JP3030499B2 - Curing agent for epoxy resin - Google Patents
Curing agent for epoxy resinInfo
- Publication number
- JP3030499B2 JP3030499B2 JP9034685A JP3468597A JP3030499B2 JP 3030499 B2 JP3030499 B2 JP 3030499B2 JP 9034685 A JP9034685 A JP 9034685A JP 3468597 A JP3468597 A JP 3468597A JP 3030499 B2 JP3030499 B2 JP 3030499B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- dihydrazide
- curing
- group
- curing agent
- 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.)
- Expired - Lifetime
Links
Landscapes
- Epoxy Resins (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、エポキシ樹脂用硬
化剤に関する。[0001] The present invention relates to a curing agent for epoxy resins.
【０００２】[0002]
【発明が解決しようとする課題】エポキシ樹脂は、その
硬化物が優れた電気絶縁性、耐湿性、耐熱性、耐ハンダ
性、耐薬品性、耐久性、接着力、機械的強度等を有する
ことから、例えば、固定抵抗器、半導体等の電子部品や
積層板の封止材、接着剤、塗料等として幅広く使用され
ている。特に電子機器の著しい発達に伴い、電子部品の
封止材としての用途は、その重要性が増大している。The cured epoxy resin has excellent electrical insulation, moisture resistance, heat resistance, solder resistance, chemical resistance, durability, adhesive strength, mechanical strength and the like. Therefore, they are widely used as sealing materials, adhesives, paints, and the like for fixed resistors, electronic components such as semiconductors, and laminated boards. In particular, with the remarkable development of electronic equipment, its use as an encapsulant for electronic components is increasing in importance.
【０００３】従来から、エポキシ樹脂の硬化は、エポキ
シ樹脂に硬化剤を添加して加熱することにより行われ
る。ここで硬化剤としては、例えば、脂肪族アミン類、
酸無水物、フェノール、イミダゾール類、ジシアンジア
ミド、三弗化硼素のアミン錯体、ジヒドラジド化合物等
が知られている。Conventionally, epoxy resin is cured by adding a curing agent to the epoxy resin and heating. Here, as the curing agent, for example, aliphatic amines,
Acid anhydrides, phenols, imidazoles, dicyandiamide, amine complexes of boron trifluoride, dihydrazide compounds and the like are known.
【０００４】これら従来の硬化剤の中、脂肪族アミン
類、酸無水物及びフェノールを用いる場合、室温でも硬
化反応が進行するため、使用直前にエポキシ樹脂と混合
しなければならず、作業性が非常に悪いという問題があ
る。一方、イミダゾール類、ジシアンジアミド及び三弗
化硼素のアミン錯体のいずれかを用いる場合は加熱する
ことが必須であるため、脂肪族アミン類等の前記３種の
硬化剤のような問題は生じないが、イミダゾール類やジ
シアンジアミドを用いて得られるエポキシ樹脂の硬化物
は耐湿性が不十分となり、特に電子部品等の封止材の用
途には不適当である。また三弗化硼素のアミン錯体は、
硬化時にアミンガスを発生し、硬化物を変色させるとい
う欠点を有している。更に、ジヒドラジド化合物以外の
従来の硬化剤は、いずれも、その一部がそのまま硬化物
中に残留し、水素イオン等のイオンを放出し、硬化物に
通電性を付与するという欠点がある。このような硬化物
を例えば電子部品等の封止材として用いると、絶縁不良
を生じ、そのため電子・電気機器の信頼性が著しく低下
するを避け得ない。When aliphatic amines, acid anhydrides, and phenols are used among these conventional curing agents, the curing reaction proceeds even at room temperature, so that they must be mixed with an epoxy resin immediately before use, resulting in poor workability. There is a problem that is very bad. On the other hand, when using any of the amine complexes of imidazoles, dicyandiamide and boron trifluoride, heating is indispensable, so that problems such as those of the above three types of curing agents such as aliphatic amines do not occur. A cured product of an epoxy resin obtained by using imidazoles or dicyandiamide has insufficient moisture resistance, and is particularly unsuitable for use as a sealing material for electronic parts and the like. The amine complex of boron trifluoride is
There is a disadvantage that amine gas is generated at the time of curing and the cured product is discolored. Further, conventional curing agents other than the dihydrazide compound have a disadvantage that part of the curing agent remains in the cured product as it is, releases ions such as hydrogen ions, and imparts electrical conductivity to the cured product. When such a cured product is used, for example, as a sealing material for electronic components or the like, insulation failure occurs, and therefore, it is inevitable that the reliability of electronic / electric devices is significantly reduced.
【０００５】これに対し、ジヒドラジド化合物は室温で
は硬化反応を起こさず、得られる硬化物の耐湿性、電気
絶縁性等の特性を損なったり、変色を誘起することもな
いので、今日まで種々のジヒドラジド化合物が提案され
ている（例えば、特開昭５７−１４５１２１号公報、特
開昭５９−４９２２４号公報、特開昭６０−２０９２７
号公報、特開昭６０−５５０２５号公報、特開昭６０−
１７７０８１号公報、特開昭６１−１２７２４号公報、
特開昭６１−３６３１８号公報、特開昭６０−１２７７
０２号公報、特開平４−１４６９８０号公報等）。On the other hand, the dihydrazide compound does not cause a curing reaction at room temperature and does not impair the properties of the obtained cured product such as moisture resistance and electrical insulation and does not induce discoloration. Compounds have been proposed (for example, JP-A-57-145121, JP-A-59-49224, and JP-A-60-20927).
JP-A-60-55025, JP-A-60-55025
No. 177081, JP-A-61-12724,
JP-A-61-36318, JP-A-60-1277
02, JP-A-4-146980, etc.).
【０００６】しかしながら、ジヒドラジド化合物を用い
て円滑なエポキシ樹脂の硬化反応を行うには、１６０℃
より低い硬化温度では硬化に長時間を要するので、１６
０〜１８０℃又はそれ以上に加熱しなければならず、エ
ネルギーコストひいてはランニングコストが著しく増大
し、工業的に好ましくない。より具体的には、例えば、
ジヒドラジド化合物の中の代表的な化合物であるアジピ
ン酸ジヒドラジドを用いる場合、１４０℃で硬化させる
と１時間近い長時間を必要とする。However, in order to carry out a smooth curing reaction of an epoxy resin using a dihydrazide compound, a temperature of 160 ° C.
Lower curing temperatures take longer to cure, so 16
It must be heated to 0 to 180 ° C. or higher, which significantly increases energy costs and thus running costs, and is not industrially preferable. More specifically, for example,
When using adipic acid dihydrazide, which is a typical compound among the dihydrazide compounds, curing at 140 ° C. requires a long time of about one hour.
【０００７】そこで、このような問題を解消するため
に、従来は硬化促進剤が添加されている。ジヒドラジド
化合物を用いてエポキシ樹脂を硬化させる際に添加され
るべき硬化促進剤としては、例えばトリ−ｎ−ブチルア
ミン、ベンジルメチルアミン、２，４，６−トリス（ジ
メチルアミノメチル）フェノール等の第三級アミン類、
２−エチルイミダゾール、２−エチル−４−メチルイミ
ダゾール、２−フェニルイミダゾール等のイミダゾール
類等が使用されている。しかるに、これらの硬化促進剤
はジヒドラジド化合物以外の従来の硬化剤と同一又は同
類のものであり、これら硬化促進剤の有効量を添加する
ことにより得られる硬化物が変色したり、通電性が付与
されるのが避けられない。Therefore, in order to solve such a problem, a curing accelerator has conventionally been added. Examples of the curing accelerator to be added when the epoxy resin is cured using the dihydrazide compound include, for example, tertiary n-butylamine, benzylmethylamine, and 2,4,6-tris (dimethylaminomethyl) phenol. Grade amines,
Imidazoles such as 2-ethylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole are used. However, these curing accelerators are the same as or similar to conventional curing agents other than the dihydrazide compound, and the cured product obtained by adding an effective amount of these curing accelerators discolors or imparts electrical conductivity. Inevitable.
【０００８】[0008]
【課題を解決するための手段】本発明者は、上記課題を
解決すべく鋭意研究を重ねた結果、エポキシ樹脂をジヒ
ドラジド化合物によって硬化させる際に、該ジヒドラジ
ド化合物の少なくとも２種以上を添加することにより、
顕著な相乗効果が発現され、硬化温度の著しい低温化及
び硬化時間の短縮が可能になり、しかも著しく高いガラ
ス転移温度を有し、耐熱性や耐ハンダ性等に優れたエポ
キシ樹脂の硬化物が得られることを見い出し、ここに本
発明を完成するに至った。Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, when curing an epoxy resin with a dihydrazide compound, adding at least two or more of the dihydrazide compounds. By
A remarkable synergistic effect is exhibited, the curing temperature can be remarkably lowered and the curing time can be shortened, and a cured product of an epoxy resin having a remarkably high glass transition temperature and excellent heat resistance and solder resistance can be obtained. We have found what we can do, and here we have completed our invention.
【０００９】即ち、本発明は、２種以上のジヒドラジド
化合物を含有することを特徴とするエポキシ樹脂用硬化
剤に係る。That is, the present invention relates to a curing agent for an epoxy resin, comprising two or more dihydrazide compounds.
【００１０】本発明のエポキシ樹脂用硬化剤を用いるこ
とにより、硬化温度の著しい低温化及び硬化時間の短縮
が可能になる。例えば、硬化温度を１６０℃より低い温
度に下げても、数分〜３０分程度の短い時間で硬化が終
了する。また、本発明の硬化剤であるジヒドラジド化合
物の組み合わせによっては、１２０℃程度の硬化温度で
も、エポキシ樹脂の硬化が可能になる。The use of the epoxy resin curing agent of the present invention makes it possible to significantly lower the curing temperature and shorten the curing time. For example, even if the curing temperature is lowered to a temperature lower than 160 ° C., the curing is completed in a short time of about several minutes to 30 minutes. Further, depending on the combination of the dihydrazide compound as the curing agent of the present invention, the epoxy resin can be cured even at a curing temperature of about 120 ° C.
【００１１】更に、本発明のエポキシ樹脂用硬化剤を用
いて得られるエポキシ樹脂の硬化物は、従来のものより
も著しく高いガラス転移温度を有し、耐熱性や耐ハンダ
性等に優れている。Further, a cured product of an epoxy resin obtained by using the curing agent for an epoxy resin of the present invention has a significantly higher glass transition temperature than conventional ones, and is excellent in heat resistance, solder resistance and the like. .
【００１２】加えて、長時間使用しても通電性を発現し
ないエポキシ樹脂の硬化物が得られる。In addition, a cured product of an epoxy resin which does not exhibit electrical conductivity even when used for a long time can be obtained.
【００１３】[0013]
【発明の実施の形態】本発明のエポキシ樹脂用硬化剤
は、少なくとも２種以上のジヒドラジド化合物を含有す
る。ジヒドラジド化合物としては公知のものを使用で
き、例えば、一般式 Ｈ2ＮＨＮ−ＣＯ−（Ａ）n−ＣＯ−ＮＨＮＨ2 （１） ［式中Ａは、置換基を有することのあるアルキレン基、
置換基を有することのあるアリーレン基又はオキソ基を
示す。ｎは０又は１を示す。］で表される２塩基酸ジヒ
ドラジド化合物等を挙げることができる。DESCRIPTION OF THE PREFERRED EMBODIMENTS The curing agent for epoxy resin of the present invention contains at least two or more dihydrazide compounds. As the dihydrazide compound, known compounds can be used. For example, a general formula H 2 NHN—CO— (A) n —CO—NHNH 2 (1) wherein A is an alkylene group which may have a substituent,
It represents an arylene group or an oxo group which may have a substituent. n represents 0 or 1. And a dibasic acid dihydrazide compound represented by the formula:
【００１４】上記一般式（１）において、Ａで示される
アルキレン基としては、例えば、メチレン基、エチレン
基、トリメチレン基、テトラメチレン基、ペンタメチレ
ン基、ヘキサメチレン基、ヘプタメチレン基、オクタメ
チレン基、ノナメチレン基、デカメチレン基、ウンデカ
メチレン基、ヘキサデカメチレン基等の炭素数１〜１４
程度の直鎖状アルキレン基を挙げることができる。アル
キレン基の置換基としては、例えば水酸基等を挙げるこ
とができる。アリーレン基としては、例えば、フェニレ
ン基、ビフェニレン基、ナフチレン基、アントリレン
基、フェナントリレン基等を挙げることができ、これら
の中でもフェニレン基、ナフチレン基等が好ましい。ア
リーレン基の置換基としては、例えば、水酸基、メチル
基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−
ブチル基、ｔｅｒｔ−ブチル基、イソブチル基等の炭素
数１〜４程度の直鎖又は分岐鎖状のアルキル基等を挙げ
ることができる。In the above formula (1), examples of the alkylene group represented by A include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, and an octamethylene group. , A nonamethylene group, a decamethylene group, an undecamethylene group, a hexadecamethylene group, etc.
Linear alkylene groups. Examples of the substituent of the alkylene group include a hydroxyl group. Examples of the arylene group include a phenylene group, a biphenylene group, a naphthylene group, an anthrylene group, and a phenanthrylene group. Of these, a phenylene group, a naphthylene group, and the like are preferable. Examples of the substituent of the arylene group include a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-
Examples thereof include a linear or branched alkyl group having about 1 to 4 carbon atoms, such as a butyl group, a tert-butyl group, and an isobutyl group.
【００１５】上記一般式（１）で表されるジヒドラジド
化合物の具体例としては、例えば、カルボヒドラジド、
シュウ酸ジヒドラジド、マロン酸ジヒドラジド、コハク
酸ジヒドラジド、アジピン酸ジヒドラジド、ピメリン酸
ジヒドラジド、スベリン酸ジヒドラジド、アゼライン酸
ジヒドラジド、セバシン酸ジヒドラジド、ドデカンジオ
ヒドラジド、ヘキサデカンジオヒドラジド、マレイン酸
ジヒドラジド、フマル酸ジヒドラジド、ジグリコール酸
ジヒドラジド、酒石酸ジヒドラジド、リンゴ酸ジヒドラ
ジド、イソフタル酸ジヒドラジド、テレフタル酸ジヒド
ラジド、２，６−ナフトエ酸ジヒドラジド、４，４’−
ビスベンゼンジヒドラジド、１，４−ナフトエ酸ジヒド
ラジド等を挙げることができる。これらの他にも、ダイ
マー酸ジヒドラジド、２，６−ピリジンジヒドラジド、
イミノジ酢酸ジヒドラジド、クエン酸トリヒドラジド、
シクロヘキサントリカルボン酸トリヒドラジド、特公平
２−４６０７号公報に記載のジヒドラジド化合物等の２
塩基酸ヒドラジド、２，４−ジヒドラジノ−６−メチル
アミノ−ｓｙｍ−トリアジン、ポリ（メタ）アクリル酸
ヒドラジド等をも使用できる。尚、本発明の硬化剤を用
いて得られるエポキシ樹脂の硬化物を電子部品の封止材
等として用いる場合には、これらのジヒドラジド化合物
の中でも２塩基酸ジヒドラジドが好ましく、イソフタル
酸ジヒドラジド、アジピン酸ジヒドラジド、ドデカンジ
オヒドラジド、グルタル酸ジヒドラジド、イミノジ酢酸
ジヒドラジド等が特に好ましい。Specific examples of the dihydrazide compound represented by the general formula (1) include, for example, carbohydrazide,
Oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, suberic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodecanediohydrazide, hexadecandiohydrazide, maleic acid dihydrazide, maleic acid dihydrazide, maleic acid dihydrazide Acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 4,4'-
Bisbenzene dihydrazide, 1,4-naphthoic acid dihydrazide and the like can be mentioned. Besides these, dimer acid dihydrazide, 2,6-pyridine dihydrazide,
Iminodiacetic acid dihydrazide, citric acid trihydrazide,
Cyclohexanetricarboxylic acid trihydrazide, dihydrazide compound described in JP-B-2-4607, etc.
Basic acid hydrazide, 2,4-dihydrazino-6-methylamino-sym-triazine, poly (meth) acrylic acid hydrazide and the like can also be used. When a cured product of the epoxy resin obtained by using the curing agent of the present invention is used as a sealing material for electronic parts, dibasic dihydrazide is preferable among these dihydrazide compounds, and isophthalic dihydrazide and adipic acid are preferable. Dihydrazide, dodecandiohydrazide, glutaric acid dihydrazide, iminodiacetic acid dihydrazide and the like are particularly preferred.
【００１６】本発明のエポキシ樹脂用硬化剤の好ましい
組み合わせとしては、例えば、イソフタル酸ジヒドラジ
ドとアジピン酸ジヒドラジド、イミノジ酢酸ジヒドラジ
ドとアジピン酸ジヒドラジド、ドデカンジオヒドラジド
とアジピン酸ジヒドラジド、グルタル酸ジヒドラジドと
アジピン酸ジヒドラジド、イミノジ酢酸ジヒドラジドと
ドデカンジオヒドラジドとアジピン酸ジヒドラジド等を
挙げることができる。Preferred combinations of the curing agents for epoxy resins of the present invention include, for example, isophthalic acid dihydrazide and adipic acid dihydrazide, iminodiacetic acid dihydrazide and adipic acid dihydrazide, dodecane dihydrazide and adipic acid dihydrazide, glutaric acid dihydrazide and adipic acid dihydrazide. And iminodiacetic acid dihydrazide, dodecandiohydrazide and adipic acid dihydrazide.
【００１７】尚、上記ジヒドラジド化合物を、通常１０
０μｍ以下、好ましくは１０μｍ以下の粒径に微粉砕す
ることにより、一層の硬化時間の短縮化を図ることがで
きる。The above dihydrazide compound is usually used in an amount of 10
By finely pulverizing to a particle size of 0 μm or less, preferably 10 μm or less, the curing time can be further shortened.
【００１８】本発明においては、上記ジヒドラジド化合
物の少なくとも２種以上を併用するが、その併用割合
は、硬化させるべきエポキシ樹脂の種類、得られるエポ
キシ樹脂硬化物の用途、設計された硬化時間や硬化温度
等の各種の条件に応じて適宜決定すればよい。例えば全
ジヒドラジド化合物中に１種のジヒドラジド化合物が通
常０．５〜９９．５重量％、好ましくは１０〜９０重量
％、より好ましくは３０〜７０重量％含有されるよう
に、２種以上のジヒドラジド化合物を併用するのがよ
い。In the present invention, at least two of the above-mentioned dihydrazide compounds are used in combination. The combination ratio depends on the type of epoxy resin to be cured, the use of the obtained epoxy resin cured product, the designed curing time and curing time. What is necessary is just to determine suitably according to various conditions, such as temperature. For example, two or more dihydrazide compounds may be used such that one dihydrazide compound is usually contained in an amount of 0.5 to 99.5% by weight, preferably 10 to 90% by weight, more preferably 30 to 70% by weight in all dihydrazide compounds. Compounds are preferably used in combination.
【００１９】ジヒドラジド化合物をエポキシ樹脂に配合
する場合、その配合量は特に制限されず、硬化させるべ
きエポキシ樹脂の種類、得られるエポキシ樹脂硬化物の
用途、設計された硬化時間や硬化温度等の各種の条件に
応じて広い範囲から適宜選択すればよいが、通常エポキ
シ樹脂１００重量部に対して５〜８０重量部程度、好ま
しくは１０〜６０重量部程度とすればよい。When the dihydrazide compound is mixed with the epoxy resin, the amount of the compound is not particularly limited, and the type of the epoxy resin to be cured, the use of the obtained epoxy resin cured product, the designed curing time and the curing temperature, etc. May be appropriately selected from a wide range depending on the conditions, but it is usually about 5 to 80 parts by weight, preferably about 10 to 60 parts by weight, per 100 parts by weight of the epoxy resin.
【００２０】本発明においては、硬化剤であるジヒドラ
ジド化合物と共に、モノヒドラジド化合物を硬化促進剤
として用いることができる。モノヒドラジド化合物の使
用によって、より一層の硬化温度の低下及び硬化時間の
短縮を図ることができる。モノヒドラジド化合物として
は、例えば、一般式 Ａｒ−ＣＯＮＨＮＨ2 （２） ［式中Ａｒは１又は２個以上の置換基を有することのあ
るアリール基を示す。］で表されるモノヒドラジド化合
物を挙げることができる。In the present invention, a monohydrazide compound can be used as a curing accelerator together with a dihydrazide compound as a curing agent. By using the monohydrazide compound, the curing temperature and the curing time can be further reduced. Examples of the monohydrazide compound include, for example, a general formula Ar-CONHNH 2 (2) wherein Ar represents an aryl group which may have one or more substituents. A monohydrazide compound represented by the formula:
【００２１】上記一般式（２）において、Ａｒで示され
るアリール基としては、例えば、フェニル基、トリル
基、キシリル基、ナフチル基等を挙げることができ、こ
れらの中でもフェニル基が好ましい。In the general formula (2), examples of the aryl group represented by Ar include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Of these, a phenyl group is preferable.
【００２２】また、アリール基に置換する基としては、
例えば、低級アルコキシ基、低級アルキル基、アミノ
基、ニトロ基、水酸基等を挙げることができ、これらの
中でも低級アルコキシ基、低級アルキル基等が好まし
い。低級アルコキシ基は、例えば、メトキシ、エトキ
シ、ｎ−プロポキシ、イソプロポキシ、ｓｅｃ−プロポ
キシ、ｎ−ブトキシ、イソブトキシ、ｔｅｒｔ−ブトキ
シ等の炭素数１〜４程度の直鎖又は分岐鎖状のアルコキ
シ基であり、低級アルキル基は、例えば、メチル、エチ
ル、ｎ−プロピル、イソプロピル、ｓｅｃ−プロピル、
ｎ−ブチル、イソブチル、ｔｅｒｔ−ブチル等の炭素数
１〜４程度の直鎖又は分岐鎖状のアルキル基である。Further, as a group to be substituted on the aryl group,
For example, a lower alkoxy group, a lower alkyl group, an amino group, a nitro group, a hydroxyl group and the like can be mentioned, and among these, a lower alkoxy group, a lower alkyl group and the like are preferable. The lower alkoxy group is, for example, a linear or branched alkoxy group having about 1 to 4 carbon atoms such as methoxy, ethoxy, n-propoxy, isopropoxy, sec-propoxy, n-butoxy, isobutoxy, and tert-butoxy. There are lower alkyl groups, for example, methyl, ethyl, n-propyl, isopropyl, sec-propyl,
It is a linear or branched alkyl group having about 1 to 4 carbon atoms such as n-butyl, isobutyl, tert-butyl and the like.
【００２３】上記一般式（２）のモノヒドラジド化合物
の具体例としては、例えば、安息香酸ヒドラジド、１−
ナフトエ酸ヒドラジド、アニス酸ヒドラジド、ｐ−メト
キシ安息香酸ヒドラジド、アミノ安息香酸ヒドラジド、
３−メトキシ−２−ナフトエ酸ヒドラジド、サリチル酸
ヒドラジド等を挙げることができ、これらの中でもアニ
ス酸ヒドラジド、サリチル酸ヒドラジド等が好ましい。Specific examples of the monohydrazide compound of the general formula (2) include, for example, benzoic acid hydrazide, 1-
Naphthoic hydrazide, anisic hydrazide, p-methoxybenzoic hydrazide, aminobenzoic hydrazide,
Examples thereof include 3-methoxy-2-naphthoic acid hydrazide and salicylic acid hydrazide. Of these, anisic acid hydrazide and salicylic acid hydrazide are preferable.
【００２４】更に本発明硬化剤の好ましい特性を損なわ
ない範囲で、従来から用いられている硬化促進剤、例え
ば、トリ−ｎ−ブチルアミン、ベンジルメチルアミン、
２，４，６−トリス（ジメチルアミノメチル）フェノー
ル等の第三級アミン類、２−メチルイミダゾール、２−
エチルイミダゾール、２−エチル−４−メチルイミダゾ
ール、２−フェニルイミダゾール等のイミダゾール類等
を使用することもできる。Further, as long as the preferable properties of the curing agent of the present invention are not impaired, conventionally used curing accelerators such as tri-n-butylamine, benzylmethylamine,
Tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol, 2-methylimidazole,
Imidazoles such as ethylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole can also be used.
【００２５】斯かる硬化促進剤は１種を単独で使用でき
或いは２種以上を併用できる。硬化促進剤の配合量は特
に制限されず、硬化させるべきエポキシ樹脂の種類、得
られるエポキシ樹脂硬化物の用途、設計された硬化時間
や硬化温度等の各種の条件に応じて広い範囲から適宜決
定すればよいが、通常エポキシ樹脂１００重量部に対し
て１〜１５重量部程度、好ましくは２〜６重量部程度と
すればよい。One of these curing accelerators can be used alone, or two or more can be used in combination. The amount of the curing accelerator is not particularly limited, and is appropriately determined from a wide range according to various kinds of conditions such as the type of epoxy resin to be cured, the use of the obtained epoxy resin cured product, the designed curing time and the curing temperature. The amount may be generally about 1 to 15 parts by weight, preferably about 2 to 6 parts by weight, per 100 parts by weight of the epoxy resin.
【００２６】本発明のエポキシ樹脂用硬化剤を適用し得
るエポキシ樹脂としては特に制限はなく、従来から知ら
れているものでよい。その一例として、ビスフェノール
Ａ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、
ビスフェノールＡＤ型エポキシ樹脂、フェノールノボラ
ック型エポキシ樹脂、クレゾールノボラック型エポキシ
樹脂、環状脂肪族エポキシ樹脂、グリシジルエステル系
樹脂、グリシジルアミン系エポキシ樹脂、複素環式エポ
キシ樹脂、ウレタン変性エポキシ樹脂、臭素化ビスフェ
ノールＡ型エポキシ樹脂等を挙げることができる。The epoxy resin to which the epoxy resin curing agent of the present invention can be applied is not particularly limited, and may be a conventionally known epoxy resin. As an example, bisphenol A type epoxy resin, bisphenol F type epoxy resin,
Bisphenol AD epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, cycloaliphatic epoxy resin, glycidyl ester resin, glycidylamine epoxy resin, heterocyclic epoxy resin, urethane-modified epoxy resin, brominated bisphenol A Epoxy resin and the like.
【００２７】本発明のエポキシ樹脂用硬化剤を適用する
エポキシ樹脂には、必要に応じて、上記の硬化促進剤の
他に、従来からエポキシ樹脂に添加されている無機充填
材や補強材等を添加することもできる。無機充填材とし
ては公知のものを使用でき、例えば、シリカ、溶融石
英、炭酸カルシウム、炭酸バリウム、硫酸バリウム、水
和アルミナ、アルミナ、水和マグネシア、ジルコン、コ
ージライト、窒化珪素、窒化硼素、窒化アルミニウム等
を挙げることができる。補強材としても公知のものを使
用でき、例えば、ガラスチョップ、アスベスト、タル
ク、マイカ等の無機材料やガラス繊維、チタン酸カリウ
ム繊維、二酸化チタン繊維、ワラストナイト、ゾノトラ
イト、珪酸亜鉛繊維等の無機繊維等を挙げることができ
る。尚、充填材及び補強材の種類、純度、添加量等を適
宜変更することにより、得られる硬化物の熱伝導率、耐
クラック性、電気特性、耐トラッキング性等を調整し得
ることは公知であるが、通常は、エポキシ樹脂１００重
量部に対して充填材及び補強材を５５〜１６０重量部程
度、好ましくは７５〜１２０重量部程度添加するのがよ
い。充填材及び補強材は、それぞれ１種を単独で使用で
き或いは２種以上を併用できる。The epoxy resin to which the curing agent for epoxy resin of the present invention is applied may include, if necessary, an inorganic filler or a reinforcing material which is conventionally added to the epoxy resin, in addition to the above-mentioned curing accelerator. It can also be added. Known inorganic fillers can be used, for example, silica, fused quartz, calcium carbonate, barium carbonate, barium sulfate, hydrated alumina, alumina, magnesia hydrate, zircon, cordierite, silicon nitride, boron nitride, nitrided Aluminum and the like can be given. Known reinforcing materials can be used, for example, inorganic materials such as glass chops, asbestos, talc, and mica, and glass fibers, potassium titanate fibers, titanium dioxide fibers, wollastonite, zonotolite, and inorganic materials such as zinc silicate fibers. Fibers and the like can be mentioned. It is known that the thermal conductivity, crack resistance, electric properties, tracking resistance, and the like of the obtained cured product can be adjusted by appropriately changing the type, purity, and addition amount of the filler and the reinforcing material. Usually, however, it is preferable to add about 55 to 160 parts by weight, preferably about 75 to 120 parts by weight of a filler and a reinforcing material to 100 parts by weight of the epoxy resin. As the filler and the reinforcing material, one type can be used alone, or two or more types can be used in combination.
【００２８】更に、本発明のエポキシ樹脂用硬化剤を適
用するエポキシ樹脂には、必要に応じて、従来からエポ
キシ樹脂の添加剤として常用されている添加剤が含まれ
ていてもよい。このような添加剤としては、例えば、無
機顔料（粒子状二酸化チタン、カーボンブラック、弁
柄、黄色酸化鉄等）、有機顔料、粘度調整剤、レベリン
グ剤、消泡剤、カップリング剤、可塑剤、希釈剤、難燃
剤、有機溶媒等を挙げることができる。Further, the epoxy resin to which the epoxy resin curing agent of the present invention is applied may contain, if necessary, an additive conventionally used as an epoxy resin additive. Examples of such additives include inorganic pigments (particulate titanium dioxide, carbon black, red iron oxide, yellow iron oxide, etc.), organic pigments, viscosity modifiers, leveling agents, defoamers, coupling agents, plasticizers , Diluents, flame retardants, organic solvents and the like.
【００２９】本発明のエポキシ樹脂用硬化剤を含むエポ
キシ樹脂（以下便宜上「本発明エポキシ樹脂組成物」と
いう）は、例えば、金属、合成樹脂、セラミックス、繊
維類、紙類等の各種素材の少なくとも１種で構成された
各種形状の物品に適用できる。具体的には、各種形状の
物品を本発明エポキシ樹脂組成物に浸漬するか又は該物
品表面に本発明エポキシ樹脂組成物を塗布又は被覆した
後、加熱して本発明エポキシ樹脂組成物を硬化させれば
よい。硬化温度、硬化時間等の硬化条件は、エポキシ樹
脂組成物の種類、ジヒドラジド化合物の種類や配合量、
他の添加剤を配合する場合はその種類や配合量等の各種
条件に応じて適宜選択すればよいが、通常１２０〜１６
０℃程度の比較的低温でよい。勿論、ジヒドラジド化合
物を硬化剤とする従来のエポキシ樹脂組成物と同様の硬
化温度（１６０〜１８０℃程度又はそれ以上）でもよ
い。The epoxy resin containing the curing agent for an epoxy resin of the present invention (hereinafter referred to as “the epoxy resin composition of the present invention” for convenience) includes, for example, at least various materials such as metals, synthetic resins, ceramics, fibers and papers. It can be applied to articles of various shapes composed of one kind. Specifically, articles of various shapes are immersed in the epoxy resin composition of the present invention or coated or coated with the epoxy resin composition of the present invention on the surface of the article, and then heated to cure the epoxy resin composition of the present invention. Just do it. Curing conditions such as curing temperature, curing time, the type of epoxy resin composition, the type and amount of dihydrazide compound,
When other additives are blended, they may be appropriately selected according to various conditions such as the type and blending amount.
A relatively low temperature of about 0 ° C. is sufficient. Of course, the curing temperature (about 160 to 180 ° C. or higher) may be the same as that of a conventional epoxy resin composition using a dihydrazide compound as a curing agent.
【００３０】また、本発明エポキシ樹脂組成物を、注型
成形等の通常の成形方法に従って任意の形状の成形物と
し、これを各種素材の少なくとも１種で構成された各種
形状の物品に、接着、嵌装等の通常の方法に従って取り
付けることもできる。成形時の硬化条件は、塗布又は被
覆の場合と同程度でよい。Further, the epoxy resin composition of the present invention is formed into a molded article having an arbitrary shape in accordance with a usual molding method such as cast molding, and is bonded to articles of various shapes composed of at least one of various materials. It can also be attached according to a normal method such as fitting. The curing conditions at the time of molding may be the same as those for coating or coating.
【００３１】本発明エポキシ樹脂組成物は、電気・電子
分野、自動車分野、土木建築分野、複合材料分野等の各
種の分野において、封止材、接着剤、塗料等として使用
され得る。The epoxy resin composition of the present invention can be used as a sealing material, an adhesive, a paint, and the like in various fields such as a field of electric / electronics, a field of automobiles, a field of civil engineering and construction, and a field of composite materials.
【００３２】[0032]
【実施例】以下に実施例及び比較例を挙げ、本発明を具
体的に説明する。以下において、「部」とあるのは「重
量部」を意味する。The present invention will be specifically described below with reference to examples and comparative examples. In the following, “parts” means “parts by weight”.
【００３３】実施例１ ビスフェノールＡ型エポキシ樹脂（商品名：エピコート
８２８、油化シェルエポキシ（株）製）１００部に、イ
ソフタル酸ジヒドラジド７．８部とアジピン酸ジヒドラ
ジド１６．２部とを添加して混合し、この混合物を３本
ロールにて６０℃の加温下に粒度４０μｍに分散混練
し、エポキシ樹脂組成物を製造した。Example 1 To 100 parts of a bisphenol A type epoxy resin (trade name: Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.), 7.8 parts of isophthalic acid dihydrazide and 16.2 parts of adipic acid dihydrazide were added. The mixture was dispersed and kneaded with a three-roll mill to a particle size of 40 μm while heating at 60 ° C. to produce an epoxy resin composition.
【００３４】比較例１ イソフタル酸ジヒドラジド７．８部に代えてアジピン酸
ジヒドラジド７．８部を使用する以外は、実施例１と同
様に操作し、エポキシ樹脂組成物を製造した。Comparative Example 1 An epoxy resin composition was produced in the same manner as in Example 1 except that 7.8 parts of adipic dihydrazide was used instead of 7.8 parts of isophthalic dihydrazide.
【００３５】試験例１ 実施例１及び比較例１で得られたエポキシ樹脂組成物に
つき、ポットライフ（貯蔵安定性）、ゲル化タイム、ガ
ラス転移温度（Ｔｇ、℃）及び硬化条件を調べた。結果
を表１に示す。Test Example 1 With respect to the epoxy resin compositions obtained in Example 1 and Comparative Example 1, pot life (storage stability), gel time, glass transition temperature (Tg, ° C.) and curing conditions were examined. Table 1 shows the results.
【００３６】（１）ポットライフ：深さ８０ｍｍ、断面
直径６０ｍｍのガラス瓶に、７０ｍｍの深さまで試料を
入れて密閉し、４０℃の恒温器中に３０日間静置して保
存した。このものの粘度を経時的にリオンビスコテスタ
ー（２０℃、単位：ポイズ）によって測定し、保存後の
粘度が保存前の粘度の２倍になる時間を求めた。(1) Pot life: A sample was placed in a glass bottle having a depth of 80 mm and a cross-sectional diameter of 60 mm to a depth of 70 mm, sealed, and stored in a thermostat at 40 ° C. for 30 days. The viscosity of this product was measured over time using a Lion Visco tester (20 ° C., unit: poise), and the time during which the viscosity after storage was twice the viscosity before storage was determined.
【００３７】（２）ゲル化タイム：１４０℃に加温した
ホットプレート上に、適量のエポキシ樹脂組成物を載
せ、これをかき混ぜ棒によってかき混ぜながら、かき混
ぜ棒を上下させ、角（つの）が出来るまでこの操作を繰
り返す。エポキシ樹脂組成物をホットプレート上に載せ
てから角が出来るまでの時間を測定し、ゲル化タイムと
した。更に、ホットプレートの温度を１２０℃又は１６
０℃とする以外は前記と同様に操作してゲル化タイムを
求めた。(2) Gel time: An appropriate amount of the epoxy resin composition is placed on a hot plate heated to 140 ° C., and while stirring the mixture with a stirring bar, the stirring bar is moved up and down to form a corner. Repeat this operation up to. The time from placing the epoxy resin composition on the hot plate until the corner was formed was measured and defined as the gel time. Further, the temperature of the hot plate is set to 120 ° C. or 16 ° C.
The gelation time was determined in the same manner as above except that the temperature was set to 0 ° C.
【００３８】（３）ガラス転移温度（Ｔｇ、℃）：線膨
張率の変化を測定し、ガラス転移温度を求めた（ＴＡＭ
法）。(3) Glass transition temperature (Tg, ° C.): The change in the coefficient of linear expansion was measured to determine the glass transition temperature (TAM).
Law).
【００３９】（４）硬化条件：硬化温度を１４５℃に設
定し、１ｍｍ厚の硬化物を得るのに、最低限必要な硬化
時間を求めた。(4) Curing conditions: The curing temperature was set to 145 ° C., and the minimum curing time required to obtain a cured product having a thickness of 1 mm was determined.
【００４０】[0040]
【表１】 [Table 1]
【００４１】表１から、本発明の硬化剤をエポキシ樹脂
に添加することにより、１４０℃という比較的低い温度
でも実用的な硬化時間で硬化が可能であること、及びガ
ラス転移温度が約２０℃も向上することが明らかであ
る。From Table 1, it can be seen that by adding the curing agent of the present invention to an epoxy resin, curing can be performed with a practical curing time even at a relatively low temperature of 140 ° C., and that the glass transition temperature is about 20 ° C. It is evident that this also improves.
【００４２】実施例２ ビスフェノールＡ型エポキシ樹脂（エピコート８２８）
１００部、イソフタル酸ジヒドラジド７．８部、アジピ
ン酸ジヒドラジド１６．２部及びサリチル酸ヒドラジド
４．８部を用い、実施例１と同様に操作して、エポキシ
樹脂組成物を製造した。Example 2 Bisphenol A type epoxy resin (Epicoat 828)
Using 100 parts, 7.8 parts of isophthalic acid dihydrazide, 16.2 parts of adipic acid dihydrazide and 4.8 parts of salicylic acid hydrazide, the same operation as in Example 1 was carried out to produce an epoxy resin composition.
【００４３】比較例２ イソフタル酸ジヒドラジド７．８部に代えてアジピン酸
ジヒドラジド７．８部を使用する以外は、実施例２と同
様に操作し、エポキシ樹脂組成物を製造した。Comparative Example 2 An epoxy resin composition was produced in the same manner as in Example 2, except that 7.8 parts of adipic dihydrazide was used instead of 7.8 parts of isophthalic dihydrazide.
【００４４】試験例２ 実施例２及び比較例２で得られたエポキシ樹脂組成物に
つき、試験例１と同様にして、ポットライフ（貯蔵安定
性）及びゲル化タイムを調べた。結果を表２に示す。Test Example 2 The pot life (storage stability) and the gel time of the epoxy resin compositions obtained in Example 2 and Comparative Example 2 were examined in the same manner as in Test Example 1. Table 2 shows the results.
【００４５】[0045]
【表２】 [Table 2]
【００４６】実施例３ 下記表３の配合量（部）で各成分を用い、実施例１と同
様に操作して、エポキシ樹脂組成物を製造した。得られ
たエポキシ樹脂組成物につき、実施例１と同様にして、
硬化温度を１６０℃に設定してゲル化タイムを求めた。
結果を表３に併記する。Example 3 An epoxy resin composition was produced in the same manner as in Example 1 except that the components were used in the amounts (parts) shown in Table 3 below. About the obtained epoxy resin composition, it carried out similarly to Example 1,
The curing time was set at 160 ° C. and the gel time was determined.
The results are also shown in Table 3.
【００４７】[0047]
【表３】 [Table 3]
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平９−48877（ＪＰ，Ａ) 特開 平９−31165（ＪＰ，Ａ) 特許2869635（ＪＰ，Ｂ２) (58)調査した分野(Int.Cl.7，ＤＢ名) C08G 59/40 - 59/66 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-9-48877 (JP, A) JP-A-9-31165 (JP, A) Patent 2869635 (JP, B2) (58) Fields investigated (Int. Cl 7, DB name) C08G 59/40 -. 59/66
Claims (2)
ジ酢酸ジヒドラジド、ドデカンジオヒドラジド及びグル
タル酸ジヒドラジドから選ばれた少なくとも１種のジヒ
ドラジド化合物と(2)アジピン酸ジヒドラジドとを含有
することを特徴とするエポキシ樹脂用硬化剤。 (1) Isophthalic acid dihydrazide, imino
Dihydrazide diacetate, dodecandiohydrazide and glu
At least one dihydric acid selected from the group consisting of tallic acid dihydrazide
A curing agent for an epoxy resin, comprising a hydrazide compound and (2) adipic dihydrazide .
合物（アニス酸ヒドラジドを除く）を含有する請求項１
に記載のエポキシ樹脂用硬化剤。2. A monohydrazide as a curing accelerator.
A compound (excluding anisic acid hydrazide).
The curing agent for epoxy resin according to 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9034685A JP3030499B2 (en) | 1997-02-19 | 1997-02-19 | Curing agent for epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9034685A JP3030499B2 (en) | 1997-02-19 | 1997-02-19 | Curing agent for epoxy resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10231353A JPH10231353A (en) | 1998-09-02 |
| JP3030499B2 true JP3030499B2 (en) | 2000-04-10 |
Family
ID=12421264
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9034685A Expired - Lifetime JP3030499B2 (en) | 1997-02-19 | 1997-02-19 | Curing agent for epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3030499B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6535291B1 (en) | 2000-06-07 | 2003-03-18 | Cyberoptics Corporation | Calibration methods for placement machines incorporating on-head linescan sensing |
| US6538244B1 (en) | 1999-11-03 | 2003-03-25 | Cyberoptics Corporation | Pick and place machine with improved vision system including a linescan sensor |
| US6608320B1 (en) | 1998-11-05 | 2003-08-19 | Cyberoptics Corporation | Electronics assembly apparatus with height sensing sensor |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5478061B2 (en) * | 2008-12-19 | 2014-04-23 | 協立化学産業株式会社 | Hydrazide mixed crystals |
| JP4961458B2 (en) * | 2009-06-10 | 2012-06-27 | 協立化学産業株式会社 | Hydrazide compound and method for producing the same, and curing agent, resin composition and cured product using the same |
| JP5736023B2 (en) * | 2013-11-05 | 2015-06-17 | 協立化学産業株式会社 | Hydrazide mixed crystals |
-
1997
- 1997-02-19 JP JP9034685A patent/JP3030499B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6608320B1 (en) | 1998-11-05 | 2003-08-19 | Cyberoptics Corporation | Electronics assembly apparatus with height sensing sensor |
| US6610991B1 (en) | 1998-11-05 | 2003-08-26 | Cyberoptics Corporation | Electronics assembly apparatus with stereo vision linescan sensor |
| US6538244B1 (en) | 1999-11-03 | 2003-03-25 | Cyberoptics Corporation | Pick and place machine with improved vision system including a linescan sensor |
| US6535291B1 (en) | 2000-06-07 | 2003-03-18 | Cyberoptics Corporation | Calibration methods for placement machines incorporating on-head linescan sensing |
| US6744499B2 (en) | 2000-06-07 | 2004-06-01 | Cyberoptics Corporation | Calibration methods for placement machines incorporating on-head linescan sensing |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10231353A (en) | 1998-09-02 |
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