JPS62205151A - Composition curable by high-frequency induction heating - Google Patents
Composition curable by high-frequency induction heatingInfo
- Publication number
- JPS62205151A JPS62205151A JP4797886A JP4797886A JPS62205151A JP S62205151 A JPS62205151 A JP S62205151A JP 4797886 A JP4797886 A JP 4797886A JP 4797886 A JP4797886 A JP 4797886A JP S62205151 A JPS62205151 A JP S62205151A
- Authority
- JP
- Japan
- Prior art keywords
- iron oxide
- frequency induction
- induction heating
- composition
- epoxy resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000010438 heat treatment Methods 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 230000006698 induction Effects 0.000 title claims abstract description 23
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003822 epoxy resin Substances 0.000 claims abstract description 24
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 10
- 239000008187 granular material Substances 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 9
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 22
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract description 4
- 235000014413 iron hydroxide Nutrition 0.000 abstract 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 abstract 1
- 229910003145 α-Fe2O3 Inorganic materials 0.000 abstract 1
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 34
- 239000000853 adhesive Substances 0.000 description 19
- 230000001070 adhesive effect Effects 0.000 description 19
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000004020 conductor Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920006332 epoxy adhesive Polymers 0.000 description 4
- 238000013007 heat curing Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000012790 adhesive layer Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000696 magnetic material Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、各種の金属、ガラスｍ維強化ポリエステル（
ＦＲＰ）等、種々の材料の接着に、あるいは、炭素繊維
やガラスＭ＆維強化のプラスチック（ＣＦＲＰ、ＧＦＲ
Ｐ）のバインダーとして有用な高周波誘導加熱硬化用組
成物に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention is applicable to various metals, glass fiber-reinforced polyesters (
For adhesion of various materials such as FRP), carbon fiber, glass M & fiber reinforced plastics (CFRP, GFR), etc.
The present invention relates to a high-frequency induction heating curing composition useful as a binder for P).
エポキシ樹脂と、その潜在性硬化剤、例えば、ジシアン
ジアミド、イミダゾール等とを配合してなる一液加熱硬
化型エボキシ接着剤が広く知られている。BACKGROUND ART A one-component heat-curable epoxy adhesive made of an epoxy resin and its latent curing agent, such as dicyandiamide, imidazole, etc., is widely known.
また、樹脂中に磁性導電体粉を分散させておき、硬化に
あたっては、高周波を印加して、樹脂中に分散している
磁性導電体粉を発熱させて硬化させる高周波誘導加熱硬
化型接着剤も知られている。There is also a high-frequency induction heating curing adhesive in which magnetic conductor powder is dispersed in a resin, and when curing, high frequency waves are applied to generate heat and harden the magnetic conductor powder dispersed in the resin. Are known.
−液液加熱硬化型イボキシ接着剤以下接着剤という。）
は通常的２Ｏ０℃に加熱すれば、速いもので１分以内、
遅いものでも５分以内に硬化が完了する。従って、接着
剤に磁性導電体粉を分散させておき、高周波を印加すれ
ば磁性導電体粉の発熱により接着剤が硬化し、短時間で
接着が完了する。- Liquid-liquid heat-curing ivoxy adhesive Hereinafter referred to as adhesive. )
If heated to 200°C, it can be heated within 1 minute.
Even if it is slow, curing is completed within 5 minutes. Therefore, if magnetic conductor powder is dispersed in the adhesive and high frequency is applied, the adhesive will harden due to the heat generated by the magnetic conductor powder, and the adhesion will be completed in a short time.
しかし、エポキシ樹脂は高温になると不安定となり、は
ぼ２８０℃以上で分解がはじまり、樹脂中に気泡を生じ
るようになる。また、さらに高温になると、完全に分解
して炭化するに至る。従って、接着剤を正常に硬化させ
るためには、温度を２８０℃、好ましくは２５０℃以下
の最適硬化温度に維持することが望ましい。However, epoxy resin becomes unstable at high temperatures, and begins to decompose at temperatures above 280°C, causing bubbles to form in the resin. Moreover, when the temperature rises further, it completely decomposes and becomes carbonized. Therefore, in order to properly cure the adhesive, it is desirable to maintain the temperature at an optimum curing temperature of 280°C, preferably 250°C or less.
ところが、接着剤の加熱を高周波により行なう従来の高
周波誘導加熱硬化型接着剤の場合は、高周波を印加して
いる限り発熱が継続するため、上記の最適硬化温度を維
持することが困難である。そのため、最適硬化温度に維
持するためには、接着剤の温度を何らかの方法で検出し
、その温度と最適硬化温度との偏差をネガティブフィー
ドバックして、高周波の出力をコントロールする自動制
御装置が必要である。そこで、接着剤の温度を正確に検
出する検出手段と、精度と応答性のすぐれた制御手段と
が必要であるが、高性能であり、しかも、簡易・廉価な
制御システムを得ることが、従来、容易ではなかった。However, in the case of conventional high-frequency induction heating curing adhesives in which the adhesive is heated using high-frequency waves, heat generation continues as long as high-frequency waves are applied, making it difficult to maintain the above-mentioned optimum curing temperature. Therefore, in order to maintain the optimum curing temperature, an automatic control device is required that detects the temperature of the adhesive in some way, provides negative feedback on the deviation between that temperature and the optimum curing temperature, and controls the high-frequency output. be. Therefore, a detection means that accurately detects the temperature of the adhesive and a control means with excellent accuracy and responsiveness are required, but it is difficult to obtain a high-performance, simple, and inexpensive control system. , it wasn't easy.
本発明の目的は、このような温度自動制御装置を必要と
することなく、簡易・廉価に、最適温度をもって短時間
に硬化しうる高周波誘導加熱硬化用組成物を提供するこ
とにある。An object of the present invention is to provide a high-frequency induction heating curing composition that can be easily and inexpensively cured at an optimum temperature in a short time without requiring such an automatic temperature control device.
上記の目的を達成するために本発明が採った手段にもと
づく高周波誘導加熱硬化用組成物は。A composition for high frequency induction heating curing is based on the means taken by the present invention to achieve the above object.
イ、エピコート（油化シェルエポキシ株製エポキシ樹脂
の商品名）等のエポキシ樹脂と、口、ジシアンジアミド
、イミダゾール系等のいわゆる潜在性硬化剤と、
ハ、好ましくは、硬化促進剤と、
二、いわゆるフェライト、特にＭｎ＊Ｚｎフェライト、
四・三酸化鉄等であって、そのキュリー点が１５０〜２
８０℃である磁性酸化鉄の粒状体と
を撹拌・混練して製造した高周波誘導加熱硬化用組成物
である。B. Epoxy resin such as Epicoat (trade name of epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.); So-called latent curing agent such as dicyandiamide, imidazole, etc. C. Preferably, a curing accelerator; B. So-called so-called Ferrite, especially Mn*Zn ferrite,
Iron trioxide, etc., whose Curie point is 150 to 2
This is a high-frequency induction heating curing composition produced by stirring and kneading magnetic iron oxide particles at 80°C.
本発明に係る高周波誘導加熱硬化用組成物の構成成分の
それぞれについて説明する。Each of the constituent components of the high frequency induction heating curing composition according to the present invention will be explained.
〈エポキシ樹脂〉
本発明に係る高周波誘導加熱硬化用組成物の構成要素と
して使用するエポキシ樹脂には全く制限がなく、−液加
熱硬化型エポキシ接着剤において使用されるエポキシ樹
脂のいずれをも用いることができる。<Epoxy resin> There are no restrictions on the epoxy resin used as a component of the high-frequency induction heat-curing composition according to the present invention, and any epoxy resin used in liquid heat-curable epoxy adhesives may be used. I can do it.
これらのエポキシ樹脂は一般に分子量が小さく、加熱溶
融した時粘度が低下して接着剤層から流れ出すことがあ
り、このような場合には。These epoxy resins generally have a small molecular weight, and when heated and melted, their viscosity decreases and may flow out of the adhesive layer.
ポリエステル樹脂のごとき粘度保持剤を本発明組成物に
配合して、組成物の流出を防止することが望ましい。It is desirable to include a viscosity-maintaining agent, such as a polyester resin, in the composition of the present invention to prevent run-off of the composition.
〈硬化剤〉
エポキシ樹脂の潜在性硬化剤としては、−液加熱硬化型
エポキシ接着剤の潜在性硬化剤として一般的に使用され
ているジシアンジアミド等のグアニジン系、あるいはイ
ミダゾール系や酸ヒドラジド系等を、何でも使用できる
が、なかでも特に通常の加熱温度よりも高い２Ｏ０℃程
度の高温で速く硬化し、かつ、高周波による急激な加熱
においても発泡や分解を生じないものが好ましい、この
ような目的からは特にアジピン酸ジヒドラジドやイソフ
タル酸ジヒドラジド等の酸ヒドラジド系（ＤＨ）とジシ
アンジアミドが好ましい、また、硬化剤の配合割合は。<Curing agent> As a latent curing agent for epoxy resin, guanidine type such as dicyandiamide, which is commonly used as a latent curing agent for liquid heat-curing epoxy adhesive, imidazole type, acid hydrazide type, etc. Although any material can be used, it is particularly preferable to use a material that hardens quickly at a high temperature of about 200°C, which is higher than the normal heating temperature, and that does not foam or decompose even when heated rapidly by high frequency. In particular, acid hydrazides (DH) such as adipic acid dihydrazide and isophthalic acid dihydrazide and dicyandiamide are preferred, and the blending ratio of the curing agent is as follows.
エポキシ樹脂中のエポキシ基に対する等当量の０．８〜
１．５倍が好ましい。0.8 to 0.8 equivalent to the epoxy group in the epoxy resin
1.5 times is preferable.
（硬化促進剤）
接着剤を高温で短時間に硬化させるためには、エポキシ
樹脂１００重量部に対し、０．１〜２．０重量部の硬化
促進剤の添加が好ましい、この目的で用いられる硬化促
進剤としては、−例として、２−フェニル−４−メチル
−５−ヒドロキシメチルイミダゾール、あるいは。(Curing accelerator) In order to cure the adhesive at a high temperature in a short time, it is preferable to add 0.1 to 2.0 parts by weight of a curing accelerator to 100 parts by weight of the epoxy resin, which is used for this purpose. As curing accelerators - by way of example - 2-phenyl-4-methyl-5-hydroxymethylimidazole or.
２．４−ジアミノ−６（２′−メチルイミダゾリル−（
ｉ） ”ｔ 、エチル−８−トリアジン等のイミダゾー
ル系や、ベンジルジメチルアミン、２．４．６−トリス
（ジメチルアミン）フェノール等の第３級アミンが挙げ
られる。2.4-diamino-6(2'-methylimidazolyl-(
i) "t", imidazole type such as ethyl-8-triazine, and tertiary amine such as benzyldimethylamine and 2.4.6-tris(dimethylamine)phenol.
〈磁性酸化鉄粒子〉
磁性酸化鉄の粒状体の材料としては、一般には磁心材料
や磁気記録材料として多用されているものがあり、化学
式ＦｅＯ（ＯＨ）で表わされ。<Magnetic Iron Oxide Particles> As a material for magnetic iron oxide particles, there are materials that are commonly used as magnetic core materials and magnetic recording materials, and are represented by the chemical formula FeO(OH).
結晶構造によりα、β、γに分類される含水酸化鉄やα
−ＦｅＯ（ヘマタイト） 、 ｙ −Ｆｅ２Ｏ３（マグ
ネタイト）、Ｆｅ５ｏａ（マグネタイト）あるいはＭＯ
・ Ｆｅ２Ｏ３（は２価の金属）で表わされるいわゆる
フェライト等が挙げられる。Hydrous iron oxide and α are classified into α, β, and γ depending on their crystal structure.
-FeO (hematite), y -Fe2O3 (magnetite), Fe5oa (magnetite) or MO
- Examples include so-called ferrite represented by Fe2O3 (a divalent metal).
本発明において使用される磁性酸化鉄は、キュリー点（
消磁開始点）が１５０〜２８０℃であることを必須条件
とするが、 １００Ｋ Ｈｚから１０ＭＨｚ程度の高周
波を印加することによ・り効果的に加熱できるものが適
している。更に高周波により効果的に加熱できる磁性酸
化鉄とじては、その磁気特性を示すヒステリシス曲線が
、磁界の強さを表わすＨ軸と交わる交点の値Ｈｅが１０
〜２Ｏ０エルステツドの範囲にあり、磁化の飽和点の大
きさσＳが５０（ｅｍｕ／ｇ）以上であるものが好適で
ある。The magnetic iron oxide used in the present invention has a Curie point (
Although it is an essential condition that the demagnetization starting point is 150 to 280°C, it is suitable to use a material that can be heated more effectively by applying a high frequency of about 100 KHz to 10 MHz. Furthermore, for magnetic iron oxide, which can be heated effectively by high frequency, the hysteresis curve showing its magnetic properties has a value He at the point of intersection with the H axis, which shows the strength of the magnetic field, of 10.
It is preferable that the magnetization saturation point size σS is in the range of ˜200 oersteds and the magnitude σS of the magnetization saturation point is 50 (emu/g) or more.
このような目的にかなうものの一つとしてはＭｎ会Ｚｎ
フェライトが挙げられる。One of the things that can serve this purpose is Mn-kai Zn.
Examples include ferrite.
磁性酸化鉄の粒状体の形状や大きさに関しては市販され
ている程度のもので良く、またその配合割合いは樹脂１
００重量部に対して５０〜１００重量部とすることが望
ましい、配合割合いがこれより多いと接着剤としての凝
集力が低下し、一方少なければ高周波による加熱効率が
下ることになる。Regarding the shape and size of the magnetic iron oxide particles, it is sufficient to use commercially available ones, and the blending ratio or resin 1
It is desirable to set the blending ratio to 50 to 100 parts by weight per 00 parts by weight.If the blending ratio is higher than this, the cohesive force of the adhesive will decrease, while if it is lower, the heating efficiency by high frequency will decrease.
高周波誘導加熱の原理は、高周波磁場により導電体内部
に生じるうず電流積と磁性材のヒステリシス現象にもと
づくヒステリシス損とであることが知られているが、磁
性酸化鉄の高周波誘導による発熱は、そうちのヒステリ
シス損によるところがほとんどであると推定される。そ
の理由は、これらの磁性酸化鉄の粒子が酸化物であるた
め、電気抵抗が極めて大きく、うず電流が流れにくいこ
とである。It is known that the principle of high-frequency induction heating is the eddy current product generated inside a conductor by a high-frequency magnetic field and the hysteresis loss based on the hysteresis phenomenon of magnetic materials, but heat generation due to high-frequency induction of magnetic iron oxide is similar. It is estimated that most of this is due to hysteresis loss. The reason is that since these magnetic iron oxide particles are oxides, their electrical resistance is extremely high, making it difficult for eddy current to flow.
酸化鉄に限らず磁性体は、温度を高めていくと、そのキ
ュリー点において磁性を消失して消磁状態になる。よっ
て、うず電流積によっても高周波加熱される磁性体は別
であるが、主としてヒステリシス損によって高周波加熱
される酸化鉄は、高周波によっては、そのキュリー点以
上には加熱されないことになる。従って、キュリー点が
１５０〜２８０ ’Ｏの範囲にある磁性酸化鉄を加熱硬
化型エポキシ樹脂組成物に均一に分散させ、高周波誘導
加熱を行なえば、温度はそのキュリー点に維持され、良
好な硬化物が得られる。When the temperature of any magnetic material, including iron oxide, is increased, it loses its magnetism at its Curie point and becomes demagnetized. Therefore, iron oxide, which is heated at high frequency mainly due to hysteresis loss, is not heated above its Curie point depending on the high frequency, except for magnetic materials that are heated at high frequency due to eddy current product. Therefore, if magnetic iron oxide with a Curie point in the range of 150 to 280'O is uniformly dispersed in a heat-curable epoxy resin composition and high-frequency induction heating is performed, the temperature will be maintained at the Curie point, resulting in good curing. You can get things.
以下、実施例１〜３および比較例１〜４により″に晶［
１１Ｉｌ／贈岨する−
まず、−液加熱硬化型エポキシ接着剤として、次の組成
からなる組成物を調製した。その組成は二ピコ−）８２
８ （油化シェルエポキシ＠製）９０重量部、エビコー
）１００９（油化シェルエポキシ株製）１０重量部、イ
ソフタル酸ジヒドラジド（硬化剤） １３重量部、イミ
ダゾール系の硬化促進剤である２ＭＺ−Ａｚ ｉ ｎ
ｅ （四国化成■製）１．５重量部、粘度保持剤である
ＰＥＳ−１７０Ｐ（東亜合成化学工業■製、ポリエステ
ル樹脂）１０重量部である。Hereinafter, according to Examples 1 to 3 and Comparative Examples 1 to 4, crystallization [
First, a composition having the following composition was prepared as a liquid heat-curable epoxy adhesive. Its composition is 2 pico)82
8 (manufactured by Yuka Shell Epoxy@) 90 parts by weight, Ebiko) 1009 (manufactured by Yuka Shell Epoxy Co., Ltd.) 10 parts by weight, isophthalic acid dihydrazide (curing agent) 13 parts by weight, 2MZ-Az which is an imidazole-based curing accelerator in
e (manufactured by Shikoku Kasei ■), 1.5 parts by weight, and 10 parts by weight of PES-170P (manufactured by Toagosei Kagaku Kogyo ■, polyester resin), which is a viscosity retaining agent.
上記組成物に磁性酸化鉄粒子（粉末）としてキュリー点
が２Ｏ０℃のＨｎ＊Ｚｎフェライト８０重量部を加え、
撹拌してペースト状になった組成物を３本ロールに２回
通して練り合わせ、硬化剤、フェライト、エピコート１
００９等の粉末が均一に液状エポキシ樹脂中に分散した
ペースト状接着・剤を製造した。Adding 80 parts by weight of Hn*Zn ferrite with a Curie point of 200°C as magnetic iron oxide particles (powder) to the above composition,
The paste-like composition was stirred and kneaded by passing it through three rolls twice, and then adding a curing agent, ferrite, and Epicoat
A paste-like adhesive/agent was produced in which powder such as 009 was uniformly dispersed in a liquid epoxy resin.
この接着剤を使用し、厚さ３■で樹脂がポリエステルで
あるＦＲＰテストピースを、ＪＩＳ−に−６８５０に従
って接着し、引張剪断強度を測定した。加熱は加熱コイ
ルとして外径８■、内径６ｍｍの銅パイプをスプリング
状に２回巻きしたコイルを使用して出力 １．５Ｋ Ｗ
、周波数４ＭＨｚ、発振時間２Ｏ秒の条件で高周波誘導
加熱により行なった（実施例１）。Using this adhesive, an FRP test piece having a thickness of 3 cm and made of polyester was adhered to JIS-6850, and the tensile shear strength was measured. For heating, a coil made of a copper pipe with an outer diameter of 8mm and an inner diameter of 6mm wound twice in a spring shape is used as a heating coil, and the output is 1.5KW.
The heating was carried out by high-frequency induction heating under the conditions of a frequency of 4 MHz and an oscillation time of 20 seconds (Example 1).
以下実施例２．３、比較例１〜４においても、各種の鉄
あるいは酸化鉄粒子を高周波誘導による発熱体とし、エ
ポキシ樹脂および硬化剤については実施例と同様のもの
につき、実施例１と同様に樹脂がポリエステルであるＦ
ＲＰのテストピースを接着し、引張剪断強度を測定した
。In the following Examples 2.3 and Comparative Examples 1 to 4, various iron or iron oxide particles are used as heating elements by high-frequency induction, and the epoxy resin and curing agent are the same as in Examples, and the same as in Example 1. F where the resin is polyester
A test piece of RP was glued together and the tensile shear strength was measured.
これらの結果を第１表にまとめた。第１表において、実
施例１〜３は本発明による接着剤を使用してＦＲＰｔ−
接着したものであり、３０秒の高周波加熱により、接着
剤は硬化し、強固な接着が得られている。他方、比較例
１〜３では、高周波加熱により急激に温度が上昇し、エ
ポキシ樹脂の分解温度を超えるため接着層が発泡し、特
に、比較例３では一部炭化まで進んでいるため、硬化物
は凝集力に乏しく、十分な接着強度は得られない。These results are summarized in Table 1. In Table 1, Examples 1 to 3 show that FRPt-
The adhesive was cured by high-frequency heating for 30 seconds, and a strong bond was obtained. On the other hand, in Comparative Examples 1 to 3, the temperature rapidly rose due to high-frequency heating and exceeded the decomposition temperature of the epoxy resin, causing foaming of the adhesive layer. Particularly in Comparative Example 3, carbonization progressed partially, so the cured product has poor cohesive force and cannot obtain sufficient adhesive strength.
参考例としての比較例４は、比較例２と同一組成の接着
剤により、高周波ではなく１５０°Ｃオーブン中で加熱
接着したものである。この場合、温度は一定に維持され
るので、良好な硬化物が得られ、接着強度は良好である
。ただし、「接着層の内部まで熱が伝わるのに時間を要
すること」、および「オーブン加熱であるため、テスト
ピース全体も加熱されることから、ＦＲＰの耐熱性との
関係で １５０℃以上には加熱できないこと」により、
接着剤を完全に硬化させるためには３０分以上必要であ
る。Comparative Example 4, which serves as a reference example, was bonded by heating in a 150° C. oven instead of using high frequency using an adhesive having the same composition as Comparative Example 2. In this case, since the temperature is maintained constant, a good cured product is obtained and the adhesive strength is good. However, ``it takes time for the heat to be transmitted to the inside of the adhesive layer'' and ``Since the heating is done in an oven, the entire test piece is also heated. Due to the inability to heat
It takes 30 minutes or more to completely cure the adhesive.
以上のように、本発明に係る高周波誘導加熱硬化用組成
物によれば、高周波加熱を効果的に利用できることにな
り、短時間で良好なエポキシ樹脂の硬化物が得られる。As described above, according to the composition for high-frequency induction heating curing according to the present invention, high-frequency heating can be effectively utilized, and a good cured epoxy resin can be obtained in a short time.
本発明に係る高周波誘導加熱硬化用組成物は、エポキシ
樹脂による接着ばかりでなく、エポキシ樹脂無機物のバ
インダーとして、あるいは、封止剤として使用する場合
等にも有用である。The high-frequency induction heating curing composition according to the present invention is useful not only for adhesion with epoxy resins, but also when used as a binder for epoxy resin inorganic substances or as a sealant.
以上説明せるとおり、本発明に係る高周波誘導加熱硬化
用組成物は、
イ、エピコート（油化シェルエポキシ株製エポキシ樹脂
の商品名）等のエポキシ樹脂と・口、ジシアンジアミド
、イミダゾール系等のいわゆる潜在性硬化剤と、
ハ、好ましくは、硬化促進剤と、
二５いわゆるフェライト、特にＭｎ＊Ｚｎフェライト、
四・三酸化鉄等であって、そのキュリー点が１５０〜２
８０℃である磁性酸化鉄の粒状体と
が撹拌・混練された組成物であるので、高周波誘導加熱
されると、ヒステリシス損により上記の磁性酸化鉄が発
熱して温度が上昇するが、磁性酸化鉄として、その固有
のキュリー点がエポキシ樹脂の加熱硬化温度範囲にある
１５０〜２８０℃のものを選択配合しているので、こ
のキュリー点に達すると消磁されて、自動的に高周波誘
導加熱硬化が停止し、この温度以上に加熱されることは
なく、選択されたエポキシ樹脂の最適硬化温度に自動的
に保持されるので、精巧な温度自動制御装置を必要とす
ることなく、極めて簡易・迅速に、最適条件をもって、
硬化接着することができる。As explained above, the composition for high-frequency induction heating curing according to the present invention is made of epoxy resins such as 1. Epikote (trade name of epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.), 2. C. Preferably, a curing accelerator; 25 So-called ferrite, especially Mn*Zn ferrite,
Iron trioxide, etc., whose Curie point is 150 to 2
Since the composition is stirred and kneaded with magnetic iron oxide granules at 80°C, when high-frequency induction heating is performed, the magnetic iron oxide generates heat due to hysteresis loss and the temperature rises. As iron, we have selected and blended iron whose unique Curie point is within the heat curing temperature range of epoxy resin (150~280℃), so when it reaches this Curie point, it is demagnetized and automatically hardens by high frequency induction heating. The curing temperature is automatically maintained at the optimum curing temperature for the selected epoxy resin, making it extremely simple and quick, without the need for elaborate temperature control equipment. , with optimal conditions,
Can be cured and bonded.
Claims (1)
１５０〜２８０℃の範囲にある磁性酸化鉄の粒状体とを
含有してなる高周波誘導加熱硬化用組成物。 ［２］前記磁性酸化鉄の粒状体は、含水酸化鉄と、α−
Ｆｅ＿２Ｏ＿３と、γ−Ｆｅ＿２Ｏ＿３と、Ｆｅ＿３Ｏ
＿４と、ＭＯ・Ｆｅ＿２Ｏ＿３（但し、Ｍは２価の金属
）とのグループより選択された磁性酸化鉄の粒状体であ
る特許請求の範囲第１項記載の高周波誘導加熱硬化用組
成物。 ［３］前記ＭＯ・Ｆｅ＿２Ｏ＿３の粒状体は、Ｍｎ・Ｚ
ｎフェライトの粒状体である特許請求の範囲第２項記載
の高周波誘導加熱硬化用組成物。[Scope of Claims] [1] A high-frequency induction heating curing composition comprising an epoxy resin, a latent curing agent, and magnetic iron oxide particles having a Curie point in the range of 150 to 280°C. [2] The magnetic iron oxide particles contain hydrated iron oxide and α-
Fe_2O_3, γ-Fe_2O_3, and Fe_3O
The composition for high-frequency induction heating curing according to claim 1, which is a granular body of magnetic iron oxide selected from the group consisting of _4 and MO.Fe_2O_3 (where M is a divalent metal). [3] The MO・Fe_2O_3 granules are Mn・Z
The composition for high frequency induction heating curing according to claim 2, which is a granular body of n-ferrite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4797886A JPS62205151A (en) | 1986-03-04 | 1986-03-04 | Composition curable by high-frequency induction heating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4797886A JPS62205151A (en) | 1986-03-04 | 1986-03-04 | Composition curable by high-frequency induction heating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62205151A true JPS62205151A (en) | 1987-09-09 |
Family
ID=12790401
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4797886A Pending JPS62205151A (en) | 1986-03-04 | 1986-03-04 | Composition curable by high-frequency induction heating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62205151A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02242856A (en) * | 1989-01-23 | 1990-09-27 | Toray Dow Corning Silicone Co Ltd | Self-heat generative polymer composition and heat generating method thereof |
| EP0359709A3 (en) * | 1988-09-14 | 1991-03-20 | Ciba-Geigy Ag | Induction heat hardenable epoxy resin composition |
| JP2007313403A (en) * | 2006-05-24 | 2007-12-06 | Nippon Paint Co Ltd | Coating method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5655474A (en) * | 1979-10-12 | 1981-05-16 | Sekisui Chem Co Ltd | Radiofrequency heating curable adhesive |
-
1986
- 1986-03-04 JP JP4797886A patent/JPS62205151A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5655474A (en) * | 1979-10-12 | 1981-05-16 | Sekisui Chem Co Ltd | Radiofrequency heating curable adhesive |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0359709A3 (en) * | 1988-09-14 | 1991-03-20 | Ciba-Geigy Ag | Induction heat hardenable epoxy resin composition |
| JPH02242856A (en) * | 1989-01-23 | 1990-09-27 | Toray Dow Corning Silicone Co Ltd | Self-heat generative polymer composition and heat generating method thereof |
| JP2007313403A (en) * | 2006-05-24 | 2007-12-06 | Nippon Paint Co Ltd | Coating method |
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