JPH0241312A - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JPH0241312A JPH0241312A JP19152688A JP19152688A JPH0241312A JP H0241312 A JPH0241312 A JP H0241312A JP 19152688 A JP19152688 A JP 19152688A JP 19152688 A JP19152688 A JP 19152688A JP H0241312 A JPH0241312 A JP H0241312A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- epoxy
- resin composition
- materials
- epichlorohydrin
- 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 40
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 40
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 7
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 238000005266 casting Methods 0.000 abstract description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002841 Lewis acid Substances 0.000 abstract description 2
- 239000004566 building material Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 150000007517 lewis acids Chemical class 0.000 abstract description 2
- 150000003512 tertiary amines Chemical class 0.000 abstract description 2
- 239000011810 insulating material Substances 0.000 abstract 1
- 238000010030 laminating Methods 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 239000004593 Epoxy Substances 0.000 description 14
- 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 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 7
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 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
- -1 laminates Substances 0.000 description 4
- KIFDSGGWDIVQGN-UHFFFAOYSA-N 4-[9-(4-aminophenyl)fluoren-9-yl]aniline Chemical compound C1=CC(N)=CC=C1C1(C=2C=CC(N)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 KIFDSGGWDIVQGN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012772 electrical insulation material Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 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
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- RBCRDGPAIUTPGK-UHFFFAOYSA-N 4-[1-(4-aminophenyl)-9h-fluoren-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C1=CC=C(C=2C(=CC=CC=2)C2)C2=C1C1=CC=C(N)C=C1 RBCRDGPAIUTPGK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-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
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 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
- 108010010803 Gelatin Proteins 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
- 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
- 150000001412 amines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 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
- 239000011248 coating agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000000945 filler Substances 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
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- LDDCTEIBGPJUOA-UHFFFAOYSA-N gold toluene Chemical compound [Au].CC1=CC=CC=C1 LDDCTEIBGPJUOA-UHFFFAOYSA-N 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は新規な特に耐熱性、耐水性にすぐれた工４キシ
耐脂組成物に関し、さらに詳細には必須のエポキシ樹脂
成分として９．９−ビス（４′−アミノフェニル）フル
オレンとエピクロルヒドリンとからなるエポキシ樹脂を
含んでなる、Ｉｆ：Ｒ層品樹脂材料、電気絶縁材料、繊
維強化複合材料、塗装材料、成型材料、接着材料などに
極めて有用な耐熱性および耐水性が飛躍的に優れるエポ
キシ樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel, particularly heat-resistant and water-resistant composition having excellent heat resistance and water resistance. - If:R layered resin materials, electrical insulation materials, fiber-reinforced composite materials, coating materials, molding materials, adhesive materials, etc., containing epoxy resins consisting of bis(4'-aminophenyl)fluorene and epichlorohydrin. The present invention relates to a useful epoxy resin composition that has dramatically superior heat resistance and water resistance.
（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り
、−船釣に機械的性質、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 produce cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc. for boat fishing. 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
らは１分子当たりのグリシジル基が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, but these have a high glycidyl group per molecule. Since there are no more than two, 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、いわゆるノゲラック型
エポキシ樹脂やジアミノジフェニルメタン、アミノフェ
ノール等をベースとするグリシジルアミン型およびグリ
シジルアミンエーテル型エデキシ樹脂等の多官能エポキ
シ樹脂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、その向上の度合は充分でなく、シか
も耐水性は逆に劣るという欠点を有する。In order to improve these drawbacks, polyfunctional epoxy resins such as so-called nogelac type epoxy resins, glycidylamine type and glycidylamine ether type edoxy resins based on diaminodiphenylmethane, aminophenol, etc. are used. In this case, although the heat resistance is certainly improved, the degree of improvement is not sufficient, and the water resistance is, on the contrary, inferior.
（課＠を解決するための手段）
本発明者らは、こうした実情に鑑みて鋭意研究した結果
、９．９−ビス（４′−アミノフェニル）フルオレンに
エピクロルヒドリンを反応させて得られる特定のグリシ
ジルアミン型工４キシ樹脂を用いると耐熱性と耐水性の
いずれＫも優れるエポキシ樹脂組成物が得られることを
見出して、本発明を完成するに至りた。(Means for Solving Section @) As a result of intensive research in view of the above circumstances, the present inventors found that a specific glycidyl compound obtained by reacting epichlorohydrin with 9,9-bis(4'-aminophenyl)fluorene. The present invention was completed based on the discovery that an epoxy resin composition having excellent heat resistance and water resistance (K) can be obtained by using an amine-type 4-oxy resin.
すなわち、本発明は、エポキシ樹脂および硬化剤、更に
必要によシ硬化促進剤から構成される工４キシ国脂組成
物において、該エポキシ樹脂成分として、
構造式ＣＩ）
で示される化合物にエピクロルヒドリンを反応させて得
られるグリシジルアミン型エデキシ樹脂を含有すること
を特徴とする新規なエポキシ樹脂組成物、
および該エポキシ樹脂成分として、
構造式〔ｌｌ）
で示されるグリシジルアミン型エポキシ樹脂を含有する
ことを特徴とする硬化性エポキシ樹脂組成物を提供する
ものである。That is, the present invention provides a composition comprising an epoxy resin, a curing agent, and optionally a curing accelerator, in which epichlorohydrin is added to a compound represented by the structural formula CI) as the epoxy resin component. A novel epoxy resin composition characterized by containing a glycidylamine type edoxy resin obtained by the reaction, and a glycidylamine type epoxy resin represented by the structural formula [ll] as the epoxy resin component. The present invention provides a curable epoxy resin composition with characteristics.
本発明で用いる構造式（ＩＩ）で示されるグリシジルア
ミン型工ｆキシ樹脂は、例えば構造式〔■〕で示すしる
９、９−ビス（４′−アミノフェニル）フルオレンにア
ルカリの存在下、エピクロルヒドリンを反応させること
によシ得られる。The glycidylamine-type engineered resin represented by the structural formula (II) used in the present invention can be prepared by, for example, adding 9,9-bis(4'-aminophenyl)fluorene represented by the structural formula [■] in the presence of an alkali. Obtained by reacting epichlorohydrin.
この場合の反応条件は従来より行なわれているエポキシ
１脂の製造条件と同じであシ、特に制限されるものでは
ない。即ち、９，９−ビス（４′−アミノフェニル）フ
ルオレンのアミン性活性水素１個に対しエピクロルヒド
リンを１〜１０そル添加し、水酸化ナトリクムのような
アルカリの存在下に２０〜１２０℃でエポキシ化反応を
行なうことが出来、アミン性活性水素に対するエピクロ
ルヒドリンの過剰率を調節することＫより、得られるエ
ポキシ化合物の分子量、エポキシ当量、欧化点を調整す
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り、靭性の高い硬化物
となり、逆に上げると分子量が低くなり、耐熱性の高い
硬化物を得ることが出来る。ただし一般にはエピクロル
ヒドリンの過剰率が４倍をこえると得られるエポキシ化
合物の分子量、エポキシ当量、軟化点はあまシ変化しな
くなるので、過剰率は５倍以下が好ましい。The reaction conditions in this case are the same as those for the conventional production of epoxy 1 resin, and are not particularly limited. That is, 1 to 10 times of epichlorohydrin is added to one aminic active hydrogen of 9,9-bis(4'-aminophenyl)fluorene, and the mixture is heated at 20 to 120°C in the presence of an alkali such as sodium hydroxide. An epoxidation reaction can be carried out, and by controlling the excess ratio of epichlorohydrin to aminic active hydrogen, the molecular weight, epoxy equivalent, and Europeanization point of the resulting epoxy compound can be adjusted. If the excess ratio of epichlorohydrin is lowered, the molecular weight of the epoxy resin will increase, resulting in a cured product with high toughness, whereas if it is increased, the molecular weight will be lowered, making it possible to obtain a cured product with high heat resistance. However, in general, if the excess ratio of epichlorohydrin exceeds 4 times, the molecular weight, epoxy equivalent, and softening point of the obtained epoxy compound will not change much, so the excess ratio is preferably 5 times or less.
本発明に使用される硬化剤としては、通常エポキシ樹脂
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、？リアミド樹脂およびこれ
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ｙ錯体、グアニジン訪導体等の潜在性硬化剤等が
挙げられる。As the curing agent used in the present invention, all compounds commonly used as curing agents for epoxy resins can be used, including aliphatic amines such as diethylenetriamine and triethylenetetramine, metaphenylenediamine, diaminodiphenylmethane, Aromatic amines such as diaminodiphenylsulfone? Lyamide resins and modified products thereof, acid anhydride curing agents such as maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, dicyandiamide, imidazole, BF3
Examples include latent curing agents such as -amy complexes and guanidine visiting conductors.
これらの硬化剤は単独でも２種以上の併用でもよい。These curing agents may be used alone or in combination of two or more.
これら硬化剤の使用量は、用いるエポキシ化合物の一分
子中に含まれるエポキシ基の数と、硬化剤中の活性水素
の数が当量付近となる量が一般的である。The amount of these curing agents used is generally such that the number of epoxy groups contained in one molecule of the epoxy compound used and the number of active hydrogens in the curing agent are approximately equivalent.
止揚された如き各化合物全硬化剤として用いる際は、硬
化促進剤を適宜使用することができる。When each compound is used as a total curing agent, a curing accelerator can be used as appropriate.
硬化促進剤としては公知慣用のものがいずれも使用でき
るが、例えは、第３級アミン、イミダゾール、有機酸金
属塩、ルイス酸、アミン錯塩等が挙げられ、これらは単
独のみならず２踵以上の併用も可能である。Any known and commonly used curing accelerator can be used, but examples include tertiary amines, imidazole, organic acid metal salts, Lewis acids, amine complex salts, etc. These can be used not only singly but also in combinations of two or more It is also possible to use them together.
本発明のエポキシ樹脂組成物には、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、ま几タール、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。The epoxy resin composition of the present invention may further contain various well-known and commonly used additives such as fillers and colorants, as required. Resin etc. can also be used together.
次に本発明を製造例、実施例および比較例によシ具体的
に説明する。尚、例中において部は特に断りのない限り
すべて重量部である。Next, the present invention will be specifically explained using manufacturing examples, working examples, and comparative examples. In addition, all parts in the examples are parts by weight unless otherwise specified.
製造例１
９．９−ビス（４′−アミノフェニル）フルオレン３４
８部全エピクロルヒドリン７４０部に溶解させ友後、攪
拌しながら５０〜６０℃で２０％水Ｎ化ナトリウム水溶
液８００部を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
を蒸留回収して反応組成物を得意。この反応組成物にト
ルエン８６０部を加えて均一に溶解させ、水２９０部を
加えて水洗した後、油水分離し、油層からトルエン金留
去させることによって、エポキシ当量が１５３なるエポ
キシ樹脂（ａ） ５４３部を得た。Production example 1 9.9-bis(4'-aminophenyl)fluorene 34
After dissolving 8 parts in 740 parts of epichlorohydrin, 800 parts of a 20% aqueous sodium nitrate solution was added dropwise over 5 hours at 50 to 60°C with stirring, and the mixture was allowed to react for an additional 1 hour, after which the aqueous layer was discarded. , we are good at distilling and recovering excess epichlorohydrin and making reactive compositions. To this reaction composition, 860 parts of toluene was added and dissolved uniformly, 290 parts of water was added and washed, oil and water were separated, and the toluene gold was distilled off from the oil layer to obtain an epoxy resin (a) having an epoxy equivalent of 153. 543 copies were obtained.
製造例２
エピクロルヒドリンの使用１ｉ５５５部とした以外は製
造例１と同様にしてエポキシ当量が１７１なるエポキシ
耐脂（ｂ） ５３５部を得た。Production Example 2 535 parts of epoxy grease-resistant (b) having an epoxy equivalent of 171 was obtained in the same manner as Production Example 1, except that 555 parts of 1i of epichlorohydrin were used.
クシ造例３
エピクロルヒドリンの使用Ａｉ１１１０部、！ニジた以
外は製造例１と同様にしてエポキシ当量が１５１なるエ
ポキシ噌脂（ｅ） ５４４部を得意。Combination Example 3 Use of epichlorohydrin Ai 1110 parts,! 544 parts of epoxy paste (e) with an epoxy equivalent of 151 was prepared in the same manner as in Production Example 1, except for the difference.
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）、フェノールノゲラツクエボキシ樹脂
エピクロンＮ−７３８（大日本インキ化学工業■製、エ
ポキシ当［１８０）又はジアミノジフ工二ルメタン型グ
リシジルアミンエ？ヤシ樹脂エビクロン４３０（同社製
、エポキシ当量１２０）を、硬化剤としてエビクロンＢ
−５７０（同社製、メチルテトラヒドロフタル酸無水物
）ヲ、硬化促進剤として２−エチル−４−メチルイミダ
ゾールをそれぞれ用い、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 Epoxy resins (a) to (C) obtained in Production Examples 1 to 3 as epoxy resins, phenol gelatin epoxy resin Epiclon N-738 (manufactured by Dainippon Ink & Chemicals) , epoxy [180) or diaminodiphenylmethane-type glycidylamine] Coconut resin Ebicuron 430 (manufactured by the same company, epoxy equivalent: 120) was used as a curing agent, Ebicuron B.
-570 (manufactured by the same company, methyltetrahydrophthalic anhydride), 2-ethyl-4-methylimidazole was used as a curing accelerator, and the acid anhydride group of the curing agent was 1 for 1 epoxy group of the epoxy resin. Epoxy resin compositions for the present invention and for comparison were obtained by blending the compositions shown in Table 1 so that the compositions were equal to each other.
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、ＪＴＳＫ−６９１１に準拠して
熱変形温度、曲げ強度、曲げ弾性率、引張シ強度、引張
り伸び率および煮沸吸水率を測定した。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, Flexural modulus, tensile strength, tensile elongation and boiling water absorption were measured. The results are shown in Table-1.
実施例４〜６および比較例３〜４
エポキシ樹脂として前記と同様に工Ｉキシ樹脂（ａ）〜
（ｃ）、エピクロンＮ−７３８又はエピクＩ：ｌ ７４
３０を、硬化剤としてＤＤＭ （ジアミノジフェニルメ
タン）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 4 to 6 and Comparative Examples 3 to 4 As epoxy resins, engineering I oxy resins (a) to
(c), Epicron N-738 or Epicron I:l 74
30 and DDM (diaminodiphenylmethane) as a curing agent, Table 1
Epoxy resin compositions for the present invention and for comparative purposes were obtained by blending the compositions shown in .
これらのエポキシ個脂組成物を８０℃で５時間、更に１
６０℃で４時間の条件で、硬化せしめて試験片とし、Ｊ
ＩＳＫ−６９１１に準拠して前記例と同様の項目を測定
した。結果全表−１に示す。These epoxy individual fat compositions were heated at 80°C for 5 hours, and then for 1 hour.
Cured at 60°C for 4 hours to prepare a test piece, J
The same items as in the above example were measured in accordance with ISK-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念硬化物は、飛
躍的に優れ九耐熱性および耐水性を有するという特徴が
ある。(Effects of the Invention) The thermocured product obtained from the epoxy resin composition of the present invention is characterized by dramatically superior heat resistance and water resistance.
従りて本発明の工Ｉ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。Therefore, the resin composition of the present invention can be used for molding materials, casting materials, jigs and tools, laminated materials, electrical insulation materials, paints, civil engineering, etc.
Extremely useful in applications such as building materials, adhesives, and composite materials.
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、 構造式〔 I 〕 ▲数式、化学式、表等があります▼・・・〔 I 〕 で示される化合物にエピクロルヒドリンを反応させて得
られるグリシジルアミン型エポキシ樹脂を含有すること
を特徴とする硬化性エポキシ樹脂組成物。 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、 構造式〔II〕 ▲数式、化学式、表等があります▼・・・〔II〕 で示されるグリシジルアミン型エポキシ樹脂を含有する
ことを特徴とする硬化性エポキシ樹脂組成物。[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 following structural formula [I] ▲ mathematical formula, chemical formula, table, etc. ▼... A curable epoxy resin composition characterized by containing a glycidylamine type epoxy resin obtained by reacting the compound represented by [I] 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 following: Structural formula [II] ▲ Numerical formula, chemical formula, table, etc. ▼... [II ] A curable epoxy resin composition characterized by containing a glycidylamine type epoxy resin represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19152688A JPH0241312A (en) | 1988-07-29 | 1988-07-29 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19152688A JPH0241312A (en) | 1988-07-29 | 1988-07-29 | Epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0241312A true JPH0241312A (en) | 1990-02-09 |
Family
ID=16276131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19152688A Pending JPH0241312A (en) | 1988-07-29 | 1988-07-29 | Epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0241312A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003007319A3 (en) * | 2001-07-10 | 2003-04-24 | 3M Innovative Properties Co | Capacitor having epoxy dielectric layer cured with aminophenylfluorenes |
| JP2008052260A (en) * | 2006-07-28 | 2008-03-06 | Jsr Corp | Liquid crystal aligning agent, liquid crystal alignment layer, and liquid crystal display element |
| JP2013203721A (en) * | 2012-03-29 | 2013-10-07 | Nagase Chemtex Corp | Epoxy compound |
| CN105860030A (en) * | 2016-04-26 | 2016-08-17 | 沈阳航空航天大学 | Cardo-structure-containing glycidyl amine epoxy resin and preparation method thereof |
| CN113045516A (en) * | 2021-05-18 | 2021-06-29 | 湖南大学 | Preparation method of tetra-functional epoxy resin containing fluorene structure |
-
1988
- 1988-07-29 JP JP19152688A patent/JPH0241312A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003007319A3 (en) * | 2001-07-10 | 2003-04-24 | 3M Innovative Properties Co | Capacitor having epoxy dielectric layer cured with aminophenylfluorenes |
| US6577492B2 (en) | 2001-07-10 | 2003-06-10 | 3M Innovative Properties Company | Capacitor having epoxy dielectric layer cured with aminophenylfluorenes |
| JP2008052260A (en) * | 2006-07-28 | 2008-03-06 | Jsr Corp | Liquid crystal aligning agent, liquid crystal alignment layer, and liquid crystal display element |
| JP2013203721A (en) * | 2012-03-29 | 2013-10-07 | Nagase Chemtex Corp | Epoxy compound |
| CN105860030A (en) * | 2016-04-26 | 2016-08-17 | 沈阳航空航天大学 | Cardo-structure-containing glycidyl amine epoxy resin and preparation method thereof |
| CN113045516A (en) * | 2021-05-18 | 2021-06-29 | 湖南大学 | Preparation method of tetra-functional epoxy resin containing fluorene structure |
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