JPH01268714A - Novel epoxy resin composition - Google Patents
Novel epoxy resin compositionInfo
- Publication number
- JPH01268714A JPH01268714A JP9678088A JP9678088A JPH01268714A JP H01268714 A JPH01268714 A JP H01268714A JP 9678088 A JP9678088 A JP 9678088A JP 9678088 A JP9678088 A JP 9678088A JP H01268714 A JPH01268714 A JP H01268714A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- formula
- epichlorohydrin
- 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.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 47
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 47
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 238000005266 casting Methods 0.000 abstract description 3
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000003973 paint Substances 0.000 abstract description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 abstract description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 8
- 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 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 230000000052 comparative effect Effects 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- -1 laminates Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 0.000 description 1
- FIGVNZUQNIUGPD-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxy-3-methylphenyl)ethyl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C(C)(C=2C=C(C)C(O)=CC=2)C=2C=C(C)C(O)=CC=2)=C1 FIGVNZUQNIUGPD-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
- 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-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
- 230000000694 effects Effects 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 230000002496 gastric effect Effects 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 229940083094 guanine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は新規にして有用なるエポキシ樹脂組成物に関し
、さらに詳細には、必須のエポキシ樹脂成分としてトリ
スフェノールのエピクロルヒドリン縮合物なるエポキシ
樹脂を用いることからなる耐熱性および機械的性質に優
れ、さらにはもろさを改良し１強靭性に富んだ、注型、
接着、積層、成型、塗料などの用途に適した樹脂組成物
に関する。Detailed Description of the Invention (Industrial Application Field) The present invention relates to a new and useful epoxy resin composition, and more particularly, it uses an epoxy resin consisting of an epichlorohydrin condensate of trisphenol as an essential epoxy resin component. Cast molding, which has excellent heat resistance and mechanical properties, as well as improved brittleness and strong toughness.
It relates to resin compositions suitable for uses such as adhesion, lamination, molding, and coatings.
（従来の技術）
エポキシ樹脂は、種々の硬化剤で硬化させることによル
、−数的に機械的性質、耐水性、耐薬品性、耐熱性、電
気的性質などの優れた硬化物となシ、接着剤、塗料、積
層板、成型材料、注型材料等、幅広い分野に使用されて
いる。(Prior art) Epoxy resins can be cured with various curing agents to form cured products with numerically excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc. It is used in a wide range of fields, including adhesives, paints, laminates, molding materials, and casting materials.
（発明が解決しようとする課題）
最も代表的なエポキシ樹脂は、ビスフェノールＡにエピ
クロルヒドリンを反応させて得られる液状および固型の
ビスフェノールＡ型エポキシ樹脂が挙げられるが、これ
らＦｉ１分子当たシのグリシジル基が２個よりは多くは
ないために硬化時の架橋密度が低く、耐熱性が劣る傾向
にある。(Problems to be Solved by the Invention) The most typical epoxy resins include liquid and solid bisphenol A type epoxy resins obtained by reacting bisphenol A with epichlorohydrin. Since there are no more than two groups, the crosslinking density during curing is low and the heat resistance tends to be poor.
この様な欠点を改良するために、いわゆる多官能工４キ
シ樹脂であるノーラック型エポキシ樹脂などが使用され
ているが、これらの場合確かに耐熱性は向上するものの
、硬化物がもろくなるという欠点を有している。In order to improve these defects, so-called multifunctional 4-oxy resins such as no-lac epoxy resins are used, but although these do improve heat resistance, they have the disadvantage that the cured product becomes brittle. have.
（問題点を解決するための手段）
本発明者らはこうした実状に鑑みて、優れた耐熱性を有
し、かつ強靭で、機械的性質にも優れた新規なエポキシ
樹脂組成物を求めて鋭意研究した結果、特定のトリスフ
ェノールにエピクロルヒドリンを反応させて得られるエ
ポキシ樹脂を用すると前述された如き特性を兼ね備えた
エポキシ樹脂組成物が得られることを見出して、本発明
を完成させるに到り六。(Means for Solving the Problems) In view of the above circumstances, the present inventors have worked diligently to find a novel epoxy resin composition that has excellent heat resistance, is strong, and has excellent mechanical properties. As a result of research, it was discovered that by using an epoxy resin obtained by reacting a specific trisphenol with epichlorohydrin, an epoxy resin composition having the above-mentioned properties could be obtained, and this led to the completion of the present invention. .
すなわち、本発明は、エポキシ樹脂および硬化剤、さら
に必要により硬化促進剤から構成されるエポキシ樹脂組
成物にお−て、該エポキシ樹脂成分として、一般式ＣＩ
）
Ｒ１
〔式中、Ｒ１，Ｒ２は同一でも異なっていてもよく、水
素原子、炭素数１〜４のアルキル基又はハロダン原子を
表わす。〕
で示されるトリスフェノールに二一り胃ルヒドリンを反
応させて得られるエポキシ樹脂を含有することを特徴と
する新規工４キシ樹脂組成物、あるいは該エポキシ樹脂
組成物として、一般式〔■〕風２
〔式中、Ｒ１，Ｒ２は同一でも異っていてもよく、水素
原子、炭素数１〜４のアルキル基又はハロゲン原子を表
わす。〕
で示されるエポキシ樹脂を含有することを特徴とする新
規工ｌキシ樹脂組成物を提供するものである。That is, the present invention provides an epoxy resin composition comprising an epoxy resin, a curing agent, and, if necessary, a curing accelerator, in which the epoxy resin component has the general formula CI
) R1 [In the formula, R1 and R2 may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halodane atom. ] A novel engineered 4-oxy resin composition characterized by containing an epoxy resin obtained by reacting trisphenol represented by the formula [■] with gastric luhydrin, or the epoxy resin composition according to the general formula [■] style. 2 [In the formula, R1 and R2 may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom. ] The present invention provides a novel synthetic resin composition characterized by containing an epoxy resin shown in the following.
本発明で用いるトリスフェノールの代表例としてハ、１
，１．１−トリス−（ｐ−とドロやジフェニル）エタン
、１，１．１−トリス−（４−ヒドロキシ−３−メチル
フェニル）エタン、１，１．１− ）リス−（４−ヒド
ロキシ−３，５−ジメチルフェニル）エタン等が挙げら
れる。この様なトリスフェノールにアルカリの存在下に
エピクロルヒドリンを反応させることにより、本発明で
使用するエポキシ樹脂が製造される。Typical examples of trisphenol used in the present invention are c.
, 1,1-tris-(p- and doroyadiphenyl)ethane, 1,1.1-tris-(4-hydroxy-3-methylphenyl)ethane, 1,1.1-)lis-(4-hydroxy) -3,5-dimethylphenyl)ethane and the like. The epoxy resin used in the present invention is produced by reacting such trisphenol with epichlorohydrin in the presence of an alkali.
この場合の反応条件は、従来より行われている工／ｄＰ
シ樹脂の製造条件と同じで６９、特に制限されるもので
はなｈ０即ち、トリスフェノールの水酸基１個に対し、
エピクロルヒドリンを０．７〜１０モル添加し、水酸化
ナトリウムのようなアルカリの存在下に２０〜１２０℃
で工？キシ化反応を行うことができ、水酸基に対するエ
ピクロルヒドリンの過剰率を調節することＫよシ、得ら
れるエポキシ化物の分子量、エポキシ当量、軟化点を調
整することができる。エピクロルヒドリンの過剰率を下
げるとエポキシ樹脂の分子量が高くなシ、靭性の高い硬
化物となシ、逆に上げると分子量が低くなシ、耐熱性の
高い硬化物となる傾向がある。The reaction conditions in this case are as follows:
Same as the production conditions for resin 69, but not particularly limited, h0, that is, for one hydroxyl group of trisphenol,
Add 0.7 to 10 moles of epichlorohydrin and heat at 20 to 120°C in the presence of an alkali such as sodium hydroxide.
Deko? Oxylation reaction can be carried out, and the molecular weight, epoxy equivalent, and softening point of the resulting epoxide can be adjusted by adjusting the excess ratio of epichlorohydrin to hydroxyl groups. If the excess ratio of epichlorohydrin is lowered, the molecular weight of the epoxy resin tends to be high, resulting in a cured product with high toughness; on the other hand, if it is increased, the molecular weight tends to be low, and the cured product with high heat resistance tends to be produced.
ただし、−数的には過剰率が４倍を越えるとあまシ変化
しなくなるので、過剰率は５倍以下にすることが望まし
い。However, numerically speaking, if the excess rate exceeds 4 times, no change will occur, so it is desirable that the excess rate is 5 times or less.
本発明に用いられる硬化剤としては、通常工２キシ樹脂
の硬化剤として常用されている化合物はすべて使用する
ことができ、ジエチレントリアミン、トリエチレンテト
ラミンなどの脂肪族アミン類、メタフェニレンジアミン
、ジアミノジフェニルメタン、ジアミノジフェニルスル
ホンなどの芳香族アミン類、ポリアミド樹脂及び゛これ
らの変性物、無水マレイン酸、無水フタル酸、無水へキ
サヒドロフタル酸、無水ピロメリット酸などの酸無水物
系硬化剤、ジシアンジアミド、イミダゾール、ＢＦ３−
アミン錯体、グアニジン誘導体などの潜在性硬化剤、ノ
？ラック樹脂などがあげられる。As the curing agent used in the present invention, all the compounds commonly used as curing agents for conventionally engineered resins can be used, including aliphatic amines such as diethylenetriamine and triethylenetetramine, metaphenylenediamine, and diaminodiphenylmethane. , aromatic amines such as diaminodiphenylsulfone, polyamide resins and modified products thereof, acid anhydride curing agents such as maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, dicyandiamide, imidazole, BF3-
Latent curing agents such as amine complexes and guanidine derivatives, no? Examples include rack resin.
止揚された如き各化合物を硬化剤として用いる際は、多
くの場合さらに硬化促進剤をも併用することが必要とな
るが、そうした場合にはジメチルベンツルアミンなどの
如き三級アミン類、イミダゾール類、または各種金属化
合物などをはじめ、公知慣用の硬化促進剤ならすべて使
用できることは勿論である。本発明の組成物には、さら
に必要に応じて、充填剤、着色剤などの公知慣用の各種
添加剤をも添加配合せしめることができ、またタール、
ピッチ、アミン樹脂、アルキッド樹脂、フェノール樹脂
なども併用することができる。When using such compounds as curing agents, it is often necessary to also use a curing accelerator, but in such cases, tertiary amines such as dimethylbenzylamine, imidazoles, Of course, all known and commonly used curing accelerators can be used, including various metal compounds. The composition of the present invention may further contain various known and commonly used additives such as fillers and colorants, as well as tar,
Pitch, amine resin, alkyd resin, phenol resin, etc. can also be used in combination.
（実施例）
次に本発明を製造例、実施例および比較例により具体的
に説明するが、以下において部は特に断シのない限シす
べて重量部であるものとする。(Example) Next, the present invention will be specifically explained with reference to Production Examples, Examples, and Comparative Examples. In the following, all parts are parts by weight unless otherwise specified.
製造例１
１．１．１−トリス−（ｐ−ヒドロキシ）エタン３０６
？（１モル）ヲエビクロルヒドリン９２５？（１０モル
）に溶解させた後、攪拌下８０℃で２０ ％ ＮａＯＨ
水溶液６６０ｆ（３，３モル）を５時間かけて滴下し、
更に１時間反応させ、次いで水層を棄却した後、過剰の
エピクロルヒドリンを蒸留回収して得られた反応生成物
に、トルエン５００？を加え均一に溶解させ、水２４０
？を加えて水洗した後、油水分離し、油層から共沸蒸留
により水を除いた後、濾過し、更にトルエンを留去させ
て、半固型でエポキシ当量が１６８なるエポキシ樹脂（
ａ）４５０ｊ’を得た。Production example 1 1.1.1-tris-(p-hydroxy)ethane 306
? (1 mol) Oebi Chlorhydrin 925? (10 mol) and then 20% NaOH at 80°C with stirring.
Aqueous solution 660f (3.3 mol) was added dropwise over 5 hours,
After reacting for an additional hour and then discarding the aqueous layer, 500% of toluene was added to the reaction product obtained by distilling and recovering excess epichlorohydrin. Add 240 ml of water and dissolve evenly.
? After washing with water, oil and water are separated, and water is removed from the oil layer by azeotropic distillation, followed by filtration, and toluene is distilled off to obtain a semi-solid epoxy resin (with an epoxy equivalent of 168).
a) 450j' was obtained.
製造例２
エピクロルヒドリンの使用量を４１６Ｐ（４，５モル）
に変更した以外は製造例１と同様にして、軟化点が５８
℃で、かつニーキシ当量が１９１なるエポキシ樹脂（ｂ
）４４０ｉ！−を得た。Production example 2 The amount of epichlorohydrin used was 416P (4.5 mol)
The softening point was 58 in the same manner as in Production Example 1 except that
℃, and an epoxy resin (b
)440i! I got -.
製造例３
ＬＬＩ −）”）スー（ｐ−ヒドロキシフェニル）エタ
ンの代りに１．１．１− ）リス−（４−ヒドロキシ−
３，５−ジメチルフェニル）エタンを用いた以外は製造
例１と同様にして半固型でエポキシ当量が８１なるエポ
キシ樹脂（ｃ）４９０ｙ−を得た。Production Example 3 1.1.1- ) lis-(4-hydroxy-
A semi-solid epoxy resin (c) 490y- having an epoxy equivalent of 81 was obtained in the same manner as in Production Example 1 except that 3,5-dimethylphenyl)ethane was used.
実施例１〜３および比較例１〜２
エポキシ樹脂として製造例１〜３で得られたエポキシ樹
脂（ａ）〜（Ｃ）、フェノールノーラック型エポキシ樹
脂エピクロンＮ−７３８（大日本インキ化学工業（株）
製、エポキシ当量１８ｏ〕又はオルソクレゾールノボラ
ック型エポキシ樹脂エピクロ：ｙＮ−６７０（同社製、
エポキシ当量２１ｏ）を、硬化剤としてエピクロンＢ−
５７０（同社製、メチルテトラヒドロフタル酸無水物）
を、便化促進剤としてジメチルベンツルアミンをそれぞ
れ用い、エポキシ樹脂のエポキシ基１個に対して硬化剤
の酸無水物基が１個になる様に表−１に示す組成で配合
して、本発明および比較対照用のエポキシ樹脂組成物を
得た。Examples 1 to 3 and Comparative Examples 1 to 2 As epoxy resins, epoxy resins (a) to (C) obtained in Production Examples 1 to 3, phenol nolac type epoxy resin Epiclon N-738 (Dainippon Ink & Chemicals Co., Ltd.) KK)
manufactured by the same company, epoxy equivalent 18o] or orthocresol novolac type epoxy resin Epiclo: yN-670 (manufactured by the same company,
Epoxy equivalent weight 21o) was used as a hardener for Epiclon B-
570 (manufactured by the same company, methyltetrahydrophthalic anhydride)
were mixed in the composition shown in Table 1, using dimethylbenzylamine as a fecalization promoter, and so that the number of acid anhydride groups in the curing agent was one for each epoxy group in the epoxy resin. Inventive and comparative epoxy resin compositions were obtained.
これらのエポキシ樹脂組成物を１００℃で２時間、次い
で１６０℃で２時間、更に１８０℃で２時間の条件で硬
化せしめて試験片とし、ＪＩＳＫ−６９１１に準拠して
熱変形温度、曲げ強度、曲げ弾性率、引張９強度、引張
シ伸び率および煮沸吸収率を測定した。結果を表−１に
示す。These epoxy resin compositions were cured at 100°C for 2 hours, then at 160°C for 2 hours, and then at 180°C for 2 hours to prepare test pieces, and the heat distortion temperature, bending strength, The flexural modulus, tensile strength, tensile elongation, and boiling absorption rate were measured. The results are shown in Table-1.
実施例４〜６および比較例３〜４
前記と同様にエポキシ樹脂（、）〜（ｃ）、エピクロン
Ｎ−７３８又はエピクロンＮ−６７０を、硬化剤として
ノボラック型フェノール樹脂ノぐ−カムＴＤ−２１３１
（同社製、軟化点８０℃）をそれぞれ用い、エポキシ樹
脂のエポキシ基１個に対して硬化剤の活性水素基が１個
になるように表−１に示す組成で配合した以外は実施例
１と同様にし１、本発明および比較対照用のエポキシ樹
脂組成物を得た。Examples 4 to 6 and Comparative Examples 3 to 4 In the same manner as above, epoxy resins (,) to (c), Epiclon N-738 or Epiclon N-670 were used as a curing agent, and novolac type phenolic resin Nogucam TD-2131 was used.
(manufactured by the same company, softening point 80°C) was used, and Example 1 was used, except that the curing agent was blended with the composition shown in Table 1 so that there was one active hydrogen group in the curing agent for one epoxy group in the epoxy resin. In the same manner as in Example 1, epoxy resin compositions for the present invention and for comparison were obtained.
これらのエポキシ樹脂組成物を１００℃で２時間、次い
で１２０℃で２時間、更に１５０℃で２時間の条件で、
硬化せしめて試験片とし、ＪＩＳＫ −６９１１に準拠
して前記例と同様の項目を測定した。結果を表−１に示
す。These epoxy resin compositions were heated at 100°C for 2 hours, then at 120°C for 2 hours, and then at 150°C for 2 hours.
It was cured to give a test piece, and the same items as in the above example were measured in accordance with JISK-6911. The results are shown in Table-1.
（発明の効果）
本発明のエポキシ樹脂組成物から得られた硬化物は、耐
熱性および機械的性質に優れ、加えて強靭性があっても
ろくないという特性を兼ね備えている。従って本発明の
エポキシ樹脂組成物は成型材料、注型材料、治工具用、
積層材料、電気絶縁材料、塗料、土木・建築材料、接着
剤、複合材料などの用途に極めて有用である。(Effects of the Invention) The cured product obtained from the epoxy resin composition of the present invention has excellent heat resistance and mechanical properties, and also has the characteristics of being tough and not brittle. Therefore, the epoxy resin composition of the present invention can be used for molding materials, casting materials, jigs and tools,
It is extremely useful for applications such as laminated materials, electrical insulation materials, paints, civil engineering and construction materials, adhesives, and composite materials.
代理人 弁理士 高 橋 勝 利Agent Patent Attorney Katsutoshi Takahashi
Claims (1)
進剤から構成されるエポキシ樹脂組成物において、該エ
ポキシ樹脂成分として、 一般式〔 I 〕 ▲数式、化学式、表等があります▼・・・・・・〔 I
〕 〔式中、Ｒ＿１、Ｒ＿２は同一でも異なつていてもよく
、水素原子、炭素数１〜４のアルキル基又はハロゲン原
子を表わす。〕 で示されるトリスフェノールにエピクロルヒドリンを反
応させて得られるエポキシ樹脂を含有することを特徴と
する新規エポキシ樹脂組成物。 ２、エポキシ樹脂および硬化剤、更に必要により硬化促
進剤から構成されるエポキシ樹脂組成物において、該エ
ポキシ樹脂成分として、 一般式〔II〕 ▲数式、化学式、表等があります▼・・・〔II〕 〔式中、Ｒ＿１、Ｒ＿２は同一でも異っていてもよく、
水素原子、炭素数１〜４のアルキル基又はハロゲン原子
を表わす。〕 で示されるエポキシ樹脂を含有することを特徴とする新
規エポキシ樹脂組成物。[Claims] 1. In an epoxy resin composition composed of an epoxy resin, a curing agent, and, if necessary, a curing accelerator, the epoxy resin components include the general formula [I] ▲ mathematical formula, chemical formula, table, etc. ▼・・・・・・〔 I
] [In the formula, R_1 and R_2 may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom. ] A novel epoxy resin composition characterized by containing an epoxy resin obtained by reacting trisphenol represented by the following with epichlorohydrin. 2. In an epoxy resin composition composed of an epoxy resin, a curing agent, and, if necessary, a curing accelerator, the epoxy resin components include the general formula [II] ▲ mathematical formula, chemical formula, table, etc. ▼... [II ] [In the formula, R_1 and R_2 may be the same or different,
Represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom. ] A novel epoxy resin composition characterized by containing an epoxy resin represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9678088A JPH01268714A (en) | 1988-04-21 | 1988-04-21 | Novel epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9678088A JPH01268714A (en) | 1988-04-21 | 1988-04-21 | Novel epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01268714A true JPH01268714A (en) | 1989-10-26 |
Family
ID=14174151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9678088A Pending JPH01268714A (en) | 1988-04-21 | 1988-04-21 | Novel epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01268714A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015119188A1 (en) * | 2014-02-06 | 2015-08-13 | 日本化薬株式会社 | Epoxy resin, curable resin composition, and cured product thereof |
| JP2018538406A (en) * | 2015-12-11 | 2018-12-27 | コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ | Polyglycidyl ether-containing polycarbonate composition |
| WO2022138178A1 (en) * | 2020-12-22 | 2022-06-30 | 本州化学工業株式会社 | Crystal of 1,1,1-tris(4-hydroxy-3,5-dimethylphenyl)ethane and production method therefor |
-
1988
- 1988-04-21 JP JP9678088A patent/JPH01268714A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015119188A1 (en) * | 2014-02-06 | 2015-08-13 | 日本化薬株式会社 | Epoxy resin, curable resin composition, and cured product thereof |
| JP2015147854A (en) * | 2014-02-06 | 2015-08-20 | 日本化薬株式会社 | Modified epoxy resin, and curable resin composition |
| KR20160118208A (en) * | 2014-02-06 | 2016-10-11 | 닛뽄 가야쿠 가부시키가이샤 | Epoxy resin, curable resin composition, and cured product thereof |
| TWI659974B (en) * | 2014-02-06 | 2019-05-21 | 日商日本化藥股份有限公司 | Epoxy resin, curable resin composition, and cured product thereof |
| JP2018538406A (en) * | 2015-12-11 | 2018-12-27 | コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ | Polyglycidyl ether-containing polycarbonate composition |
| WO2022138178A1 (en) * | 2020-12-22 | 2022-06-30 | 本州化学工業株式会社 | Crystal of 1,1,1-tris(4-hydroxy-3,5-dimethylphenyl)ethane and production method therefor |
| KR20230123465A (en) | 2020-12-22 | 2023-08-23 | 혼슈우 카가쿠고교 가부시키가이샤 | Crystals of 1,1,1-tris(4-hydroxy-3,5-dimethylphenyl)ethane and method for producing the same |
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