JPH02105817A - Curable epoxy resin composition - Google Patents
Curable epoxy resin compositionInfo
- Publication number
- JPH02105817A JPH02105817A JP25982888A JP25982888A JPH02105817A JP H02105817 A JPH02105817 A JP H02105817A JP 25982888 A JP25982888 A JP 25982888A JP 25982888 A JP25982888 A JP 25982888A JP H02105817 A JPH02105817 A JP H02105817A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- agent
- epoxy
- curing
- 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
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 42
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000004593 Epoxy Substances 0.000 claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 150000003222 pyridines Chemical class 0.000 claims description 11
- 239000011342 resin composition Substances 0.000 claims description 3
- GRFNBEZIAWKNCO-UHFFFAOYSA-N 3-pyridinol Chemical compound OC1=CC=CN=C1 GRFNBEZIAWKNCO-UHFFFAOYSA-N 0.000 abstract description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 2
- SHNUBALDGXWUJI-UHFFFAOYSA-N pyridin-2-ylmethanol Chemical compound OCC1=CC=CC=N1 SHNUBALDGXWUJI-UHFFFAOYSA-N 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 7
- 238000001879 gelation Methods 0.000 description 7
- 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 6
- 150000008065 acid anhydrides Chemical class 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- ROHTVIURAJBDES-UHFFFAOYSA-N 2-n,2-n-bis(prop-2-enyl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N(CC=C)CC=C)=N1 ROHTVIURAJBDES-UHFFFAOYSA-N 0.000 description 2
- MVQVNTPHUGQQHK-UHFFFAOYSA-N 3-pyridinemethanol Chemical compound OCC1=CC=CN=C1 MVQVNTPHUGQQHK-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- DHLUJPLHLZJUBW-UHFFFAOYSA-N 6-methylpyridin-3-ol Chemical compound CC1=CC=C(O)C=N1 DHLUJPLHLZJUBW-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 150000002357 guanidines Chemical class 0.000 description 2
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 2
- 150000004806 hydroxypyridines Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical compound OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- OUJMXIPHUCDRAS-UHFFFAOYSA-N 2-(5-ethylpyridin-2-yl)ethanol Chemical compound CCC1=CC=C(CCO)N=C1 OUJMXIPHUCDRAS-UHFFFAOYSA-N 0.000 description 1
- QJHOHDKABVJMEC-UHFFFAOYSA-N 2-(6-methylpyridin-2-yl)ethanol Chemical compound CC1=CC=CC(CCO)=N1 QJHOHDKABVJMEC-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- BXGYBSJAZFGIPX-UHFFFAOYSA-N 2-pyridin-2-ylethanol Chemical compound OCCC1=CC=CC=N1 BXGYBSJAZFGIPX-UHFFFAOYSA-N 0.000 description 1
- JGXRFQKRGPKWPP-UHFFFAOYSA-N 2-pyridin-2-ylpropane-1,3-diol Chemical compound OCC(CO)C1=CC=CC=N1 JGXRFQKRGPKWPP-UHFFFAOYSA-N 0.000 description 1
- DWPYQDGDWBKJQL-UHFFFAOYSA-N 2-pyridin-4-ylethanol Chemical compound OCCC1=CC=NC=C1 DWPYQDGDWBKJQL-UHFFFAOYSA-N 0.000 description 1
- GCNTZFIIOFTKIY-UHFFFAOYSA-N 4-hydroxypyridine Chemical compound OC1=CC=NC=C1 GCNTZFIIOFTKIY-UHFFFAOYSA-N 0.000 description 1
- ALEBYBVYXQTORU-UHFFFAOYSA-N 6-hydrazinyl-6-oxohexanoic acid Chemical compound NNC(=O)CCCCC(O)=O ALEBYBVYXQTORU-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- XNCOSPRUTUOJCJ-UHFFFAOYSA-N Biguanide Chemical compound NC(N)=NC(N)=N XNCOSPRUTUOJCJ-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- WWFMINHWJYHXHF-UHFFFAOYSA-N [6-(hydroxymethyl)pyridin-2-yl]methanol Chemical compound OCC1=CC=CC(CO)=N1 WWFMINHWJYHXHF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- -1 bisphenol Δ type Chemical compound 0.000 description 1
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- PTMBWNZJOQBTBK-UHFFFAOYSA-N pyridin-4-ylmethanol Chemical compound OCC1=CC=NC=C1 PTMBWNZJOQBTBK-UHFFFAOYSA-N 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は硬化性エポキシ樹脂組成物に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to curable epoxy resin compositions.
エポキシ樹脂の常温で不活性な硬化剤としてはジシアン
ジアミド、Ｎ、Ｎ−ジアリルメラミン。Examples of curing agents for epoxy resins that are inactive at room temperature include dicyandiamide and N,N-diallylmelamine.
４．４′−ジアミノジフェニルスルホン、有機酸ヒドラ
ジド、酸無水物などが知られている。しかしながら、こ
れらの硬化剤例えばジシアンジアミドにおいては、エポ
キシ樹脂の硬化を短時間で行なうには１８０℃以トとい
う高温を要し、１５０℃以下の温度では硬化反応が非常
に遅い。4.4'-diaminodiphenylsulfone, organic acid hydrazide, acid anhydride, etc. are known. However, these curing agents, such as dicyandiamide, require a high temperature of 180°C or higher to cure the epoxy resin in a short time, and the curing reaction is extremely slow at temperatures below 150°C.
こめため、かかる硬化剤とエポキシ樹脂との組成物は、
高温による悪影響を受ける分腎では作業性が悪く利用し
難い。The composition of such a curing agent and an epoxy resin is
It is difficult to work with kidneys that are adversely affected by high temperatures and is difficult to use.
本発明の目的はより低温で速硬化性をイｉする硬化性エ
ポキシ樹脂組成物を提供することにある。An object of the present invention is to provide a curable epoxy resin composition that exhibits rapid curing at lower temperatures.
〔課題を解決するための手段Ｊ
本発明者らは、エポキシ樹脂と常温で不活性な硬化剤か
らなる組成物について鋭意検討を行なった結果、硬化促
進剤として少なくとも１個のヒドロキシ基を分子内に有
するピリジン誘導体を配合すると、得られる硬化性エポ
キシ樹脂組成物がより低温で迅速に硬化すること、また
当該ピリジン誘導体が加熱下でエポキシ樹脂への相溶性
に優れており均一性のある硬化物が得られることを見出
し本発明を完成するに至った。[Means for Solving the Problems J] As a result of intensive studies on compositions consisting of epoxy resins and curing agents that are inactive at room temperature, the present inventors found that at least one hydroxyl group is incorporated into the molecule as a curing accelerator. When a pyridine derivative having a pyridine derivative is blended, the resulting curable epoxy resin composition cures quickly at a lower temperature, and the pyridine derivative has excellent compatibility with the epoxy resin under heating, resulting in a uniform cured product. The present invention was completed based on the discovery that the following can be obtained.
すなわち、本発明は、（＾）エポキシ樹脂、（Ｂ）常温
で不活性な硬化剤及び（Ｃ）硬化促進剤として少なくと
もｌ個のヒドロキシ基を分子内に有するピリジン誘導体
を含有することを特徴とする硬化性エポキシ樹脂組成物
である。That is, the present invention is characterized by containing (^) an epoxy resin, (B) a curing agent that is inactive at room temperature, and (C) a pyridine derivative having at least l hydroxy groups in the molecule as a curing accelerator. This is a curable epoxy resin composition.
本発明に用いられるエポキシ樹脂としては市販のものが
使用できる。エポキシ樹脂成形品、積層板及び粉体塗装
用としては、エポキシ当：ｉ′１が１８０〜２０００、
十均分子けが３００〜３０００程度のものが好ましい。Commercially available epoxy resins can be used in the present invention. For epoxy resin molded products, laminates and powder coatings, epoxy weight: i'1 is 180 to 2000,
It is preferable to use a material having a tenth molecular weight of about 300 to 3,000.
代表的なエポキシ樹脂としてビスフェノールΔ型、ビス
フェノールＡ Ｄ型、ビスフェノールＳ型゛型、ビスフ
ェノールＳ型、レゾール型、ノボラック型等の各種のエ
ポキシ樹脂が挙げられ、これらを１１ｉ独又は２種以上
併用して使用できる。Typical epoxy resins include various epoxy resins such as bisphenol Δ type, bisphenol A D type, bisphenol S type, bisphenol S type, resol type, and novolak type. It can be used as
常温で不活性な硬化剤としては、ジシア゛ンジアミド、
グアニジン、ジグアニドなどのグアニジン化合物：コハ
ク酸ヒドラジド、アジピン酸ヒドラジドなどの有機酸ヒ
ドラジド：メタフェニレンジアミン、ジアミノジフェニ
ルメタン、４．４′−ジアミノジフェニルスルホンなど
の芳香族ジアミン類：無水トリメリット酸、無水へキサ
ヒドロフタル酸、無水メチルテトラヒドロフタル酸など
の酸無水物、Ｎ、Ｎ−ジアリルメラミンなどのメラミン
誘導体、ＢＦ、−アミン錯体等があげれる。本発明の硬
化剤のエポキシ樹脂に対する使用雀ついては、グアニジ
ン化合物、有機酸ヒドラジド、芳香族ジアミン類及びメ
ラミン誘導体の場合はエポキシ当量あたり活性水素当量
０．５〜２．５好ましくは０．７〜２．０となるように
。Examples of curing agents that are inactive at room temperature include dicyandiamide,
Guanidine compounds such as guanidine and diguanide: Organic acid hydrazides such as succinic acid hydrazide and adipic acid hydrazide: Aromatic diamines such as metaphenylene diamine, diaminodiphenylmethane, and 4,4'-diaminodiphenylsulfone: Trimellitic anhydride, anhydride Examples include acid anhydrides such as xahydrophthalic acid and methyltetrahydrophthalic anhydride, melamine derivatives such as N,N-diallylmelamine, and BF, -amine complexes. Regarding the use of the curing agent of the present invention for epoxy resins, in the case of guanidine compounds, organic acid hydrazides, aromatic diamines, and melamine derivatives, the active hydrogen equivalent per epoxy equivalent is 0.5 to 2.5, preferably 0.7 to 2. So that it becomes .0.
酸無水物の場合はエポキシ当量あたり酸無水物光１ｉ１
０．５〜２．５好ましくは０．７〜２．０となるように
用いればよく、またＢＦ３−アミン錯体の場合はエポキ
シ樹脂＋００ｆｆ１１部あたりＩ〜ＩＯ好ましくは２〜
７重量部用いればよい。これらの範囲外になると機械的
強度などの硬化物物性が充分なものとならない場合があ
る。In the case of acid anhydride, acid anhydride light 1i1 per epoxy equivalent
0.5 to 2.5, preferably 0.7 to 2.0, and in the case of BF3-amine complex, I to IO, preferably 2 to 1, per 11 parts of epoxy resin +00ff.
7 parts by weight may be used. Outside these ranges, the cured product may not have sufficient physical properties such as mechanical strength.
本発明において硬化促進剤として用いられる少なくとも
１個のヒドロキシ基を分子内に有するピリジン誘導体に
おいて、ヒドロキシ基はピリジン核に結合してしてもよ
いし、またピリジン核の側鎖に結合していてもよい。本
発明の少な（とも１個のヒドロキシ基を分子内に有する
ピリジン誘導体としては、ヒドロキシピリジン類、アル
キルヒドロキシピリジン類、ヒドロキシアルキルピリジ
ン類、アルキル−ヒドロキシアルキルピリジン類などが
あげられ、またそのアルキルとしては炭素数１〜３のも
のがあげられる。本発明の少なくとも１個のヒドロキシ
基を分子内に有するピリジン誘導体の代表的なものを次
にあげる。In the pyridine derivative having at least one hydroxy group in the molecule used as a curing accelerator in the present invention, the hydroxy group may be bonded to the pyridine nucleus or may be bonded to the side chain of the pyridine nucleus. Good too. Examples of the pyridine derivatives having one hydroxy group in the molecule of the present invention include hydroxypyridines, alkylhydroxypyridines, hydroxyalkylpyridines, alkyl-hydroxyalkylpyridines, etc. Examples include those having 1 to 3 carbon atoms.Representative examples of the pyridine derivatives having at least one hydroxy group in the molecule of the present invention are listed below.
すなわち、ヒドロキシピリジン類としては２−ヒドロキ
シピリジン、３−ヒＹロキシビリジン、４−ヒドロキシ
ピリジン、２．６−シヒドロキシビリジンなどがあげら
れる。アルキル−ヒドロキシピリジン類としては５−ヒ
ドロキシ−２−メチルビリジン、３−ヒドロキシ−６−
メチルビリジンなどがあげられる。ヒドロキシアルキル
ピリジン類としては２−ヒドロキシメチルピリジン、３
−ヒドロキシメチルピリジン、４−ヒドロキシメチルピ
リジン、２．６−ジ（ヒドロキシメチル）ピリジン、２
−ヒドロキシエチルピリジン、４−ヒドロキシエチルピ
リジン。That is, examples of hydroxypyridines include 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, and 2,6-cyhydroxypyridine. Examples of alkyl-hydroxypyridines include 5-hydroxy-2-methylpyridine, 3-hydroxy-6-
Examples include methylpyridine. Hydroxyalkylpyridines include 2-hydroxymethylpyridine, 3
-Hydroxymethylpyridine, 4-hydroxymethylpyridine, 2,6-di(hydroxymethyl)pyridine, 2
-Hydroxyethylpyridine, 4-hydroxyethylpyridine.
２−（２−ピリジル）−１，３−プロパンジオール、２
−ヒドロキシメチル−２−（４−ピリジル）−１，３−
プロパンジオールなどがあげられる。アルキル−ヒドロ
キシアルキルピリジン類としては２−ヒドロキシエチル
−６−メチルビリジン、２−ヒドロキシエチル−５−エ
チルピリジンなどがあげられる。2-(2-pyridyl)-1,3-propanediol, 2
-Hydroxymethyl-2-(4-pyridyl)-1,3-
Examples include propanediol. Examples of alkyl-hydroxyalkylpyridines include 2-hydroxyethyl-6-methylpyridine and 2-hydroxyethyl-5-ethylpyridine.
本発明の少なくとも１個のヒドロキシ基を分子内に有す
るピリジン誘導体は単独または２種以上併用で使用して
も差し支えない。当該ピリジン誘導体はエポキシ樹脂に
対してＯ，１〜１５巾λ％好ましくは０．２５〜１０重
量％で充分である。The pyridine derivatives of the present invention having at least one hydroxy group in the molecule may be used alone or in combination of two or more. It is sufficient to use the pyridine derivative in an amount of 0.1 to 15% by weight, preferably 0.25 to 10% by weight, based on the epoxy resin.
０．１重量％よりも少ないと硬化促進剤としての効果が
充分ではなく、１５重量％よりも多く加えてもその効果
は変わらずかえって硬化物の物性に悪い影響を与える場
合がある。If the amount is less than 0.1% by weight, the effect as a curing accelerator will not be sufficient, and if more than 15% by weight is added, the effect will not change and the physical properties of the cured product may be adversely affected.
本発明の硬化性エポキシ樹脂組成物は、エポキシ樹脂、
硬化剤及び硬化促進剤を、必要に応じ適宜な溶剤を用い
て、充分混合して調製される。The curable epoxy resin composition of the present invention comprises an epoxy resin,
It is prepared by sufficiently mixing a curing agent and a curing accelerator using an appropriate solvent as necessary.
本発明の硬化性エポキシ樹脂組成物の硬化は。Curing of the curable epoxy resin composition of the present invention.
１３０〜１８０℃程度で数分〜数十分程度で可能であり
、それ以上の温度ではより短時間で達成される。This can be achieved in several minutes to several tens of minutes at temperatures of about 130 to 180°C, and can be achieved in a shorter time at higher temperatures.
以下に、実施例及び比較例を示す。Examples and comparative examples are shown below.
実施例１〜４
エポキシ当量１８６の液状ビスフェノールΔ型エポキシ
樹脂「エピコート８２８」 （油化シェルエポキシ■″
！Ａ）ｔｏｏ重り部と粉末状ジシアンジアミド１０重：
４部と表−１に示す硬化促進剤６１重量部とを充分に混
合して、それぞれの液状エポキシ樹脂組成物を得た。１
５０℃、１８０℃及び２００℃における当該エポキシ樹
脂組成物のゲル化時間を、ＪＩＳ Ｃ−２１０４型ゲ
ル化試験器（日新科学■製）を用いて測定した。その結
果を表−１に示す。また、得られるゲル化物（１５０℃
）は均一性が良好であった。Examples 1 to 4 Liquid bisphenol Δ-type epoxy resin “Epicote 828” with an epoxy equivalent weight of 186 (oiled shell epoxy
! A) Too weight part and powdered dicyandiamide 10 weight part:
4 parts by weight and 61 parts by weight of the curing accelerator shown in Table 1 were thoroughly mixed to obtain respective liquid epoxy resin compositions. 1
The gelation time of the epoxy resin composition at 50°C, 180°C, and 200°C was measured using a JIS C-2104 type gelling tester (manufactured by Nisshin Kagaku ■). The results are shown in Table-1. In addition, the obtained gelled product (150℃
) had good uniformity.
比較例１
硬化促進剤を使用しないこと以外は実施例１〜４と同様
にして、エポキシ樹脂組成物の調製及びゲル化時間測定
を行なった。その結果を表−１に示す。また、１５０℃
におけるエポキシ樹脂組成物の均一性の結果を表−１に
示す。Comparative Example 1 An epoxy resin composition was prepared and the gelation time was measured in the same manner as in Examples 1 to 4 except that no curing accelerator was used. The results are shown in Table-1. Also, 150℃
Table 1 shows the results of the uniformity of the epoxy resin composition.
（以下余白）
表
実施例５〜９
メチルエチルケトン＝Ｓ００１丁１：１１部Ｉこエポキ
シ゛１１ｉ＋１２１５のタレゾールノボラック型同形エ
ポキシ樹脂［エビクロンＮ−６９５Ｊ（大］−１本イン
キ■製） ｌ ００１１ｔ；ｔｔ部を加えて溶解させ
てエポキシ樹脂溶液を得た。粉末状ジシアンジアミドｌ
Ｏ、’ｆｉ ｒＩｔ部と表−１に示す硬化促進剤との混
合物を乳鉢で粉砕した後、エポキシ樹脂溶液に加え、攪
拌混合しながら常温減圧下でメチルエチルケトンを蒸発
させて、それぞれの粉末状エポキシ樹脂組成物を得た。(Margins below) Table Examples 5 to 9 Methyl ethyl ketone = S001 1:11 part I epoxy 11i + 1215 Talesol novolac type isomorphic epoxy resin [made by Ebicuron N-695J (large) - 1 ink ■] l 0011t; tt part was added and dissolved to obtain an epoxy resin solution. Powdered dicyandiamide l
After pulverizing the mixture of the O,'fi rIt part and the curing accelerator shown in Table 1 in a mortar, it was added to the epoxy resin solution, and the methyl ethyl ketone was evaporated at room temperature and under reduced pressure while stirring and mixing to obtain each powdered epoxy. A resin composition was obtained.
１３０℃、１５０℃、１８０℃及び２００℃における当
該エポキシ樹脂組成物のゲル化時間を、実施例１〜４と
同様なゲル化試験器を用いて測定した。その結果を表−
２に示す。また、得られるゲル化物（１５０℃）は均一
性が良好であった。The gelation time of the epoxy resin composition at 130°C, 150°C, 180°C and 200°C was measured using the same gelation tester as in Examples 1-4. Table the results.
Shown in 2. Further, the obtained gelled product (150°C) had good uniformity.
比較例２
硬化促進剤を使用しないこと以外は実施例５〜９と同様
にして、エポキシ樹脂組成物の調製及びゲル化時間測定
を行なった。その結果を表−２に示す。また、１５０℃
におけるエポキシ樹脂組成物の均一性の結果を表−１に
示す。Comparative Example 2 An epoxy resin composition was prepared and the gelation time was measured in the same manner as in Examples 5 to 9 except that no curing accelerator was used. The results are shown in Table-2. Also, 150℃
Table 1 shows the results of the uniformity of the epoxy resin composition.
（以ド余自）
実施例１０
メチルエチルケトン３００ ＜ｎ ｔｄ部にエポキシ当
：＋ｔ ２ｔ １５のクレゾールノボラック型固形エポ
キシ樹脂［エピクロンＮ−６９５Ｊ（大日木インキ■製
） ＋ ００ ｉ’ｌ’ｉ Ｍ部を加えて溶解させて
エポキシ樹脂溶液を得た。粉末状ジシアンジアミド＋
ｏ ’ｎ ｌｅｔ部と表−３に示す各（ｎ ｒｉ１部の
３−ヒドロキシピリジンとの混合物を乳鉢で粉砕した後
、エポキシ樹脂溶液に加え、攪拌混合しながら常温減圧
ドでメチルエチルケトンを蒸発させて、それぞれの粉末
状エポキシ樹脂組成物を得た。１３０℃、１５０℃、１
８０℃及び２００℃における当該エポキシ樹脂組成物の
ゲル化時間を、実施例１〜４と同様なゲル化試験器を用
いて測定した。その結果を表−３に示す。Example 10 Methyl ethyl ketone 300 <n Epoxy on td part: +t 2t 15 cresol novolak type solid epoxy resin [Epicron N-695J (manufactured by Dainichi Ink ■) + 00 i'l'i M 1 part was added and dissolved to obtain an epoxy resin solution. Powdered dicyandiamide+
After crushing a mixture of o'n let part and 1 part of 3-hydroxypyridine shown in Table 3 in a mortar, add it to the epoxy resin solution, and evaporate the methyl ethyl ketone in a vacuum oven at room temperature while stirring and mixing. , respective powdered epoxy resin compositions were obtained.130°C, 150°C, 1
The gelation time of the epoxy resin composition at 80°C and 200°C was measured using the same gelation tester as in Examples 1-4. The results are shown in Table-3.
（以Ｆ余白）
実施例！ｌ
エポキシ当：Ｊ Ｉ ８６の液状ビスフェノールΔ型エ
ポキシ樹脂「エピコート８２８Ｊ （油化シェルエポ
キシ■製）ｌｏＯｉ量部と粉末状ジシアンジアミドＩ
Ｏ；ｆＥ ′ｕｉ部と表−４に示す硬化促進剤各ｌ ＋
ｒ＋：１を部とを充分に混合して、それぞれの液状エポ
キシ樹脂組成物を得た６当該工ポキシ樹脂組成物を用い
て鋼板を被着材とした。ＪＩＳＫ−６８５０に基く引張
剪断試験を行なった。その結果を表−４に示す。また、
得られる硬化物は均一性が良好であった。(F margin below) Example! l Epoxy: J I 86 liquid bisphenol Δ type epoxy resin "Epicoat 828J (manufactured by Yuka Shell Epoxy ■) loOi parts and powdered dicyandiamide I
O; fE 'ui part and each curing accelerator shown in Table 4 +
Each liquid epoxy resin composition was obtained by thoroughly mixing 1 part r+: 6. A steel plate was made into an adherend using the liquid epoxy resin composition. A tensile shear test based on JISK-6850 was conducted. The results are shown in Table 4. Also,
The resulting cured product had good uniformity.
比較例３
硬化促進剤を使用しないこと以外は実施例１１と同様に
してエポキシ樹脂組成物の調製し、鋼板に塗布し実施例
１１と同様な条件で硬化させたが、いずれの硬化時間に
おいても不均一な未硬化物が得られ、引張剪断試験を行
なうことができなかった。Comparative Example 3 An epoxy resin composition was prepared in the same manner as in Example 11 except that no curing accelerator was used, and it was applied to a steel plate and cured under the same conditions as in Example 11. A non-uniform uncured product was obtained, making it impossible to perform a tensile shear test.
本発明の樹脂組成物は、より低温゛Ｆで迅速に硬化し、
しかも得られる硬化物が充分な機械的強度さらに良好な
均一性をイｆしており、その用途は極めて広いものであ
る。The resin composition of the present invention cures quickly at lower temperatures,
Furthermore, the cured product obtained has sufficient mechanical strength and good uniformity, and its uses are extremely wide.
特許出願人 広栄化′を工業株式会社Patent applicant: Koei Hwa Industrial Co., Ltd.
Claims (1)
及び（Ｃ）硬化促進剤として少なくとも１個のヒドロキ
シ基を分子内に有するピリジン誘導体を含有することを
特徴とする硬化性エポキシ樹脂組成物。1) A curable epoxy containing (A) an epoxy resin, (B) a curing agent that is inactive at room temperature, and (C) a pyridine derivative having at least one hydroxy group in the molecule as a curing accelerator. Resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25982888A JPH02105817A (en) | 1988-10-14 | 1988-10-14 | Curable epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25982888A JPH02105817A (en) | 1988-10-14 | 1988-10-14 | Curable epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02105817A true JPH02105817A (en) | 1990-04-18 |
Family
ID=17339556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25982888A Pending JPH02105817A (en) | 1988-10-14 | 1988-10-14 | Curable epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02105817A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0596622A2 (en) * | 1992-11-02 | 1994-05-11 | Lord Corporation | Epoxy resin structural adhesive composition having high temperature resistance |
| WO2009094235A1 (en) | 2008-01-23 | 2009-07-30 | Dow Global Technologies Inc. | Epoxy resin hardener compositions and epoxy resin compositions containing such hardener compositions |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6389521A (en) * | 1986-10-03 | 1988-04-20 | Nippon Mining Co Ltd | Curing agent for epoxy resin |
| JPS6389673A (en) * | 1986-10-03 | 1988-04-20 | Nippon Mining Co Ltd | Plating resist composition |
-
1988
- 1988-10-14 JP JP25982888A patent/JPH02105817A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6389521A (en) * | 1986-10-03 | 1988-04-20 | Nippon Mining Co Ltd | Curing agent for epoxy resin |
| JPS6389673A (en) * | 1986-10-03 | 1988-04-20 | Nippon Mining Co Ltd | Plating resist composition |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0596622A2 (en) * | 1992-11-02 | 1994-05-11 | Lord Corporation | Epoxy resin structural adhesive composition having high temperature resistance |
| EP0596622A3 (en) * | 1992-11-02 | 1995-05-10 | Lord Corp | Epoxy resin structural adhesive composition having high temperature resistance. |
| WO2009094235A1 (en) | 2008-01-23 | 2009-07-30 | Dow Global Technologies Inc. | Epoxy resin hardener compositions and epoxy resin compositions containing such hardener compositions |
| US20100317768A1 (en) * | 2008-01-23 | 2010-12-16 | Joseph Gan | Epoxy resin hardener compositions and epoxy resin compositions containing such hardener compositions |
| US8389652B2 (en) | 2008-01-23 | 2013-03-05 | Dow Global Technologies Llc | Epoxy resin hardener compositions and epoxy resin compositions containing such hardener compositions |
| US8927663B2 (en) | 2008-01-23 | 2015-01-06 | Dow Global Technologies Llc | Epoxy resin hardener compositions and epoxy resin compositions containing such hardener compositions |
| EP2824127A1 (en) | 2008-01-23 | 2015-01-14 | Dow Global Technologies LLC | Isocyanate resin solvent-free composition |
| US9133301B2 (en) | 2008-01-23 | 2015-09-15 | Dow Global Technologies Llc | Epoxy resin hardener compositions and epoxy resin compositions containing such hardener compositions |
| US9371415B2 (en) | 2008-01-23 | 2016-06-21 | Blue Cube Ip Llc | Epoxy resin hardener compositions and epoxy resin compositions containing such hardener compositions |
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