JPH02202512A - Epoxy resin composition and molded article produced by curing the same - Google Patents
Epoxy resin composition and molded article produced by curing the sameInfo
- Publication number
- JPH02202512A JPH02202512A JP1983489A JP1983489A JPH02202512A JP H02202512 A JPH02202512 A JP H02202512A JP 1983489 A JP1983489 A JP 1983489A JP 1983489 A JP1983489 A JP 1983489A JP H02202512 A JPH02202512 A JP H02202512A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- curing
- resin composition
- epichlorohydrin
- epoxy
- 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.)
- Granted
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 61
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 61
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 claims 1
- 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 4
- 239000012778 molding material Substances 0.000 abstract description 4
- 239000003973 paint Substances 0.000 abstract description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 abstract description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-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
- 239000004848 polyfunctional curative Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 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 14
- 239000000047 product Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 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 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- 239000003921 oil Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- -1 laminates Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- DEQUKPCANKRTPZ-UHFFFAOYSA-N (2,3-dihydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1O DEQUKPCANKRTPZ-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- 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
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 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
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004985 diamines Chemical class 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
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant 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
- 125000003055 glycidyl group Chemical group C(C1CO1)* 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
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 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および
それを用いてなる物品に関し、さらに詳細には、４．４
’−ジヒドロキシベンゾフェノンとエピクロルヒドリン
とを反応させて得られるエポキシ樹脂を用いた樹脂組成
物および耐熱性と靭性に優れた成形品に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a new and useful epoxy resin composition and an article made using the same, and more specifically, 4.4.
The present invention relates to a resin composition using an epoxy resin obtained by reacting '-dihydroxybenzophenone and epichlorohydrin, and a molded article having excellent heat resistance and toughness.
（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り、接着剤、塗料、積
層板、成型材料、注型材料など幅広い分野に使用されて
いる。(Prior art) By curing epoxy resin with various curing agents, it becomes a cured product with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., and can be used as an adhesive. It is used in a wide range of fields, including paints, laminates, molding materials, and casting materials.
最も汎用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型エポキシ樹脂であり、これらは靭性
には優れる硬化物を与えるが、１分子当りのグリシジル
基が２個より多くはないために架橋密度が低く、耐熱性
に劣る硬化物になる１頃向にある。The most commonly used epoxy resins are liquid and solid bisphenol A type epoxy resins, which are obtained by reacting bisphenol A with epichlorohydrin.These resins give cured products with excellent toughness, but the number of glycidyl groups per molecule is low. Since there are no more than two, the crosslinking density is low and the cured product has poor heat resistance.
この様な欠点を改良するために、いわゆる多官能エポキ
シ樹脂であるノボ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、靭性が低いという欠点を有している
。In order to improve these defects, so-called multifunctional epoxy resins such as novolak epoxy resins are used, but although these do improve heat resistance, the cured product is brittle and has low toughness. It has drawbacks.
（発明が解決しようとする課題）
そこでビスフェノールＡ型エポキシ樹脂の靭性とノボラ
ック型エポキシ樹脂の耐熱性を兼ね備えたエポキシ樹脂
の開発が行われているが、これら２つの性能を併存する
硬化物を与えるエポキシ樹脂組成物はない。加えてより
耐熱性の優れるエポキシ樹脂組成物の開発が望まれてい
る。(Problem to be solved by the invention) Therefore, epoxy resins that have both the toughness of bisphenol A type epoxy resins and the heat resistance of novolac type epoxy resins are being developed. There is no epoxy resin composition. In addition, it is desired to develop an epoxy resin composition that has better heat resistance.
（課題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、ノボラック型エポ
キシ樹脂より優れた耐熱性を有し、かつビスフェノール
Ａ型エポキシ樹脂の様に強靭なエポキシ樹脂組成物を求
めて鋭意研究した結果、４．４′−ジヒドロキシベンゾ
フェノンにエピクロルヒドリンを反応させて得られるエ
ポキシ樹脂を必須の成分とし、かかるエポキシ樹脂成分
に硬化剤と、さらに必要に応じて硬化促進剤とを配合せ
しめてなる樹脂組成物が、前述された如き特性を兼ね備
えたものであることを見出して、本発明を完成させるに
到った。(Means for Solving the Problems) In view of these actual circumstances, the present inventors sought an epoxy resin composition that has superior heat resistance than novolac type epoxy resins and is as tough as bisphenol A type epoxy resins. As a result of intensive research, an epoxy resin obtained by reacting 4,4'-dihydroxybenzophenone with epichlorohydrin was used as an essential component, and a curing agent and, if necessary, a curing accelerator were added to the epoxy resin component. The present inventors have now completed the present invention by discovering that a resin composition comprising the above-mentioned resin composition has the above-mentioned properties.
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ろエポキシ樹脂組
成物において、該エポキシ樹脂成分として、４，４′−
ジヒドロキシベンゾフェノンと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
するエポキシ樹脂組成物およびそれを硬化せしめてなる
成形品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 4,4'-
The present invention provides an epoxy resin composition containing an epoxy resin obtained by reacting dihydroxybenzophenone and epichlorohydrin, and a molded article obtained by curing the same.
本発明で用いるエポキシ樹脂は、４，４′−ジヒドロキ
シヘンシフエノン、即ち、構造式（１）％式％
エポキシ化の際に用いる塩基は、特に限定されるもので
はないが、水酸化カリウム、水酸化ナトリウム、炭酸カ
リウム、炭酸ナトリウム等が例示される。The epoxy resin used in the present invention is 4,4'-dihydroxyhensiphenone, that is, structural formula (1)% formula% The base used in epoxidation is not particularly limited, but potassium hydroxide, Examples include sodium hydroxide, potassium carbonate, and sodium carbonate.
上記の様にして得られるエポキシ樹脂は、通粛一般弐（
ｎ）、
で示される化合物に塩基の存在下エピクロルヒドリンを
反応せしめることにより容易に得られる。The epoxy resin obtained as described above is
n), can be easily obtained by reacting the compound represented by the following with epichlorohydrin in the presence of a base.
この場合の反応条件は、従来より行なわれているエポキ
シ樹脂の製造条件と同じであり、特に制限されるもので
はない。例えば４．４′−ジヒドロキシヘンシフエノン
の１モルに対し、エピクロルヒドリンを１．４〜２０モ
ル添加し、塩基の存在下に２０〜１２０°Ｃで２〜７時
間エポキシ化を行う〔ｎはＯ〜１０を表わす。〕
で示されるエポキシ樹脂を主成分として含有したもので
ある。また４、４′−ジヒドロキシベンゾフェノンのモ
ル数に対するエピクロルヒドリンのモル数の過剰率を調
節することにより、得られるエポキシ樹脂の分子量、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
高くなり、靭性の高い硬化物を与える様になり、逆に上
げると分子量が低くなり、耐熱性の高い硬化物を与える
様になる傾向がある。ただし、−船釣には過剰率が８倍
を越えるとそれ以上耐熱性に優れた硬化物を与えるエポ
キシ樹脂は得られにくくなるので、過剰率は１０倍以下
にすることが望ましい。The reaction conditions in this case are the same as those conventionally used for producing epoxy resins, and are not particularly limited. For example, 1.4 to 20 mol of epichlorohydrin is added to 1 mol of 4.4'-dihydroxyhensiphenone, and epoxidation is carried out at 20 to 120°C for 2 to 7 hours in the presence of a base [n is O ~10. ] Contains an epoxy resin shown as the main component. Furthermore, by adjusting the excess ratio of the number of moles of epichlorohydrin to the number of moles of 4,4'-dihydroxybenzophenone, the molecular weight, epoxy equivalent, and softening point of the resulting epoxy resin can be adjusted. If the excess ratio of epichlorohydrin is lowered, the molecular weight of the epoxy resin will increase and a cured product with high toughness will be obtained, whereas if it is increased, the molecular weight will be lowered and a cured product with high heat resistance will be obtained. However, for boat fishing, if the excess ratio exceeds 8 times, it becomes difficult to obtain an epoxy resin that gives a cured product with excellent heat resistance, so it is desirable that the excess ratio is 10 times or less.
本発明のエポキシ樹脂組成物は、４．４′−ジヒドロキ
シベンゾフェノンとエピクロルヒドリンとを反応させて
得られるエポキシ樹脂と硬化剤と、必要に応じて硬化促
進剤を公知慣用の方法で混合せしめれば容易に得ること
ができる。The epoxy resin composition of the present invention can be easily prepared by mixing an epoxy resin obtained by reacting 4,4'-dihydroxybenzophenone with epichlorohydrin, a curing agent, and, if necessary, a curing accelerator using a known and commonly used method. can be obtained.
本発明に用いられる硬化剤は、特に限定されるものでは
なく、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、トリエチル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、ＢＰ、−アミン錯体、グアニジン誘導体など
の潜在性硬化剤などがあげられる。The curing agent used in the present invention is not particularly limited, and all compounds commonly used as curing agents for epoxy resins can be used, including aliphatic amines such as diethylenetriamine and triethyltetramine, metaphenylene Aromatic amines such as diamine, diaminodiphenylmethane, and diaminodiphenylsulfone, polyamide resins and modified products thereof, acid anhydride curing agents such as maleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, and pyromellitic anhydride. , dicyandiamide, imidazole, BP, -amine complexes, guanidine derivatives, and other latent curing agents.
硬化剤の使用量は、特に限定されるものではないが、エ
ポキシ樹脂の一分子中に含まれるエポキシ基の数と、硬
化剤中のアミノ基またはイミノ基、フェノール性水酸基
等の活性水素基の数あるいは酸無水物基の数が当量付近
となる量が一般的である。The amount of curing agent used is not particularly limited, but it depends on the number of epoxy groups contained in one molecule of the epoxy resin and the number of active hydrogen groups such as amino groups, imino groups, and phenolic hydroxyl groups in the curing agent. Generally, the amount is such that the number or the number of acid anhydride groups is close to the equivalent.
上掲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ジルアミンなどの
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０本発明の組成物には、さら
に必要に応じて、公知慣用のエポキシ樹脂や充填剤、着
色剤、難燃剤、離型剤、シランカップリング刑などの各
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、アミノ樹脂、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 each of the compounds listed above as a curing agent, in many cases it is necessary to also use a curing accelerator, but in such cases, tertiary amines such as dimethylbenzylamine, imidazoles, etc. Of course, all known and commonly used curing accelerators can be used, including various metal compounds, etc. The composition of the present invention may further contain known and commonly used epoxy resins, fillers, colorants, Various additives such as flame retardants, mold release agents, and silane coupling additives can also be added, and tar, pitch, amino resins, alkyd resins, phenol resins, etc. can also be used together.
本発明のエポキシ樹脂組成物は、耐熱性と靭性のいずれ
にも優れているので、例えば樹脂封止電気電子部品、プ
リプレグ、積層板、塗料、接着剤、構造材料、成形材料
、注型材料等各種の分野で利用できる。The epoxy resin composition of the present invention has excellent heat resistance and toughness, so it can be used, for example, in resin-sealed electrical and electronic parts, prepregs, laminates, paints, adhesives, structural materials, molding materials, casting materials, etc. It can be used in various fields.
例えば本発明のエポキシ樹脂組成物は、任意の形状に保
って加熱硬化せしめることにより、耐熱性と靭性を併有
する各種成形品を得ることができる。For example, the epoxy resin composition of the present invention can be kept in an arbitrary shape and cured by heating to obtain various molded products having both heat resistance and toughness.
（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りのない限りす
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 by weight unless otherwise specified.
製造例１
４．４′−ジヒドロキシベンゾフェノン２１４ｇ（１モ
ル）をエピクロルヒドリン７４０ｇ（８モル）に溶解さ
せた後、撹拌下８０°Ｃで２０％Ｎ ａ ＯＨ水溶液４
４０ｇ（２，２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４９０ｇを加え均一に溶解させ、水１６０ｇ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、エポ
キシ当量が１８０なるエポキシ樹脂ｆａ）３１０ｇを得
た。Production Example 1 After dissolving 214 g (1 mol) of 4.4'-dihydroxybenzophenone in 740 g (8 mol) of epichlorohydrin, a 20% NaOH aqueous solution 4 was prepared at 80°C with stirring.
40 g (2.2 mol) was added dropwise over 5 hours, reacted for an additional hour, and then the aqueous layer was discarded. Excess epichlorohydrin was distilled and recovered. To the reaction product obtained, 490 g of toluene was added and the mixture was homogenized. After adding 160 g of water and washing with water, oil and water are separated, and water is removed from the oil layer by azeotropic distillation, filtered, and toluene is further distilled off to obtain 310 g of epoxy resin fa) with an epoxy equivalent of 180. I got it.
製造例２
エピクロルヒドリンの使用量を３２４ｇ（３，５モル）
に変更した以外は製造例１と同様にして、エポキシ当量
が１９７なるエポキシ樹脂（ｂｌ ３０５ｇを得た。Production example 2 The amount of epichlorohydrin used was 324 g (3.5 mol)
An epoxy resin (305 g of BL) having an epoxy equivalent of 197 was obtained in the same manner as in Production Example 1 except that the epoxy resin was changed to .
製造例３
４．４′−ジヒドロキシベンゾフェノン２１４ｇ（１モ
ル）をエピクロルヒドリン２３１ｇ（２，５モル）およ
びトルエン５４ｇの混合物に溶解させた後、撹拌下８０
℃”’ｉ’ ２０ ％ＮａＯＨ水溶液４４０ｇ（２，２
モル）を５時間かけて滴下し、更に１時間反応させ、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次いでトルエン４９０ｇを加
えて均一に溶解させ水１６０ｇ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、エポキシ当量が２０８
なるエポキシ樹脂（ｃ） ３００ ｇを得た。Production Example 3 214 g (1 mol) of 4.4'-dihydroxybenzophenone was dissolved in a mixture of 231 g (2.5 mol) of epichlorohydrin and 54 g of toluene, and then stirred for 80 min.
℃"'i' 440g of 20% NaOH aqueous solution (2,2
mol) was added dropwise over 5 hours, reacted for another 1 hour, discarded the aqueous layer, recovered the excess epichlorohydrin by distillation, and then 490 g of toluene was added to the reaction product obtained, which was uniformly dissolved and dissolved in 160 g of water. was added and washed with water, oil and water were separated, and water was removed from the oil layer by azeotropic distillation, followed by filtration, and toluene was distilled off to obtain an epoxy equivalent of 208
300 g of epoxy resin (c) was obtained.
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ｔａ）〜ｆｃ）、フェノールノボラック型エポキシ樹
脂エビクロンＮ−７３８（大日本インキ化学工業■製、
エポキシ当１１８０）又はビスフェノールＡ型エポキシ
樹脂エビクロン８４０（同社製、エポキシ当３１１８５
）、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￥ｙＪ）、硬化促進剤とし
て２−エチル−４−メチルイミダゾールを用い、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 include epoxy resins ta) to fc) obtained in Production Examples 1 to 3, phenol novolac type epoxy resin Evicron N-738 (manufactured by Dainippon Ink & Chemicals,
Epoxy 1180) or bisphenol A epoxy resin Ebicuron 840 (manufactured by the same company, epoxy 31185)
), Evicron B-570 (manufactured by the same company, methyltetrahydrophthalic anhydride ¥yJ) as a curing agent, and 2-ethyl-4-methylimidazole as a curing accelerator. Epoxy resin compositions for the present invention and for comparison were obtained by blending the compositions shown in Table 1 so that the number of acid anhydride groups was one.
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、ＪＩＳ Ｋ６９１１に準拠して
熱変形温度、曲げ強度、曲げ弾性率、引張り強度、引張
り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. The elastic modulus, tensile strength, tensile elongation and boiling absorption rate were measured. The results are shown in Table-1.
表
（発明の効果）
本発明のエポキシ樹脂組成物は従来のビスフェノールＡ
型エポキシ樹脂硬化物の靭性とノボラック型エポキシ樹
脂硬化物の耐熱性を併有する硬化物を与えることができ
る。しかも耐熱性に関してはノボラック型エポキシ樹脂
硬化物に比べて優れたものとなる。Table (Effects of the Invention) The epoxy resin composition of the present invention is similar to conventional bisphenol A.
It is possible to provide a cured product that has both the toughness of a type epoxy resin cured product and the heat resistance of a novolak type epoxy resin cured product. Moreover, in terms of heat resistance, it is superior to a novolac type epoxy resin cured product.
従って、本発明のエポキシ樹脂組成物は、樹脂封止電気
電子部品、プリプレグ、積層板、塗料、接着剤、構造材
料、成形材料、注型材料等各種の分野で利用できる。Therefore, the epoxy resin composition of the present invention can be used in various fields such as resin-sealed electrical and electronic parts, prepregs, laminates, paints, adhesives, structural materials, molding materials, and casting materials.
代理人 弁理士 高 橋 勝 利Agent Patent Attorney Katsutoshi Takahashi
Claims (1)
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、４、４′−ジヒドロキシベン
ゾフェノンと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エポキシ樹脂
組成物。 ２、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いて、該
エポキシ樹脂成分として一般式〔II〕で示されるエポキ
シ樹脂を含有することを特徴とするエポキシ樹脂組成物
。 ▲数式、化学式、表等があります▼〔II〕 〔ｎは０〜１０を表わす。〕 ３、請求項１記載の組成物を硬化せしめてなる成形品。 ４、請求項１記載の組成物を硬化せしめてなる積層板。 ５、請求項１記載の組成物で半導体を封止せしめてなる
部品。[Scope of Claims] 1. In an epoxy resin composition composed of an epoxy resin, a curing agent, and, if necessary, a curing accelerator, the epoxy resin component is obtained by reacting 4,4'-dihydroxybenzophenone with epichlorohydrin. An epoxy resin composition characterized by containing an epoxy resin. 2. An epoxy resin composition comprising an epoxy resin, a curing agent, and, if necessary, a curing accelerator, containing an epoxy resin represented by the general formula [II] as the epoxy resin component. thing. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] [n represents 0 to 10. 3. A molded article obtained by curing the composition according to claim 1. 4. A laminate obtained by curing the composition according to claim 1. 5. A component obtained by sealing a semiconductor with the composition according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1983489A JP2715512B2 (en) | 1989-01-31 | 1989-01-31 | Epoxy resin composition and molded article obtained by curing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1983489A JP2715512B2 (en) | 1989-01-31 | 1989-01-31 | Epoxy resin composition and molded article obtained by curing the same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1532596A Division JP2713281B2 (en) | 1996-01-31 | 1996-01-31 | Epoxy resin composition for semiconductor encapsulant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02202512A true JPH02202512A (en) | 1990-08-10 |
| JP2715512B2 JP2715512B2 (en) | 1998-02-18 |
Family
ID=12010311
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1983489A Expired - Lifetime JP2715512B2 (en) | 1989-01-31 | 1989-01-31 | Epoxy resin composition and molded article obtained by curing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2715512B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008184598A (en) * | 2007-01-31 | 2008-08-14 | Adeka Corp | Curable epoxy resin composition |
| WO2009123058A1 (en) * | 2008-03-31 | 2009-10-08 | 新日鐵化学株式会社 | Epoxy resin composition and molded object |
| JP2013155234A (en) * | 2012-01-27 | 2013-08-15 | Dic Corp | Epoxy resin, curable resin composition, cured material thereof, semiconductor sealing material, and semiconductor apparatus |
| JP2017179172A (en) * | 2016-03-31 | 2017-10-05 | 東洋インキＳｃホールディングス株式会社 | Novel alicyclic epoxy compound and curable composition |
| JP2021113293A (en) * | 2020-01-21 | 2021-08-05 | 日鉄ケミカル＆マテリアル株式会社 | Aromatic ketone-type polymer and method for producing the same, and resin composition and resin molding containing aromatic ketone-type polymer |
-
1989
- 1989-01-31 JP JP1983489A patent/JP2715512B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008184598A (en) * | 2007-01-31 | 2008-08-14 | Adeka Corp | Curable epoxy resin composition |
| WO2009123058A1 (en) * | 2008-03-31 | 2009-10-08 | 新日鐵化学株式会社 | Epoxy resin composition and molded object |
| JP5312447B2 (en) * | 2008-03-31 | 2013-10-09 | 新日鉄住金化学株式会社 | Epoxy resin composition and molded article |
| KR101507933B1 (en) * | 2008-03-31 | 2015-04-06 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Epoxy resin composition and molded object |
| TWI494341B (en) * | 2008-03-31 | 2015-08-01 | Nippon Steel & Sumikin Chem Co | Epoxy resin compositions and shaped articles |
| JP2013155234A (en) * | 2012-01-27 | 2013-08-15 | Dic Corp | Epoxy resin, curable resin composition, cured material thereof, semiconductor sealing material, and semiconductor apparatus |
| JP2017179172A (en) * | 2016-03-31 | 2017-10-05 | 東洋インキＳｃホールディングス株式会社 | Novel alicyclic epoxy compound and curable composition |
| JP2021113293A (en) * | 2020-01-21 | 2021-08-05 | 日鉄ケミカル＆マテリアル株式会社 | Aromatic ketone-type polymer and method for producing the same, and resin composition and resin molding containing aromatic ketone-type polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2715512B2 (en) | 1998-02-18 |
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