JPS59124972A - Conductive resin composition for seal excellent in adhesion to oily surface - Google Patents
Conductive resin composition for seal excellent in adhesion to oily surfaceInfo
- Publication number
- JPS59124972A JPS59124972A JP23197982A JP23197982A JPS59124972A JP S59124972 A JPS59124972 A JP S59124972A JP 23197982 A JP23197982 A JP 23197982A JP 23197982 A JP23197982 A JP 23197982A JP S59124972 A JPS59124972 A JP S59124972A
- Authority
- JP
- Japan
- Prior art keywords
- conductive
- resin composition
- long
- adhesion
- seal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【発明の詳細な説明】
この発明は自動車、飛行機の車体、家電製品、各種機器
の金属部材の接着シール用に用いられ、油面接着性にす
ぐれると共にスポット溶接性や電着塗装性にすぐれるシ
ール用導電性樹1指組成物に関する。[Detailed Description of the Invention] This invention is used for adhesive sealing of metal parts of automobiles, airplane bodies, home appliances, and various devices, and has excellent oil surface adhesion and is easy to spot weld and electrodeposit. The present invention relates to a conductive wood one-finger composition for seals.
物
従来、金属横引よ、溶接、塗装等の工程の前に各種コム
や樹脂組成物で接着ソールを行っている。Conventionally, adhesive soles are made using various combs or resin compositions before processes such as metal horizontal drawing, welding, and painting.
しかし、これら組成物は本来絶縁体であり、シール用に
用いた場合電着液が付着ぜす、ために樹脂シール層と金
属板との界面において塗装付が悪く錆の発生を招(場合
かあった。これを防ぐ為、金属粉等を混入したゴム組成
物を用いて接着シールを行っているが、耐熱性や耐久性
に劣り、また未処理鋼板等の油膜の付着した部材に用い
た場合には密着性が悪く、貼り付は作業性が劣ったり、
シール漏れを起こす等不都合かあった。However, these compositions are originally insulators, and when used for sealing, the electrodeposition liquid will adhere to them, resulting in poor coating adhesion and rust formation at the interface between the resin sealing layer and the metal plate (in some cases). To prevent this, adhesive sealing is performed using a rubber composition mixed with metal powder, etc., but it has poor heat resistance and durability, and is not used on parts with oil films such as untreated steel plates. In some cases, the adhesion is poor and the workability of pasting is poor,
There were some inconveniences such as seal leakage.
この発明者らは、かかる従来技術の欠点を改良する為種
々検討した結果、長鎖アルキル主鎖を有する液状又は半
固形状のエポキシ樹脂に硬化剤と導電性光てん剤とを配
合することにより@記問題を回避できることを知った。As a result of various studies in order to improve the drawbacks of the prior art, the present inventors discovered that by blending a curing agent and a conductive photonic agent into a liquid or semi-solid epoxy resin having a long alkyl main chain. I learned that I can avoid the @ problem.
また、上記配合物にさらに発泡剤を配合することにより
シール特性を一段と改善できることを見い出した。It has also been found that the sealing properties can be further improved by further adding a foaming agent to the above formulation.
すなわち、この発明は、長鎖アルキル主鎖を有する液状
または半固、形状のエポキシ樹脂に硬化剤と導電性光て
ん剤とを加えてなる油面接着性にすぐれるシール用導電
性樹脂組成物に係る第1の発明と、上記配合物中にさら
に発泡剤を配合してなる油面接着性にすぐれる発泡性の
シール用導電性樹脂組成物に係る第2の発明とからなる
ものである。That is, the present invention provides a conductive resin composition for seals with excellent oil surface adhesion, which is prepared by adding a curing agent and a conductive photonic agent to a liquid or semi-solid epoxy resin having a long alkyl main chain. and a second invention relating to a foamable conductive resin composition for seals with excellent oil surface adhesion, which is obtained by further blending a foaming agent into the above-mentioned formulation. .
この発明により得られるシール用導電性樹脂組成物は油
膜鋼板面にも初期接着性が良く、ためにシール作業性を
改善できまたシール漏れを回避できる。また塗装の焼き
付は工程等で加熱硬化させることにより機械強度、耐熱
性、耐久性に優れるシール層を形成でき、このシール層
はスポット溶接性や電着塗装性が良好なため金属板との
界面において錆の発生をきたすことがなくまた外観にも
すくれたものとなる。さらに発泡剤を配合したものでは
上記特性に加えて発泡構造のシール層を与えるから密着
シール性やシール特性が一段と改善される。The electrically conductive resin composition for sealing obtained by the present invention has good initial adhesion even to oil-film steel plate surfaces, thereby improving sealing workability and avoiding seal leakage. In addition, by heating and curing the paint during the process, it is possible to form a sealing layer with excellent mechanical strength, heat resistance, and durability.This sealing layer has good spot weldability and electrodeposition coating properties, so it is compatible with metal plates. Rust does not occur at the interface, and the appearance becomes dull. Further, when a foaming agent is added, in addition to the above-mentioned properties, a sealing layer having a foamed structure is provided, so that the adhesive sealing properties and sealing properties are further improved.
この発明に用いられる長鎖アルキル主鎖を有する液状又
は半固形状のエポキシ樹脂は、アルキル鎖が疎水性基で
あるため油脂分との相溶性が良く、油膜鋼板との初期接
着性の向上に寄与する。長鎖アルキル主鎖としては炭素
数が5〜50程度のものである。このような樹脂として
は、ポリエチレングリコール、ポリプロピレングリコー
ル、エチレンオキシドとプロピレンオキシドとのブロッ
ク状コポリマーのα・ω−グリコールなどのポリマーと
エピクロルヒドリンとの反応によるエポキシ樹脂;ポリ
塩化ビニル、ポリアクロレインやポリビニルケトンのカ
ルボニル基とS−イリドの反応より誘導されたエポキシ
樹脂;ダイマー酸、トリマー酸、不飽和制級脂肪酸また
はそのエステルから誘導されたエポキシ樹脂等が挙げら
れる。The liquid or semi-solid epoxy resin having a long alkyl main chain used in this invention has good compatibility with oils and fats because the alkyl chain is a hydrophobic group, and is effective in improving initial adhesion to oil film steel sheets. Contribute. The long alkyl main chain has about 5 to 50 carbon atoms. Such resins include epoxy resins produced by reacting epichlorohydrin with polymers such as polyethylene glycol, polypropylene glycol, and α/ω-glycol, which is a block copolymer of ethylene oxide and propylene oxide; polyvinyl chloride, polyacrolein, and polyvinyl ketone. Epoxy resins derived from the reaction of a carbonyl group and S-ylide; epoxy resins derived from dimer acids, trimer acids, unsaturated primary fatty acids or esters thereof, and the like.
上記エポキシ樹脂のなかでも炭素数10〜2゜の長鎖ダ
イマー酸・より誘導されたエポキシ樹脂が好ましく用い
られ、例としてリノール酸ダイマーとエピクロルヒドリ
ンとから誘導されたエポキシ樹脂等が挙げられる。これ
らの樹脂を用いると、油面接着性にとくに好結果が得ら
れ、また耐水性や耐薬品性等に優れたシール用導電性樹
脂組成物が得られる。Among the above epoxy resins, epoxy resins derived from long-chain dimer acids having a carbon number of 10 to 2 degrees are preferably used, such as epoxy resins derived from linoleic acid dimer and epichlorohydrin. When these resins are used, particularly good results can be obtained in terms of adhesion to oil surfaces, and conductive resin compositions for seals having excellent water resistance, chemical resistance, etc. can be obtained.
なお、上記の長鎖アルキル主鎖を有するエポキシ樹脂と
共に通常のエポキシ樹脂を全体の50重量%以下の割合
で併用することは可能である。Note that it is possible to use an ordinary epoxy resin together with the above-mentioned epoxy resin having a long alkyl main chain in a proportion of 50% by weight or less of the total.
エポキシ樹脂を硬化させる硬化剤としては、加熱により
硬化作用を発揮する通常の硬化剤であれはよく、たとえ
ばジシアンジアミド、4・4′−ジアミノジフェニルス
ルホン、2−n−ペプタデシオ尿素誘導体などが用いら
れる。使用量は、エポキシ樹脂100重量部に対して通
常1〜15重量部の割合でよい。The curing agent for curing the epoxy resin may be any conventional curing agent that exhibits curing action upon heating, such as dicyandiamide, 4,4'-diaminodiphenylsulfone, 2-n-peptadesiourea derivatives, and the like. The amount used may be generally 1 to 15 parts by weight per 100 parts by weight of the epoxy resin.
この発明においては導電性光てん剤を混合することが重
要であるが、このような充てん剤としては銀、パラジウ
ム、銅、アルミニウム、鉄、ニッケル等の金属粉末や、
カーボンブラック、グラファイト等の金属粉末以外の無
機物質が挙げられる。In this invention, it is important to mix a conductive optical filler, and such fillers include metal powders such as silver, palladium, copper, aluminum, iron, nickel, etc.
Examples include inorganic substances other than metal powders such as carbon black and graphite.
使用量は導電性光てん剤の種類、形状2粒子径等により
異なるが通常エポキシ樹脂100 重ic部ニ対して1
0〜700重量部の割合で用いられる。The amount used varies depending on the type, shape, particle size, etc. of the conductive photonic agent, but it is usually 100% of the epoxy resin and 1% of the heavy IC part.
It is used in a proportion of 0 to 700 parts by weight.
この発明において発泡性のシール用導電性樹脂組成物を
得るには、上記成分のほか発泡剤が世いられる。この発
泡剤を配合することにより加熱硬化と共に樹脂の発泡が
起こり、シール部位に発泡体層が形成されより完全な密
着シールが行なわれる。In this invention, in order to obtain a foamable conductive resin composition for seals, a foaming agent is used in addition to the above-mentioned components. By blending this foaming agent, the resin foams as it heats and hardens, forming a foam layer at the sealing site, resulting in more complete sealing.
このような発泡剤としては、一般的にはアゾジカルボン
アシド、アゾビスイソブチロニトリルのようなアソ系化
合物、ジニトロソペンタメチレンテトラミンのようなニ
トロソ化合物、パラトルエンスルボニルヒドラジッド、
4・4′−オキシビスベンゼンスルホニルヒドラジンド
のようなヒドラジッド系化合物などを広く使用できる。Such blowing agents generally include azodicarbonate, aso compounds such as azobisisobutyronitrile, nitroso compounds such as dinitrosopentamethylenetetramine, paratoluenesulfonyl hydrazide,
Hydrazide compounds such as 4,4'-oxybisbenzenesulfonylhydrazide can be widely used.
これらは単独又は混合して場合によっては尿素、カルボ
ン酸の金属塩などの発泡助剤と共に用いてもよい。These may be used alone or in combination, optionally together with foaming aids such as urea and metal salts of carboxylic acids.
このような発泡剤(もしくはこれと発泡助剤)の使用割
合は一般に樹脂分100重量部に対して1〜25重量部
程置部あって、硬化させる温度で発泡が起こり、加熱後
の発泡倍率が実用上約2〜30倍となるようにするのが
よい。The proportion of such blowing agents (or foaming aids) is generally 1 to 25 parts by weight per 100 parts by weight of the resin, so that foaming occurs at the curing temperature and the foaming ratio after heating increases. Practically speaking, it is preferable that the amount is about 2 to 30 times larger.
この発明におけるシール用導電性樹脂組成物および発泡
性のシール用導電性樹脂組成物には、上記の各成分の他
に必要に応じて各種の配合剤を添加することかできる。In addition to the above-mentioned components, various compounding agents can be added to the conductive resin composition for seals and the foamable conductive resin composition for seals according to the present invention, if necessary.
たとえは耐熱性をより向上させる目的でフェニル−β−
ナフチルアミン、ジフェニル−P−フェニレンジアミン
、ジターシャリフチルー4−メチルフェノール、バラフ
ェニルフェノール、ステアリン酸カルシウム、ジラウ1
ノルチオジプロピオネートなどの安定剤や老化防止剤を
、接着性をより向−ヒさせる目的でジエステル類、エス
テルガム、アルキッド樹脂、クマロン樹脂を、組成物タ
レ防止コストダウンを図る目的でクレー、タルク、炭酸
カルシウム、シ1ツカ、炭酸バリウム、アスベストなど
の充てん剤を、そオtそれ添加することができる。その
細首色剤などを配合してもよい。これらの配合量は、エ
ポキシ樹脂100重量部に対して5〜300重量部程重
量部柱ばよい。For example, phenyl-β-
Naphthylamine, diphenyl-P-phenylenediamine, ditertiaryphthyl-4-methylphenol, paraphenylphenol, calcium stearate, dilau 1
Stabilizers and anti-aging agents such as northiodipropionate are added, diesters, ester gums, alkyd resins, and coumaron resins are added to improve adhesion, and clay is added to prevent compositions from sagging and reduce costs. Fillers such as talc, calcium carbonate, silica, barium carbonate, asbestos, etc. can be added. A fine neck coloring agent or the like may be added. The blending amount of these components may be about 5 to 300 parts by weight per 100 parts by weight of the epoxy resin.
この発明のシール用導電性樹脂組成物および発泡性のシ
ール用導電性樹脂組成物を得るには、前記エポキシ樹脂
に硬化剤と導電性光てん剤を加え、発泡性とするときは
これにさらに発泡剤を加え、その他必要に応じて各種の
添加剤を加えて、常温又は硬化や発泡等の起こらない程
度の温度(わずかに起こってもよい)で混合撹拌釜、各
種ニーダ類、二本又は三本ミキシングロール等で混合す
れば゛よい。In order to obtain the conductive resin composition for seals and the foamable conductive resin composition for seals of the present invention, a curing agent and a conductive photonic agent are added to the epoxy resin, and when the resin composition is made foamable, further added. Add a foaming agent and other various additives as necessary, and mix at room temperature or at a temperature that does not cause curing or foaming (although it may occur slightly) in a stirring pot, various kneaders, two or It may be mixed using a three-roll mixing roll or the like.
この発明によるシール用導電性樹脂組成物および発泡性
のシール用導電性樹脂組成物は、液状あるいは半固形状
でそのままシール部位に塗付して用いることができるほ
か、ガラス、ポリエステル等のクロス、不織布か各種フ
ィルムにシート状に塗工し、シート状物として用いるこ
とかできる。The conductive resin composition for seals and the foamable conductive resin composition for seals according to the present invention can be used in liquid or semi-solid form by being applied directly to the seal area, and can also be used with cloth made of glass, polyester, etc. It can be used as a sheet by coating it on non-woven fabric or various films.
以下に、この発明を実施例により具体的に説明する。実
施例中の部は重量部である。The present invention will be specifically explained below using examples. Parts in the examples are parts by weight.
実施例】
エピツー1−拝871(油化シェル社製ダイマー酸変性
エポキシ樹脂)80部、エピコート:l−1=1001
(油化シェル社製ビスフェノールA型固形エポキシ樹脂
)20部を、溶解釜にて溶融混合し粘稠な組成物を得た
。この組成物100部にジシアンジアミド(日本カーバ
イド社製エポキシ樹脂硬化剤)5部、キュアゾール2M
Z−AZINE (四国化成社製エポキシ樹脂硬化剤)
5部、グラファイト粉末100部、アスベスト粉末3部
を配合し、通常のミキシングロールにて混練りすること
により樹脂即成物を得、これをフィルムセパレータ上に
直圧式プレスにてシート状に成形して厚さ0.5叫から
なる未硬化状態のシール用導電性樹脂シートを得た。Examples: 80 parts of Epi2 1-Hai 871 (dimer acid-modified epoxy resin manufactured by Yuka Shell Co., Ltd.), Epicoat: l-1=1001
(Bisphenol A type solid epoxy resin manufactured by Yuka Shell Co., Ltd.) 20 parts were melted and mixed in a melting pot to obtain a viscous composition. 100 parts of this composition, 5 parts of dicyandiamide (epoxy resin curing agent manufactured by Nippon Carbide Co., Ltd.), and 2M of Curesol.
Z-AZINE (Epoxy resin curing agent manufactured by Shikoku Kasei Co., Ltd.)
5 parts of graphite powder, 100 parts of graphite powder, and 3 parts of asbestos powder were mixed and kneaded with a normal mixing roll to obtain a resin ready-made product, which was then formed into a sheet on a film separator using a direct pressure press. An uncured conductive resin sheet for sealing having a thickness of 0.5 mm was obtained.
この樹脂シートを油分の付着した2枚の鋼板の間隙に挿
入シールし、その後電着塗装、アクリル焼付塗装を行っ
た。加熱は各180℃×20分。This resin sheet was inserted into the gap between two oily steel plates and sealed, followed by electrodeposition coating and acrylic baking coating. Heating was at 180℃ for 20 minutes each.
160℃×30分であった。加熱工程で樹脂シートは硬
化して鋼板間の間隙を良好にシールし、又電着塗料が樹
脂表面にも付着し、界面塗装性も良好なものてあった。The temperature was 160°C for 30 minutes. The resin sheet hardened during the heating process, sealing the gap between the steel plates well, and the electrodeposition paint also adhered to the resin surface, giving good interfacial coating properties.
実施例2
実施例1て用いた粘稠な組成物100部に、ジシアンジ
アミド(実施例1のものと同じ)5部、キュアゾール2
MZ−AZINE (前出)5部、グラファイト粉末1
00部、ネオセルボンP#1000(水和化成社製の発
泡剤)2部、アスベスト粉末3部を配合し、実施例1と
同様に混線およびシート化し、0.3叫厚のシート状物
を作製した。このシート状物を油分の付着した2枚の鋼
板間に挿入し、スポット溶接を行った。その後、電着塗
装、アクリル塗装を行った。両塗装時の加熱によって樹
脂は硬化と共に発泡し、2枚の鋼板間は非常に良好に密
猫シールされた。シール部は発泡構造であるためシール
特性が良好で、また界面の塗装性も良好であり、錆の発
生等も防止された。Example 2 To 100 parts of the viscous composition used in Example 1, 5 parts of dicyandiamide (same as in Example 1) and 2 parts of Curesol were added.
MZ-AZINE (mentioned above) 5 parts, graphite powder 1
00 parts, Neocellvon P#1000 (a foaming agent manufactured by Hydraulic Chemical Co., Ltd.) 2 parts, and 3 parts of asbestos powder were blended, and mixed and formed into a sheet in the same manner as in Example 1 to produce a sheet with a thickness of 0.3 mm. did. This sheet-like material was inserted between two steel plates to which oil was attached, and spot welding was performed. After that, electrodeposition painting and acrylic painting were performed. Due to the heating during both coatings, the resin hardened and foamed, creating a very good tight seal between the two steel plates. Since the seal part has a foamed structure, the sealing properties are good, and the paintability of the interface is also good, and the occurrence of rust etc. is prevented.
特許出願人 日東電気工業株式会社Patent applicant: Nitto Electric Industry Co., Ltd.
Claims (5)
エポキシ樹脂に硬化剤と導電、外光てん剤とを加えてな
る油面接着性にすくれるシール用導電性樹脂組成物。(1) A conductive resin composition for seals that has adhesion to oil surfaces and is prepared by adding a curing agent, a conductive agent, and an external light-proofing agent to a liquid or semi-solid epoxy resin having a long alkyl main chain.
エポキシ樹脂が炭素数10〜20の長鎖ダイマー酸から
誘導されたものである特許請求の範囲第(1)項記載の
浦面接猫性にすぐれるシール用導電性樹脂組成物。(2) The Uramen Neko according to claim (1), wherein the liquid or semi-solid epoxy resin having a long-chain alkyl main chain is derived from a long-chain dimer acid having 10 to 20 carbon atoms. A conductive resin composition for seals with excellent properties.
第(1)項または第(2)項記載の曲面接着性にすぐれ
るシール用導電性樹脂組成物。(3) A conductive resin composition for a seal having excellent curved surface adhesion according to claim (1) or (2), wherein the conductive filler is a metal powder.
トの如き金属粉末以外の無機物質からなる特許請求の範
囲第(1)項または第(2)項記載の油面接着性にすぐ
れるシール用導電性樹脂組成物。(4) A conductive seal with excellent oil surface adhesion according to claim (1) or (2), wherein the conductive filler is made of an inorganic substance other than metal powder such as carphone flank or graphite. resin composition.
エポキシ樹脂に硬化剤と導電性充てん剤と発泡剤とを加
えてなる油面接着性にすくれる発泡性のシール用導電性
樹脂組成物。(5) A foamable conductive resin composition for seals that has adhesive properties on oil surfaces and is made by adding a curing agent, a conductive filler, and a foaming agent to a liquid or semi-solid epoxy resin having a long alkyl main chain. thing.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP23197982A JPS59124972A (en) | 1982-12-29 | 1982-12-29 | Conductive resin composition for seal excellent in adhesion to oily surface |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP23197982A JPS59124972A (en) | 1982-12-29 | 1982-12-29 | Conductive resin composition for seal excellent in adhesion to oily surface |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS59124972A true JPS59124972A (en) | 1984-07-19 |
JPS6244031B2 JPS6244031B2 (en) | 1987-09-17 |
Family
ID=16932036
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP23197982A Granted JPS59124972A (en) | 1982-12-29 | 1982-12-29 | Conductive resin composition for seal excellent in adhesion to oily surface |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59124972A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100357583B1 (en) * | 2000-08-22 | 2002-10-18 | 현대자동차주식회사 | Adhesive composition for automobile hem flange structures and process for manufacturing automobile hem flange structures using same |
JP2006137924A (en) * | 2004-07-01 | 2006-06-01 | Murata Mfg Co Ltd | Electroconductive resin composition, electroconductive resin cured product, and electronic component module |
CN103694640A (en) * | 2013-12-20 | 2014-04-02 | 北京郁懋科技有限责任公司 | Preparation method of conductive thermo-cured epoxy resin system |
-
1982
- 1982-12-29 JP JP23197982A patent/JPS59124972A/en active Granted
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100357583B1 (en) * | 2000-08-22 | 2002-10-18 | 현대자동차주식회사 | Adhesive composition for automobile hem flange structures and process for manufacturing automobile hem flange structures using same |
JP2006137924A (en) * | 2004-07-01 | 2006-06-01 | Murata Mfg Co Ltd | Electroconductive resin composition, electroconductive resin cured product, and electronic component module |
CN103694640A (en) * | 2013-12-20 | 2014-04-02 | 北京郁懋科技有限责任公司 | Preparation method of conductive thermo-cured epoxy resin system |
Also Published As
Publication number | Publication date |
---|---|
JPS6244031B2 (en) | 1987-09-17 |
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