JPH03207746A - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JPH03207746A JPH03207746A JP270290A JP270290A JPH03207746A JP H03207746 A JPH03207746 A JP H03207746A JP 270290 A JP270290 A JP 270290A JP 270290 A JP270290 A JP 270290A JP H03207746 A JPH03207746 A JP H03207746A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- polyallylphenol
- weight
- copolymer
- parts
- 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 46
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 46
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 229920001577 copolymer Polymers 0.000 claims abstract description 17
- 239000004793 Polystyrene Substances 0.000 claims abstract description 14
- 229920002223 polystyrene Polymers 0.000 claims abstract description 14
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000005977 Ethylene Substances 0.000 claims abstract description 7
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 7
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 7
- 239000004711 α-olefin Substances 0.000 claims abstract description 7
- 229920001400 block copolymer Polymers 0.000 claims description 6
- 229920006027 ternary co-polymer Polymers 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 11
- 239000011256 inorganic filler Substances 0.000 abstract description 9
- 229910003475 inorganic filler Inorganic materials 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 8
- 239000007822 coupling agent Substances 0.000 abstract description 4
- 230000002209 hydrophobic effect Effects 0.000 abstract description 3
- 229920003986 novolac Polymers 0.000 abstract 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 abstract 2
- 229940106691 bisphenol a Drugs 0.000 abstract 1
- 238000004040 coloring Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 229920001897 terpolymer Polymers 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000843 powder Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 238000006243 chemical reaction 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
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229920006015 heat resistant resin Polymers 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- -1 glycidyl ester Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920002633 Kraton (polymer) Polymers 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 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 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- WBODDOZXDKQEFS-UHFFFAOYSA-N 1,2,3,4-tetramethyl-5-phenylbenzene Chemical group CC1=C(C)C(C)=CC(C=2C=CC=CC=2)=C1C WBODDOZXDKQEFS-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-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
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 1
- IQUPXPVVJHIBFQ-UHFFFAOYSA-N CCCCCCCCOP(O)OCCCCCCCC.CCCCCCCCOP(O)OCCCCCCCC Chemical compound CCCCCCCCOP(O)OCCCCCCCC.CCCCCCCCOP(O)OCCCCCCCC IQUPXPVVJHIBFQ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 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
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】 〔概 要〕 エポキシ樹脂組成物に関し。[Detailed description of the invention] 〔overview〕 Regarding epoxy resin compositions.
耐熱性、可とう性、耐クラツク性及び疎水性に優れたエ
ポキシ樹脂組成物を提供することを目的とし。The purpose of the present invention is to provide an epoxy resin composition with excellent heat resistance, flexibility, crack resistance, and hydrophobicity.
エポキシ樹脂100重量部に対して、下式(1)で表さ
れる構成単位を分子中に複数個有するポリアリルフェノ
ール30〜120重量部、及び、エチレン/α−オレフ
ィン共重合体、ポリスチレン/ポリブタジェン/ポリス
チレン末端ブロック共重合体、エチレン/プロピレン系
三成分共重合体からなる群から選ばれる共重合体5〜8
0重量部を含むようにエポキシ樹脂組成物を構成する。For 100 parts by weight of epoxy resin, 30 to 120 parts by weight of polyallylphenol having a plurality of structural units represented by the following formula (1) in the molecule, ethylene/α-olefin copolymer, polystyrene/polybutadiene Copolymers 5 to 8 selected from the group consisting of /polystyrene end block copolymer, ethylene/propylene ternary copolymer
The epoxy resin composition is configured to contain 0 parts by weight.
本発明はエポキシ樹脂組成物に関し、さらに詳しく述べ
ると、特に耐熱性、可とう性、耐クランク性及び疎水性
にすぐれたエポキシ樹脂組成物に関する0本発明のエポ
キシ樹脂組成物は上記したような優れた性質を有してい
るので、いろいろな分野において、特に多層積層用樹脂
、導電性ベースト電子素子保護膜、接着剤、vi料、封
止材料および成形材料の分野で有利に用いることができ
る。The present invention relates to an epoxy resin composition, and more specifically, relates to an epoxy resin composition that is particularly excellent in heat resistance, flexibility, crank resistance, and hydrophobicity.The epoxy resin composition of the present invention has the above-mentioned advantages. Because of its properties, it can be advantageously used in various fields, particularly in the fields of multilayer lamination resins, conductive base electronic device protective films, adhesives, VI materials, sealing materials, and molding materials.
近年1電子、電電機器、輸送機などの小型軽量化、高性
能化が進み、これに伴い耐熱性に優れた材料が望まれて
いる。BACKGROUND ART In recent years, electronics, electrical and electrical equipment, transportation equipment, etc. have become smaller, lighter, and more sophisticated, and along with this, materials with excellent heat resistance are desired.
耐熱性樹脂としてはポリイミド樹脂が一般に知られてい
るが、脱水縮合型であるために反応に伴い生じる縮合水
のために硬化物にボイドが発生しやすく、また硬化物の
信頼性を低下させる。一方ポリイミド自身は不溶、不融
となるために成形が困難である。Polyimide resin is generally known as a heat-resistant resin, but since it is a dehydration condensation type, voids are likely to occur in the cured product due to condensation water generated during the reaction, and the reliability of the cured product is reduced. On the other hand, polyimide itself is difficult to mold because it is insoluble and infusible.
成形加工性を改良したポリイミドとしてビスマーイミド
樹脂が公知であるが、成形には200℃以上の温度を必
要とし9作業性が悪い、さらに。Bismer imide resin is known as a polyimide with improved moldability, but it requires temperatures of 200°C or higher for molding, resulting in poor workability.
ビスマレイミド樹脂は疎水性に乏しく、硬化物の信頼性
を著しく低下させている。Bismaleimide resin has poor hydrophobicity, which significantly reduces the reliability of the cured product.
本発明の目的は、上記したような従来の技術の欠点を解
消すること、換言すると1種々の分野において有利に使
用することのできる。耐熱性、可とう性、耐クラツク性
及び疎水性に優れたエポキシ樹脂組成物を提供すること
にある。An object of the present invention is to eliminate the drawbacks of the conventional techniques as described above, in other words, the present invention can be advantageously used in various fields. An object of the present invention is to provide an epoxy resin composition having excellent heat resistance, flexibility, crack resistance, and hydrophobicity.
上記した目的は1本発明によれば、エポキシ樹脂100
重量部に対して、下式(1)で表される構成単位を分子
中に複数個有するポリアリルフェノール30〜120重
量部、及び、エチレン/α−オレフィン共重合体、ポリ
スチレン/ポリブタジェン/ポリスチレン末端ブロック
共重合体、エチレン/プロピレン系三成分共重合体から
なる群から選ばれる共重合体5〜80重量部を含むエポ
キシ樹脂組成物により達成される。According to the present invention, epoxy resin 100
Based on the weight part, 30 to 120 parts by weight of polyallylphenol having a plurality of structural units represented by the following formula (1) in the molecule, ethylene/α-olefin copolymer, polystyrene/polybutadiene/polystyrene terminal This is achieved by using an epoxy resin composition containing 5 to 80 parts by weight of a copolymer selected from the group consisting of block copolymers and ethylene/propylene ternary copolymers.
上記ポリアリルフェノールとして下式(2)で表される
ポリアリルフェノールを用いることができる。As the above-mentioned polyallylphenol, polyallylphenol represented by the following formula (2) can be used.
又、上記ポリアリルフェノールとして下式(3)で表さ
れるポリアリルフェノールを用いることができる。Further, as the above-mentioned polyallylphenol, polyallylphenol represented by the following formula (3) can be used.
本発明の組成物において基材樹脂として用いられるエポ
キシ樹脂は任意である。しがし1発明者らの知見によれ
ば、有利に使用しうるエポキシ樹脂の例として、ビスフ
ェノールA型エポキシ樹脂、タレゾールノボラック型エ
ポキシ樹脂、フェノールノボラック型エポキシ樹脂3テ
トラメチルビフエニル型エポキシ樹脂などのグリシジル
エーテル型エポキシIM脂、グリシジルエステル型エポ
キシ樹脂、グリシジルアミン型エポキシ樹脂、ハロゲン
化エポキシ樹脂など、−分子中にエポキシ基を2個以上
有するエポキシ樹脂を挙げることができる。これらのエ
ポキシ樹脂は単独で使用してもあるいは2種類以上の混
合系で使用してもよい。The epoxy resin used as the base resin in the composition of the present invention is arbitrary. According to the findings of the inventors, examples of epoxy resins that can be advantageously used include bisphenol A epoxy resin, Talezol novolac epoxy resin, and phenol novolak epoxy resin 3 Tetramethylbiphenyl epoxy resin Examples include epoxy resins having two or more epoxy groups in the molecule, such as glycidyl ether type epoxy IM resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, and halogenated epoxy resins. These epoxy resins may be used alone or in a mixture of two or more.
本発明の組成物において硬化剤として用いられるポリア
リルフェノールは前述のように上記(1)<2)(3)
式で表されるものが適用しうる。The polyallylphenol used as a curing agent in the composition of the present invention is as described above (1)<2)(3).
The expression expressed by the formula can be applied.
ポリアリルフェノールは暗褐色の粘稠体であり、温度8
0℃で25〜35P(ポイズ)程度の粘度を呈し無機質
充填材等の充填材を増量できる。Polyarylphenol is a dark brown viscous substance with a temperature of 8
It exhibits a viscosity of about 25 to 35 P (poise) at 0°C, and the amount of filler such as inorganic filler can be increased.
また、ポリアリルフェノールの当量(OH基−個あたり
の分子量)が135〜160程度のものを好ましく用い
得る。Further, polyallylphenol having an equivalent weight (molecular weight per OH group) of about 135 to 160 can be preferably used.
エポキシ樹脂と硬化剤として用いられるポリアリルフェ
ノール((R)、φ−0H)との硬化反応は下記の如(
進行する。Rはアリル基、φはベンゼン環である。
(触媒)(R)、φ−0−CH,−C
HR’ −−−→0−CH,−CHR’
H
−−→硬化
硬化剤としてポリアリルフェノールを用いることにより
、樹脂硬化物の耐熱性及び疎水性を向上できる。これは
、ポリアリルフェノールの持つアリル基による効果であ
る。ポリアリルフェノールの配合量はエポキシ樹脂10
0重量部に対して約30〜120重量部であることが好
ましい、ポリアリルフェノールの配合量が30重量部未
満では硬化反応が十分に進まず、120重量部を超える
と硬化物の耐熱性が劣化する。The curing reaction between epoxy resin and polyallylphenol ((R), φ-0H) used as a curing agent is as follows (
proceed. R is an allyl group, and φ is a benzene ring.
(Catalyst) (R), φ-0-CH, -C
HR' ---→0-CH, -CHR' H ---→ Curing By using polyallylphenol as a curing agent, the heat resistance and hydrophobicity of the cured resin product can be improved. This effect is due to the allyl group of polyallylphenol. The blending amount of polyallylphenol is 10% of the epoxy resin.
The amount of polyallylphenol is preferably about 30 to 120 parts by weight relative to 0 parts by weight. If the amount of polyallylphenol is less than 30 parts by weight, the curing reaction will not proceed sufficiently, and if it exceeds 120 parts by weight, the heat resistance of the cured product will deteriorate. to degrade.
本発明において基材樹脂としてのエポキシ樹脂に添加さ
れる共重合体は、特に耐クラツク性及び可とう性を同時
に改良するのに有効であることが判明した。なお、以下
単に「共重合体」と記載した場合にはこれらの共重合体
を指すこととする。It has been found that the copolymer added to the epoxy resin as the base resin in the present invention is particularly effective in simultaneously improving crack resistance and flexibility. Note that the term "copolymer" hereinafter refers to these copolymers.
本発明のエポキシ樹脂組成物において、共重合体は、い
ろいろな構造を有することができ、また実際、いろいろ
な形で市販されている。−例を示すと、エチレン/α−
オレフィン共重合体はタフマーP P−0280(三
井石油化学製)として、ポリスチレン/ポリブタジェン
/ポリスチレン末端ブロック共重合体はクレイトンG−
1652(シェル化学Iりとして、エチレン/プロピレ
ン系三成分共重合体はJSI157P(日本合成ゴム製
)としてそれぞれ入手可能である。これらの共重合体は
一般にゴム状共重合体である。In the epoxy resin composition of the present invention, the copolymer can have a variety of structures and is, in fact, commercially available in a variety of forms. -For example, ethylene/α-
The olefin copolymer is Tafmer P P-0280 (manufactured by Mitsui Petrochemical), and the polystyrene/polybutadiene/polystyrene terminal block copolymer is Kraton G-
The ethylene/propylene ternary copolymer is available as JSI157P (manufactured by Japan Synthetic Rubber Co., Ltd.).These copolymers are generally rubbery copolymers.
上記した共重合体は、その所望とする添加効果等に応じ
てエポキシ樹脂組成物中でいろいろな配合量で使用する
ことができる。この配合量は通常広く変更することがで
きるものの、−船釣にはエポキシ樹脂100重量部に対
して約5〜80重量部であるのが好ましい、これは以下
の実施例の項で詳説するように、5重量部未満では添加
の効果が現れず、80重量部を超えるとエポキシ樹脂の
耐熱性InAl1としての特性が劣化するからである。The above-mentioned copolymers can be used in various amounts in the epoxy resin composition depending on the desired effect of addition. Although this amount can usually vary widely, - for boat fishing, it is preferably about 5 to 80 parts by weight per 100 parts by weight of epoxy resin, as detailed in the Examples section below. On the other hand, if it is less than 5 parts by weight, the effect of addition will not be apparent, and if it exceeds 80 parts by weight, the properties of the epoxy resin as heat-resistant InAl1 will deteriorate.
本発明における組成物には必要に応じて以下の成分(1
)〜(5)等を添加することができる。The composition of the present invention may contain the following components (1) as necessary.
) to (5) etc. can be added.
(1)溶融シリカ、結晶シリカ、アルミナ、炭酸カルシ
ウムなどの粉末状の無機質充填材、無機質充填材の添加
量は組成物全体の30〜85wt%の範囲にあることが
好ましい、この理由は、無機質充基材の添加量が30w
t%より少ないと添加効果が小さく、85wt%より多
いと流れ性の低下から作業性が低下する可能性が生じる
からである。(1) Powdered inorganic fillers such as fused silica, crystalline silica, alumina, and calcium carbonate, and the amount of inorganic fillers added is preferably in the range of 30 to 85 wt% of the entire composition. The amount of added base material is 30w
This is because if it is less than t%, the effect of addition will be small, and if it is more than 85wt%, there is a possibility that workability will be lowered due to a decrease in flowability.
(2)エポキシ樹脂とポリアリルフェノールの硬化反応
を促進させるための硬化促進剤、硬化促進剤の添加量は
エポキシ樹脂100重量部に対して0゜2〜lO重量部
程度が好ましい、硬化促進剤としては2−メチルイミダ
ゾールなどのイミダゾール系、トリフェニルホスフィン
などのホスフィン系、DBUのフェノール塩などのDB
U (ジアザビシクロウンデセン)系などが用いられる
。(2) A curing accelerator for accelerating the curing reaction between the epoxy resin and polyallylphenol. The amount of the curing accelerator added is preferably about 0.2 to 10 parts by weight per 100 parts by weight of the epoxy resin. Examples include imidazole series such as 2-methylimidazole, phosphine series such as triphenylphosphine, and DB such as phenol salts of DBU.
U (diazabicycloundecene) type etc. are used.
(3)無機質充填材を添加する場合樹脂との相溶性を向
上させるためのカップリング剤0例えば3−アミノプロ
ピルトリエトキシシラン等のシラン系カップリング剤3
或いはテトラオクチルビス(ホスファイト)チタネート
等のチタン系カップリング剤等が用いられる。カップリ
ング剤の添加量は使用する無機質充填剤の種類、量、比
表面積およびカップリング剤の最小被覆面積にもよるが
1本発明においては、無機質充填材100重量部に対し
0.1〜15重量部が好ましい。(3) When adding an inorganic filler, there is no coupling agent used to improve compatibility with the resin. For example, a silane coupling agent such as 3-aminopropyltriethoxysilane 3
Alternatively, a titanium-based coupling agent such as tetraoctyl bis(phosphite) titanate may be used. The amount of the coupling agent added depends on the type, amount, specific surface area, and minimum coverage area of the inorganic filler used, but in the present invention, it is 0.1 to 15 parts by weight per 100 parts by weight of the inorganic filler. Parts by weight are preferred.
(4)離型荊としてカルナバワックス、ステアリン酸お
よびその金属塩、モンタンワックス等を、難燃剤として
臭素化エポキシ樹脂や、二酸化アンチモン等を、顔料と
してカーボンブラックなどを、添加するも差支えない。(4) Carnauba wax, stearic acid and its metal salts, montan wax, etc. may be added as release agents, brominated epoxy resins, antimony dioxide, etc. may be added as flame retardants, and carbon black, etc. may be added as pigments.
(5)着色側としては1例えば二酸化チタン、カーボン
ブラック等の顔料が用いられる。(5) For the colored side, pigments such as titanium dioxide and carbon black are used.
本発明のエポキシ樹脂組成物は、上記に列挙した成分を
、ロール、ニーダ−、エクストルーダー等の手段を用い
て約60〜80℃の温度で加熱することによって調製す
ることができる。また、本発明の樹脂組成物において、
それを成形加工した後のアフタキュアは、硬化物中の未
硬化エポキシ樹脂等の硬化反応を完結させるために、行
うことが望ましい、成形加工した後のアフタキュアは成
形加工時の温度と同程度の温度の恒温槽中所定時間熱処
理すればよい。The epoxy resin composition of the present invention can be prepared by heating the components listed above at a temperature of about 60 to 80°C using a means such as a roll, kneader, or extruder. Moreover, in the resin composition of the present invention,
After-curing after molding is preferably carried out in order to complete the curing reaction of the uncured epoxy resin in the cured product. After-curing after molding is carried out at a temperature similar to that during molding. Heat treatment may be performed for a predetermined period of time in a constant temperature bath.
本発明によるエポキシ樹脂組成物では、基材樹脂として
用いられるエポキシ樹脂に対して、硬化剤として用いら
れるポリアリルフェノールが硬化物の耐熱性及び疎水性
向上に有効に作用し、さらに共重合体が耐クラツク性改
良材として有効に作用する結果、耐熱性、可とう性及び
耐クラツク性の改善を実現することができる。In the epoxy resin composition according to the present invention, the polyallylphenol used as a curing agent effectively acts on the epoxy resin used as the base resin to improve the heat resistance and hydrophobicity of the cured product, and furthermore, the copolymer As a result of acting effectively as a crack resistance improving material, improvements in heat resistance, flexibility and crack resistance can be realized.
次いで4本発明を実施例及び比較例を参照し詳述する。 Next, the present invention will be described in detail with reference to Examples and Comparative Examples.
(実施例I) 実施例1〜9.比較例1〜4 本例では1次のような原材料を使用した。(Example I) Examples 1-9. Comparative examples 1 to 4 In this example, the following primary raw materials were used.
・エポキシ樹脂
クレゾールノボラシク型エポキシ樹脂 日本北東EOC
N−1025
・ポリアリルフェノール
上記(3)式で表されるポリアリルフェノール・共重合
体添加剤
タフマーP P−0280として入手可能な、三井石油
化学■のエチレン/α−オレフィン共重合体。・Epoxy resin cresol novolasic type epoxy resin Japan Northeast EOC
N-1025 - Polyallylphenol Polyallylphenol/copolymer additive represented by formula (3) above. Ethylene/α-olefin copolymer from Mitsui Petrochemicals, available as Tafmer P P-0280.
実施例および比較例に示される組成物は、これらの原材
料を下記の第1表に記載の量比で加圧双腕ニーダで約6
0〜80℃の温度で混練することにより目的の組成物を
調製した。The compositions shown in the Examples and Comparative Examples were prepared by mixing these raw materials in the amount ratios listed in Table 1 below in a pressurized double-arm kneader.
The desired composition was prepared by kneading at a temperature of 0 to 80°C.
また試験片の作製は以下のように行った。In addition, the test pieces were prepared as follows.
まず、混線により得られた組成物を8メツシユパスのパ
ウダーとし、このパウダーをプレス金型に移し、200
℃、80kg/dにて20分間圧縮成形したものをさら
に200℃8時間の条件でアフターキュアした。First, the composition obtained by mixing wire was made into powder with 8 mesh passes, this powder was transferred to a press mold, and 200
The material was compression molded at 80 kg/d for 20 minutes at 200° C. and after-cured for 8 hours at 200° C.
このようにして得られた組成物について、特性評価を以
下のごとく行った。Characteristics of the composition thus obtained were evaluated as follows.
・ガラス転移温度 熱機械分析装置(真空理工)に
て測定
・曲げ強度 JIS K6911による。・Glass transition temperature Measured using a thermomechanical analyzer (Shinku Riko) ・Bending strength According to JIS K6911.
・クランク 成形冷却後の試料(lQx5X
30ms)の断面を顕微鏡にて評価。・Crank sample after molding and cooling (lQx5X
30ms) section was evaluated using a microscope.
・吸水率 JIS K6911による;
煮沸吸収率。・Water absorption rate according to JIS K6911;
Boiling absorption rate.
本実施例1における実施例および比較例の結果を第1表
に示す、記載の結果、特に実施例1〜5及び比較例1.
2よりエチレン−αオレフィン共重合体を添加すること
により硬化物の靭性および可とう性が向上し、添加量は
5〜80重量部が良く、添加量が5重量部未満では添加
効果が現れず、80重量部を超えると耐熱性樹脂として
の特性が劣化することがわかる。The results of Examples and Comparative Examples in Example 1 are shown in Table 1, especially Examples 1 to 5 and Comparative Example 1.
From 2, adding the ethylene-α olefin copolymer improves the toughness and flexibility of the cured product, and the amount added is preferably 5 to 80 parts by weight, and the addition effect will not appear if the amount added is less than 5 parts by weight. , it can be seen that when the amount exceeds 80 parts by weight, the properties as a heat-resistant resin deteriorate.
実施例6〜9及び比較例3.4より硬化剤としてポリア
リルフェノールを用いることにより、疎水性に優れた樹
脂組成物を得ることができ、添加量は30〜120重量
部が良く、添加量が30重量部未満では硬化反応が充分
に進まず疎水性及び耐熱性特性の樹脂組成物が得られな
い、また、120重量部を超えると硬化物の耐熱性が劣
化することがわかる。From Examples 6 to 9 and Comparative Example 3.4, by using polyallylphenol as a curing agent, a resin composition with excellent hydrophobicity can be obtained, and the amount added is preferably 30 to 120 parts by weight. It can be seen that if the amount is less than 30 parts by weight, the curing reaction does not proceed sufficiently and a resin composition with hydrophobic and heat resistant properties cannot be obtained, and if it exceeds 120 parts by weight, the heat resistance of the cured product deteriorates.
(実施例■)
実施例10〜18.比較例5〜8
前記した実施例■(実施例1〜9、比較例1〜4)の手
法を繰り返した。但し、本例では、原材料の内、共重合
体添加剤としてクレイトンG−1652として入手可能
な、シェル化学−のポリスチレン/ポリブタジェン/ポ
リスチレン末端ブロック共重合体を使用した。得られた
組成物を前記した実施例■と同様にして特性評価したと
ころ、第2表に示すような結果が得られた。(Example ■) Examples 10 to 18. Comparative Examples 5 to 8 The method of Example 1 (Examples 1 to 9, Comparative Examples 1 to 4) described above was repeated. However, in this example, among the raw materials, a polystyrene/polybutadiene/polystyrene end block copolymer available from Shell Chemical, available as Kraton G-1652, was used as a copolymer additive. The properties of the resulting composition were evaluated in the same manner as in Example 2 above, and the results shown in Table 2 were obtained.
実施例10〜14及び比較例5.6よりポリスチレン/
ポリブタジェン/ポリスチレン末端ブロック共重合体を
添加することにより硬化物の靭性および可とう性が向上
し、添加量は5〜80重量部が良く、添加量が5重量部
未満では添加効果が現れず、80重量部を超えると耐熱
性樹脂としての特性が劣化することがわかる。実施例1
5〜18及び比較例7.8より硬化剤としてポリアリル
フェノールを用いることにより、疎水性に優れた樹脂組
成物を得ることができ、添加量は30〜120重量部が
良く、添加量が30重量部未満では硬化反応が充分に進
まず疎水性及び耐熱性特性の硬化物が得られず、また、
12−0重量部を超えると硬化物の耐熱性が劣化するこ
とがわかる。From Examples 10 to 14 and Comparative Example 5.6, polystyrene/
By adding the polybutadiene/polystyrene terminal block copolymer, the toughness and flexibility of the cured product are improved, and the addition amount is preferably 5 to 80 parts by weight, and if the addition amount is less than 5 parts by weight, the addition effect will not appear. It can be seen that when the amount exceeds 80 parts by weight, the properties as a heat-resistant resin deteriorate. Example 1
5 to 18 and Comparative Example 7.8, by using polyallylphenol as a curing agent, a resin composition with excellent hydrophobicity can be obtained, and the amount added is preferably 30 to 120 parts by weight; If it is less than 1 part by weight, the curing reaction will not proceed sufficiently and a cured product with hydrophobic and heat resistant properties will not be obtained.
It can be seen that when the amount exceeds 12-0 parts by weight, the heat resistance of the cured product deteriorates.
(実施例■)
実施例19〜27.比較例9〜12
前記した実施例1(実施例1〜9、比較例1〜4)の手
法を繰り返した。但し、本例では、原材料の内、共重合
体添加剤としてJSR57Pとして入手可能な2日本合
成ゴム−のエチレン/プロピレン系三成分共重合体を使
用した。得られた組成物を前記した実施例Iと同様にし
て特性評価したところ、第3表に示すような結果が得ら
れた。(Example ■) Examples 19 to 27. Comparative Examples 9-12 The method of Example 1 (Examples 1-9, Comparative Examples 1-4) described above was repeated. However, in this example, among the raw materials, an ethylene/propylene ternary copolymer manufactured by Nippon Synthetic Rubber, available as JSR57P, was used as a copolymer additive. The properties of the resulting composition were evaluated in the same manner as in Example I above, and the results shown in Table 3 were obtained.
実施例19〜23及び比較例9.10よりエチレン/プ
ロピレン系三成分共重合体を添加することにより硬化物
の靭性および可とう性が向上し。From Examples 19 to 23 and Comparative Examples 9 and 10, the addition of the ethylene/propylene ternary copolymer improved the toughness and flexibility of the cured product.
添加量は5〜80重量部が良く、添加量が5重量部未満
では添加効果が現れず、80重量部を超えると耐熱性樹
脂としての特性が劣化することがわかる。実施例24〜
27及び比較例11.12より硬化剤としてポリアリル
フェノールを用いることにより、疎水性に優れた樹脂組
成物を得ることができ、添加量は30〜120重量部が
良く、添加量が30重量部未満では硬化反応が充分に進
まず疎水性及び耐熱性特性に優れた硬化物が得られない
、また、120重量部を超えると硬化物の耐熱性が劣化
することがわかる。It can be seen that the amount added is preferably 5 to 80 parts by weight; if the amount added is less than 5 parts by weight, no effect of the addition is exhibited, and if it exceeds 80 parts by weight, the properties as a heat-resistant resin deteriorate. Example 24~
27 and Comparative Example 11.12, by using polyallylphenol as a curing agent, a resin composition with excellent hydrophobicity can be obtained, and the amount added is preferably 30 to 120 parts by weight, and the amount added is 30 parts by weight. It can be seen that if the amount is less than 120 parts by weight, the curing reaction will not proceed sufficiently and a cured product with excellent hydrophobicity and heat resistance properties cannot be obtained, and if it exceeds 120 parts by weight, the heat resistance of the cured product will deteriorate.
(実施例■)
実施例28〜32.比較例13
本例では、第1表の実施例2のエポキシ樹脂組成に無機
質充填材としてシリカ粉末(龍森■製RD−8)を組成
物全体に対して20〜90wt%添加することにより充
填材の添加効果を評価した。(Example ■) Examples 28 to 32. Comparative Example 13 In this example, the epoxy resin composition of Example 2 in Table 1 was filled by adding 20 to 90 wt% of silica powder (RD-8 manufactured by Tatsumori Corporation) as an inorganic filler to the entire composition. The effect of adding materials was evaluated.
実施例および比較例に示される組成物の原材料を第4表
に記載の量比で加圧双腕ニーダで80℃の温度で混練す
ることにより目的の組成物をlit!した。尚、無機質
充填材であるシリカ粉末の添加量はエポキシ樹脂組成物
全体に対するwt%で表した。試験片の作製は実施例1
と同様に行った。混線により得られた組成物を8メンシ
ユバスのパウダーとしこのパウダーをプレス金型に移し
、200°c、80kg/dにて20分間圧縮成形した
ものをさらに200℃8時間の条件でアフターキュアを
行い、大きさが1010X5X30の試験片を作製した
。得られた組成物の特性評価したところ、第4表に示す
結果が得られた。尚、溶融粘度は島原製作所製フローテ
スタで、所定混合比のエポキシ樹脂、ポリアリルフェノ
ール、エチレン/αオレフィン及びシリカ粉末の混合物
を加圧双腕ニーダで80°Cの温度で混線調製した組成
物について温度170 ’Cでの粘度を測定したもので
ある。By kneading the raw materials for the compositions shown in the Examples and Comparative Examples in the quantitative ratios listed in Table 4 in a pressurized double-arm kneader at a temperature of 80°C, the desired composition was prepared. did. The amount of silica powder, which is an inorganic filler, added was expressed in wt% with respect to the entire epoxy resin composition. Preparation of test piece is as per Example 1
I did the same thing. The composition obtained by mixing was made into an 8-mole bath powder, this powder was transferred to a press mold, compression molded at 200°C and 80kg/d for 20 minutes, and then after-cured at 200°C for 8 hours. A test piece with a size of 1010 x 5 x 30 was prepared. When the properties of the obtained composition were evaluated, the results shown in Table 4 were obtained. The melt viscosity was measured using a flow tester manufactured by Shimabara Seisakusho. A mixture of epoxy resin, polyallylphenol, ethylene/α-olefin, and silica powder at a predetermined mixing ratio was prepared using a pressurized double-arm kneader at a temperature of 80°C. The viscosity was measured at a temperature of 170'C.
記載の結果より、シリカ粉末の添加により曲げ強度が実
施例2の7 kg/@s”から9〜18kg/箇1に向
上する。シリカ粉末の添加量は実施例28〜31に示さ
れるように組成物全体の30〜85wt%程度であるこ
とが好ましい、シリカ粉末の添加量が20wt%の実施
例32は曲げ強度が9 kg/sn”で添加効果が小さ
い、シリカ粉末の添加量が90wt%の比較例13では
170℃での溶融粘度が1000P(ボイズ)と高粘度
であり流れ性の低下から作業性が低下する。From the results described, the bending strength is improved from 7 kg/@s'' in Example 2 to 9 to 18 kg/s by adding silica powder.The amount of silica powder added is as shown in Examples 28 to 31. Example 32 in which the amount of silica powder added is 20 wt%, which is preferably about 30 to 85 wt% of the total composition, has a bending strength of 9 kg/sn'' and the effect of addition is small, and the amount of silica powder added is 90 wt%. In Comparative Example 13, the melt viscosity at 170° C. was as high as 1000 P (voids), and workability was lowered due to lower flowability.
(実施例■)
前記した実施例Iの手法を繰り返した。但し、本例では
、原材料の内、ポリアリルフェノールとして上記(2)
式で表されるポリアリルフェノールを使用した。得られ
た組成物を前記した実施例Iと同様にして特性評価した
ところ実施例Iと同様の結果を得た。(Example ■) The procedure of Example I described above was repeated. However, in this example, among the raw materials, the above (2) as polyallylphenol was used.
Polyallylphenol represented by the formula was used. The properties of the obtained composition were evaluated in the same manner as in Example I described above, and the same results as in Example I were obtained.
本発明によれば、基材樹脂としてのエポキシ樹脂に対し
て、ポリアリルフェノールを硬化剤として用い、特定の
共重合体を添加することにより。According to the present invention, polyallylphenol is used as a curing agent and a specific copolymer is added to an epoxy resin as a base resin.
耐熱性、可とう性、耐クラック性、及び疎水性に優れた
樹脂組成物を得ることができる。A resin composition having excellent heat resistance, flexibility, crack resistance, and hydrophobicity can be obtained.
Claims (3)
で表される構成単位を分子中に複数個有するポリアリル
フェノール30〜120重量部、及び、エチレン/α−
オレフィン共重合体、ポリスチレン/ポリブタジエン/
ポリスチレン末端ブロック共重合体、エチレン/プロピ
レン系三成分共重合体からなる群から選ばれる共重合体
5〜80重量部を含む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▼・・・(1)(1) For 100 parts by weight of epoxy resin, the following formula (1)
30 to 120 parts by weight of polyallylphenol having a plurality of structural units represented by in the molecule, and ethylene/α-
Olefin copolymer, polystyrene/polybutadiene/
An epoxy resin composition comprising 5 to 80 parts by weight of a copolymer selected from the group consisting of a polystyrene end block copolymer and an ethylene/propylene ternary copolymer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1)
るポリアリルフェノールである請求項1記載のエポキシ
樹脂組成物。 ▲数式、化学式、表等があります▼・・・(2)(2) The epoxy resin composition according to claim 1, wherein the polyallylphenol is represented by the following formula (2). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(2)
るポリアリルフェノールである請求項1記載のエポキシ
樹脂組成物。(3) The epoxy resin composition according to claim 1, wherein the polyallylphenol is represented by the following formula (3).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP270290A JPH03207746A (en) | 1990-01-10 | 1990-01-10 | Epoxy resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP270290A JPH03207746A (en) | 1990-01-10 | 1990-01-10 | Epoxy resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH03207746A true JPH03207746A (en) | 1991-09-11 |
Family
ID=11536620
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP270290A Pending JPH03207746A (en) | 1990-01-10 | 1990-01-10 | Epoxy resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH03207746A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2020241594A1 (en) * | 2019-05-30 | 2020-12-03 |
-
1990
- 1990-01-10 JP JP270290A patent/JPH03207746A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2020241594A1 (en) * | 2019-05-30 | 2020-12-03 | ||
WO2020241594A1 (en) * | 2019-05-30 | 2020-12-03 | 京セラ株式会社 | Encapsulating resin composition and electronic component device |
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