JPH02117913A - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JPH02117913A JPH02117913A JP26814588A JP26814588A JPH02117913A JP H02117913 A JPH02117913 A JP H02117913A JP 26814588 A JP26814588 A JP 26814588A JP 26814588 A JP26814588 A JP 26814588A JP H02117913 A JPH02117913 A JP H02117913A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- formula
- curing agent
- resin composition
- represented
- 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 45
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 45
- 239000000203 mixture Substances 0.000 title claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 19
- 229920003986 novolac Polymers 0.000 abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 abstract description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 abstract 1
- 230000001588 bifunctional effect Effects 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- 230000009477 glass transition Effects 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 8
- 238000006243 chemical reaction Methods 0.000 description 6
- -1 acid anhydride compounds Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 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 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000000034 method Methods 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
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- QGMGHALXLXKCBD-UHFFFAOYSA-N 4-amino-n-(2-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1C(=O)NC1=CC=CC=C1N QGMGHALXLXKCBD-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241001342895 Chorus 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- HAORKNGNJCEJBX-UHFFFAOYSA-N cyprodinil Chemical compound N=1C(C)=CC(C2CC2)=NC=1NC1=CC=CC=C1 HAORKNGNJCEJBX-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
硬化物を与えるエポキシ樹脂組成物に係り、さらに詳し
くは、半導体封止用として、また、複合材料マトリック
スとして好適に用いられるエポキシ樹脂組成物に関する
。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an epoxy resin composition that provides a cured product, and more particularly to an epoxy resin composition that is suitably used for semiconductor encapsulation and as a composite material matrix.
［従来の技術］
エポキシ樹脂は、その優れた耐熱性、力学的強度、絶縁
性により、接着剤、塗料、積層材、電気絶縁材料等の産
業上広い分野に亘って使用されている。[Prior Art] Epoxy resins are used in a wide range of industrial fields such as adhesives, paints, laminated materials, and electrical insulation materials due to their excellent heat resistance, mechanical strength, and insulation properties.
近年、特に先端材料分野の進歩に伴い、より高性能なエ
ポキシ樹脂が求められている。例えば、航空宇宙産業に
使用される複合材マトリックス樹脂としてのエポキシ樹
脂には高靭性や高耐水性が強く求められており、また、
電子材料分野、例えば半導体封止用材料のペースエポキ
シ樹脂においても、半導体パッケージの大面積化や薄型
化に伴い、耐クラツク性が強く望まれている。In recent years, especially with advances in the field of advanced materials, higher performance epoxy resins have been required. For example, epoxy resins used as composite matrix resins used in the aerospace industry are strongly required to have high toughness and high water resistance.
In the field of electronic materials, for example, in pace epoxy resins used as semiconductor sealing materials, crack resistance is strongly desired as semiconductor packages become larger in area and thinner.
ところで、従来、この種のエポキシ樹脂としては、ビス
フェノールＡ型エポキシ樹脂ヤフェノールノボラック型
エポキシ樹脂をフェノールノボラック、酸無水物系化合
物、ポリアミン系化合物等で硬化させたものが知られて
いる（特開昭６３−２１８．７２５号公報等）。By the way, conventionally known epoxy resins of this type include those obtained by curing bisphenol A type epoxy resin and phenol novolac type epoxy resin with phenol novolac, acid anhydride compounds, polyamine compounds, etc. Publication No. 1983-218.725, etc.).
しかしながら、これらのエポキシ樹脂の硬化物は、その
いずれも靭性に欠けるものであり、特に架橋密度を高め
、耐熱性を高くしたものについてはこの靭性が著しく低
い。However, the cured products of these epoxy resins all lack toughness, and especially those with increased crosslink density and heat resistance have extremely low toughness.
［発明が解決しようとする問題点］
そこで、本発明者らは、エポキシ樹脂硬化物の耐熱性を
保ち、かつ、その靭性を改善すべく鋭意検討を重ねた結
果、高耐熱性を保持したまま、従来のエポキシ樹脂に比
へてはるかに高い靭性を示す硬化物を与えるエポキシ樹
脂組成物を見い出し、本発明に到達した。[Problems to be Solved by the Invention] Therefore, the present inventors have conducted intensive studies to maintain the heat resistance of cured epoxy resin products and improve their toughness. They have discovered an epoxy resin composition that provides a cured product with much higher toughness than conventional epoxy resins, and have arrived at the present invention.
［問題点を解決するための手段］
すなわち、本発明は、−絞入（１）
（但し、式中Ａ及び８は下記式（ａ）又は（ｂ）で表さ
れるものであってＡ／＝８であり、ｎは０．１〜１０の
有理数を示す）で表されるエポキシ樹脂及び硬化剤を配
合してなるエポキシ樹脂組成物である。[Means for Solving the Problems] That is, the present invention provides - Narrowing down (1) (wherein A and 8 are represented by the following formula (a) or (b), and A/ = 8, n is a rational number from 0.1 to 10) and a curing agent.
（但し、Ｒは水素又は低数アルキル基を承り）式（ｂ）
−ｏ−ｏ−ｘＱｏ−（ｂ）（但し、Ｘは２価の基を
示す）
本発明において、−絞入（１）で示される基本構造を有
するエポキシ樹脂において、Ａ及びＢは式（ａ）又は（
ｂ）で表されるものであるが、Ａ≠８であるので八が（
ａ）のとき８は式（ｂ）であり、八が式（ｂ）であると
きＢは式（ａ）である。そして、好ましくは前者の組合
わせである。(However, R can be hydrogen or a low alkyl group) Formula (b)
-o-o-xQo-(b) (where, ) or (
b), but since A≠8, eight is (
When a), 8 is the formula (b), and when 8 is the formula (b), B is the formula (a). The former combination is preferred.
式（ａ）において、置換基Ｒは炭素数１〜４のアルキル
基であるが、好ましくはメチル基である。In formula (a), the substituent R is an alkyl group having 1 to 4 carbon atoms, preferably a methyl group.
また、式（ｂ）において、Ｘは２価の基であるが、好ま
しくは−Ｃ１１２−１−Ｃ（ＣＨ３） ２−１る。Furthermore, in formula (b), X is a divalent group, preferably -C112-1-C(CH3)2-1.
一般式（１）において、ｎは平均の重合度を示すもので
あり、その値は０．１〜１０の範囲である。In general formula (1), n indicates the average degree of polymerization, and its value is in the range of 0.1 to 10.
ｎの値は、本発明に示す組成物の溶融粘度、軟化点に大
きく影響し、本発明のエポキシ樹脂組成物を適用しよう
とする目的や用途により適宜選択される。The value of n greatly influences the melt viscosity and softening point of the composition according to the present invention, and is appropriately selected depending on the purpose and use to which the epoxy resin composition of the present invention is to be applied.
本発明の一般式（１）で示されるエポキシ樹脂は例えば
次の方法で合成される。The epoxy resin represented by the general formula (1) of the present invention is synthesized, for example, by the following method.
すなわち、次式（２）
（但し、Ｒは水素原子又は炭素数１〜４のアルキル基を
示す）で表されるエポキシ化合物（２）と次式（３）
％式％（３）
で表されるビスフェノール化合物とを、モル比（（ａ）
／（ｂ） ） １ 、１ ＝ １１ （ＤＫｅ’ＪＩＪ
”’ＣａＣａ合唱反応６゜この際、反応を促進させるた
めに、アミン系化合物、イシダブール類、有機ボスフィ
ン類等を触媒として用いることかてぎる。反応温度とし
ては７０〜１６０’Ｃが適当であり、また、この反応の
際に適当な溶媒を用いてもよい。この溶媒としては、例
えばベンゼン、トルエン、キシレン等の炭化水素溶剤や
、メチルエチルケトン、メヂルイソブチルケ１〜ン等の
ケトン系溶剤等が好ましい。That is, an epoxy compound (2) represented by the following formula (2) (wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) and an epoxy compound (2) represented by the following formula (3) % formula % (3) bisphenol compound and the molar ratio ((a)
/(b) ) 1 , 1 = 11 (DKe'JIJ
``'CaCa Chorus Reaction 6゜ At this time, in order to accelerate the reaction, it is necessary to use amine compounds, isidabures, organic bosphines, etc. as catalysts. 70 to 160'C is suitable as the reaction temperature. In addition, an appropriate solvent may be used during this reaction. Examples of this solvent include hydrocarbon solvents such as benzene, toluene, and xylene, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. is preferred.
また、本発明で使用する硬化剤としては、多価フェノー
ル系、酸無水物系、アミン系等、一般にエポキシ樹脂の
硬化剤として使用されているものであればそのいずれも
使用可能である。そして、上記多価フェノール系硬化剤
としてはフェノールノボラック、ポリビニルフェノール
等を挙げることができ、また、酸無水物系硬化剤として
は無水フタル酸、デラヒトロ無水フタル酸、ヘキサヒド
ロ無水フタル酸、無水トリメリット酸、無水ペンゾフエ
ノンテ］〜ラカルボン酸等を挙げることができ、ざらに
、アミン系硬化剤としてはメヂレンジアニリン、ジアミ
ノジフェニルエーテル、ジアミノジフェニルスルホン等
を挙げることができる。Further, as the curing agent used in the present invention, any curing agent that is generally used as a curing agent for epoxy resins, such as polyhydric phenol type, acid anhydride type, and amine type, can be used. Examples of the polyhydric phenol curing agent include phenol novolak, polyvinylphenol, etc., and examples of the acid anhydride curing agent include phthalic anhydride, delahydrophthalic anhydride, hexahydrophthalic anhydride, and trimeritic anhydride. Examples of the curing agent include medilene dianiline, diaminodiphenyl ether, diaminodiphenyl sulfone, and the like.
上記エポキシ樹脂と硬化剤の配合比は、通常その官能基
のモル比が０．７〜１．３の範囲、好ましくは０．９〜
１．１となるように決定される。The blending ratio of the above-mentioned epoxy resin and curing agent is such that the molar ratio of their functional groups is usually in the range of 0.7 to 1.3, preferably 0.9 to 1.3.
1.1.
本発明のエポキシ樹脂組成物中には、必要に応じて、２
−メチルイミダゾール、２−エチル−４−メチルイミダ
ゾール、２−ウンデシルイミダゾール、２−ヘプタデシ
ルイミダゾール、２−フェニルイミダゾール等のイミダ
ゾール類、アミン類、トリノエニルホスフィンで代表さ
れる有機ボスフィン類等の硬化促進剤や、各種ワックス
、高級脂肪酸あるいはそのカルシウム塩等の滑剤や、シ
ランカップリング剤等の表面処理剤や、シリカ、アルミ
ナ、ガラス繊維、タルク等の無機充填剤等を配合するこ
ができる。In the epoxy resin composition of the present invention, 2
- Curing of imidazoles such as methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, and 2-phenylimidazole, amines, and organic bosphines represented by trinoenylphosphine, etc. Accelerators, various waxes, lubricants such as higher fatty acids or their calcium salts, surface treatment agents such as silane coupling agents, and inorganic fillers such as silica, alumina, glass fiber, and talc can be blended.
本発明のエポキシ樹脂組成物は、上記−絞入（１）で表
されるエポキシ樹脂と所定の硬化剤とを所定の割合で配
合し、ざらに必要に応じて添加される種々の添加剤を混
合し、ミキサー、ロール、ニーダ−等の手段で均一に混
合し混練することにより調製される。The epoxy resin composition of the present invention is prepared by blending the epoxy resin represented by the above-mentioned (1) with a predetermined curing agent in a predetermined ratio, and adding various additives as necessary to the coating. It is prepared by uniformly mixing and kneading using a mixer, roll, kneader, or other means.
［実施例］
以下、実施例及び比較例に基いて、本発明を具体的に説
明する。[Examples] The present invention will be specifically described below based on Examples and Comparative Examples.
実施例１
４．４゛−ジヒドロキン−３，３°、５，５°−テトラ
メチルビフェニルジグリシジルエーテル２４０９と９．
９−ビス（４−ヒドロキシフェニル）フルオレン５６ｇ
を１５０’Ｃで溶融混合し、ざらにトリノ■ニルホス７
イン１ ｇヲ）Ｊｔｌｔ、１５０’ＣＴ’３時間反応
さけてエポキシ樹脂を１９だ。このエポキシ樹脂ｌ脂の
エポキシ当量は３１７であり、軟化点は８２°Ｃであっ
た。Example 1 4.4'-dihydroquine-3,3',5,5'-tetramethylbiphenyl diglycidyl ether 2409 and 9.
9-bis(4-hydroxyphenyl)fluorene 56g
Melt and mix at 150'C, add trinonylphos 7
In 1 gwo) Jtlt, 150'CT'3 hours reaction, epoxy resin 19. The epoxy equivalent of this epoxy resin was 317, and the softening point was 82°C.
このようにして得られたエポキシ樹脂１００ｇ、フェノ
ールノボラック（フェノール当！１０４、軟化点７０℃
）３３ｇ及びトリフェニルホスフィン１゜３９を１００
℃で１４分間溶融混練し、微粉砕後１５０℃、４分間の
条件でトランフッ１−成形し試験片を調製し、この試験
片を使用してガラス転移点、破壊靭性及び吸水率を測定
した。結果を第１表に示す。100 g of the epoxy resin thus obtained, phenol novolak (phenol equivalent! 104, softening point 70°C)
)33g and triphenylphosphine 1°39 to 100g
The mixture was melt-kneaded at 150° C. for 14 minutes, pulverized, and then truncate-molded at 150° C. for 4 minutes to prepare a test piece. Using this test piece, the glass transition point, fracture toughness, and water absorption were measured. The results are shown in Table 1.
なお、ガラス転移点は熱機械分析装置を使用して７℃／
ｍｉｎの昇温速度で測定した。また、破壊靭性はジャー
ナル・オブ・マデリアル・ザイエンス第２１巻第２４６
２頁（１９８６）に記載された方法に準じて測定した。The glass transition point was measured using a thermomechanical analyzer at 7℃/
The temperature was measured at a temperature increase rate of min. In addition, fracture toughness is reported in Journal of Material Science, Vol. 21, No. 246.
It was measured according to the method described on page 2 (1986).
さらに、吸水率は１３３℃、３気圧の水蒸気中で１００
時間吸湿させて求めた。Furthermore, the water absorption rate is 100% in water vapor at 133°C and 3 atm.
It was determined by absorbing moisture for a period of time.
実施例２
４．４“−ジヒドロキシ−３，３°、５．５’−テトラ
メチルビフェニルジグリシジルエーテルを２４０９．９
゜９−ビス（４−ヒドロキシフェニル）フルオレンを７
５３とした以外は上記実施例１と同様に反応させ、エポ
キシ当Ｎ３８４及び軟化点１００℃のエポキシ樹脂を得
た。Example 2 4.4"-dihydroxy-3,3°,5.5'-tetramethylbiphenyl diglycidyl ether 2409.9
゜9-bis(4-hydroxyphenyl)fluorene 7
The reaction was carried out in the same manner as in Example 1 except that the epoxy resin was changed to 53 to obtain an epoxy resin having an epoxy weight of N384 and a softening point of 100°C.
ｊｑられたエポキシ樹脂１００９に対し、硬化剤として
フェノールノボラック（フェノール当量１０４、軟化点
７０℃）２７９を使用し、実施例］と同様に試験片を調
製してガラス転移点、破ｙＡ靭性及び吸水率を測定した
。結果を第１表に示す。Using phenol novolak (phenol equivalent: 104, softening point: 70°C) 279 as a curing agent for the epoxy resin 1009, test pieces were prepared in the same manner as in Example], and the glass transition point, fracture toughness, and water absorption were determined. The rate was measured. The results are shown in Table 1.
実施例３
９．９−ビス（４−ヒドロキシフェニル）フルオレンジ
グリシジルエーテル２４０ｇ、４，４°−ジヒドロキシ
ビフェニル３０ｙ及びトリノエニルホスフィン１．０ｇ
をメチルイソブチルケトン２０Ｏｄ中に溶解し、加熱還
流下に６時間反応させたのち、減圧下に溶媒を留去して
エポキシ樹脂を１ｑた。１ｑられたエポキシ樹脂のエポ
キシ当量は３７０であり、軟化点は１２３℃であった。Example 3 240 g of 9.9-bis(4-hydroxyphenyl)fluorenedi glycidyl ether, 30y of 4,4°-dihydroxybiphenyl and 1.0g of trinoenylphosphine
was dissolved in 20 Od of methyl isobutyl ketone and reacted under heating and reflux for 6 hours, and then the solvent was distilled off under reduced pressure to obtain 1 q of epoxy resin. The epoxy equivalent of the 1q epoxy resin was 370, and the softening point was 123°C.
このようにして得られたエポキシ樹脂１００ｇに対し、
硬化剤としてフェノールノボラック（フェノール当ω１
０４、軟化点７０℃）２８ｇを使用し、実施例１と同様
に試験片を調製してガラス転移点、破壊靭性及び吸水率
を測定した。結果を第１表に示す。For 100g of epoxy resin obtained in this way,
Phenol novolac (phenol equivalent ω1) is used as a curing agent.
04, softening point 70° C.), a test piece was prepared in the same manner as in Example 1, and the glass transition point, fracture toughness, and water absorption were measured. The results are shown in Table 1.
実施例４
ビスフェノールＡジグリシジルエーテル２４０Ｊ、４．
４″−ジヒドロキシビフェニル６０ｇ及びトリフェニル
ホスフィン１．Ｃ）ｇを使用し、上記実施例３と同様に
反応させてエポキシ樹脂を調製した。１ｑられたエポキ
シ樹脂のエポキシ当量は４７７であり、軟化点は７９℃
であった。Example 4 Bisphenol A diglycidyl ether 240J, 4.
Using 60 g of 4''-dihydroxybiphenyl and 1.C) g of triphenylphosphine, an epoxy resin was prepared by reacting in the same manner as in Example 3. The epoxy equivalent of the 1q epoxy resin was 477, and the softening point was is 79℃
Met.
このようにして得られたエポキシ樹脂１００７に対し、
硬化剤としてフェノールノボラック（フェノール当ｍ１
０４、軟化点７０℃）２２ｇを用いて上記実施例１と同
様に試験片を調製してガラス転移点、破壊靭性及び吸水
率を測定した。結果を第１表に示す。For the epoxy resin 1007 obtained in this way,
Phenol novolac (phenol/m1) as a curing agent
A test piece was prepared in the same manner as in Example 1 above using 22 g of 04, softening point 70°C), and the glass transition point, fracture toughness, and water absorption were measured. The results are shown in Table 1.
実施例５
４．４゛−ジヒドロキシ−３，３’、５．５’−テトラ
メチルビフェニルジグリシジルエーテル２４０ｇと４，
４゜−ジヒドロキシジフェニルスルホン１０７ｇとを実
施例３と同様に反応させ、エポキシ化ｆｆ１４０５及び
軟化点９０℃のエポキシ樹脂を調製した。Example 5 240 g of 4.4'-dihydroxy-3,3',5.5'-tetramethylbiphenyl diglycidyl ether and 4,
107 g of 4°-dihydroxydiphenyl sulfone was reacted in the same manner as in Example 3 to prepare epoxidized ff1405 and an epoxy resin having a softening point of 90°C.
このようにして１ｑられたエポキシ樹脂１００ｇに対し
、硬化剤としてフェノールノボラック（フェノール当量
１０４、軟化点７０℃）２６ｇ用いて実施例１と同様に
試験片を調製してガラス転移点、破壊靭性及び吸水率を
測定した。結果を第１表に示す。Test specimens were prepared in the same manner as in Example 1 using 26 g of phenol novolac (phenol equivalent: 104, softening point: 70°C) as a hardening agent for 100 g of the epoxy resin prepared in this manner. The water absorption rate was measured. The results are shown in Table 1.
比較例１
エポキシ樹脂としてビスフェノールＡジグリシジルエー
テルを使用し、硬化剤としてフェノールノボラック（軟
化点７０℃）を使用し、実施例１と同様に試験片を調製
してガラス転移点、破壊靭性及び吸水率を測定した。結
果を第１表に示す。Comparative Example 1 Using bisphenol A diglycidyl ether as the epoxy resin and using phenol novolak (softening point 70°C) as the hardening agent, test pieces were prepared in the same manner as in Example 1, and the glass transition point, fracture toughness, and water absorption were measured. The rate was measured. The results are shown in Table 1.
比較例２
エポキシン樹脂として叶タレゾールノ小ラックエポキシ
（軟化点８０°Ｃ）を使用し、硬化剤とじてフェノール
ノボラック（軟化点７０℃）を使用し、実施例１と同様
に試験片を調製してガラス転移点、破壊靭性及び吸水率
を測定した。結果を第１表に示す。Comparative Example 2 A test piece was prepared in the same manner as in Example 1, using Kotaresol Novolak epoxy (softening point 80°C) as the epoxy resin and phenol novolak (softening point 70°C) as the hardening agent. The glass transition point, fracture toughness and water absorption were measured. The results are shown in Table 1.
比較例３
エポキシン樹脂として４，４°−ジヒドロキシ−３゜３
’、５，５°−テトラメチルビフェニルジグリシジルエ
ーテルを使用し、硬化剤としてフェノールノボラック（
軟化点７０℃）を使用し、実施例１と同様に試験片を調
製してガラス転移点、破壊靭性及び吸水率を測定した。Comparative Example 3 4,4°-dihydroxy-3°3 as epoxy resin
', 5,5°-tetramethylbiphenyl diglycidyl ether and phenol novolak (
A test piece was prepared in the same manner as in Example 1, and the glass transition point, fracture toughness, and water absorption were measured.
結果を第１表に示す。The results are shown in Table 1.
第 １ 表
［発明の効果］
本発明のエポキシ樹脂組成物は、優れた耐熱性や耐水性
を有するだけでなく、高い靭性を有するエポキシ硬化物
を与えるものであり、産業上惨めで有用なものである。Table 1 [Effects of the Invention] The epoxy resin composition of the present invention not only has excellent heat resistance and water resistance, but also provides a cured epoxy product with high toughness, and is useful in industrial applications. It is.
Claims (3)
れるものであってＡ≠Ｂであり、ｎは０．１〜１０の有
理数を示す）で表されるエポキシ樹脂に硬化剤を配合し
てなるエポキシ樹脂組成物。 式（ａ）▲数式、化学式、表等があります▼（ａ） （但し、Ｒは水素又は低数アルキル基を示す）式（ｂ）
▲数式、化学式、表等があります▼（ｂ） （但し、Ｘは２価の基を示す）(1) General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) (However, in the formula, A and B are represented by the following formula (a) or (b), and A≠B An epoxy resin composition prepared by blending a curing agent into an epoxy resin represented by the following formula (where n is a rational number from 0.1 to 10). Formula (a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (a) (However, R represents hydrogen or a lower alkyl group) Formula (b)
▲There are mathematical formulas, chemical formulas, tables, etc.▼(b) (However, X indicates a divalent group)
ものであり、Ｂが式（ｂ）で表されるものである請求項
１記載のエポキシ樹脂組成物。(2) The epoxy resin composition according to claim 1, wherein in general formula (1), A is represented by formula (a) and B is represented by formula (b).
▲数式、化学式、表等があります▼である請求項１又は
２記載のエポキシ樹脂組成物。(3) The epoxy resin composition according to claim 1 or 2, wherein R in formula (a) is a methyl group, and X in formula (b) is ▲a numerical formula, a chemical formula, a table, etc. ▼.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26814588A JPH02117913A (en) | 1988-10-26 | 1988-10-26 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26814588A JPH02117913A (en) | 1988-10-26 | 1988-10-26 | Epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02117913A true JPH02117913A (en) | 1990-05-02 |
Family
ID=17454519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26814588A Pending JPH02117913A (en) | 1988-10-26 | 1988-10-26 | Epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02117913A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5710234A (en) * | 1993-07-20 | 1998-01-20 | Nippon Steel Chemical Co., Ltd. | Ortho spiroesters and curable and cured resin compositions of same |
| US5814373A (en) * | 1991-11-26 | 1998-09-29 | Dow Chemical Company | Heat-resistant hydroxy-functional polyethers as thermoplastic barrier resins |
| JP2010001379A (en) * | 2008-06-20 | 2010-01-07 | Nippon Kayaku Co Ltd | Epoxy resin, epoxy resin composition, and its cured product |
| US7999042B2 (en) * | 2004-06-25 | 2011-08-16 | Intel Corporation | Low coefficient of thermal expansion (CTE) thermosetting resins for integrated circuit applications |
-
1988
- 1988-10-26 JP JP26814588A patent/JPH02117913A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5814373A (en) * | 1991-11-26 | 1998-09-29 | Dow Chemical Company | Heat-resistant hydroxy-functional polyethers as thermoplastic barrier resins |
| US5710234A (en) * | 1993-07-20 | 1998-01-20 | Nippon Steel Chemical Co., Ltd. | Ortho spiroesters and curable and cured resin compositions of same |
| US7999042B2 (en) * | 2004-06-25 | 2011-08-16 | Intel Corporation | Low coefficient of thermal expansion (CTE) thermosetting resins for integrated circuit applications |
| US8242216B2 (en) | 2004-06-25 | 2012-08-14 | Intel Corporation | Low coefficient of thermal expansion (CTE) thermosetting resins for integrated circuit applications |
| US20120282462A1 (en) * | 2004-06-25 | 2012-11-08 | Matayabas Jr James C | Low coefficient of thermal expansion (cte) thermosetting resins for integrated circuit applications |
| US8431223B2 (en) * | 2004-06-25 | 2013-04-30 | Intel Corporation | Low coefficient of thermal expansion (CTE) thermosetting resins for integrated circuit applications |
| JP2010001379A (en) * | 2008-06-20 | 2010-01-07 | Nippon Kayaku Co Ltd | Epoxy resin, epoxy resin composition, and its cured product |
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