crosslinking agent. The C0PNA resin composition is chemically bonded and cured in the presence of a conductivity promoting catalyst, and then imparts conductivity based on an aromatic conjugated system, resulting in heat resistance, water resistance,
This is a method of manufacturing a conductive joint structure with high dimensional stability, strength, thermal conductivity, etc.

以下、この導電性接ｎ構造物を構成するＣ０ＰＮＡ樹脂
組Ｉｊｉｕ物接着剤の成分である縮合多環芳香族化合物
、架橋剤、酸触媒１表面処理剤、添加剤導電性化Ｏ触媒
及び−１ｉ材について説明する。Hereinafter, the components of the C0PNA resin composite adhesive constituting this conductive contact structure, such as a condensed polycyclic aromatic compound, a crosslinking agent, an acid catalyst, a surface treatment agent, an additive, a conductive catalyst, and a -1i Explain the material.

本発明の縮合多環芳香族化合物にはナフタレン、アント
ラセン、フェナントレン、ビレン、クリセン、ナフタセ
ン、アセナフテン、アセナフチレン、ペリレン、コロネ
ン、及びこれらを主骨格とする１誘導体の中から選ばれ
る一種又は二種以上の混合物或いは、石炭系若しくは石
油系の改質油、タール、ピッチ及びこれらの誘導体の中
から選ばれる一種又は二挿具１−の混合物を使用てきる
。The fused polycyclic aromatic compound of the present invention is one or more selected from naphthalene, anthracene, phenanthrene, birene, chrysene, naphthacene, acenaphthene, acenaphthylene, perylene, coronene, and one derivative having these as the main skeleton. or a mixture of one or two inserts selected from coal-based or petroleum-based reformate, tar, pitch, and derivatives thereof.

次に本発明の架橋剤には、ヒドロキシメチル基、ハロメ
チルノ、（のいずれか少なくとも一種の」、（を二個以
上イ１する一環または二環以［−の芳香原がら成る芳香
族化合物、倒えばｐ−キシリレンシクロライト、１．４
−ベンゼンジメタツール、（ｐ−キシリレンクリコール
）、９．１０−アントラセンジメタツール等を使用てき
る。Next, the crosslinking agent of the present invention includes an aromatic compound consisting of at least one of hydroxymethyl group, halomethyl, For example, p-xylylene cyclolite, 1.4
-Benzene dimetatool, (p-xylylene glycol), 9.10-anthracene dimetatool, etc. can be used.

また、本発明の酸触媒には、塩化アルミニウム、弗化ホ
ウ麦、硫酸、リン酸、有機スルホン耐、カルボン酸、及
びこれらの、Ａ導体の中から選ばれる一種又は二種以上
−の混合物を使用てきる。Further, the acid catalyst of the present invention may contain one or a mixture of two or more selected from aluminum chloride, boron fluoride, sulfuric acid, phosphoric acid, organic sulfone resistant, carboxylic acid, and conductors A. I can use it.

前記縮合多環芳香族化合物、架橋剤、酸触媒をＣ０ＰＮ
Ａ樹脂組成物接着剤と１−るための混合比率については
、架橋剤／縮合多環芳香族＝０，５〜４．０（モル比）
の範囲；酸触媒添加ニー−については、架橋剤／縮合多
環芳香族の混合物に対して０．１〜ｌ　０ｗｔ％か好適
な範囲であることが実験的に確認された。The fused polycyclic aromatic compound, crosslinking agent, and acid catalyst are COPN
Regarding the mixing ratio for A resin composition adhesive and 1-, crosslinking agent/fused polycyclic aromatic = 0.5 to 4.0 (molar ratio)
It has been experimentally confirmed that the acid catalyst addition knee is in a suitable range of 0.1 to 10 wt% based on the mixture of crosslinking agent/fused polycyclic aromatic.

また、Ｃ０ＰＮＡ樹脂組成物を加熱反応させてなる実質
的に熱可塑性をイ１する熱硬化性中間反応生成物（Ｂス
テージ樹脂）を得るための反応温度範囲は６０〜３００
℃が好適な範囲であることが実験的に確認された。以［
−のようにしで、Ｃ０ＰＮＡ８４脂組成物を加熱反応さ
せることにより所謂Ｂステージ樹脂か得られる。In addition, the reaction temperature range for obtaining a thermosetting intermediate reaction product (B stage resin) that is substantially thermoplastic by subjecting the C0PNA resin composition to a heating reaction is 60 to 300°C.
It was experimentally confirmed that the temperature is within a suitable range. From [
- A so-called B-stage resin can be obtained by subjecting a C0PNA84 resin composition to a heat reaction.

次に本発明における表面処理剤及び添加剤については、
ヒドロキシメチル基、へロメチル基のいずれか少なくと
も一種の基を二個以上有する一環または二環以トの芳香
環から成る芳香族架橋剤。Next, regarding the surface treatment agent and additives in the present invention,
An aromatic crosslinking agent consisting of one or two or more aromatic rings having two or more of at least one of hydroxymethyl and heromethyl groups.

若しくは前記芳香族架橋剤と前記酸触媒との混合物であ
り、混合物の融点以上の温度に加熱溶融させ液状とし、
若しくは溶剤に溶解させ溶液として使用することもてき
るものである。また、表面処理剤或いは添加剤の添加７
，１．４よ特に規定されるものではないか１表面処理剤
としては溶剤に溶解させ１〜ｌ　０ｗｔ％のｅ度の溶液
として数回塗Ｉ１１する方法か、添加剤として予め接着
剤組成物に添加する場合には０．０１〜５ｗｔ％の範囲
か好適である。or a mixture of the aromatic crosslinking agent and the acid catalyst, heated and melted at a temperature higher than the melting point of the mixture to form a liquid;
Alternatively, it can be dissolved in a solvent and used as a solution. In addition, addition of surface treatment agents or additives 7
, 1.4.1 The surface treatment agent may be dissolved in a solvent and applied several times as a solution with a concentration of 1 to 0 wt%, or it may be added to the adhesive composition in advance as an additive. When added to the water, a range of 0.01 to 5 wt% is suitable.

本発明の導電性化促進触媒としては、空気、酸素、オゾ
ン、イオウ、過酸化水素、二酸化マンガン、炬硝酸、硝
酸、過マンガン酸、クロム酸、塩素酸５次亜塩素酸の中
から選ばれる一種又は二種以上の混合物から成る酸化剤
たけ、或いはこれらの酸化剤と塩化アルミニウム、弗化
ホウ素、硫酸、リン酸、４１機スルホン酸、カルボン酸
、及びこれらの誘導体の中から選ばれる一種又は一種以
上の混合物とを組み合わせか有効であり、前記導電性化
促進触媒か常温で気体の場合はその存在Ｆて１液体又は
固体の場合は添加して使用することがてきる。The conductivity promoting catalyst of the present invention is selected from air, oxygen, ozone, sulfur, hydrogen peroxide, manganese dioxide, nitric acid, nitric acid, permanganic acid, chromic acid, chloric acid, and pentahypochlorous acid. An oxidizing agent consisting of one or a mixture of two or more of these oxidizing agents and one selected from aluminum chloride, boron fluoride, sulfuric acid, phosphoric acid, sulfonic acid, carboxylic acid, and derivatives thereof. It is effective to use a combination of one or more types of mixtures, and if the conductivity promoting catalyst is a gas at room temperature, its presence may be added.If it is a liquid or a solid, it can be used.

導電性化促進触媒の添加！ｄは特に限定されるものでは
ないか、酸化剤のうち気体のものについては、その雰囲
気中て接着操作を行なうたけて効果かあり、液体、固体
の場合は、０．０１〜３％の範囲か好適である。また酸
の場合には表面処理剤、添加剤、Ｃ０ＰＮＡ樹脂組成物
中に含まれているため、これを必ｆｉ　ｙ、＋より過剰
に加えるか、または別途０．０１〜１％程度添加するの
か好適である。酸の場合は強酸はど効果は大きく、酸化
剤との併用によりさらにその効果は増大する。Addition of conductivity promoting catalyst! d is not particularly limited; gaseous oxidizing agents are more effective if the bonding operation is performed in that atmosphere; liquids and solids are in the range of 0.01 to 3%. or suitable. In addition, in the case of acid, it is included in surface treatment agents, additives, and C0PNA resin compositions, so it is necessary to add it in excess of the amount required, or add it separately by about 0.01 to 1%. suitable. In the case of acids, the effect of strong acids is large, and the effect is further increased when used in combination with an oxidizing agent.

本発明における導電性発現のメカニズムは以下の如くで
あると推老される。The mechanism of conductivity development in the present invention is presumed to be as follows.

（１）接着剤を構成するＣ０ＰＮＡ樹脂組成物の硬化体
中の芳香環に直結したメチレンか、酸化剤によって酸化
を受はハイドロパーオキサイド経由し、脱水によりカル
ボニル基となる。(1) The methylene directly bonded to the aromatic ring in the cured product of the C0PNA resin composition constituting the adhesive is oxidized by an oxidizing agent and becomes a carbonyl group by dehydration via hydroperoxide.

このカルボニル基は両側の芳香環と共役関係にあり、従
って導電性か発現する。This carbonyl group has a conjugated relationship with the aromatic rings on both sides, and therefore exhibits electrical conductivity.

これをビレンをモデルとして式で表すと以ドのようであ
る。Expressing this in a formula using Biren as a model is as follows.

（２）接着剤を構成するＣ０ＰＮＡ樹脂組成物の硬化体
中の芳香環に直結したメチレンのうち、架橋剤に由来す
る芳香環か縮合多環芳香族由来の芳香環に対し”Ｃ１１
γ体障害位置にある場合（式中Ａの剤に由来する芳香環
か縮合多環芳香族由来の芳香環に対しで、立体障害位置
にある場合（式中Ａの部分）１？ｉ合多環芳香族由来の
芳香環か酸による親電子置換を受け、その結果化体障害
位置にある架橋剤に由来する芳香環を親電ｆ的に攻撃し
、その部分か閉環する。この際に酸化剤かメチレン水素
及び閉環位の水素を脱水の形て引き抜くことにより、よ
り低温から芳香化か進行し、共役系による導電性か発現
する。(2) Among the methylenes directly bonded to the aromatic rings in the cured product of the C0PNA resin composition constituting the adhesive, "C11
When it is in a γ-hindered position (with respect to the aromatic ring derived from the agent in formula A or the aromatic ring derived from a condensed polycyclic aromatic) and in a sterically hindered position (part A in the formula) 1?i combination The aromatic ring derived from the aromatic ring undergoes electrophilic substitution by the acid, and as a result, the aromatic ring derived from the crosslinking agent at the hindrance position of the compound is electrophilically attacked, resulting in ring closure of that part.At this time, oxidation By extracting methylene hydrogen and hydrogen at ring-closing positions from the agent in the form of dehydration, aromatization progresses from a lower temperature, and conductivity due to the conjugated system is developed.

これをビレンをモデルとして式て表すと以ドのよってあ
る。Expressing this using Biren as a model is as follows.

ヒ記何れのメカニズムにおいても、実際に導電性接着剤
としである程度の接ノ１厚みの間に導電性を賦榮しよう
とする場合には、縮合多環芳香族由来の芳香環はその距
離に対応した共役系を有する大きさであることが必要と
なる。このため本発明においては、特に安価であり、な
おかつ巨大な縮合多環芳香族分子（ピッチてはこの大き
さか数百ミクロンに及ぶ場合かある。）を含む石炭系若
しくは石油系の重質油、タール、ピッチ等か有利である
が、微小部分での導電性についてはビレンをモデルとし
て示した如く、二環以上の芳香族化合物てあれば同様な
メカニズムのよって得たれること（ま自す１である。In any of the mechanisms described above, when actually using a conductive adhesive to impart conductivity within a certain thickness of contact, the aromatic ring derived from the fused polycyclic aromatic It is necessary that the size has a corresponding conjugate system. Therefore, in the present invention, coal-based or petroleum-based heavy oil, which is particularly inexpensive and contains huge condensed polycyclic aromatic molecules (the pitch may reach this size or several hundred microns), Tar, pitch, etc. are advantageous, but as shown using birene as a model, conductivity in minute parts can be obtained by a similar mechanism if it is an aromatic compound with two or more rings. It is.

本発明ては被着材としで、水素、ハロゲン、ヒドロキシ
ル基、カルボニル基、カルボキシル基、アルデビト基、
エポキシ構造、ラクトン構造、エーテル構造、酸無水物
構造の中から選ばれる一種又は二種以上を少なくとも表
面に有し、かつ導電性を有するｔＲＬＷ、黒鉛、金属、
金属炭化物、全屈珪化物、金属硼化物、及びこれらの前
駆体或いは複合材料を使用することができる。被着材の
表面官能基等については、ｒ・めこれらか存在している
ものはそのまま、存在しても***゛である場合には酸化
剤による湿式酸化及び酸素等による乾式酸化、或いは水
素化等の還元処理による導入か有効である。In the present invention, the adherends include hydrogen, halogen, hydroxyl group, carbonyl group, carboxyl group, aldevit group,
tRLW, graphite, metal, which has at least one type or two or more selected from epoxy structure, lactone structure, ether structure, and acid anhydride structure on the surface and has conductivity;
Metal carbides, total silicides, metal borides, and precursors or composites thereof can be used. Regarding the surface functional groups of the adherend, if any of these exist, leave them as they are, or if they are present but have small holes, wet oxidation with an oxidizing agent, dry oxidation with oxygen, etc., or hydrogenation. It is effective to introduce it through reduction processing such as

１′Ｏ１記被着材界面における結合のメカニズムは以下
の如くであると推考される。即ち、表面処理剤中、添加
剤中若しくはＣ０ＰＮＡ樹脂組成物接着剤中に含まれる
酸触媒の作用より、表面処理剤中、添加剤中の二官鋤性
以ｌ二の芳香族架橋剤か被着材表面の水素、ハロゲン、
ヒドロシルノ、（、カルボニル基、（、カルボキシル基
１（、アルデヒトフ、（、エポキシ構造、ラクトン構造
、エーテル構造、酸無水物構造等と脱水、脱ハロゲン、
脱ハロゲン化水素等の反応より結合し、一方ては、Ｃ０
ＰＮＡ樹脂接ｒｉ剤中の芳香族水、靴、ハロゲン、ヒド
ロキシル）、＄　ｋｇ−と同様に反応することによっで
、結果的に被着材とＣ０ＰＮＡ樹脂組１＆、物接着剤か
強固に結合する。The mechanism of bonding at the interface of the adherend 1'O1 is thought to be as follows. That is, due to the action of the acid catalyst contained in the surface treatment agent, additive, or C0PNA resin composition adhesive, the difunctional aromatic crosslinking agent in the surface treatment agent or additive is hydrogen, halogen,
Hydrosylno, (, carbonyl group, (, carboxyl group 1 (, aldehyde, (, epoxy structure, lactone structure, ether structure, acid anhydride structure, etc. and dehydration, dehalogenation,
It is bonded through reactions such as dehydrohalogenation, and on the other hand, C0
By reacting in the same way as the aromatic water, halogen, hydroxyl), $ kg- in the PNA resin adhesive, the adherend and C0PNA resin group 1 & material adhesive are firmly bonded. do.

本発明の接着剤を構成するＣ０ＰＮＡｖＡ脂組成物は、
不０■逆的反応により、水あるいは１′１１化水７ｋを
放出するため、硬化は氷中ても起こる。又、その硬化体
は極性基を含まない。これらの理由から＋ｉｉｉ記接着
剤を構成するＣ０ＰＮＡ樹脂組成物は耐水性に優れてい
る。The C0PNAvA fat composition constituting the adhesive of the present invention is
Hardening occurs even in ice because water or 1'11 water is released by the reverse reaction. Moreover, the cured product does not contain polar groups. For these reasons, the C0PNA resin composition constituting the adhesive described in +iii has excellent water resistance.

本発明の方法としては、ｒ・め被着材表面を表面処理剤
によって処理しておく方υ：、及び表面処理剤を添加剤
としてＣ０ＰＮＡ樹脂組成物接着剤に添加しておく方法
を使用することができ１表面処理剤若しくは添加剤をそ
れらの融点以１の温度に加熱溶融させ液状とし、若しく
は溶剤に溶解させ溶液として使用することがてきるか、
これらのうち、溶剤に溶解させ溶液として被着材表面を
表面処理剤によってｒ・め処理しておく方法を用いるこ
とがｒｌ−ｒ適である。The method of the present invention includes a method in which the surface of the adherend is treated with a surface treatment agent, and a method in which the surface treatment agent is added as an additive to the C0PNA resin composition adhesive. Is it possible to melt the surface treatment agent or additive by heating to a temperature higher than their melting point to form a liquid, or dissolve it in a solvent and use it as a solution?
Among these methods, it is suitable to use a method in which the surface of the adherend is treated with a surface treatment agent by dissolving it in a solvent and using a solution.

本発明によれば、Ｃ０ＰＮＡ樹脂接着剤を：（１）未反
応の粉末混合物としで、（２）所謂Ｂステージ樹脂の粉
末としで、（３）所謂Ｂステージ樹脂を加熱溶融させ液
状としで、或いは（４）所謂Ｂステージ樹脂を溶剤に溶
解させ液状として：使用することがてきる。According to the present invention, the C0PNA resin adhesive is: (1) as an unreacted powder mixture, (2) as a powder of a so-called B-stage resin, and (3) as a liquid by heating and melting the so-called B-stage resin. Alternatively, (4) the so-called B-stage resin can be dissolved in a solvent and used as a liquid.

また、接、７１方法としては、ホットプレス、治具によ
る固定、ねし等による同定等の方法か使用てきる。この
際、接着温度範囲は、１００〜４００℃か好適で、接着
後接７．剤か充分可塑化した後に熱硬化するように接着
、硬化温度及び時間を設定することが肝要である。In addition, as the contact method 71, methods such as hot pressing, fixing with a jig, identification using screws, etc. can be used. At this time, the adhesion temperature range is preferably 100 to 400°C, and the adhesion temperature range is 7. It is important to set the adhesion, curing temperature and time so that the adhesive is sufficiently plasticized and then thermally cured.

次に本発明によれば、後硬化温度は１００〜４００℃か
好適な範囲であり、後硬化時間はｌＯ〜３０１１１ｆ間
の範囲か好適である。この後硬化により兵役系の発達か
促進され接着部の導電性は向上する。Next, according to the present invention, the post-curing temperature is preferably in the range of 100 to 400°C, and the post-curing time is preferably in the range of IO to 30111f. After curing, the development of military service is promoted and the conductivity of the bonded area is improved.

以上の様にして耐熱性、ｉ耐水性、寸法安定性、強度、
熱導電性等に富んだ導電性接着剤構造物を得ることがて
きる。As described above, heat resistance, water resistance, dimensional stability, strength,
A conductive adhesive structure with high thermal conductivity etc. can be obtained.

ところで、本発明においては導電性骨材を使用せずに導
電性接着剤構造物か（すられる。そこで本発明のＣ０Ｐ
ＮＡ樹脂組成物接着剤に導電性骨材として炭素、黒鉛、
炭素前駆体、銀、ｔ′＃４等の金属を混合することのよ
り、より大きな導電性か得られると共に、従来の熱硬化
性樹脂に比べ著しく導′市性骨材の添加量か少なくとも
同様の効果か１１）られる。また、本発明のうち特にピ
ッチ系Ｃ０ＰＮＡ樹脂組成物接ｎ剤は箸しく高い炭化数
十をイ１するため、炭素、黒鉛、炭素前駆体を本発明に
従って接着した後、これを焼成、黒鉛化することにより
接６一部は完全に炭化、黒鉛化し、従来の；ノ素、黒鉛
材の機械油［を大幅に簡略化しコストなＦげることがで
きる。By the way, in the present invention, the conductive adhesive structure is made without using conductive aggregate. Therefore, the C0P of the present invention
Carbon, graphite, etc. are used as conductive aggregates in NA resin composition adhesive.
By mixing carbon precursors, silver, and metals such as T'#4, greater conductivity can be obtained, and the amount of conductive aggregate added is significantly greater than that of conventional thermosetting resins, or at least the same. 11). In addition, in particular, the pitch-based C0PNA resin composition adhesive of the present invention has extremely high carbonization resistance, so after bonding carbon, graphite, and a carbon precursor according to the present invention, it is fired and graphitized. By doing so, a part of the contact 6 is completely carbonized and graphitized, which greatly simplifies and reduces the cost of conventional machine oil made of carbon and graphite materials.

また１本発明のＣ０ＰＮＡ樹脂組成物接着剤に・９電性
骨材として１ン素、黒鉛、炭素前駆体、銀、銅等の金）
−を混合したものは接着剤のみならず優れた耐熱性、２
ｑ雛強度、熱伝導性を有する導電性塗ネ１、フェスとし
ても使用てき、帯電防１Ｆ、’Ｉｌｉ、磁波シールド、
放射板用塗料、面発熱体等の用途に使用できる。In addition, the C0PNA resin composition adhesive of the present invention can be used as an electrically conductive aggregate such as carbon, graphite, carbon precursor, gold such as silver, copper, etc.
The mixture of - is not only an adhesive but also has excellent heat resistance.
Conductive coating 1 with strength and thermal conductivity, can also be used as a festival, anti-static 1F, 'Ili, magnetic shield,
Can be used for applications such as paint for radiant plates and surface heating elements.

（実施例） 次に、本発明を実施例について更に詳細に説明する。(Example) Next, the present invention will be described in more detail with reference to examples.

実施例１゜ 小成の高密度高強度等方性黒鉛材（商品名　エーロ　イ
ビデン株式会社製９曲げ強度１０００ｋｇ　／　ｃ　ｒ
ｎ’　）を、２０Ｘ２０Ｘ２０ｍｍのブロックに加重し
、空気中、４００℃て３時間加熱し、表面に酩素を含む
官鋤基を導入した後、ｐ−キシリレングリコール：　５
ｗｔ％、ｐ−トルエンスルホン酸：１ｗｔ％のエタノー
ル溶液から成る表面処理剤を接着面に塗布し、空気中１
５０℃で３０分間熱処理しこれを被着材とした。ピッチ
系Ｃ０ＰＮＡ樹脂組成物接着剤としては、軟化点８０℃
の石油系ピッチのベンゼンｉ＋（溶分（平均分）　礒３
４０）とｐ−キシリレンクリコールをモル比てｌ：２の
割合て混合し、そこに１ｗｔ％のＰ−）−ルエンスルホ
ン酸を加えた混合物を１２０℃て４０分間反応させたＢ
ステージ樹脂を用いた。このＢステージ樹脂を空気中１
３０℃て溶融させ、被ｒ１材の接着面に塗／Ｉｉ　Ｌ／
被着材同志を接着後、治具て固定し、空気中１８０℃１
時間熱処理し硬化させた。後硬化は空気中２００℃て２
０時間行なった。Example 1 Kosei's high-density, high-strength isotropic graphite material (product name: Aero Ibiden Co., Ltd. 9 bending strength 1000 kg/cr
n') was loaded into a block of 20 x 20 x 20 mm and heated in air at 400°C for 3 hours to introduce a functional group containing a fluorine to the surface, and then p-xylylene glycol: 5
A surface treatment agent consisting of a 1 wt% ethanol solution of p-toluenesulfonic acid and p-toluenesulfonic acid was applied to the adhesive surface, and
This was heat treated at 50° C. for 30 minutes and used as an adherend. As a pitch-based C0PNA resin composition adhesive, the softening point is 80°C.
Benzene i+ (soluble content (average content) of petroleum pitch 3
40) and p-xylylene glycol at a molar ratio of 1:2, and 1 wt% of P-)-luenesulfonic acid was added thereto, and the mixture was reacted at 120°C for 40 minutes B.
Stage resin was used. This B-stage resin is placed in the air.
Melt it at 30℃ and apply it to the adhesive surface of the target r1 material /Ii L/
After adhering the adherends together, fix them using a jig and heat them in air at 180°C.
It was heat treated for a period of time to harden it. Post-curing is done at 200℃ in air.
I did it for 0 hours.

比較のため市販の二液混合エボキシ系接１１剤（商品名
アラルタイト・チハガイギ−（株）製）て同様の処理を
した被ｒ１材を接着後、治具て固定し、空気中５０’Ｃ
て硬化させた。この両者について。For comparison, a material to be treated in the same manner using a commercially available two-component mixed epoxy adhesive (trade name: Arartite, manufactured by Chiha Geigy Co., Ltd.) was bonded, fixed with a jig, and heated at 50°C in air.
and cured. About both of them.

接着部の比抵抗（四端子−法）、電気抵抗（テスター）
、接着剤層の厚みを測定した。この結果を第１表に示し
た。Specific resistance of adhesive part (four-terminal method), electrical resistance (tester)
, the thickness of the adhesive layer was measured. The results are shown in Table 1.

第１表 また、実施例１の接着物の接１８部について曲げ強度を
測定したところ、ｃＩ材破断を起こし接着面には変化か
なかった。Table 1 Also, when the bending strength of the 18 contact portions of the adhesive of Example 1 was measured, the cI material broke and there was no change in the adhesive surface.

実施例２゜ 市販の軟鋼及び真鍮を２０Ｘ２０Ｘ２０ｍｒｒ＋ｃ７）
フロックに加「し、ｐ−キシリレンクリコール５　ｗ　
ｔ％、ｐ−トルエンスルホン酸　１ｗｔ％のエタノール
溶液から成る表面処理剤を接着面に塗１／ｉｊ　Ｌ／、
空気中１５０℃て３０分間熱処理しこれを被着材とした
。ピッチ系Ｃ０ＰＮＡ樹脂組成物接着剤としては、軟化
点４９℃の石炭系ピッチ（（ｉ均分子：、＋−３００）
とｐ−キシリレンクコールをモル比てｌ　２の−１，ｌ
１合で混合し、そこにｌ　ｗ　ｔ％のＰ−）−ルエンス
ルホン酸な加えた混合物を１２０００４０分間反応させ
たＢステージ樹脂を用いた。Example 2゜Commercially available mild steel and brass 20X20X20mrr+c7)
Add p-xylylene glycol 5 to the floc
t%, p-toluenesulfonic acid 1 wt% ethanol solution is applied to the adhesive surface 1/ij L/,
This was heat treated in air at 150° C. for 30 minutes and used as an adherend. As the pitch-based C0PNA resin composition adhesive, coal-based pitch with a softening point of 49°C ((i-equal molecular weight:, +-300) is used.
and p-xylylene cucol in a molar ratio of l 2 -1,l
A B-stage resin was used in which a mixture of 1 wt % of P-)-luenesulfonic acid was added thereto and reacted for 12,000,040 minutes.

このＢステージ樹脂を空気中１３０℃て溶融させ、被着
材の接着面に塗ｒ（ｊ　シ被着材同志を接着後、治具て
固定し、空気中１８０℃１時間熱処理し硬化させた。後
硬化は空気中２００℃て２０時間行なった。異なる被着
材同志の接着部の′電気抵抗を調べるため、軟鋼−真鍮
、軟鋼−軟鋼、真鍮−真鍮の組み合わせについてテスタ
ーて測定した。この結果を第２表に示した。This B-stage resin was melted at 130°C in the air and applied to the bonding surface of the adherends. After adhering the adherends together, they were fixed using a jig and heat treated in the air at 180°C for 1 hour to harden. Post-curing was carried out in air at 200°C for 20 hours.In order to investigate the electrical resistance of bonded parts between different adherends, measurements were made using a tester for combinations of mild steel and brass, mild steel and mild steel, and brass and brass. The results are shown in Table 2.

第２表 実施例３゜ 市販の炭化珪素焼結体を空気中６００℃１時間熱処理し
、表面に酸素を含む官能基を導入した後、これを被着材
とした。接着剤としては、軟化点８３℃の石炭系ピッチ
のベンゼンｉ１７溶分（ＩＰ均分子Ｆ、ｊ　３６０　）
とｐ−キシリレシクロライトをモル比てｌ：２のＭ合て
混合し、そこにｌ　ｗ　ｔ％のρ−無水塩化アルミニウ
ムを加えた混合物を１３００Ｃて４０分間反応させたＢ
ステージ樹脂を用いた。このＢステージ樹脂に導電性化
促進触媒として無水塩化アルミニウムを０．５ｗｔ％添
加した混合物を１３０℃て溶融させ、炭化珪素焼結体　
に塗りつけ、炭化珪素焼結体同志を治具て固定し、１５
０℃て接ｊ？＆ｊ！化させた。引き続き２００℃て１０
時間後硬化処理をした。＃熱性を調べる［１的で、この
接着構造物を７宋中て２０℃／ｍｉｎの昇温速度て加熱
し、上品減少を測定した。この結果、４５０℃まて全＜
　Ｉ　ＩＩ’Ｃ減少は認められなかった。また、導電性
を調べる［１的で、定電流電源を用いてＩＯＡの電波を
この接ｒ１構造物の両端に流したところ、電圧は４ｖを
示し局部発熱は認められなかった。Table 2 Example 3 A commercially available sintered silicon carbide body was heat treated in air at 600°C for 1 hour to introduce oxygen-containing functional groups onto the surface, and then used as an adherend. As an adhesive, benzene i17 soluble portion of coal-based pitch with a softening point of 83°C (IP homogeneous molecular weight F, j 360) is used.
B and p-xylylecyclolite were mixed in a molar ratio of 1:2, and 1 wt% of ρ-anhydrous aluminum chloride was added thereto, and the mixture was reacted at 1300C for 40 minutes.
Stage resin was used. A mixture of this B-stage resin and 0.5 wt% of anhydrous aluminum chloride added as a catalyst for promoting conductivity is melted at 130°C to form a sintered silicon carbide.
The silicon carbide sintered bodies were fixed together using a jig, and 15
Is it touching at 0℃? &j! turned into Continue at 200℃ for 10
After some time, it was cured. # Examining thermal properties [1] This adhesive structure was heated at a temperature increase rate of 20° C./min during the 7th century, and the reduction in quality was measured. As a result, all <
I II'C reduction was not observed. In addition, conductivity was investigated [1] When IOA radio waves were passed through both ends of this contact r1 structure using a constant current power supply, the voltage was 4 V and no local heat generation was observed.

実施例４゜ 市販の黒鉛材を空気中、５００℃て３０分間熱処理し、
表面に酸素を含む官住基を導入した後、ｐ−キシリレシ
クロライト：５ｗｔ％、ｐ−トルエンスルホン酸・１ｗ
ｔ％のエタノール溶液から成る表面処理剤に浸した後、
空気中１５０’ｃて３０分間熱処理し、これを被７７材
とした。接着剤としては、ナフタレンとｐ−キシリレン
クリコールをモル比ｌ・１．７５の割合で混合し、そこ
に１ｗｔ％のＰ−トルエンスルホン酸を加えた混合物を
空気中１３０℃て４０分間反応させたＢステージ樹脂を
用いた。このＢステージ８４脂に導電性化促進触媒とし
て無水Ｉ′ｉＬ化アルミニウムを０．５ｗｔ％、導電性
骨材として３５０メツシユ以ｒに粉砕した黒鉛粉末を１
０ｗｔ％添加した庚、空気中１４０　”Ｃて溶融させた
。溶融物を常温まて冷却した後これを粉末として被７ｉ
材に挟み、治具て固定し、１５０℃に加熱しなから接着
面を締めつけ接ｒ１硬化させた。接着構造物は２５０℃
て１０時間後硬化処理をした。接着部の電気抵抗を調べ
るため、デスタ〜て４１１１定した。この結果接着部は
接着厚み４０μｍて０．１Ωの電気抵抗を示した。Example 4 A commercially available graphite material was heat treated in air at 500°C for 30 minutes,
After introducing oxygen-containing kanju groups to the surface, p-xylylecyclolite: 5wt%, p-toluenesulfonic acid 1w
After soaking in a surface treatment agent consisting of t% ethanol solution,
It was heat treated in air at 150'C for 30 minutes, and this was used as material 77. The adhesive was prepared by mixing naphthalene and p-xylylene glycol at a molar ratio of l·1.75, adding 1 wt% of p-toluenesulfonic acid thereto, and reacting the mixture in air at 130°C for 40 minutes. A B-stage resin was used. To this B-stage 84 fat, 0.5 wt% of anhydrous aluminum chloride was added as a catalyst to promote conductivity, and 1 % of graphite powder crushed to a mesh size of 350 mesh or less was added as a conductive aggregate.
0 wt % added was melted in air at 140"C. After the melt was cooled to room temperature, it was made into a powder for 7 days.
It was sandwiched between two pieces of material, fixed with a jig, heated to 150°C, and the adhesive surface was tightened to cure the adhesive r1. Adhesive structure is 250℃
After 10 hours, a curing treatment was performed. In order to examine the electrical resistance of the bonded portion, a test sample of 4111 was determined. As a result, the bonded portion exhibited an electrical resistance of 0.1Ω with a bonding thickness of 40 μm.

実施例５゜ 出限の黒鉛材（引っばり強度２５０　ｋ　ｇ　／　ｃ　
ｍ’）を２０Ｘ２０Ｘ２０ｍｍに加工し、空気中５００
℃て３０分間熱処理し１表面に酸素を含む官能基を導入
した後、ｐ−キシリレンクリコール・５ｗｔ％、ｐ−ト
ルエンスルホン酸・１ｗｔ％のエタノール溶液から成る
表面処理材に浸した後、空気中１５０℃て３０分間熱処
理し、これを被着材とした。接着剤としては、Ｔ＆化点
点８３℃石炭系ピウチのベンゼンｎ（溶分（モ均分子呈
３６０　）とｐ−キシリレンクリコールをモル比ｌ；２
の割合て混合し、そこに１ｗｔ％のｐ−トルエンスルホ
ン酸を加えた混合物を１３０℃で４０分間反応させたＢ
ステージ８１脂を用いた。このＢステージ樹脂に導電性
化促進触媒として無水塩化アルミニウムを０．５ｗｔ％
添加した混合物を空気中１３０００で溶融させ、被着材
の接着面に塗布し被着材同志を接着後、冶具て固定し空
気中１８０℃１時間熱処理し硬化させた。後硬化は空気
中２００℃て２０時間行った。接１１強度を調べる目的
で引っ張り強度を測定したところ、破断は被着材の部分
から起こり接Ｉｉ面には変化がなかった。Example 5 Graphite material with a tensile strength of 250 kg/c
m') to 20X20X20mm and 500mm in air.
After heat treatment at ℃ for 30 minutes to introduce oxygen-containing functional groups onto the surface, it was immersed in a surface treatment material consisting of an ethanol solution of p-xylylene glycol 5 wt% and p-toluenesulfonic acid 1 wt%. This was heat-treated at 150° C. for 30 minutes and used as an adherend. As an adhesive, a molar ratio of p-xylylene glycol and p-xylylene glycol was used.
1 wt% of p-toluenesulfonic acid was added thereto, and the mixture was reacted at 130°C for 40 minutes.
Stage 81 fat was used. 0.5wt% of anhydrous aluminum chloride was added to this B-stage resin as a catalyst to promote conductivity.
The added mixture was melted in air at 13,000° C., applied to the adhesion surfaces of adherends, and after adhering the adherends together, they were fixed using a jig and cured by heat treatment in air at 180° C. for 1 hour. Post-curing was carried out in air at 200° C. for 20 hours. When the tensile strength was measured for the purpose of examining the contact 11 strength, it was found that the fracture occurred from the adherend and there was no change in the contact Ii surface.

゛ｙｈ例６゜ ￥流側１において接γ１材組成物に出限の銀粉（モ均顆
子径２ルｍ）を５ｗｔ％添加した後、実施例１と同様に
接着を行った。この結果電気抵抗は接ｒｉ厚み２８ルｍ
て０．０８Ωとなった。゛yh Example 6゜After adding 5 wt % of the limited amount of silver powder (monocurd diameter 2 m) to the contact gamma 1 material composition on the flow side 1, adhesion was carried out in the same manner as in Example 1. As a result, the electrical resistance is 28 m thick
The result was 0.08Ω.

実施例７゜ 実施例５て接着した黒鉛材を接着面を′上流か流れるよ
うに、放゛屯加玉機ＥＰ−６０Ｋ　（三菱′心気（株）
）に固定しで、軟鋼を相手材としケロシン中てピーク電
流２０Ａ、パルス幅６０ｇ５ｅｃの条件て放電加「を行
った。この結果、２詩間て軟鋼に２０Ｘ２０Ｘ１０ｍｍ
の底付き穴加重をしたか接着部には変化かなかった。Example 7 The graphite material bonded in Example 5 was placed in a droplet beading machine EP-60K (Mitsubishi Shinki Co., Ltd.) so that it flowed upstream along the bonded surface.
), and using mild steel as the mating material, electrical discharge was applied in kerosene with a peak current of 20 A and a pulse width of 60 g, 5 ec.
Even though the bottom hole was loaded, there was no change in the adhesive part.

実施例８゜ 実施例１て１１ｔられた接着構造物を洟とう水中て３０
０時間処理したか全く変化は認められなかった。Example 8゜The adhesive structure prepared in Example 1 by 11 tons was soaked in water for 30 minutes.
No change was observed after 0 hours of treatment.

（発明の効果） 以上説明した如く、未発り１の導電性接着構造物はＣ０
ＰＮＡ樹脂組成物接着剤と表面に水素、ハロゲン、ヒド
ロキシル基、カルボニル基、カルボキシル基、アルデヒ
ド基、エポキシ構造、ラクトン構造、エーテル構造、酸
無水物構造から選ばれる少なくとも一種を右し若しくは
導入された被着材とが、前記被着材と接着剤の界面にお
いで、前記表面処理封着しくは前記添加剤を介して結合
し、かつ導電性化促進触媒の存在ドてこのＣ０ＰＮＡ樹
脂組成物の硬化体か芳香族共役系に基づく導電性を示す
導電性接着構造物であり、従来の導電性接着構造物には
見られない導電性骨材を必要としないて導゛屯性を発現
する導電性接着構造物であるのみならず、優れた耐熱性
、耐水性１寸法安定性１強度４熱電動性等をも備えた導
電性接着構造物である。(Effects of the invention) As explained above, the conductive adhesive structure of unreleased 1 is C0
At least one selected from hydrogen, halogen, hydroxyl group, carbonyl group, carboxyl group, aldehyde group, epoxy structure, lactone structure, ether structure, and acid anhydride structure is introduced or introduced into the PNA resin composition adhesive and the surface. The C0PNA resin composition is bonded to the adherend through the surface treatment sealing or the additive at the interface between the adherend and the adhesive, and is levered by the presence of the conductivity promoting catalyst. It is a conductive adhesive structure that exhibits conductivity based on a cured product or an aromatic conjugated system, and it is a conductive adhesive structure that exhibits conductivity without the need for conductive aggregate, which is not found in conventional conductive adhesive structures. It is not only a conductive adhesive structure but also has excellent heat resistance, water resistance, 1-dimensional stability, 1-strength, 4-thermoelectricity, etc.

この優れた耐熱性、耐水性、・１−法安定性、強度、熟
′屯動性等を備えた導電性接着構造物は構造材料、断熱
材料、′心気、電子用材料、しゅう動部材、帯伝防１Ｆ
−１’ｉｌｊ磁波シールド笠の用途に使用することがて
き、産業−Ｌに大きく寄与する効果か考えられる。This conductive adhesive structure with excellent heat resistance, water resistance, legal stability, strength, and aging properties can be used as structural materials, insulation materials, core materials, electronic materials, and sliding parts. , Obidenbo 1F
-1'ilj It can be used for magnetic wave shielding shade, and it is thought that it will have an effect that greatly contributes to industry-L.

４￥許出願人　イビデン株式会社 手続７市正書　（自発） 昭和６１年ＩＯ月ＩＩ日 特許庁長官　黒１）明雄　殿　　　′↑゛１゛−２゛ １、ｊｊ￥件の表示 昭和６０年特許願第２７８８００号 ２）、発明の名称 導電性接着構造物及びその製造方法 ３、補正をする者 事件との関係　　特許出願人 住　所　　岐阜県大垣市神田町二丁目１番地名　称　　
（ＯｔＳ）イビデン株式会社代表者　多賀潤一部 ４、代理人 住　所　岐阜市長住町１丁目１１番地 マルキチビル３階 ５、補正の対象 ■）明細書の特許請求の範囲の欄 ２）明細書の発明の詳細な説明の欄 ６、補正の内容 別紙のとおり（補正の対象に記載した゛扛項以外は内容
に変更なし。） ７、添付８類の目録 ｌ）全文訂正明細書・・・１通 明　　細　　書 １、発明の名称 導電性接着構造物及びその製造方法 ２）、特許請求の範囲 １）ｔＩｄ合多環芳香族化合物、芳香族架橋剤、酸触媒
が反応して威る熱硬化性組成物から成る接着剤と：被着
材とが：前記被着材と前記接着剤の界面においで、前記
芳香族架橋剤を主体とする表面処理剤若しくは添加剤を
介する結合を有し、かつ前記接着剤が導電性化促進触媒
によって実質的に導電性を示す共役系を形成して成るこ
とを特徴とする導電性接着構造物。4￥ Applicant: IBIDEN Co., Ltd. Procedural 7 City Authorization (Spontaneous) Date of IO, February 2, 1985 Commissioner of the Patent Office Black 1) Mr. Akio Application No. 2788002), Title of the invention: Conductive adhesive structure and its manufacturing method 3, Relationship with the amended case Patent applicant address: 2-1 Kanda-cho, Ogaki City, Gifu Prefecture Name:
(OtS) IBIDEN Co., Ltd. Representative: Jun Taga Part 4, Agent address: 3rd floor 5, Marukichi Building, 1-11 Nagasumi-cho, Gifu Subject of amendment ■) Scope of claims in the specification 2) Inventions in the specification Detailed explanation column 6, Contents of the amendment As shown in the attached sheet (there are no changes in the content other than the items listed in the subject of amendment.) 7. Attached list of category 8 l) Full text revised specification... 1 copy Specification 1, Name of the invention Conductive adhesive structure and method for producing the same 2) Claims 1) Thermosetting composition in which a tId-coated polycyclic aromatic compound, an aromatic crosslinking agent, and an acid catalyst react with each other. an adhesive consisting of: an adherend: has a bond via a surface treatment agent or additive mainly composed of the aromatic crosslinking agent at the interface between the adherend and the adhesive; 1. An electrically conductive adhesive structure, characterized in that the adhesive forms a conjugated system that is substantially electrically conductive using a catalyst that promotes electrical conductivity.

２）、特許請求の範囲第１項記載の導電性接着構造物に
おいで、前記接着剤か前記縮合多環芳香族化合物と前記
芳香族架橋剤と前記酸触媒の混合物。2) The conductive adhesive structure according to claim 1, which is a mixture of the adhesive, the fused polycyclic aromatic compound, the aromatic crosslinking agent, and the acid catalyst.

もしくはこれらの熱硬化性中間反応生成物の中から選ば
れる、少なくとも一種が反応により熱硬化されて成るこ
とを特徴とする導電性接着構造物。Alternatively, an electrically conductive adhesive structure characterized in that at least one selected from these thermosetting intermediate reaction products is thermally cured by reaction.

３）特許請求の範囲第１項記載の導電性接着構造物にお
いで、前記縮合多環芳香族化合物はナフタレン、アント
ラセン、フェナントレン、ビレン、クリセン、ナフタセ
ン、アセナフテン、アセナフチレン、ペリレン、コロネ
ン、及びこれらを主骨格とする誘導体の中から選ばれる
一種又は二種以上の混合物或いは、石炭系若しくは石油
系の徽賀油、タール、ピッチ及びこれらの誘導体の中か
ら選ばれる−・種又は二種以上の混合物であることを特
徴とする導電性接着構造物。3) In the conductive adhesive structure according to claim 1, the fused polycyclic aromatic compound includes naphthalene, anthracene, phenanthrene, birene, chrysene, naphthacene, acenaphthene, acenaphthylene, perylene, coronene, and any of these. One or a mixture of two or more types selected from the derivatives used as the main skeleton, or a species or a mixture of two or more types selected from the group consisting of coal-based or petroleum-based Hika oil, tar, pitch, and their derivatives. A conductive adhesive structure characterized by:

４）特許請求の範囲第１項記載の導電性接着構造物にお
いで、前記芳香族架橋剤はヒドロキシメチル基、ハロメ
チル基のいずれか少なくとも一種の基を二個以上有する
一環または二環以上の芳香環から成る芳香族ＩＣＣ副剤
あることを特徴とする導電性接着構造物。4) In the conductive adhesive structure according to claim 1, the aromatic crosslinking agent is a one- or two- or more-ring aromatic having two or more of at least one of hydroxymethyl groups and halomethyl groups. A conductive adhesive structure comprising an aromatic ICC adjuvant consisting of a ring.

５）特許請求の範囲第１項記載の導電性接着構造物にお
いで、前記酸触媒は、塩化アルミニウム、弗化ホウ素、
硫酸、リン酸、有機スルホン酸、カルボン酸、及びこれ
らの誘導体の中から選ばれる−・種又は二種具」−の混
合物であることを特徴とする導電性接着構造物。5) In the conductive adhesive structure according to claim 1, the acid catalyst is aluminum chloride, boron fluoride,
A conductive adhesive structure characterized in that it is a mixture of sulfuric acid, phosphoric acid, organic sulfonic acid, carboxylic acid, and derivatives thereof.

６）特許請求の範囲第１項記載の導電性接着構造物にお
いで、前記被着材は、１ノ素、黒鉛、金属、金属炭化物
、金属珪化物、金属硼化物、及びこれらの前駆体若しく
は複合材料の中から選ばれる同種又は異種の組み合わせ
であり、前記被着材１１体か導電性を有し、かつ少なく
ともその表面に水、ｋ、ハロゲン、ヒドロキシル基、カ
ルボニル７５．カルボキシル基、アルデヒド基、エポキ
シ構造、ラクトン構造、エーテル構造、酸無水物構造の
中から選ばれる一種又は二種以−ヒを有するもの、若し
くはこれらが導入されたものであることを特徴とする導
電性接着構造物。6) In the electrically conductive adhesive structure according to claim 1, the adherend material is monomer, graphite, metal, metal carbide, metal silicide, metal boride, and precursors or precursors thereof. It is a combination of the same type or different types selected from composite materials, and the adherend 11 has conductivity, and at least its surface contains water, k, halogen, hydroxyl group, carbonyl 75. A conductive material having one or more selected from carboxyl groups, aldehyde groups, epoxy structures, lactone structures, ether structures, and acid anhydride structures, or into which these are introduced. adhesive structure.

７）特許請求の範囲第１項記載の導電性接着構造物にお
いで、前記導電性化促進触媒は空気、酸素、オゾン、イ
オウ、過酸化水素、二酸化マンガン、亜硝酸、硝酸、過
マンガン酸、クロム酸、塩素酸、次亜塩素酸の中から選
ばれる一種又は二種具」二の混合物から成る酸化剤であ
ることを特徴とする導電性接着構造物。7) In the conductive adhesive structure according to claim 1, the conductivity promoting catalyst is air, oxygen, ozone, sulfur, hydrogen peroxide, manganese dioxide, nitrous acid, nitric acid, permanganic acid, A conductive adhesive structure characterized in that the oxidizing agent is composed of one or a mixture of two selected from chromic acid, chloric acid, and hypochlorous acid.

８）特許請求の範囲第１項記載の導電性接着構造物にお
いで、前記導電性化促進触媒は空気、酸素、オゾン、−
ｆ才つ、過酸化水素、二酸化マンカン、亜硝酸、硝酸、
過マンガン酸、クロム酸、塩素酸、次亜塩素酸の中から
選ばれる一種又は二種以上の混合物から成る酸化剤と塩
化アルミニウム。8) In the conductive adhesive structure according to claim 1, the conductivity promoting catalyst is air, oxygen, ozone, -
Hydrogen peroxide, mankan dioxide, nitrous acid, nitric acid,
An oxidizing agent consisting of one or a mixture of two or more selected from permanganic acid, chromic acid, chloric acid, and hypochlorous acid, and aluminum chloride.

弗化ホウ素、硫酸、リン酸、有機スルホン酸、カルボン
酸、及びこれらの誘導体の中から選ばれる一種又は二種
以上の混合物とを組み合わせて成ることを特徴とする導
電性接着構造物。1. A conductive adhesive structure comprising a combination of one or a mixture of two or more selected from boron fluoride, sulfuric acid, phosphoric acid, organic sulfonic acid, carboxylic acid, and derivatives thereof.

９）特許請求の範囲第１項記載の導電性接着構造物にお
いで、前記表面処理剤及び前記添加剤はヒドロキシメチ
ル基、ハロメチル基のいずれか少なくとも一種の基を二
個以上有する一環または二環以上の芳香環から成る芳香
族架橋剤若しくは、前記芳香族架橋剤と前記酸触媒との
混合物から成る架橋能を有する組成物であり、なおかつ
前記被着材表面の水素、ハロゲン、ヒドロキシル基、カ
ルボニル基、カルボキシル基、アルデヒド基、エポキシ
構造、ラクトン構造、エーテル構造、酸無水物構造と前
記接着剤とを化学的に結合せしめて成ることを特徴とす
る導電性接着構造物。9) In the conductive adhesive structure according to claim 1, the surface treatment agent and the additive are monocyclic or bicyclic compounds having two or more groups of at least one of hydroxymethyl groups and halomethyl groups. A composition having a crosslinking ability consisting of an aromatic crosslinking agent consisting of the above aromatic ring or a mixture of the aromatic crosslinking agent and the acid catalyst, and hydrogen, halogen, hydroxyl group, carbonyl on the surface of the adherend. 1. A conductive adhesive structure, characterized in that the adhesive is chemically bonded to a group, a carboxyl group, an aldehyde group, an epoxy structure, a lactone structure, an ether structure, or an acid anhydride structure.

１０）下記（ａ）〜（ｄ）のシーケンスから成ることを
特徴とする導電性接着構造物の製造方法。10) A method for producing a conductive adhesive structure, comprising the following sequences (a) to (d).

（ａ）水素、ハロゲン、ヒドロキシル基、カルボニル基
、カルボキシル基、アルデヒド基、エポキシ構造、ラク
トン構造、エーテル構造、酸無水物構造の中から選ばれ
る一種又は二種具りを少なくとも表面に有する被着材の
該表面を、ヒドロキシメチル基、ハロメチル基のいずれ
か少なくとも一種の基を一個以上有する一環または二環
以上の芳香環から成る芳香族架橋剤を１体とする表面処
理剤によって被覆せしめた後、熱処理を行う工程：（ｂ
）縮合多環芳香族化合物と、前記芳香族架橋剤と、酸触
媒とを組合ヒて成る熱硬化性！ｌ成物から成る接着剤？
Ａ成物を導電性化促進触媒の存在下で、可塑化若しくは
液化させる工程： （ｃ）前記（ｂ）工程で可塑化若しくは液化された接着
剤組成物を介して前記（ａ）工程で被覆された被着材匹
望を接着させ、酸化性雰囲気中１００〜４００℃の温度
範囲に加熱し、前記接着剤組成物を熱硬化させると共に
、実質的に導電性を有する共役系の形成を促す接着工程
； （ｄ）前記成形硬化体を酸化性又は非酸化性雰囲気中１
００〜４００℃の温度範囲に加熱し、３０分間以ト１０
０時間以下の時間、前記温度範囲に保持し、実質的に導
電性を有する共役系の発達を促進させる後硬化工程。(a) A coating having at least one or two selected from hydrogen, halogen, hydroxyl group, carbonyl group, carboxyl group, aldehyde group, epoxy structure, lactone structure, ether structure, and acid anhydride structure on its surface. After the surface of the material is coated with a surface treatment agent containing an aromatic crosslinking agent consisting of one or two or more aromatic rings having one or more groups of at least one of hydroxymethyl group and halomethyl group. , step of heat treatment: (b
) A thermosetting product made by combining a fused polycyclic aromatic compound, the aromatic crosslinking agent, and an acid catalyst! Adhesives made of l compounds?
A step of plasticizing or liquefying the product A in the presence of a conductivity promoting catalyst: (c) Coating in the step (a) with the adhesive composition plasticized or liquefied in the step (b). The adhesive composition is heated to a temperature range of 100 to 400° C. in an oxidizing atmosphere to thermally cure the adhesive composition and promote the formation of a conjugated system having substantially electrical conductivity. Adhesion step; (d) The molded cured body is placed in an oxidizing or non-oxidizing atmosphere.
Heat to a temperature range of 00 to 400℃ for 30 minutes or more.
A post-curing step in which the temperature is maintained in the temperature range for no more than 0 hours to promote the development of a conjugated system that is substantially electrically conductive.

１１）特許請求の範囲第１０項記載の製造方法においで
、前記表面処理剤はヒドロキシメチル基、へロメチル基
のいずれか少なくとも一種の基を二個以上有する一環ま
たは二環以上の芳香環から成る芳香族架橋剤であり、前
記芳香族架橋剤の融点以上の温度に加熱溶融させ液状と
し、若しくは溶剤に溶解させ溶液として使用することを
特徴とする導電性接着構造物の製造方法。11) In the manufacturing method according to claim 10, the surface treatment agent consists of one or two or more aromatic rings having two or more of at least one of hydroxymethyl group and heromethyl group. 1. A method for producing a conductive adhesive structure, which is an aromatic crosslinking agent, and the method comprises heating and melting the aromatic crosslinking agent at a temperature higher than its melting point to form a liquid, or dissolving it in a solvent and using it as a solution.

１２）、特許請求の範囲第１０項記載の製造方法におい
で、前記表面処理剤は前記芳香族架橋剤と前記酸触媒と
の混合物であり、混合物の融点以上の温度に加熱溶融さ
せ液状とし、若しくは溶剤に溶解させ溶液として使用す
ることにより前記被着材の表面官能基と前記芳香族架橋
剤とを前記熱処理により反応せしめることを特徴とする
導電性接着構造物の製造方法。12) In the manufacturing method according to claim 10, the surface treatment agent is a mixture of the aromatic crosslinking agent and the acid catalyst, and is melted by heating to a temperature equal to or higher than the melting point of the mixture to form a liquid; Alternatively, a method for producing a conductive adhesive structure, characterized in that the surface functional group of the adherend is reacted with the aromatic crosslinking agent by the heat treatment by dissolving it in a solvent and using it as a solution.

１３）特許請求の範囲第１０項記載の製造方法においで
、前記接着剤組成物は縮合多環芳香族化合物と、前記芳
香族架橋剤と、酸触媒とを組み合わせて成る熱硬化性組
成物の粉末混合物であることを特徴とする導電性接着構
造物の製造方法。13) In the manufacturing method according to claim 10, the adhesive composition is a thermosetting composition comprising a combination of a fused polycyclic aromatic compound, the aromatic crosslinking agent, and an acid catalyst. A method for producing a conductive adhesive structure, characterized in that it is a powder mixture.

１４）特許請求の範囲第１０項記載の製造方法においで
、前記接着剤組成物は前記熱硬化性組成物を酸化性又は
非酸化性雰囲気中６０〜３００℃の温度範囲に加熱反応
させてなる実質的に熱可塑性を有する熱硬化性中間反応
生成物であることを特徴とする導電性接着構造物の製造
方法。14) In the manufacturing method according to claim 10, the adhesive composition is obtained by subjecting the thermosetting composition to a heating reaction in an oxidizing or non-oxidizing atmosphere at a temperature in the range of 60 to 300°C. A method for producing a conductive adhesive structure, characterized in that the thermosetting intermediate reaction product is substantially thermoplastic.

１５）特許請求の範囲第１０項記載の製造方法においで
、前記導電性化促進触媒は空気、酸素、オゾン、イオウ
、過酸化水素、二酸化マンガン、亜硝酸、硝酸、過マン
ガン酸、クロム酸、塩素酸、次亜塩素酸の中から選ばれ
る一種又は二種以上の混合物から成る酸化剤であり、前
記導電性化促進触媒か常温で気体の場合はその存在Ｆで
、液体又は固体の場合は添加して使用することを特徴と
する導電性接着構造物の製造方法。15) In the manufacturing method according to claim 10, the conductivity promoting catalyst is air, oxygen, ozone, sulfur, hydrogen peroxide, manganese dioxide, nitrous acid, nitric acid, permanganic acid, chromic acid, It is an oxidizing agent consisting of one type or a mixture of two or more selected from chloric acid and hypochlorous acid, and if the conductivity promoting catalyst is a gas at room temperature, its presence is F, and if it is a liquid or solid, its presence is F. A method for manufacturing a conductive adhesive structure, characterized in that the conductive adhesive structure is used by adding the same.

１６）特許請求の範囲第１０項記載の製造方法においで
、前記導電性化促進触媒は空気、酸素、オゾン、イオウ
、過酸化水素、二酸化マンガン、亜硝酸、硝酸、過マン
ガン酸、クロム酸、塩素酸１次亜塩素酸の中から選ばれ
る一種又は二種以上の混合物から成る酸化剤と塩化アル
ミニウム、弗化ホウ素、Ｇ＆酸、リン酸、有機スルホン
酸、カルボン酸、及びこれらの誘導体の中から選ばれる
一種又は二種以上の混合物との組み合わせであり、前記
導電性化促進触媒が常温で気体の場合はその存在下で、
液体又は固体の場合は添加して使用することを特徴とす
る導電性接着構造物の製造方法。16) In the manufacturing method according to claim 10, the conductivity promoting catalyst is air, oxygen, ozone, sulfur, hydrogen peroxide, manganese dioxide, nitrous acid, nitric acid, permanganic acid, chromic acid, An oxidizing agent consisting of one or a mixture of two or more selected from chloric acid and primary hypochlorous acid, aluminum chloride, boron fluoride, G& acid, phosphoric acid, organic sulfonic acid, carboxylic acid, and derivatives thereof. A combination of one or a mixture of two or more selected from
A method for producing a conductive adhesive structure, characterized in that a liquid or solid is used by adding it.

１７）特許請求の範囲第１０項記佐の製造方法においで
、前記可塑化は前記接着剤組成物を酸化性又は非酸化性
雰囲気中６０〜３００℃の温度範囲に加熱して成ること
を特徴とする導電性接着構造物の製造方法。17) The manufacturing method according to claim 10, wherein the plasticizing step is performed by heating the adhesive composition to a temperature range of 60 to 300°C in an oxidizing or non-oxidizing atmosphere. A method for manufacturing a conductive adhesive structure.

１８）特許請求の範囲第１０項記載の製造方法においで
、前記液化は前記接着剤組成物を溶剤に溶解させて成る
ことを特徴とする導電性接着構造物の製造方法。18) The method of manufacturing a conductive adhesive structure according to claim 10, wherein the liquefaction is performed by dissolving the adhesive composition in a solvent.

１９）下記（ａ）〜（ｃ）のシーケンスから成ることを
特徴とする導電性接着構造物の製造方法。19) A method for producing a conductive adhesive structure, comprising the following sequences (a) to (c).

（ａ）　ｍ合多環芳香族化合物と、ヒドロキシメチル基
、へロメチル基のいずれか少なくとも一種の基を二個以
上有する一環または二環以上の芳香環から成る芳香族架
橋剤と、酸触媒とを組み合わせて成る熱硬化性組成物か
ら成る接着剤組成物に過剰の前記芳香族架橋剤若しくは
前記芳香族架橋剤と前記酸触媒の混合物から成る添加剤
を加え、導電性化促進触媒の存在下で、接着剤組成物を
可塑化若しくは液化させる工程： （ｂ）前記（ａ）　、：Ｃ程で可塑化若しくは液化させ
た接着剤組成物を介しで、水素、ハロゲン、ヒドロキシ
ル基、カルボニル基、カルボキシル基、アルデヒド基、
エポキシ構造、ラクトン構造、エーテル構造、酸無水物
構造の中から選ばれる一種又は二種具りを少なくとも表
面に有する被着材戦塵を接着させ、酸化性雰囲気中１０
０〜４００℃の温度範囲に加熱し、前記接着剤組成物を
熱硬化させると共に、実質的に導電性を有する共役系の
形成を促す接着工程： （ｃ）前記成形硬化体を酸化性又は非酸化性雰囲気中１
００〜４００℃の温度範囲に加熱し、３０分間以上１０
０時間以下の時間、前記温度範囲に保持し、実質的に導
電性を有する共役系の発達を促進させる後硬化工程。(a) an m-polycyclic aromatic compound, an aromatic crosslinking agent consisting of one or two or more aromatic rings having two or more of at least one of hydroxymethyl groups and heromethyl groups, and an acid catalyst. An excess amount of an additive consisting of the aromatic crosslinking agent or a mixture of the aromatic crosslinking agent and the acid catalyst is added to an adhesive composition consisting of a thermosetting composition consisting of a combination of the above in the presence of a conductivity promoting catalyst. Step of plasticizing or liquefying the adhesive composition: (b) Hydrogen, halogen, hydroxyl group, carbonyl group, carboxyl group, aldehyde group,
An adherend material having at least one or two types of structures selected from epoxy structure, lactone structure, ether structure, and acid anhydride structure on the surface is adhered, and 10
An adhesion step in which the adhesive composition is heated to a temperature range of 0 to 400°C, and the adhesive composition is thermally cured, and the adhesive composition is promoted to form a conjugated system that is substantially conductive. In an oxidizing atmosphere 1
Heat to a temperature range of 00 to 400℃ for 30 minutes or more.
A post-curing step in which the temperature is maintained in the temperature range for no more than 0 hours to promote the development of a conjugated system that is substantially electrically conductive.

２）、特許請求の範囲第１９項記載の製造方法においで
、前記接着剤組成物は縮合多環芳香族化合物と、前記芳
香族架橋剤と、酸触媒とを組み合わせて成る熱硬化性組
成物の粉末混合物であることを特徴とする導電性接着構
造物の製造方法。2) In the manufacturing method according to claim 19, the adhesive composition is a thermosetting composition comprising a combination of a condensed polycyclic aromatic compound, the aromatic crosslinking agent, and an acid catalyst. A method for producing a conductive adhesive structure, characterized in that the powder mixture is a powder mixture of:

２）、特許請求の範囲第１９項記載の製造方法においで
、前記接着剤紋虚〕は前記縮合多環芳香族化合物と、前
記芳香族架橋剤と、酸触媒とを組み合わせて酸化性又は
非酸化性雰囲気中６０〜３００℃の温度範囲に加熱反応
させてなる実質的に熱可塑性を有する熱硬化性中間反応
生成物であることを特徴とする導電性接着構造物の製造
方法。2) In the manufacturing method according to claim 19, the adhesive embossment is made by combining the fused polycyclic aromatic compound, the aromatic crosslinking agent, and an acid catalyst. 1. A method for producing a conductive adhesive structure, characterized in that it is a thermosetting intermediate reaction product having substantially thermoplastic properties, which is obtained by heat-reacting in an oxidizing atmosphere at a temperature in the range of 60 to 300°C.

２）、特許請求の範囲第１９項記載の製造方法においで
、前記導電性化促進触媒は空気、酸素、オゾン、イオウ
、過酸化水素、二酸化マンガン、亜硝酸、硝酸、過マン
ガン酸、クロム酸、塩素酸１次亜塩素酸の中から選ばれ
る一種又は二種具１の混合物から成る酸化剤であり、前
記導電性化促進触媒が常温て気体の場合はその存在下で
、液体又は固体の場合は添加して使用することを特徴と
する導電性接着構造物の製造方法。2) In the manufacturing method according to claim 19, the conductivity promoting catalyst is air, oxygen, ozone, sulfur, hydrogen peroxide, manganese dioxide, nitrous acid, nitric acid, permanganic acid, chromic acid. It is an oxidizing agent consisting of one or a mixture of two selected from chloric acid and primary hypochlorous acid, and when the conductivity promoting catalyst is a gas at room temperature, in its presence, it is oxidized into a liquid or solid state. A method for manufacturing a conductive adhesive structure, characterized in that the conductive adhesive structure is used by adding a conductive adhesive structure.

２）、特許請求の範囲第１９項記載の製造方法においで
、前記導電性化促進触媒は空気、酸素、オゾン、イオウ
、過酸化水素、二酸化マンガン、亜硝酸、硝酸、過マン
ガン酸、クロム酸、塩素酸、次亜塩素酸の中から選ばれ
る一種又は二種以上の混合物から成る酸化剤と塩化アル
ミニウム、弗化ホウ素、硫酸、リン酸、有機スルホン酸
、カルボン酸、及びこれらの誘導体の中から選ばれる一
種又は二種具りの混合物との組み合わせであり、前記導
電性化促進触媒か常温で気体の場合はその存在Ｆで、液
体又は固体の場合は添加して使用することを特徴とする
導電性接着構造物の製造方法。2) In the manufacturing method according to claim 19, the conductivity promoting catalyst is air, oxygen, ozone, sulfur, hydrogen peroxide, manganese dioxide, nitrous acid, nitric acid, permanganic acid, chromic acid. An oxidizing agent consisting of one or a mixture of two or more selected from , chloric acid, and hypochlorous acid, and aluminum chloride, boron fluoride, sulfuric acid, phosphoric acid, organic sulfonic acid, carboxylic acid, and derivatives thereof. It is a combination with one or a mixture of two selected from the following, and is characterized in that when the conductivity promoting catalyst is a gas at room temperature, its presence F is used, and when it is a liquid or solid, it is used in addition. A method for manufacturing a conductive adhesive structure.

２）、特許請求の範囲第１９項記載の製造方法においで
、前記液化は前記接着剤組成物を溶剤に溶解させて成る
ことを特徴とする導電性接着構造物の製造方法。2) The method of manufacturing a conductive adhesive structure according to claim 19, wherein the liquefaction is performed by dissolving the adhesive composition in a solvent.

２）、特許請求の範囲第１９項記載の製造方法においで
、前記添加剤を融点以上の温度に加熱溶融させ、液状と
し、若しくは溶剤に溶解させ溶液とし゛Ｃ使用すること
を特徴とする導電性接着構造物の製造方法。2) In the manufacturing method according to claim 19, the additive is melted by heating to a temperature higher than the melting point to form a liquid, or dissolved in a solvent and used as a solution. A method for manufacturing a bonded structure.

３、発明の詳細な説明 （産業上の利用分野） 本発明は特に導電性骨材を必要としない導電性接着構造
物及びその製造方法に関し、特に本発明は新規な８硬化
性樹脂を接着剤とする導電性接着構造物及びその製造方
法に関するものである。3. Detailed description of the invention (industrial application field) The present invention particularly relates to a conductive adhesive structure that does not require a conductive aggregate and a method for manufacturing the same. The present invention relates to a conductive adhesive structure and a method for manufacturing the same.

（従来の技術） 従来、熱硬化性樹脂を接着剤とする導電性接着構造物と
しては導電性の骨材を添加せずに導電性か発現した例を
見ない。(Prior Art) Conventionally, there has been no example of a conductive adhesive structure using a thermosetting resin as an adhesive that exhibits conductivity without adding conductive aggregate.

（発明か解決しようとする問題点） 従来の導電性接着剤はすべて銀、銅、黒鉛、炭鵞等の導
電性骨材の存在なしに導電性を賦与させることができな
い欠点を有していた。(Problem to be solved by the invention) All conventional conductive adhesives have the disadvantage that they cannot impart conductivity without the presence of conductive aggregates such as silver, copper, graphite, and charcoal. .

（問題点を解決するための手段及び作用）本発明は、銀
、銅、黒鉛、炭素等の導電性骨材の存在なしに導電性を
賦与させることがｎ（能な導電性接着剤から成る導電性
接着構造物及びその製造方法を提供することを目的とす
るものである。(Means and effects for solving the problems) The present invention is made of a conductive adhesive that is capable of imparting conductivity without the presence of a conductive aggregate such as silver, copper, graphite, or carbon. An object of the present invention is to provide a conductive adhesive structure and a method for manufacturing the same.

末完１！１名らのうち一人は昭和６０年１０月ｏ４０に
金沢市において開催された日本化学会第５１秋季年会に
おいで、主として二環以ヒの縮合多環芳香族化合物と、
ヒドロキシメチル基、へロメチル基のいずれか少なくと
も一種の基を二個以上有する一環または二環以ヒの芳香
環から成る芳香族架橋剤と、酸触媒とを組み合わせて成
るｆ！Ｓ硬化性組成物（以下Ｃ０ＰＮＡ樹脂組成物と略
記）について発表を行った。（シンポジウム講演予稿集
■、ｐ５３９−５４２） 本発明は、前記本発明者らのうち一人か発表した、Ｃ０
ＰＮＡ樹脂組成物のうち縮合多環芳香族化合物としてナ
フタレン、アントラセン、フＪナントレン、ビレン、ク
リセン、ナフタセン、アセナフテン、アセナフチレン、
ペリレン、コロネン、及びこれらを主骨格とする誘導体
の中から選ばれる一種又は二種以上の混合物或いは、石
炭系若しくは石油系の改質油、タール、ピッチ及びこれ
らの誘導体を用いた場合、導電性化促進触媒の存在下で
、このＣ０ＰＮＡ樹脂組成物か硬化した後に芳香族共役
系に基づく導電性を示すことに着目し、これを導電性接
着剤として適用し、特に表面に各種の表面官能基を有し
、若しくはこれらが導入された被着材と前記接着剤とを
表面処理剤若しくは添加剤を介してより強固に結合させ
、かつ実質的に導電性を示す導電性接着構造物を提供す
ることを目的とするものであり、特許請求の範囲記載の
導電性接着構造物とその製造方法を提供することによっ
て前記目的を達成することができる。At the 51st Autumn Annual Meeting of the Chemical Society of Japan held in Kanazawa City on October 40, 1985, one of the participants reported that fused polycyclic aromatic compounds, mainly bicyclic or more,
The f! A presentation was made on the S curable composition (hereinafter abbreviated as C0PNA resin composition). (Symposium Lecture Proceedings ■, p539-542) The present invention is based on the C0
Among the PNA resin compositions, the condensed polycyclic aromatic compounds include naphthalene, anthracene, nanthrene, birene, chrysene, naphthacene, acenaphthene, acenaphthylene,
When one or a mixture of two or more selected from perylene, coronene, and derivatives having these as main skeletons, coal-based or petroleum-based reformed oil, tar, pitch, and these derivatives are used, conductivity We focused on the fact that this C0PNA resin composition exhibits conductivity based on an aromatic conjugated system after being cured in the presence of a catalyst that promotes chemical conversion. or an adherend having these introduced therein and the adhesive are bonded more firmly via a surface treatment agent or an additive, and a conductive adhesive structure exhibiting substantially electrical conductivity is provided. This object can be achieved by providing a conductive adhesive structure and a method for manufacturing the same as described in the claims.

次に本発明の詳細な説明する。Next, the present invention will be explained in detail.

即ち、この第一の発明はＣ０ＰＮＡ樹脂組成物接若剤と
、表面に水諧、ハロゲン、ヒトロキシルノ、（、カルボ
ニル基、カルボキシル基、アルデヒド基、エポキシ構造
、ラクトン構造、エーテル構造、酸無水物構造から選ば
れる少なくとも一種を有し、若しくは導入された被着材
とが、前記被着材と接着剤の界面においで、前記表面処
理剤若しくは前記添加剤を介して結合しかつ、導電性化
促進触媒の存在下てこのＣ０ＰＮＡ樹脂組成物が硬化し
た後に芳香族共役系に基づく導電性を示す、耐熱性、耐
水性、寸法安定性、強度、熱伝導性等に富んだ導電性接
着構造物である。That is, this first invention uses a C0PNA resin composition as an attractive agent, and the surface has aqueous, halogen, hydroxyl, (, carbonyl group, carboxyl group, aldehyde group, epoxy structure, lactone structure, ether structure, acid anhydride structure). The adherend having or introduced at least one selected from the following is bonded via the surface treatment agent or the additive at the interface between the adherend and the adhesive, and promotes conductivity. After the C0PNA resin composition is cured in the presence of a catalyst, it exhibits conductivity based on an aromatic conjugated system, and is a conductive adhesive structure rich in heat resistance, water resistance, dimensional stability, strength, thermal conductivity, etc. be.

また、第二、第三の発明はＣ０ＰＮＡ樹脂組成物接着剤
と１表面官能基を有し、若しくはこれが導入された被着
材とを芳香族架橋剤を主体とする表面処理剤若しくは添
加剤によって化学的に結合させ、かつ導電性化促進触媒
の存在下てこのＣ０ＰＮＡ樹脂組成物が硬化した後に芳
香族共役系に基づく導電性を賦与させて成る耐熱性、耐
水性、寸法安定性、強度、熱伝導性笠に富んだ導電性接
着構造物を製造する方法である。In addition, the second and third inventions provide a C0PNA resin composition adhesive and an adherend having one surface functional group or having one surface functional group introduced therein by using a surface treatment agent or additive mainly containing an aromatic crosslinking agent. Heat resistance, water resistance, dimensional stability, strength, which is obtained by chemically bonding and imparting conductivity based on an aromatic conjugated system after the C0PNA resin composition is cured in the presence of a conductivity promoting catalyst. This is a method of manufacturing a conductive adhesive structure rich in thermal conductivity.

以下、この導電性接着構造物を構成するＣ０ＰＮＡ８４
脂組成物接ｒ♂剤の成分である縮合多環芳香族化合物、
芳香族架橋剤、酸触媒、表面処理剤。Hereinafter, C0PNA84 constituting this conductive adhesive structure will be described.
A fused polycyclic aromatic compound that is a component of a fat composition contact agent,
Aromatic crosslinking agent, acid catalyst, surface treatment agent.

添加剤導電性化促進触媒及び被着材について説明する。The additive conductivity promoting catalyst and the adherend will be explained.

本発明の縮合多環芳香族化合物にはナフタレン、アント
ラセン、フェナントレン、ビレン、クリセン、ナフタセ
ン、アセナフテン、アセナフチレン、ペリレン、コロネ
ン、及びこれらを主骨格とする誘導体の中から選ばれる
一種又は二挿具１ユの混合物或いは、石炭系若しくは石
油系の重質油、タール、ピッチ及びこれらの誘導体の中
から選ばれる一種又は二種以上の混合物を使用できる。The fused polycyclic aromatic compound of the present invention includes one or two compounds selected from naphthalene, anthracene, phenanthrene, birene, chrysene, naphthacene, acenaphthene, acenaphthylene, perylene, coronene, and derivatives having these as main skeletons. It is possible to use one or a mixture of two or more selected from the group consisting of coal-based or petroleum-based heavy oil, tar, pitch, and derivatives thereof.

次に未発１］の芳香族架橋剤には、ヒドロキシメチル基
、ハロメチル基Ｓのいずれか少なくとも一種のノ＾を二
個以−Ｌ有する一環または二環以Ｅの芳香環から成る芳
香族化合物、例えばｐ−キシリレンシクロライト、ｌ、
４−ベンゼンジメタツール、（ｐ−キシリレングリコー
ル）、９．１０−アントラセンジメタツール等を使用で
きる。Next, the aromatic crosslinking agent of unreleased 1] is an aromatic compound consisting of a one- or two-ring or more E aromatic ring having two or more -L of at least one type of either a hydroxymethyl group or a halomethyl group S. , e.g. p-xylylene cyclolite, l,
4-benzene dimetatool, (p-xylylene glycol), 9.10-anthracene dimetatool, etc. can be used.

また、本発明の酸触媒には、塩化アルミニウム、弗化ホ
ウ素等のルイス酸、あるいは、硫酸、リン酸、有機スル
ホン酸、カルボン酸等のプロトン酸、及びこれらの誘導
体の中から選ばれる一種又は二挿具」−の混合物を使用
できる。In addition, the acid catalyst of the present invention includes Lewis acids such as aluminum chloride and boron fluoride, protonic acids such as sulfuric acid, phosphoric acid, organic sulfonic acids, and carboxylic acids, and one or more derivatives thereof. A mixture of two "inserts" can be used.

前記縮合多環芳香族化合物、芳香族架橋剤、酸触媒なＣ
０ＰＮＡ樹脂組成物接着剤とするための混合比率につい
ては２芳香族架橋剤／縮合多環芳香族化合物＝０．５〜
４．０（モル比）の範囲：酸触媒添加Ｈ）については、
芳香族架橋剤／縮合多環芳香族化合物の混合物に対して
Ｏ，ｌ〜ｌｏｗ七％か好適な範囲であることが￥映画に
確認された。The fused polycyclic aromatic compound, aromatic crosslinking agent, acid catalyst C
The mixing ratio for making a 0PNA resin composition adhesive is 2 aromatic crosslinking agent/fused polycyclic aromatic compound = 0.5~
4.0 (molar ratio) range: For acid catalyst addition H),
It was confirmed in the movie that the O,L to low 7% is a suitable range for the mixture of aromatic crosslinking agent/fused polycyclic aromatic compound.

また、Ｃ０ＰＮＡ樹脂組成物を加熱反応させてなる実質
的に熱ｉｆ塑性を有する熱硬化性中間反応生成物（Ｂス
テージ樹脂）を得るための反応温度範囲については、６
０〜３００℃が好適な範囲であることが実験的に確認さ
れた。以上のようにしで、Ｃ０ＰＮＡ樹脂組成物を加熱
反応させることにより所謂Ｂステージ樹脂か得られる。In addition, regarding the reaction temperature range for obtaining a thermosetting intermediate reaction product (B stage resin) having substantially thermal if plasticity by subjecting the C0PNA resin composition to a thermal reaction,
It was experimentally confirmed that 0 to 300°C is a suitable range. In the manner described above, a so-called B-stage resin can be obtained by subjecting the C0PNA resin composition to a heating reaction.

次に本発明における表面処理剤及び添加剤については、
ヒドロキシメチル基、ハロメチル基のいずれか少なくと
も一種の基を二個以ト有する一環または二環以トの芳香
環から成る芳香族架橋剤、若しくは前記芳香族架橋剤と
前記酸触媒との混合物であり、混合物の融点以トの温度
に加熱溶融させ液状とし、若しくは溶剤に溶解させ溶液
として使用することもできる。また表面処理剤或いは添
加剤の添加￥は特に規定されるものではないか、表面処
理剤としては溶剤に溶解させｌ〜ｌ　０ｗｔ％の濃度の
溶液として数回塗布する方法か、添加剤として予め接着
剤組成物に添加する場合には、０．０１〜５　ｗ　ｔ％
の範囲か好適である。Next, regarding the surface treatment agent and additives in the present invention,
An aromatic crosslinking agent consisting of one or two or more aromatic rings having two or more of at least one of hydroxymethyl groups and halomethyl groups, or a mixture of the aromatic crosslinking agent and the acid catalyst. The mixture may be melted by heating to a temperature above the melting point of the mixture to form a liquid, or dissolved in a solvent and used as a solution. Also, is there no particular regulation regarding the addition of surface treatment agents or additives?A surface treatment agent may be dissolved in a solvent and applied several times as a solution with a concentration of 1 to 0 wt%, or it may be added in advance as an additive. When added to the adhesive composition, 0.01 to 5 wt%
range is preferred.

本発明の導電性化促進触媒としては、空気、酸素、オゾ
ン、イオウ、過酸化水素、二酸化マンガン、亜硝酸、硝
酸、ｉＭマンガン酸、クロム酸、塩素酸、次亜塩素酸の
中からきばれる一種又は二種以上の混合物から成る酸化
剤たけ、或いはこれらの酸化剤と塩化アルミニウム、弗
化ホウ素、硫酸、リン酸、有機スルホン酸、カルボン酸
、及びこれらの誘導体の中から選ばれる一種又は二挿具
」二の混合物との組み合わせか有効であり、前記導電性
化促進触媒が常温で気体の場合はその存在下で、液体又
は固体の場合は添加して使用することがてきる。The conductivity promoting catalyst of the present invention is a type selected from air, oxygen, ozone, sulfur, hydrogen peroxide, manganese dioxide, nitrous acid, nitric acid, iM manganic acid, chromic acid, chloric acid, and hypochlorous acid. or an oxidizing agent consisting of a mixture of two or more of these oxidizing agents and one or two selected from aluminum chloride, boron fluoride, sulfuric acid, phosphoric acid, organic sulfonic acids, carboxylic acids, and derivatives thereof. A combination with a mixture of (2) and (2) is effective, and if the conductivity promoting catalyst is a gas at room temperature, it can be used in its presence, or if it is a liquid or solid, it can be used by adding it.

導電性化促進触媒の添加量は特に限定されるものではな
いか、酸化剤のうち気体のものについては、その雰囲気
中で接着操作を行なうたけて効果かあり、液体、固体の
場合は、０．０１〜３％の範囲が好適である。また酸の
場合には表面処理剤、添加剤、Ｃ０ＰＮＡ樹脂組成物中
に含まれているため、これを必要？より過剰に加えるか
、または別途０．Ｏ１〜１％程度添加するのか好適であ
る。酸の場合は強酸はと効果は大きく、酸化剤との併用
によりさらにその効果は増大する。Isn't there a particular limit to the amount of the conductivity-promoting catalyst added? Gaseous oxidizing agents are more effective if the adhesion operation is performed in that atmosphere, while liquids and solids are more effective. A range of .01 to 3% is preferred. Also, in the case of acids, they are included in surface treatment agents, additives, and C0PNA resin compositions, so are they necessary? Add more excess or add 0. It is preferable to add about 1 to 1% of O. In the case of acids, strong acids have a great effect, and the effect is further increased when used in combination with an oxidizing agent.

本発明における導゛屯性発現のメカニズムは以↑゛の２
つの如くであると推考される。The mechanism of ductile expression in the present invention is as follows.
It is assumed that this is the case.

（１）接着剤を構成するＣ０ＰＮＡ樹脂組成物の硬化体
中の芳香環に直結したメチレンか、酸化剤によって酸化
を受はハイドロパーオキサイドを経由し、脱水によりカ
ルボニル基となる。このカルボニル基は両側の芳香環と
共役関係にあり、従って導電性か発現する。又、別のメ
カニズムとして。(1) The methylene directly bonded to the aromatic ring in the cured product of the C0PNA resin composition constituting the adhesive is oxidized by an oxidizing agent and becomes a carbonyl group by dehydration via hydroperoxide. This carbonyl group has a conjugated relationship with the aromatic rings on both sides, and therefore exhibits electrical conductivity. Also, as another mechanism.

メチレン水素を１つひきぬくと、キノイドａｍとなり同
様の共役系か成立する。If one methylene hydrogen is removed, it becomes a quinoid am, and a similar conjugated system is established.

これをビレンをモデルとして式て表すと以下のようであ
る。Expressing this using Biren as a model is as follows.

（２）接着剤を構成するＣ０ＰＮＡ樹脂ｍＩ成物の硬化
体中の芳香環に直結したメチレンのうち、芳香族架橋剤
に由来する芳香環が縮合多環芳香族由来の芳香環に対し
で、ケ体障害位置にある場合（式中Ａの部分）１ｉｉ合
多環芳香族由来の芳香環か酸による親電子置換を受け、
その結果）γ体障害位置にある芳香族架橋剤に由来する
芳香環を親電子的に攻撃し、その部分が閉環する。この
際に酸化剤かメチレン水）３及び閉環位の水素を脱水の
形で由き抜くことにより、より低温から芳香化か進行し
、共役系による導電性か発現する。(2) Among the methylenes directly bonded to aromatic rings in the cured product of the C0PNA resin mI product constituting the adhesive, the aromatic ring derived from the aromatic crosslinking agent is relative to the aromatic ring derived from the condensed polycyclic aromatic, When the compound is in a hindrance position (part A in the formula), the aromatic ring derived from the 1ii combined polycyclic aromatic undergoes electrophilic substitution by an acid,
As a result) the aromatic ring derived from the aromatic crosslinking agent at the γ-body disordered position is electrophilically attacked, and that part undergoes ring closure. At this time, by extracting the oxidizing agent (methylene water) 3 and hydrogen at the ring-closing position in the form of dehydration, aromatization proceeds from a lower temperature and conductivity due to the conjugated system is developed.

これをとレンをモデルとして式て表すと以下のようであ
る。This can be expressed in the following equation using and as a model.

」―配回れのメカニズムにおいても、実際に導電性接着
剤としである程度の接着厚み間に導電性を賦ｊｊシよう
とする場合には、縮合多環芳香族由来の環芳香はその距
離に対応した共役系を有する大きさであることが必要で
ある。このため本発明においては、特に安価であり、な
おかつ巨大な縮合多環芳香族分子（ピッチではこの大き
さが数百ミクロンに及ぶ場合かある。）を含む石炭系若
しくは石油系の改質油、タール、ピッチ等が有利である
が、微小部分での導電性についてはビレンなモデルとし
て示した如く、二環以上の芳香族化合物てあれば同様な
メカニズムによって得られることは自明である。” - In terms of the distribution mechanism, when actually using a conductive adhesive and trying to impart conductivity between a certain adhesive thickness, the ring aroma derived from the condensed polycyclic aromatic will correspond to that distance. It is necessary to have a size that has a conjugated system. Therefore, in the present invention, coal-based or petroleum-based reformed oil, which is particularly inexpensive and contains huge condensed polycyclic aromatic molecules (in pitch, this size may reach several hundreds of microns), Tar, pitch, etc. are advantageous, but it is obvious that conductivity in minute areas can be obtained by the same mechanism as shown in the birene model if it is an aromatic compound having two or more rings.

本発明では被着材としで、水素、ハロゲン、ヒドロキシ
ル基、カルボニル基、カルボキシル基。In the present invention, the adherends include hydrogen, halogen, hydroxyl group, carbonyl group, and carboxyl group.

アルデヒド基、エポキシ構造、ラクトン構造、エーテル
構造、酸無水物構造の中から選ばれる一種又は二種以上
を少なくとも表面に有し、かつ導電性を有する炭素、黒
鉛、金属、金属炭化物、金属珪化物、金属硼化物、及び
これらの前駆体或いは複合材料を使用することができる
。被着材の表面官能基等については、予めこれらが存在
しているものはそのまま、存在していても少にである場
合には酸化剤による湿式酸化及ぶ酸素等による乾式酸化
、或いは水素化等の還元処理による導入か有効である。Carbon, graphite, metal, metal carbide, and metal silicide that have at least one type or two or more selected from aldehyde groups, epoxy structures, lactone structures, ether structures, and acid anhydride structures on the surface and have conductivity. , metal borides, and their precursors or composites can be used. Regarding the surface functional groups, etc. of the adherend, if these are present in advance, they can be treated as is, or if they are present in small quantities, wet oxidation with an oxidizing agent, dry oxidation with oxygen, etc., or hydrogenation, etc. It is effective to introduce it through reduction processing.

前記被着材界面における結合のメカニズムは以下の如く
であると推考される。即ち、表面処理剤中、添加剤中若
しくはＣ０ＰＮＡ樹脂組成物接着剤中に含まれる酸触媒
の作用により１表面処理剤中、添加剤中のニー官面性以
上の芳香族架橋剤か被着材表面の水素、ハロゲン、ヒド
ロキシル基、カルボニル基、カルボキシル基、アルデヒ
ド基、エポキシ構造、ラクトン構造、エーテル構造４酸
無水物構造等に脱水、脱ハロゲン、脱ハロゲン化水素等
の反応により結合し、一方ては、Ｃ０ＰＮＡ樹脂接着剤
中の環芳族水素、ハロゲン、ヒドロキシル基等と同様に
反応することによっで、結果的に被着材とＣ０ＰＮＡ樹
脂組成物接着剤か強固に結合する。The mechanism of bonding at the adherend interface is thought to be as follows. That is, due to the action of the acid catalyst contained in the surface treatment agent, additive, or C0PNA resin composition adhesive, the aromatic crosslinking agent or adherend with a knee surface property higher than that in the surface treatment agent or additive. Bonds to hydrogen, halogen, hydroxyl group, carbonyl group, carboxyl group, aldehyde group, epoxy structure, lactone structure, ether structure, tetraacid anhydride structure, etc. on the surface through reactions such as dehydration, dehalogenation, dehydrohalogenation, etc. By reacting in the same manner as the ring aromatic hydrogen, halogen, hydroxyl group, etc. in the C0PNA resin adhesive, the adhesive and the C0PNA resin composition adhesive are firmly bonded as a result.

末完榎１の接着剤を構成するＣ０ＰＮＡ樹脂組成物は、
不ｒｉ（逆的反応により、木あるいは１１！化水素を放
出するため、硬化は水中でも起こる。これらの理由から
前記接着剤を構成するＣ０ＰＮＡ樹脂ＭＩ成物は耐水性
に優れている。The C0PNA resin composition constituting the adhesive of Suekan Enoki 1 is
Curing occurs even in water because it releases wood or 11!hydrogen oxide through a reverse reaction.For these reasons, the C0PNA resin MI composition constituting the adhesive has excellent water resistance.

本発明の方法としては、予め被着材表面を表面処理剤に
よって処理しておく方法、及び表面処理剤を添加剤とし
てＣ０ＰＮＡ樹脂組成物接着剤に添加しておく方法を使
用することがてき、表＋０７処理剤若しくは添加剤をそ
れらの融点以上の温度に加熱溶融させ液状とし、若しく
は溶剤に溶解させ溶液として使用することができるか、
これらのうち、溶剤に溶解させ溶液として被着剤表面を
表面処理剤によって予め処理しておく方法を用いること
が好適である。As the method of the present invention, a method in which the surface of the adherend is treated with a surface treatment agent in advance, and a method in which the surface treatment agent is added as an additive to the C0PNA resin composition adhesive can be used. Table +07 Can processing agents or additives be melted by heating to a temperature above their melting point to form a liquid, or dissolved in a solvent and used as a solution?
Among these, it is preferable to use a method in which the surface of the adhesive is previously treated with a surface treatment agent by dissolving it in a solvent and using a solution.

本発明によれば、Ｃ０ＰＮＡ樹脂接着剤を：（１）未反
応の粉末混合物としで、（２）所ｒｔＢステージ樹脂の
粉末としで、（３）所謂Ｂステージ樹脂を加熱溶融させ
液状としで、或いは（４）所Ｗ　Ｂステージ樹脂を溶剤
に溶解させ液状として：使用することができる。According to the present invention, the C0PNA resin adhesive is prepared: (1) as an unreacted powder mixture, (2) as a powder of rtB stage resin, and (3) as a liquid by heating and melting the so-called B stage resin. Alternatively, (4) W B stage resin can be dissolved in a solvent and used as a liquid.

また、接着方法としては、ホットプレス、治具による固
定、ねじ等による固定等の方法か使用てきる。この際、
接着温度範囲は、１００〜４００℃が好適で、接着後接
着剤か充分可塑化した後に熱硬化する壱暴−−４接着、
硬化温度及び時間を設定することが肝要である。Further, as the bonding method, methods such as hot pressing, fixing with a jig, fixing with screws, etc. can be used. On this occasion,
The adhesion temperature range is preferably 100 to 400°C, and after adhesion, the adhesive is sufficiently plasticized and then thermally cured.
It is important to set the curing temperature and time.

次に本発明によれば、後硬化温度は１００〜４００℃か
好適な範囲であり、後硬化時間は１０〜３０時間の範囲
か好適である。この後硬化により共役系の発達か促進さ
れ接着部の導電性は向−トする。Next, according to the present invention, the post-curing temperature is preferably in the range of 100 to 400°C, and the post-curing time is preferably in the range of 10 to 30 hours. After curing, the development of the conjugated system is promoted and the conductivity of the bonded area is improved.

以Ｉ―の様にして耐熱性、耐水性１寸法安定性、強度、
熱伝導性等に富んだ導電性接着構造物を得ることができ
る。Heat resistance, water resistance, dimensional stability, strength,
A conductive adhesive structure with high thermal conductivity etc. can be obtained.

ところで、本発明においては導電性骨材を使用せずに導
電性接着構造物か得られる。そこで本発明のＣ０ＰＮＡ
樹脂組成物接着剤の導電性骨材として炭素、黒鉛、炭素
前駆体、銀、銅等の金属を混合することにより、より大
きな導゛−Ｅ性か得られると共に、従来の熱硬化性樹脂
に比べ著しく導電性骨材の添加がか少なくとも同様の効
果が得られる。また、本発明のうち特にピッチ系Ｃ０Ｐ
ＮＡ樹脂組成物接着剤は著しく高い炭素化収率を有する
ため、炭素、黒鉛、炭Ｊ前駆体を本発明に従って接着し
た後、これを焼成、黒鉛化することにより接着部は完全
に炭素化、黒鉛化し、従来の炭素、黒鉛材の機械加工を
大幅に簡略４Ｗストを下げることができる。By the way, in the present invention, a conductive adhesive structure can be obtained without using conductive aggregate. Therefore, the C0PNA of the present invention
By mixing carbon, graphite, carbon precursors, silver, copper, and other metals as conductive aggregates in resin composition adhesives, it is possible to obtain greater conductivity and to improve the conductivity of conventional thermosetting resins. At least the same effect can be obtained by adding significantly more conductive aggregate. In addition, in the present invention, especially pitch-based C0P
Since the NA resin composition adhesive has a significantly high carbonization yield, by bonding carbon, graphite, and Charcoal J precursor according to the present invention, and then firing and graphitizing it, the bonded portion can be completely carbonized. By graphitizing, machining of conventional carbon and graphite materials can be greatly simplified and the 4W cost can be lowered.

また、本発明のＣ０ＰＮＡ樹脂組成物接着剤に導電性骨
材として炭素、黒鉛、炭素前駆体、銀、銅等の金属を混
合したムのは接着剤のみならず優れた耐熱性、剥離強度
、熱伝導性を有する導電性使用できる。In addition, the C0PNA resin composition adhesive of the present invention mixed with carbon, graphite, a carbon precursor, and metals such as silver and copper as a conductive aggregate is not only an adhesive but also has excellent heat resistance, peel strength, Can be used for electrical conductivity with thermal conductivity.

（実施例） 次に、本発明を実施例について更に詳細に説明する。(Example) Next, the present invention will be described in more detail with reference to examples.

亙蓮例１゜ 市販の高密度高強度等方性黒鉛材（商品名　工−６イビ
デン（性）製：曲げ強度１０００ｋｇ／　ｃ　ｒｎ’　
）を、２０Ｘ２０Ｘ２０ｍｍのブロックに加工し、空気
中、４００℃て３時間加熱し１表面に酸素を含む官虎基
を導入した後、ｐ−キシリレングリコール：　５ｗｔ％
、ｐ−トルエンスルホン酸：１ｗｔ％のエタノール溶液
から成る表面処理剤を接着面に塗布し、空気中ｉｓｏ’
ｃで３０分間熱処理しこれを被着材とした。ピッチ系Ｃ
０ＰＮＡ樹脂組ｒ＆物接着剤としては、軟化点８０℃の
石油系ピッチのベンゼン可溶分（モ均分子？３４０）と
ｐ−キシリレンクリコールをモル比で１＝２の、１１１
合て混合し、そこに１ｗｔ％のＰ−トルエンスルホン酸
を加えた混合物を１２０℃で４０分間反応させたＢステ
ージ樹脂を用いた。このＢステージ樹脂を空気中１３０
℃で溶融させ、被着材の接着部に塗布し被着材同志を接
着後、治具て固定し、空気中１８０℃ｔ咋間熱処理し硬
化させた。亙议例1゜Commercially available high-density, high-strength isotropic graphite material (product name Ko-6 made by IBIDEN): bending strength 1000 kg/crn'
) was processed into a block of 20 x 20 x 20 mm, heated in air at 400°C for 3 hours, and after introducing an oxygen-containing monomer on one surface, p-xylylene glycol: 5 wt%
, p-toluenesulfonic acid: A surface treatment agent consisting of a 1 wt% ethanol solution was applied to the adhesive surface, and the iso'
C for 30 minutes, and this was used as an adherend. Pitch system C
The 0PNA resin composite adhesive is made of benzene-soluble content of petroleum pitch with a softening point of 80°C (monotropic molecular weight: 340) and p-xylylene glycol in a molar ratio of 1=2, 111
A B-stage resin was used, which was obtained by reacting a mixture in which 1 wt % of P-toluenesulfonic acid was added at 120° C. for 40 minutes. 130% of this B-stage resin in the air.
It was melted at 180° C., applied to the bonded portion of adherends, and after adhering the adherends together, was fixed in a jig and heat-treated in air at 180° C. for curing.

後硬化は空気中２００℃て２０時間行なった。比較のた
め市販の二液混合エポキシ系接着剤（商品名アラルタイ
ト：チへガイギー（株）製）て同様の処理をした被着材
を接着後、治具で固定し、空気中５０℃で硬化させた。Post-curing was carried out in air at 200° C. for 20 hours. For comparison, adherends treated in the same manner using a commercially available two-component epoxy adhesive (trade name: Arartite, manufactured by Chihe Geigy Co., Ltd.) were bonded, fixed with a jig, and cured at 50°C in air. I let it happen.

このＰ４名についで、接着部の比抵抗（四端子法）、電
気抵抗（テスター）、接着剤層の厚みを測定した。この
結果を第１表に示した。For these four participants, the specific resistance of the bonded portion (four-terminal method), electrical resistance (tester), and thickness of the adhesive layer were measured. The results are shown in Table 1.

第１表 また、実施例１の接着構造物の接着部について曲げ強度
を測定したところ、母材破断を起こし、接着面には変化
かなかった。Table 1 Also, when the bending strength of the bonded portion of the bonded structure of Example 1 was measured, the base material broke and there was no change in the bonded surface.

実］１四」工 市販の軟鋼及び真鍮を２０Ｘ２０Ｘ２０ｍｍのブロック
に加工し、Ｐ−キシリレングリコール：５　ｗ　ｔ％、
ｐ−トルエンスルホン酸：　１ｗｔ％のエタノール溶液
から成る表面処理剤を接着面にや布し、空気中１５０℃
て３０分間熱処理しこれを被着材とした。ピッチ系Ｃ０
ＰＮＡ樹脂組成物接着剤としては、軟化点４９℃の石炭
系ピッチ（＋均分子量３００）とｐ−キシリレングコー
ルをモル比てｌ：２の割合て混合し、そこに１ｗｔ％の
ｐ−トルエンスルホン酸を加えた混合物を１２０℃４０
分間反応させたＢステージ樹脂を用いた。Commercially available mild steel and brass were processed into blocks of 20 x 20 x 20 mm, P-xylylene glycol: 5 wt%,
p-Toluenesulfonic acid: Apply a surface treatment agent consisting of a 1 wt% ethanol solution to the adhesive surface, and heat in air at 150°C.
This was heat-treated for 30 minutes and used as an adherend. Pitch system C0
The PNA resin composition adhesive was prepared by mixing coal-based pitch (+average molecular weight 300) with a softening point of 49°C and p-xylylene glycol at a molar ratio of 1:2, and adding 1 wt% of p-toluene thereto. The mixture to which sulfonic acid was added was heated to 120℃40
A B-stage resin reacted for minutes was used.

このＢステージ樹脂を空気中１３０℃で溶融させ被着材
の接着面に塗布し被着材同志を接着後、治具て固定し、
空気中１８０℃で１時間熱処理し硬化させた。後硬化は
空気中２００℃で２０ＩｒｌＦ間行なった。異なる被着
材同志の接着部の電気抵抗を調べるため、軟鋼−真鍮、
軟鋼−軟鋼、真鍮−真鍮の組み合わせについてテスター
て測定した。This B-stage resin is melted in air at 130°C, applied to the bonding surface of the adherend, and after bonding the adherends together, they are fixed using a jig.
It was heat treated in air at 180°C for 1 hour to harden it. Post-curing was carried out in air at 200° C. for 20 IrIF. In order to investigate the electrical resistance of bonded parts between different adherend materials, mild steel-brass,
Measurements were made using a tester for combinations of mild steel-mild steel and brass-brass.

この結果を第２表に示した。The results are shown in Table 2.

第２表 実施例３゜ 市販の炭化珪素焼結体を空気中６００℃１１ｌシ間熱処
理し、表面に酸素を含む官能基を導入した後、これを被
着材とした。Ｃ０ＰＮＡ樹脂組成物接着剤としては、軟
化点８３℃の石炭系ピッチのベンゼン【ｉＴ溶分（Ｖ均
分子１３６０）とｐ−キシリレンジクロライトをモル比
でｌ：２の１１１合て混合し、そこに１ｗｔ％の無水塩
化アルミニウムを加えた混合物を１３０℃て４０分間反
応させたＢステージ樹脂を用いた。このＢステージ樹脂
に導′市性化促進触媒として無水塩化アルミニウムを０
゜５　ｗ　ｔ％添加した混合物を１３０’ｃて溶融させ
。Table 2 Example 3 A commercially available silicon carbide sintered body was heat treated in air at 600°C for 11 liters to introduce oxygen-containing functional groups onto the surface, and then used as an adherend. The C0PNA resin composition adhesive was prepared by mixing benzene [iT solution (V average molecular weight: 1360) of coal-based pitch with a softening point of 83°C and p-xylylene dichlorite in a molar ratio of 1:2, A B-stage resin prepared by reacting a mixture of 1 wt % of anhydrous aluminum chloride at 130° C. for 40 minutes was used. Anhydrous aluminum chloride was added to this B-stage resin as a catalyst to promote commercialization.
The mixture containing 5 wt% was melted at 130'c.

炭化珪素焼結体に塗りつけ、炭化珪素焼結体同志をＩ？
具で固定し、１５０℃て接古硬化させた。引き続き２０
０℃て１０時間後硬化処理をした。耐熱性を調べる目的
で、この接着構造物を窒素中て２０℃／　ｍ　ｉ　ｎの
昇温速度で加熱し、東驕減少をΔ１罎定した。この結果
、４５０℃まて全く数量減少は認められなかったつまた
、導電性を調べる目的で、定電流電源を用いてＩＯＡの
電流をこの接着構造物の両端に流したところ、電圧は４
ｖを示し局部発熱は認められなかった。Apply it to the silicon carbide sintered body, and apply I? to the silicon carbide sintered body.
It was fixed with a tool and cured at 150°C. Continued 20
Post-curing treatment was performed at 0°C for 10 hours. For the purpose of examining heat resistance, this adhesive structure was heated in nitrogen at a temperature increase rate of 20° C./min, and the temperature reduction was determined to be Δ1. As a result, no decrease in quantity was observed at 450°C.Also, in order to examine the conductivity, when a current of IOA was passed across both ends of this bonded structure using a constant current power supply, the voltage was 4.
v, and no local fever was observed.

実施例４゜ １１１１の黒鉛材を空気中、ｓ　ｏ　ｏ　’ｃて３０分
間熱処理し、表面にＭｔ素を含む官使基を導入した後、
ｐ−キシリレンジクロライト：５ｗｔ％、Ｐ−トルエン
スルホン酸：　１　ｗ　ｔ％のエタノール溶液から成る
表面処理剤に浸した後、空気中１５０℃で３０分間熱処
理し、これを被着材とした。Ｃ０ＰＮＡ樹脂組Ｌ＆、糊
接着剤としては、ナフタレンとｐ−キシリレンクリコー
ルをモル比１　：　１．７５の割合て混合し、そこに１
ｗｔ％のＰ−トルエンスルホン酸を加えた混合物を空気
中１３０℃て４０分間反応させたＢステージ樹脂を用い
た。このＢステージ樹脂に導電性化促進触媒として無水
塩化アルミニウムを０．５ｗｔ％、導電性骨材として３
５０メツシユ以下に粉砕した黒鉛粉末を１０ｗｔ％添加
した後、空気中１４０℃で溶融させた。Example 4 The graphite material of 1111 was heat-treated in air for 30 minutes in s o 'c, and after introducing a kanji group containing Mt element to the surface,
After immersing it in a surface treatment agent consisting of an ethanol solution of p-xylylene dichlorite: 5 wt% and p-toluenesulfonic acid: 1 wt%, it was heat-treated in air at 150°C for 30 minutes, and this was used as an adherend. . C0PNA resin set L&, as adhesive, naphthalene and p-xylylene glycol were mixed at a molar ratio of 1:1.75, and 1:1.
A B-stage resin prepared by reacting a mixture containing wt% of P-toluenesulfonic acid in air at 130° C. for 40 minutes was used. To this B-stage resin, 0.5 wt% of anhydrous aluminum chloride was added as a catalyst to promote conductivity, and 3 wt% was added as a conductive aggregate.
After adding 10 wt % of graphite powder pulverized to 50 meshes or less, it was melted in air at 140°C.

溶融物を常温まで冷却した後これを粉末として被着材に
挟み、治具て固定し、１５０℃に加熱しなから接着面を
締めつけ接着硬化させた。接着構造物は２５０　’Ｃで
１０時間後硬化処理をした。接着部の電気抵抗を調べる
ためテスターて測定した。After the melt was cooled to room temperature, it was powdered and sandwiched between adherends, fixed with a jig, heated to 150° C., and the adhesive surfaces were tightened to cure the adhesive. The bonded structures were post-cured at 250'C for 10 hours. A tester was used to measure the electrical resistance of the adhesive.

この結果接着部は接着厚み４０ｐ−ｍてＯ，ｌΩの電気
抵抗を示した。As a result, the bonded portion exhibited an electrical resistance of 0.1Ω at a bonding thickness of 40 p-m.

実施例５゜ 市販の黒鉛材（引っばり強度２５０　ｋ　ｇ　／　ｃゴ
）を２０Ｘ２０Ｘ２０ｍｍに加工し、空気中５００℃で
３０分間熱処理し、表面に酸素を含む官能基を導入した
後、ｐ−キシリレンクリコール＝５ｗｔ％、ｐ−トルエ
ンスルホン酸：　１ｗｔ％のエタノール溶液から成る表
面処理剤に浸した後、空気中１５０℃て３０分間熱処理
し、これを被着材とした。Ｃ０ＰＮＡ樹脂組成物接着剤
としては、軟化点８３℃の石炭系ピッチのベンセン１り
溶分（平均分子星３６０　）とｐ−キシリレンクリコー
ルをモル比てｌ：２の；１□１合で混合し、そこにｌ　
ｗ　ｔ。Example 5 A commercially available graphite material (tensile strength 250 kg/c) was processed into 20 x 20 x 20 mm, heat treated in air at 500°C for 30 minutes to introduce oxygen-containing functional groups onto the surface, and then p-xylene. After immersing it in a surface treatment agent consisting of an ethanol solution containing 5 wt % of len glycol and 1 wt % of p-toluenesulfonic acid, it was heat-treated in air at 150° C. for 30 minutes, and this was used as an adherend. The C0PNA resin composition adhesive is a mixture of benzene monomer (average molecular star 360) of coal-based pitch with a softening point of 83°C and p-xylylene glycol in a molar ratio of 1:2; And there l
wt.

％のｐ−トルエンスルホン酸を加えた混合物を１３０℃
て４０分間反応させたＢステージ樹脂を用いた。このＢ
ステージ樹脂に導電性化促進触媒として無水塩化アルミ
ニウムを０．５ｗｔ％添加した混合物を空気中１３０℃
て溶融させ、被着材の接着面に塗布し、被着材同志を接
着後、治具て固定し空気中１８０　’Ｃ１時間熱処理し
硬化させた。% of p-toluenesulfonic acid was added to the mixture at 130°C.
A B-stage resin that had been reacted for 40 minutes was used. This B
A mixture in which 0.5 wt% of anhydrous aluminum chloride was added as a conductivity promoting catalyst to the stage resin was heated in air at 130°C.
After adhering the adherends together, they were fixed using a jig and heat treated in air at 180'C for 1 hour to cure.

後硬化は空気中２００　’Ｃて２０時間行った。接着強
度を調べる目的で引っ張り強度を測定したところ、破断
は被着材の部分から起こり接着面には変化がなかった。Post-curing was carried out in air at 200'C for 20 hours. When tensile strength was measured for the purpose of examining adhesive strength, the breakage occurred from the adherend and there was no change in the adhesive surface.

火源例６゜ 実施例１においてＣ０ＰＮＡ樹脂組成物接着剤−市販の
銀粉（平均粒子径２ＪＬｍ）を５　ｗ　ｔ％楕加した後
、実施例１と同様に接着を行った。この結果電気抵抗は
接着厚み２８ＪＬｍて０．０８Ωとなった。Fire Source Example 6 In Example 1, 5 wt% of commercially available silver powder (average particle size: 2 JLm) was added to the C0PNA resin composition adhesive, and then adhesion was carried out in the same manner as in Example 1. As a result, the electrical resistance was 0.08Ω with an adhesive thickness of 28JLm.

友ＪＬｆＬＬユ 実施例５で接着した黒鉛材を接着面を電流か流れるよう
に、放電加工機ＥＰ−６０Ｋ　（三菱電気（株））に固
定しで、軟鋼を相手材としケロシン中でビーク′ｉ［１
２０Ａ、パルス幅６０ＩＬｓｅｃの条件て放電加工を行
った。その後、２待間て軟鋼に２０Ｘ２０Ｘ１０ｍｍの
底付き穴加工をしたか接着部には変化かなかった。The graphite material bonded in Example 5 was fixed to an electric discharge machine EP-60K (Mitsubishi Electric Corporation) so that a current would flow through the bonded surface, and the beak was heated in kerosene using mild steel as the mating material. [1
Electric discharge machining was performed under the conditions of 20A and a pulse width of 60ILsec. After that, I drilled a hole with a bottom of 20 x 20 x 10 mm in the mild steel for 2 minutes, but there was no change in the bonded area.

実−基土（Ｌユ 実施例１て得られた接着構造物を清とう水中て３００時
間処理したか全く変化は認められなかった。When the adhesive structure obtained in Example 1 was treated in clear water for 300 hours, no change was observed.

（発明の効果） 以−Ｌ説明した如く、本発明の導電性接着構造物はＣ０
ＰＮＡ樹脂組成物接着剤と表面に水素、ハロゲン、ヒド
ロキシル基、カルボニル基、カルボキシル基、アルデヒ
ド基、エポキシ構造、ラクトン構造、エーテル構造、酸
無水物構造から選ばれる少なくとも一種を有し、若しく
は導入された被、ｎ材とが、前記被り材と接着剤の界面
において。(Effects of the Invention) As explained below, the conductive adhesive structure of the present invention has C0
The PNA resin composition adhesive has or has been introduced with at least one selected from hydrogen, halogen, hydroxyl group, carbonyl group, carboxyl group, aldehyde group, epoxy structure, lactone structure, ether structure, and acid anhydride structure on the surface. the covering material and the n material at the interface between the covering material and the adhesive.

前記表面処理剤若しくは前記添加剤を介して結合し、か
つ導電性化促進触媒の存在下でこのＣ０ＰＮＡ樹脂組成
物の硬化体か芳香族共役系に基づく導電性を示す導電性
接着４Ｗ造物であり、従来の導電性接着構造物には見ら
れない導電性骨材を必要としないで導電性を発現する導
電性接着構造物であるのみならず、優れた！耐熱性、耐
水性、寸法安定性、強度、熱伝導性等をも備えた導電性
接着４造物である。The cured product of this C0PNA resin composition is a conductive adhesive 4W product that is bonded via the surface treatment agent or the additive and exhibits conductivity based on an aromatic conjugated system in the presence of a conductivity promoting catalyst. This is not only a conductive adhesive structure that exhibits conductivity without the need for conductive aggregate, which is not found in conventional conductive adhesive structures, but also an excellent! It is a conductive adhesive product that also has heat resistance, water resistance, dimensional stability, strength, thermal conductivity, etc.

この優れたｒＭ熱性、耐水性、寸法安定性、強度、熱伝
導性等を備えた導電性接着４造物は構造材料、耐熱材料
、断熱材料、電気、電子用材料、しゅう動部材、帯電防
止、電磁波シールド等の用途に使用することができ、産
業−Ｌに太きく　寄’Ｊ−する効果か考えられる。These four conductive adhesive products with excellent rM heat resistance, water resistance, dimensional stability, strength, thermal conductivity, etc. are structural materials, heat-resistant materials, insulation materials, electrical and electronic materials, sliding members, antistatic materials, It can be used for purposes such as electromagnetic shielding, and it is thought that it has an effect that is strongly related to industry.

Claims (1)

【特許請求の範囲】 １）、縮合多環芳香族化合物、芳香族架橋剤、酸触媒が
反応して成る熱硬化性組成物から成る接着剤と：被着材
とが：前記被着材と前記接着剤の界面において、前記芳
香族架橋剤を主体とする表面処理剤若しくは添加剤を有
する結合を有し、かつ前記接着剤が導電性化促進触媒に
よって実質的に導電性を示す共役系を形成して成ること
を特徴とする導電性接着構造物。 ２）、特許請求の範囲第１項記載の導電性接着構造物に
おいて、前記接着剤が前記縮合多環芳香族混合物と前記
芳香族架橋剤と前記酸触媒の混合物、もしくはこれらの
熱硬化性中間反応生成物の中から選ばれる、少なくとも
一種が反応により熱硬化されて成ることを特徴とする導
電性接着構造物。 ３）、特許請求の範囲第１項記載の導電性接着構造物に
おいて、前記縮合多環芳香族化合物はナフタレン、アン
トラセン、フェナントレン、ビレン、クリセン、ナフタ
セン、アセナフテン、アセナフチレン、ペリレン、コロ
ネン、及びこれらを主骨格とする誘導体の中から選ばれ
る一種又は二種以上の混合物或いは、石炭系若しくは石
油系の重質油、タール、ピッチ及びこれらの誘導体の中
から選ばれる一種又は二種以上の混合物であることを特
徴とする導電性接着構造物。 ４）、特許請求の範囲第１項記載の導電性接着構造物に
おいて、前記芳香族架橋剤はヒドロキシメチル基、ハロ
メチル基のいずれか少なくとも一種の基を二個以上有す
る一環または二環以上の芳香環から成る芳香族架橋剤で
あることを特徴とする導電性接着構造物。 ５）、特許請求の範囲第１項記載の導電性接着構造物に
おいて、前記酸触媒は、塩化アルミニウム、弗化ホウ素
、硫酸、リン酸、有機スルホン酸、カルボン酸、及びこ
れらの誘導体の中から選ばれる一種又は二種以上の混合
物であることを特徴とする導電性接着構造物。 ６）、特許請求の範囲第１項記載の導電性接着構造物に
おいて、前記被着材は、炭素、黒鉛、金属、金属炭化物
、金属珪化物、金属硼化物、及びこれらの前駆体若しく
は複合材料の中から選ばれる同種又は異種の組み合わせ
であり、前記被着材自体が導電性を有し、かつ少なくと
もその表面に水素、ハロゲン、ヒドロキシル基、カルボ
ニル基、カルボキシル基、アルデヒド基、エポキシ構造
、ラクトン構造、エーテル構造、酸無水物構造の中から
選ばれる一種又は二種以上を有するもの、若しくはこれ
らが導入されたものであることを特徴とする導電性接着
構造物。 ７）、特許請求の範囲第１項記載の導電性接着構造物に
おいて、前記導電性化促進触媒は空気、酸素、オゾン、
イオウ、過酸化水素、二酸化マンガン、亜硝酸、硝酸、
過マンガン酸、クロム酸、塩素酸、次亜塩素酸の中から
選ばれる一種又は二種以上の混合物から成る酸化剤であ
ることを特徴とする導電性接着構造物。 ８）、特許請求の範囲第１項記載の導電性接着構造物に
おいて、前記導電性化促進触媒は空気、酸素、オゾン、
イオウ、過酸化水素、二酸化マンガン、亜硝酸、硝酸、
過マンガン酸、クロム酸、塩素酸、次亜塩素酸の中から
選ばれる一種又は二種以上の混合物から成る酸化剤と塩
化アルミニウム、弗化ホウ素、硫酸、リン酸、有機スル
ホン酸、カルボン酸、及びこれらの誘導体の中から選ば
れる一種又は二種以上の混合物とを組み合わせて成るこ
とを特徴とする導電性接着構造物。 ９）、特許請求の範囲第１項記載の導電性接着構造物に
おいて、前記表面処理剤及び前記添加剤はヒドロキシメ
チル基、ハロメチル基のいずれか少なくとも一種の基を
二個以上有する一環または二環以上の芳香環から成る芳
香族架橋剤若しくは、前記芳香族架橋剤と前記酸触媒と
の混合物から成る架橋能を有する組成物であり、なおか
つ前記被着材表面の水素、ハロゲン、ヒドロキシル基、
カルボニル基、カルボキシル基、アルデヒド基、エポキ
シ構造、ラクトン構造、エーテル構造、酸無水物構造と
前記接着剤とを化学的に結合せしめて成ることを特徴と
する導電性接着構造物。 １０）、下記（ａ）〜（ｄ）のシーケンスから成ること
を特徴とする導電性接着構造物の製造方法。 （ａ）水素、ハロゲン、ヒドロキシル基、カルボニル基
、カルボキシル基、アルデヒド基、エポキシ構造、ラク
トン構造、エーテル構造、酸無水物構造の中から選ばれ
る一種又は二種以上を少なくとも表面に有する被着材の
該表面を、ヒドロキシメチル基、ハロメチル基のいずれ
か少なくとも一種の基を二個以上有する一環または二環
以上の芳香環から成る芳香族架橋剤を主体とする表面処
理剤によって被覆せしめた後、熱処理を行う工程；（ｂ
）縮合多環芳香族混合物と、前記芳香族架橋剤と、酸触
媒とを組合せて成る熱硬化性組成物から成る接着剤組成
物を導電性化促進触媒の存在下で、可塑化若しくは液化
させる工程； （ｃ）前記（ｂ）工程で可塑化若しくは液化された接着
剤組成物により前記（ａ）工程で被覆された被着材を接
着させ、酸化性雰囲気中１００〜４００℃の温度範囲に
加熱し、前記接着剤組成物を熱硬化させると共に、実質
的に導電性を有する共役系の形成を促す接着工程； （ｄ）前記成形硬化体を酸化性又は非酸化性雰囲気中１
００〜４００℃の温度範囲に加熱し、３０分間以上１０
０時間以下の時間、前記温度範囲に保持し、実質的に導
電性を有する共役系の発達を促進させる後硬化工程； １１）、特許請求の範囲第１０項記載の製造方法におい
て、前記表面処理剤はヒドロキシメチル基、ハロメチル
基のいずれか少なくとも一種の基を二個以上有する一環
または二環以上の芳香環から成る芳香族架橋剤であり、
前記架橋剤の融点以上の温度に加熱溶融させ液状とし、
若しくは溶剤に溶解させ溶液として使用することを特徴
とする導電性接着構造物の製造方法。 １２）、特許請求の範囲第１０項記載の製造方法におい
て、前記表面処理剤は前記芳香族架橋剤と前記酸触媒と
の混合物であり、混合物の融点以上の温度に加熱溶融さ
せ液状とし、若しくは溶剤に溶解させ溶液として使用す
ることにより前記被着材の表面官能基と前記架橋剤とを
前記熱処理により反応せしめることを特徴とする導電性
接着構造物の製造方法。 １３）、特許請求の範囲第１０項記載の製造方法におい
て、前記接着剤は縮合多環芳香族化合物と、前記芳香族
架橋剤と、酸触媒とを組み合わせて成る熱硬化性組成物
の粉末混合物であることを特徴とする導電性接着構造物
の製造方法。 １４）、特許請求の範囲第１０項記載の製造方法におい
て、前記接着剤は前記熱硬化性組成物を酸化性又は非酸
化性雰囲気中６０〜３００℃の温度範囲に加熱反応させ
てなる実質的に熱可塑性を有する熱硬化性中間反応生成
物であることを特徴とする導電性接着構造物の製造方法
。 １５）、特許請求の範囲第１０項記載の製造方法におい
て、前記導電性化促進触媒は空気、酸素、オゾン、イオ
ウ、過酸化水素、二酸化マンガン、亜硝酸、硝酸、過マ
ンガン酸、クロム酸、塩素酸、次亜塩素酸の中から選ば
れる一種又は二種以上の混合物から成る酸化剤であり、
前記導電性化促進触媒が常温で気体の場合はその存在下
で、液体又は固体の場合は添加して使用することを特徴
とする導電性接着構造物の製造方法。 １６）、特許請求の範囲第１０項記載の製造方法におい
て、前記導電性化促進触媒は空気、酸素、オゾン、イオ
ウ、過酸化水素、二酸化マンガン、亜硝酸、硝酸、過マ
ンガン酸、クロム酸、塩素酸、次亜塩素酸の中から選ば
れる一種又は二種以上の混合物から成る酸化剤と塩化ア
ルミニウム、弗化ホウ素、硫酸、リン酸、有機スルホン
酸、カルボン酸、及びこれらの誘導体の中から選ばれる
一種又は二種以上の混合物との組み合わせであり、前記
導電性化促進触媒が常温で気体の場合はその存在下で、
液体又は固体の場合は添加して使用することを特徴とす
る導電性接着構造物の製造方法。 １７）、特許請求の範囲第１０項記載の製造方法におい
て、前記可塑化は前記接着剤組成物を酸化性又は非酸化
性雰囲気中６０〜３００℃の温度範囲に加熱して成るこ
とを特徴とする導電性接着構造物の製造方法。 １８）、特許請求の範囲第１０項記載の製造方法におい
て、前記液化は前記接着剤組成物を溶剤に溶解させて成
ることを特徴とする導電性接着構造物の製造方法。 １９）、下記（ａ）〜（ｃ）のシーケンスから成ること
を特徴とする導電性接着構造物の製造方法。 （ａ）縮合多環芳香族混合物と、ヒドロキシメチル基、
ハロメチル基のいずれか少なくとも一種の基を二個以上
有する一環または二環以上の芳香環から成る芳香族架橋
剤と、酸触媒とを組み合わせて成る熱硬化性組成物から
成る接着剤に過剰の前記架橋剤若しくは前記架橋剤と前
記酸触媒の混合物から成る添加剤を加え、導電性化促進
触媒の存在下で、接着剤組成物を可塑化若しくは液化さ
せる工程； （ｂ）前記（ａ）工程で可塑化若しくは液化させた接着
剤組成物と、水素、ハロゲン、ヒドロキシル基、カルボ
ニル基、カルボキシル基、アルデヒド基、エポキシ構造
、ラクトン構造、エーテル構造、酸無水物構造の中から
選ばれる一種又は二種以上を少なくとも表面に有する被
着材とを接着させ、酸化性雰囲気中１００〜４００℃の
温度範囲に加熱し、前記接着剤組成物を熱硬化させると
共に、実質的に導電性を有する共役系の形成を促す接着
工程； （ｃ）前記成形硬化体を酸化性又は非酸化性雰囲気中１
００〜４００℃の温度範囲に加熱し、３０分間以上１０
０時間以下の時間、前記温度範囲に保持し、実質的に導
電性を有する共役系の発達を促進させる後硬化工程； ２０）、特許請求の範囲第１９項記載の製造方法におい
て、前記接着剤は縮合多環芳香族混合物と、前記芳香族
架橋剤と、酸触媒とを組み合わせて成る熱硬化性組成物
の粉末混合物であることを特徴とする導電性接着構造物
の製造方法。 ２１）、特許請求の範囲第１９項記載の製造方法におい
て、前記接着剤は前記縮合多環芳香族化合物と、前記芳
香族架橋剤と、酸触媒とを組み合わせて酸化性又は非酸
化性雰囲気中６０〜３００℃の温度範囲に加熱反応させ
てなる実質的に熱可塑性を有する熱硬化性中間反応生成
物であることを特徴とする導電性接着構造物の製造方法
。 ２２）、特許請求の範囲第１９項記載の製造方法におい
て、前記導電性化促進触媒は空気、酸素、オゾン、イオ
ウ、過酸化水素、二酸化マンガン、亜硝酸、硝酸、過マ
ンガン酸、クロム酸、塩素酸、次亜塩素酸の中から選ば
れる一種又は二種以上の混合物から成る酸化剤であり、
前記導電性化促進触媒が常温で気体の場合はその存在下
で、液体又は固体の場合は添加して使用することを特徴
とする導電性接着構造物の製造方法。 ２３）、特許請求の範囲第１９項記載の製造方法におい
て、前記導電性化促進触媒は空気、酸素、オゾン、イオ
ウ、過酸化水素、二酸化マンガン、亜硝酸、硝酸、過マ
ンガン酸、クロム酸、塩素酸、次亜塩素酸の中から選ば
れる一種又は二種以上の混合物から成る酸化剤と塩化ア
ルミニウム、弗化ホウ素、硫酸、リン酸、有機スルホン
酸、カルボン酸、及びこれらの誘導体の中から選ばれる
一種又は二種以上の混合物との組み合わせであり、前記
導電性化促進触媒が常温で気体の場合はその存在下で、
液体又は固体の場合は添加して使用することを特徴とす
る導電性接着構造物の製造方法。 ２４）、特許請求の範囲第１９項記載の製造方法におい
て、前記液化は前記接着剤組成物を溶剤に溶解させて成
ることを特徴とする導電性接着構造物の製造方法。 ２５）、特許請求の範囲第１９項記載の製造方法におい
て、前記添加剤を融点以上の温度に加熱溶融させ、液状
とし、若しくは溶剤に溶解させ溶液として使用すること
を特徴とする導電性接着構造物の製造方法。[Claims] 1) An adhesive comprising a thermosetting composition formed by reacting a fused polycyclic aromatic compound, an aromatic crosslinking agent, and an acid catalyst; and an adherend; At the interface of the adhesive, the adhesive has a conjugated system that has a surface treatment agent or an additive containing the aromatic crosslinking agent as a main component, and the adhesive has a conjugated system that is substantially electrically conductive due to a conductivity promoting catalyst. A conductive adhesive structure characterized by forming a conductive adhesive structure. 2) The conductive adhesive structure according to claim 1, wherein the adhesive is a mixture of the condensed polycyclic aromatic mixture, the aromatic crosslinking agent, and the acid catalyst, or a thermosetting intermediate thereof. 1. A conductive adhesive structure characterized in that at least one selected from reaction products is thermally cured by reaction. 3) In the conductive adhesive structure according to claim 1, the fused polycyclic aromatic compound includes naphthalene, anthracene, phenanthrene, birene, chrysene, naphthacene, acenaphthene, acenaphthylene, perylene, coronene, and the like. One or a mixture of two or more types selected from the derivatives used as the main skeleton, or one or a mixture of two or more types selected from coal-based or petroleum-based heavy oil, tar, pitch, and their derivatives. A conductive adhesive structure characterized by: 4) In the conductive adhesive structure according to claim 1, the aromatic crosslinking agent is a one- or two- or more-ring aromatic compound having two or more groups of at least one of hydroxymethyl groups and halomethyl groups. A conductive adhesive structure characterized by being an aromatic crosslinking agent consisting of a ring. 5) In the conductive adhesive structure according to claim 1, the acid catalyst is selected from among aluminum chloride, boron fluoride, sulfuric acid, phosphoric acid, organic sulfonic acids, carboxylic acids, and derivatives thereof. A conductive adhesive structure characterized by being one selected from the group or a mixture of two or more selected types. 6) In the conductive adhesive structure according to claim 1, the adherend is carbon, graphite, metal, metal carbide, metal silicide, metal boride, and precursors or composite materials thereof. A combination of the same or different types selected from among the above, and the adherend itself has conductivity, and at least its surface contains hydrogen, halogen, hydroxyl group, carbonyl group, carboxyl group, aldehyde group, epoxy structure, lactone. 1. An electrically conductive adhesive structure having one or more selected from the group consisting of an ether structure, an ether structure, and an acid anhydride structure, or one in which these are introduced. 7) In the conductive adhesive structure according to claim 1, the conductivity promoting catalyst is air, oxygen, ozone,
Sulfur, hydrogen peroxide, manganese dioxide, nitrous acid, nitric acid,
A conductive adhesive structure characterized in that the oxidizing agent is one or a mixture of two or more selected from permanganic acid, chromic acid, chloric acid, and hypochlorous acid. 8) In the conductive adhesive structure according to claim 1, the conductivity promoting catalyst is air, oxygen, ozone,
Sulfur, hydrogen peroxide, manganese dioxide, nitrous acid, nitric acid,
An oxidizing agent consisting of one or a mixture of two or more selected from permanganic acid, chromic acid, chloric acid, hypochlorous acid, aluminum chloride, boron fluoride, sulfuric acid, phosphoric acid, organic sulfonic acid, carboxylic acid, and one or a mixture of two or more selected from these derivatives. 9) In the conductive adhesive structure according to claim 1, the surface treatment agent and the additive are monocyclic or bicyclic having two or more groups of at least one of hydroxymethyl groups and halomethyl groups. A composition having a crosslinking ability consisting of an aromatic crosslinking agent consisting of the above aromatic ring or a mixture of the aromatic crosslinking agent and the acid catalyst, and hydrogen, halogen, hydroxyl groups on the surface of the adherend,
1. A conductive adhesive structure characterized by chemically bonding a carbonyl group, a carboxyl group, an aldehyde group, an epoxy structure, a lactone structure, an ether structure, or an acid anhydride structure to the adhesive. 10) A method for producing a conductive adhesive structure, comprising the following sequences (a) to (d). (a) Adherent having at least one or more types selected from hydrogen, halogen, hydroxyl group, carbonyl group, carboxyl group, aldehyde group, epoxy structure, lactone structure, ether structure, and acid anhydride structure on the surface After coating the surface with a surface treatment agent mainly consisting of an aromatic crosslinking agent consisting of one or two or more aromatic rings having two or more of at least one of hydroxymethyl groups and halomethyl groups, Step of performing heat treatment; (b
) Plasticizing or liquefying an adhesive composition comprising a thermosetting composition comprising a combination of a condensed polycyclic aromatic mixture, the aromatic crosslinking agent, and an acid catalyst in the presence of a conductivity promoting catalyst. Step; (c) The adherend coated in step (a) is bonded with the adhesive composition plasticized or liquefied in step (b), and heated to a temperature range of 100 to 400°C in an oxidizing atmosphere. An adhesion step of heating and thermosetting the adhesive composition and promoting the formation of a conjugated system having substantially electrical conductivity; (d) placing the molded and cured body in an oxidizing or non-oxidizing atmosphere;
Heat to a temperature range of 00 to 400℃ for 30 minutes or more.
11) A post-curing step of maintaining the temperature in the temperature range for 0 hours or less to promote the development of a conjugated system having substantially electrical conductivity; 11) In the manufacturing method according to claim 10, the surface treatment The agent is an aromatic crosslinking agent consisting of one or two or more aromatic rings having two or more of at least one of hydroxymethyl group and halomethyl group,
Melt by heating to a temperature higher than the melting point of the crosslinking agent to form a liquid,
Alternatively, a method for producing a conductive adhesive structure characterized by dissolving it in a solvent and using it as a solution. 12) In the manufacturing method according to claim 10, the surface treatment agent is a mixture of the aromatic crosslinking agent and the acid catalyst, and is melted by heating to a temperature equal to or higher than the melting point of the mixture to form a liquid, or A method for producing a conductive adhesive structure, characterized in that the surface functional group of the adherend is reacted with the crosslinking agent by the heat treatment by dissolving it in a solvent and using it as a solution. 13) In the manufacturing method according to claim 10, the adhesive is a powder mixture of a thermosetting composition comprising a combination of a condensed polycyclic aromatic compound, the aromatic crosslinking agent, and an acid catalyst. A method for producing a conductive adhesive structure, characterized in that: 14) In the manufacturing method as set forth in claim 10, the adhesive is substantially formed by subjecting the thermosetting composition to a temperature range of 60 to 300°C in an oxidizing or non-oxidizing atmosphere. 1. A method for producing a conductive adhesive structure, characterized in that the intermediate reaction product is a thermosetting intermediate reaction product having thermoplasticity. 15) In the manufacturing method according to claim 10, the conductivity promoting catalyst is air, oxygen, ozone, sulfur, hydrogen peroxide, manganese dioxide, nitrous acid, nitric acid, permanganic acid, chromic acid, An oxidizing agent consisting of one type or a mixture of two or more selected from chloric acid and hypochlorous acid,
A method for producing a conductive adhesive structure, characterized in that when the conductivity promoting catalyst is a gas at room temperature, it is used in its presence, and when it is a liquid or solid, it is used in addition. 16) In the manufacturing method according to claim 10, the conductivity promoting catalyst is air, oxygen, ozone, sulfur, hydrogen peroxide, manganese dioxide, nitrous acid, nitric acid, permanganic acid, chromic acid, An oxidizing agent consisting of one or a mixture of two or more selected from chloric acid and hypochlorous acid, and aluminum chloride, boron fluoride, sulfuric acid, phosphoric acid, organic sulfonic acids, carboxylic acids, and derivatives thereof. It is a combination of one selected type or a mixture of two or more types, and when the conductivity promoting catalyst is a gas at room temperature, in its presence,
A method for producing a conductive adhesive structure, characterized in that a liquid or solid is used by adding it. 17) In the manufacturing method according to claim 10, the plasticization is performed by heating the adhesive composition to a temperature range of 60 to 300°C in an oxidizing or non-oxidizing atmosphere. A method for manufacturing a conductive adhesive structure. 18) The method of manufacturing a conductive adhesive structure according to claim 10, wherein the liquefaction is performed by dissolving the adhesive composition in a solvent. 19) A method for producing a conductive adhesive structure, comprising the following sequences (a) to (c). (a) a fused polycyclic aromatic mixture and a hydroxymethyl group,
In an adhesive comprising a thermosetting composition comprising a combination of an aromatic crosslinking agent consisting of one or two or more aromatic rings having two or more of at least one type of halomethyl group and an acid catalyst, an excess of the above-mentioned Adding an additive consisting of a crosslinking agent or a mixture of the crosslinking agent and the acid catalyst to plasticize or liquefy the adhesive composition in the presence of a conductivity promoting catalyst; (b) in step (a) above; A plasticized or liquefied adhesive composition, and one or two selected from hydrogen, halogen, hydroxyl group, carbonyl group, carboxyl group, aldehyde group, epoxy structure, lactone structure, ether structure, and acid anhydride structure. The adhesive composition is bonded to an adherend having at least the above on its surface, heated to a temperature range of 100 to 400°C in an oxidizing atmosphere, and the adhesive composition is thermally cured. Adhesion step to promote formation; (c) The molded cured product is placed in an oxidizing or non-oxidizing atmosphere.
Heat to a temperature range of 00 to 400℃ for 30 minutes or more.
20) In the manufacturing method according to claim 19, the adhesive is maintained in the temperature range for a time of 0 hours or less to promote the development of a conjugated system having substantially electrical conductivity; 1. A method for producing a conductive adhesive structure, characterized in that the method is a powder mixture of a thermosetting composition comprising a condensed polycyclic aromatic mixture, the aromatic crosslinking agent, and an acid catalyst. 21) In the manufacturing method according to claim 19, the adhesive is prepared by combining the fused polycyclic aromatic compound, the aromatic crosslinking agent, and an acid catalyst in an oxidizing or non-oxidizing atmosphere. 1. A method for producing a conductive adhesive structure, characterized in that the intermediate reaction product is a thermosetting intermediate reaction product having substantially thermoplastic properties, which is obtained by heating and reacting at a temperature in the range of 60 to 300°C. 22) In the manufacturing method according to claim 19, the conductivity promoting catalyst is air, oxygen, ozone, sulfur, hydrogen peroxide, manganese dioxide, nitrous acid, nitric acid, permanganic acid, chromic acid, An oxidizing agent consisting of one type or a mixture of two or more selected from chloric acid and hypochlorous acid,
A method for producing a conductive adhesive structure, characterized in that when the conductivity promoting catalyst is a gas at room temperature, it is used in its presence, and when it is a liquid or solid, it is used in addition. 23) In the manufacturing method according to claim 19, the conductivity promoting catalyst is air, oxygen, ozone, sulfur, hydrogen peroxide, manganese dioxide, nitrous acid, nitric acid, permanganic acid, chromic acid, An oxidizing agent consisting of one or a mixture of two or more selected from chloric acid and hypochlorous acid, and aluminum chloride, boron fluoride, sulfuric acid, phosphoric acid, organic sulfonic acids, carboxylic acids, and derivatives thereof. It is a combination of one selected type or a mixture of two or more types, and when the conductivity promoting catalyst is a gas at room temperature, in its presence,
A method for producing a conductive adhesive structure, characterized in that a liquid or solid is used by adding it. 24) The method of manufacturing a conductive adhesive structure according to claim 19, wherein the liquefaction is performed by dissolving the adhesive composition in a solvent. 25) In the manufacturing method according to claim 19, the conductive adhesive structure is characterized in that the additive is melted by heating to a temperature equal to or higher than the melting point to form a liquid, or is dissolved in a solvent and used as a solution. How things are manufactured.
JP27880085A 1985-12-10 1985-12-10 Conductive adhesive structure and method for manufacturing the same Expired - Lifetime JPH0623348B2 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP27880085A JPH0623348B2 (en) 1985-12-10 1985-12-10 Conductive adhesive structure and method for manufacturing the same
US06/938,253 US4911983A (en) 1985-12-10 1986-12-05 Adhesion structures and method of producing the same
EP19860309562 EP0225802B1 (en) 1985-12-10 1986-12-09 Adhesion structures and method of producing the same
DE19863686561 DE3686561T2 (en) 1985-12-10 1986-12-09 ADHESIVE STRUCTURES AND METHOD FOR THE PRODUCTION THEREOF.
US07/460,620 US5017431A (en) 1985-12-10 1990-01-03 Adhesion structures and method of producing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP27880085A JPH0623348B2 (en) 1985-12-10 1985-12-10 Conductive adhesive structure and method for manufacturing the same

Publications (2)

Publication Number Publication Date
JPS62135580A true JPS62135580A (en) 1987-06-18
JPH0623348B2 JPH0623348B2 (en) 1994-03-30

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62138569A (en) * 1985-12-12 1987-06-22 Ibiden Co Ltd Electrically conductive adhesive
CN106590710A (en) * 2016-11-21 2017-04-26 神雾环保技术股份有限公司 Utilizing method and system of long flame coal

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62138569A (en) * 1985-12-12 1987-06-22 Ibiden Co Ltd Electrically conductive adhesive
JPH0657824B2 (en) * 1985-12-12 1994-08-03 イビデン株式会社 Conductive adhesive
CN106590710A (en) * 2016-11-21 2017-04-26 神雾环保技术股份有限公司 Utilizing method and system of long flame coal

Also Published As

Publication number Publication date
JPH0623348B2 (en) 1994-03-30

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