JPS63273624A - Epoxy resin composition - Google Patents
Epoxy resin compositionInfo
- Publication number
- JPS63273624A JPS63273624A JP10622287A JP10622287A JPS63273624A JP S63273624 A JPS63273624 A JP S63273624A JP 10622287 A JP10622287 A JP 10622287A JP 10622287 A JP10622287 A JP 10622287A JP S63273624 A JPS63273624 A JP S63273624A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin
- hydrogenated
- group
- functional group
- 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 51
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 51
- 239000000203 mixture Substances 0.000 title claims abstract description 14
- 125000000524 functional group Chemical group 0.000 claims abstract description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 8
- 229920001195 polyisoprene Polymers 0.000 claims abstract description 8
- 239000011256 inorganic filler Substances 0.000 claims abstract description 7
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 4
- 239000011630 iodine Substances 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 26
- 239000011347 resin Substances 0.000 abstract description 26
- 229920003986 novolac Polymers 0.000 abstract description 16
- 238000007789 sealing Methods 0.000 abstract description 12
- 239000004065 semiconductor Substances 0.000 abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 4
- 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 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- 229930003836 cresol Natural products 0.000 abstract description 3
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005350 fused silica glass Substances 0.000 abstract description 2
- -1 curing accelerator Substances 0.000 abstract 1
- 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 11
- 239000004593 Epoxy Substances 0.000 description 6
- 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 6
- 150000002989 phenols Chemical class 0.000 description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 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
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 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
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 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
- 239000010419 fine particle 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
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［発明の技術分野］
本発明は、優れた低応力性および耐熱性を有するエポキ
シ樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to an epoxy resin composition having excellent low stress properties and heat resistance.
［従来の技術およびその問題点］
一般に、電子部品のパッケージング方法は、大別して、
気密封止（ハーメチックシール）と樹脂封止（レジンシ
ール・プラスチックパッケージング）に分けられる。気
密封止は、主としてセラミック封止が使用され、信頼性
の面では優れているが、製造コストが高くつくので、民
生用あるいは低パワーのデバイスには、生産性、経済性
の面で優れている樹脂封止が用いられている。[Prior art and its problems] In general, packaging methods for electronic components can be broadly divided into:
It can be divided into hermetic sealing and resin sealing (resin seal/plastic packaging). Hermetic sealing is mainly used for ceramic sealing, which is excellent in terms of reliability, but the manufacturing cost is high, so it is not suitable for consumer or low-power devices in terms of productivity and economy. Resin sealing is used.
従来、樹脂封止には、主としてエポキシ樹脂やシリコン
樹脂が用いられてきたが、エポキシ樹脂の方が安価なた
め、封止用樹脂として多く用いられている０例えば、ト
ランスファー成形用の封止用樹脂としては、オルソクレ
ゾールノボラック型エポキシ樹脂とノボラック型フェノ
ール樹脂との硬化物が主流となってきている。Conventionally, epoxy resins and silicone resins have been mainly used for resin sealing, but epoxy resins are cheaper, so they are often used as sealing resins.For example, epoxy resins are often used as sealing resins for transfer molding. As resins, cured products of orthocresol novolac type epoxy resins and novolac type phenol resins have become mainstream.
電子部品の封止用樹脂としては、ＩＣ，ＬＳＩの採用に
よって、これらの機器の小型化、高性能化を図るために
、成形性、耐熱性９機械的強度。As a resin for sealing electronic parts, moldability, heat resistance, 9 mechanical strength, etc. are used to make these devices smaller and higher performance due to the adoption of ICs and LSIs.
電気絶縁性、誘電特性、耐湿性等に優れているものが求
められている。特に、樹脂封止の場合、半・導体チップ
、コネクタ線およびリード部と封止用樹脂とが直接接触
する界面に、樹脂と金属の接着界面が形成され、直接的
な相互作用をすることになる。そのため、封止用樹脂は
、半導体封止部品の動作特性や信頼性に直接影響を与え
る。There is a demand for materials with excellent electrical insulation, dielectric properties, moisture resistance, etc. In particular, in the case of resin encapsulation, an adhesive interface between the resin and metal is formed at the interface where the semiconductor/conductor chip, connector wire, and lead part are in direct contact with the encapsulating resin, resulting in direct interaction. Become. Therefore, the encapsulating resin directly affects the operating characteristics and reliability of the semiconductor encapsulating component.
例えば、封止用樹脂と金属との熱膨張係数の違いによっ
てデバイスにストレスがかかり、故障の原因となったり
、封止用樹脂とリード線との接着不足や封止用樹脂の透
湿性のため、配線間の電流のリークや金属材料の腐食の
原因となっている。For example, the difference in thermal expansion coefficient between the encapsulating resin and the metal may put stress on the device and cause it to malfunction, or insufficient adhesion between the encapsulating resin and lead wires, or the moisture permeability of the encapsulating resin. , causing current leakage between wiring and corrosion of metal materials.
更に、最近の半導体素子は益々高集積化が進行しており
、これに応じて封止用樹脂には、樹脂封止されたデバイ
スの特性低下を防止するために、低弾性率である、熱膨
張係数が小さく、熱衝撃によってクラックを発生しない
、リード線との接着が良好である、水蒸気透過性が小さ
い、＃熱性が良好である、及び不純物を含まない等の特
性が必要となってきている。Furthermore, recent semiconductor devices are becoming more and more highly integrated, and in response to this trend, encapsulating resins are made with low elastic modulus and thermal Characteristics such as a low coefficient of expansion, no cracking due to thermal shock, good adhesion to lead wires, low water vapor permeability, good thermal properties, and no impurities have become necessary. There is.
［問題点を解決するための手段］
本発明は、優れた低応力性を示し、かつガラス転移温度
を低下させることなく、また耐熱性にも優れており、半
導体装置やその他の電子回路部品の封止用樹脂として使
用されるエポキシ樹脂組成物を提供することにある。[Means for Solving the Problems] The present invention exhibits excellent low stress properties, does not lower the glass transition temperature, and has excellent heat resistance, and is suitable for semiconductor devices and other electronic circuit components. An object of the present invention is to provide an epoxy resin composition used as a sealing resin.
上記目的を達成すべく鋭意検討した結果、ａ）多官能エ
ポキシ樹脂
ｂ）エポキシ樹脂の硬化剤
Ｃ）硬化促進剤
ｄ）無機質充填剤
ｅ）末端に官能基を有するポリイソプレンの水添物また
は、末端に官能基を有するイソプレン／スチレン共重合
体の水添物
からなることを特徴とするエポキシ樹脂組成物を見い出
すに至った。As a result of intensive studies to achieve the above objectives, we found that a) polyfunctional epoxy resin b) curing agent for epoxy resin C) curing accelerator d) inorganic filler e) hydrogenated polyisoprene having a functional group at the end, or An epoxy resin composition characterized by being composed of a hydrogenated isoprene/styrene copolymer having a functional group at its terminal has been discovered.
本発明に使用される、
ａ）多官能エポキシ樹脂としては、特に限定されず、通
常知られている多官能エポキシ化合物、例えば、ノボラ
ック型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂
、脂環式エポキシ樹脂、−グリシジルエステル系エポキ
シ樹脂、線状、脂肪族エポキシ樹脂等が挙げられる。上
記エポキシ樹脂は、単独で用いても良く、また２種以上
の混合系にして用いても良い、上記エポキシ樹脂の中で
も電気特性、耐熱性等の面からノボラック型エポキシ樹
脂が好ましい、ノボラック型エポキシ樹脂としては、ク
レゾールノボラック型エポキシ樹脂およびフェノールノ
ボラック型エポキシ樹脂を挙げることができる。The a) polyfunctional epoxy resin used in the present invention is not particularly limited, and includes commonly known polyfunctional epoxy compounds such as novolak epoxy resins, bisphenol A epoxy resins, alicyclic epoxy resins, -Glycidyl ester type epoxy resins, linear and aliphatic epoxy resins, etc. can be mentioned. The above-mentioned epoxy resins may be used alone or in a mixture of two or more types. Among the above-mentioned epoxy resins, novolac-type epoxy resins are preferable from the viewpoint of electrical properties, heat resistance, etc. Examples of the resin include cresol novolac type epoxy resin and phenol novolac type epoxy resin.
ｂ）エポキシ樹脂の硬化剤としては、例えば、フェノー
ル樹脂や多価フェノール化合物、Ｓ無水物類、アミン類
、ポリサルファイド樹脂等が挙げられる。具体的には、
フェノール樹脂や多価フェノール化合物の例としては、
フェノールノボラック樹脂、クレゾールノボラック樹脂
等のノボラック型樹脂、またレゾール型フェノール樹脂
、ビスフェ／−ルＡ等が挙げられる。また、酸無水物類
の例としては、無水フタル酸、無水ピロメリット酸、テ
トラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸等
が挙げられる。また、アミン類の例としては、ジエチル
アミノプロビルアミン、Ｎ−アミノエチルピペラジン、
ｍ−キシレンジアミン等が挙げられる。これらの硬化剤
は、単独で用いても良く、また２種以上併用しても良い
、上記の硬化剤のうちノボラック型樹脂が最も好ましい
。b) Examples of curing agents for epoxy resins include phenol resins, polyhydric phenol compounds, S anhydrides, amines, and polysulfide resins. in particular,
Examples of phenolic resins and polyhydric phenol compounds include:
Novolac type resins such as phenol novolac resin and cresol novolac resin, resol type phenol resin, bispher/-A, etc. can be mentioned. Further, examples of acid anhydrides include phthalic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and the like. Examples of amines include diethylaminopropylamine, N-aminoethylpiperazine,
Examples include m-xylene diamine. These curing agents may be used alone or in combination of two or more types. Among the curing agents mentioned above, novolak type resins are most preferred.
上記硬化剤の量は、前記エポキシ樹脂を硬化させうるに
十分な量であれば良く、硬化剤の種類によっても異なる
が、前記エポキシ樹脂の１エポキシ当量当たり、通常０
．４〜２．０当量、好ましくは０．６〜１．５当量であ
る。具体的には、前記エポキシ樹脂Ｍ脂の１エポキシ当
量に対して、ノボラック型樹脂を用いる場合には、通常
０．５〜２．０当量、好ましくは０．８〜１．５出量、
敢無水物類を用いる場合には、通常０．４〜１．２当量
、好ましくは０．６〜１．０当量、アミン類を用いる場
合には、通常０．５〜２．０当量、好ましくは０．８〜
１．５当量とされる。The amount of the curing agent is sufficient as long as it is sufficient to cure the epoxy resin, and although it varies depending on the type of curing agent, it is usually 0 per 1 epoxy equivalent of the epoxy resin.
．． 4 to 2.0 equivalents, preferably 0.6 to 1.5 equivalents. Specifically, when using a novolak type resin, it is usually 0.5 to 2.0 equivalent, preferably 0.8 to 1.5 equivalent, per 1 epoxy equivalent of the epoxy resin M resin.
When using anhydrides, it is usually 0.4 to 1.2 equivalents, preferably 0.6 to 1.0 equivalents, and when amines are used, it is usually 0.5 to 2.0 equivalents, preferably is 0.8~
It is assumed to be 1.5 equivalents.
Ｃ）硬化促進剤としては、２−エチル−４−メチルイミ
ダゾール、２−メチルイミダゾール。C) As a curing accelerator, 2-ethyl-4-methylimidazole, 2-methylimidazole.
２−フェニルイミダゾール、２−ウンデシルイミダゾー
ル等のイミダゾール類、２−（ジメチルアミノメチル）
フェノール、 ２，４．８−トリス（ジメチルアミノ
メチル）フェノール、ベンジルジメチルアミン等の第３
級アミン、トリフェニルホスフィン、トリブチルホスフ
ィン、メチルジフェニルホスフィン、トリシクロヘキシ
ルホスフィン等の有機ホスフィン類、 １．８−ジアザ
ビシクロ（５，４，０）ウンデセン−７，１，８−ジア
ザビシクロ（７，２，０）ウンデセン−８，１，８−ジ
アザビシクロ（７，５，０）テトラデセン−８，１，５
−ジアザビシクロ（４，３，０）ノネン−５，１，５−
ジアザビシクロ（４，２，０）オクテン−５等のジアザ
ビシクロアルケン類、またはこれらのフェノール塩、ギ
醜塩、アジピン猷塩等が挙げられる。これらの群より選
ばれた１種または２種以上のものが使用される。Imidazoles such as 2-phenylimidazole and 2-undecylimidazole, 2-(dimethylaminomethyl)
phenol, 2,4.8-tris(dimethylaminomethyl)phenol, benzyldimethylamine, etc.
organic phosphines such as triphenylphosphine, tributylphosphine, methyldiphenylphosphine, tricyclohexylphosphine, 1,8-diazabicyclo(5,4,0)undecene-7,1,8-diazabicyclo(7,2,0) ) undecene-8,1,8-diazabicyclo(7,5,0)tetradecene-8,1,5
-diazabicyclo(4,3,0)nonene-5,1,5-
Examples include diazabicycloalkenes such as diazabicyclo(4,2,0)octene-5, phenol salts thereof, adipine salts, adipine salts, and the like. One or more types selected from these groups are used.
ｄ）無機質充填剤としては、溶融シリカ、結晶性シリカ
、酸化マグネシウム、アルミナ、炭酸カルシウム等が挙
げられる。d) Examples of inorganic fillers include fused silica, crystalline silica, magnesium oxide, alumina, and calcium carbonate.
無機質充填剤の添加量は全組成物に対して６０〜８５重
量％が望ましく、８５重量％以上になると組成物の流動
性が低く、成形性が悪くなる。また６０重量％以下では
線膨張率が大きくなるなどの問題が生じる。したがって
、無機質充填剤の種類により異なるが、６０〜８５重量
％の範囲で適宜配合される。The amount of the inorganic filler added is preferably 60 to 85% by weight based on the total composition, and if it exceeds 85% by weight, the fluidity of the composition will be low and the moldability will be poor. Moreover, if it is less than 60% by weight, problems such as an increase in linear expansion coefficient occur. Therefore, although it varies depending on the type of inorganic filler, it is appropriately blended in the range of 60 to 85% by weight.
ｅ）末端に官能基を有するポリイソプレンの水添物また
は、末端に官能基を有するイソプレン／スチレン共重合
体の水添物としては、耐熱性を得るためにヨウ素価は１
２０以下であることが好ましく、更に好ましくは８０以
下である。e) The hydrogenated product of polyisoprene having a functional group at the end or the hydrogenated product of isoprene/styrene copolymer having a functional group at the end has an iodine value of 1 in order to obtain heat resistance.
It is preferably 20 or less, more preferably 80 or less.
また、ゴム粒子を微細粒子状に均一にエポキシ樹脂マト
リックス中に分散させるために分子量は１，０００〜５
０．０００、好ましくは１．５００〜１０，０００であ
る。スチレン含量は、エポキシ樹脂マトリックス中に粒
子として分散したときにこの粒子がゴム弾性を失なわな
い範囲である必要があり、３０モル％以下、好ましくは
２５モル％以下である。更には、末端に有する官能基は
カルボキシル基、エポキシ基、水酸基。In addition, in order to uniformly disperse the rubber particles in the epoxy resin matrix in the form of fine particles, the molecular weight is 1,000 to 5.
0.000, preferably 1.500 to 10,000. The styrene content must be within a range such that the particles do not lose their rubber elasticity when dispersed as particles in the epoxy resin matrix, and is 30 mol% or less, preferably 25 mol% or less. Furthermore, the functional groups at the ends are carboxyl, epoxy, and hydroxyl groups.
アミノ基、チオール基およびビニル基等であることが好
ましい。Preferred are amino groups, thiol groups, vinyl groups, and the like.
末端に官能基を有するポリイソプレンの水添物または、
末端に官能基を有するイソプレン／スチレン共重合体の
水添物の添加方法としては、特に制限はないが、エポキ
シ樹脂および／または、エポキシ樹脂の硬化剤に適量を
加え、溶融混合物とする方法、官能基がカルボキシル基
、アミノ基の場合は、エポキシ樹脂に添加し、反応物と
する方法、官能基がエポキシ基の場合は、エポキシ樹脂
の硬化剤に添加し、反応物とする方法、または、すべて
の配合成分を同時に混合する方法等が挙げられる。Hydrogenated polyisoprene having a functional group at the end, or
There are no particular limitations on the method of adding the hydrogenated isoprene/styrene copolymer having a functional group at the end, but a method of adding an appropriate amount to an epoxy resin and/or a curing agent for the epoxy resin to form a molten mixture; When the functional group is a carboxyl group or an amino group, it is added to an epoxy resin and used as a reactant; when the functional group is an epoxy group, it is added to an epoxy resin curing agent and used as a reactant, or Examples include a method of mixing all the ingredients at the same time.
また上記重合体の添加量は、（全エポキシ樹脂＋エポキ
シ樹脂の硬化剤）１００重量部に対して３〜５０重量部
、好ましくは５〜４０重量部であ″る。すなわち３１ｉ
量部以下では応力の低下が少なく、５０重量部以上では
流動性が低下したり、成形体の機械的強度が低下する等
の弊害がある。The amount of the polymer added is 3 to 50 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of (total epoxy resin + epoxy resin curing agent).
If the amount is less than 50 parts by weight, the stress decreases little, and if it is more than 50 parts by weight, there are disadvantages such as a decrease in fluidity and a decrease in the mechanical strength of the molded product.
本発明においてはｔａ）〜ｅ）のほかに、必要に応じて
天然ワックス、合成ワックス、高級脂肪酸およびその金
属塩などの離型剤、シラン系カップリング剤やチタン系
カップリング剤などのカップリング剤、カーボンのよう
な着色剤、さらに臭素化フェノールノボ′ラック型エポ
キシ樹脂、臭素化ビスフェノールＡ型エポキシ樹脂など
の難燃剤、三酸化アンチモン、五酸化アンチモンなどの
難燃助剤を添加することもできる。In the present invention, in addition to ta) to e), coupling agents such as natural waxes, synthetic waxes, mold release agents such as higher fatty acids and metal salts thereof, silane coupling agents and titanium coupling agents may be used as necessary. In addition, flame retardants such as brominated phenol novolac epoxy resins, brominated bisphenol A epoxy resins, and flame retardant aids such as antimony trioxide and antimony pentoxide may also be added. can.
また本発明においては、成分ａ）〜ｅ）およびその他の
成分を配合し、ヘンシェルミキサーなどで混合して、ロ
ール、ニーダ−等により７０〜１１０℃で混練すること
により、目的とする優れた特性の成形材料を得ることが
できる。In addition, in the present invention, components a) to e) and other components are blended, mixed with a Henschel mixer, etc., and kneaded at 70 to 110°C with a roll, kneader, etc., to achieve the desired excellent properties. molding material can be obtained.
［発明の効果］
本発明のエポキシ樹脂組成物は、優れた低応力性を示し
、かつガラス転移温度を低下させることなく、また耐熱
性″にも優れており、半導体装置やその他の電子回路部
品の封止用樹脂として良好に使用される。[Effects of the Invention] The epoxy resin composition of the present invention exhibits excellent low stress properties, does not lower the glass transition temperature, and has excellent heat resistance, and can be used in semiconductor devices and other electronic circuit parts. It is well used as a sealing resin.
［発明の実施例］
以下に実施例および比較例に使用する材料を、また配合
量（重量部）を第１表に示す。[Examples of the Invention] Table 1 below shows the materials used in the Examples and Comparative Examples and the blended amounts (parts by weight).
（１）エポキシ樹脂
（Ｉ）オルソクレゾールノボラック型エポキシ樹脂（エ
ポキシ当量１９７．軟化点７３℃）（■）臭素化フェノ
ールノボラック型エポキシ樹脂（エポキシ当量２７５．
軟化点８４℃）（２）エポキシ樹脂の硬化剤
フェノールノボラック樹脂（水酸基当量１０８、軟化点
９６℃）
（３）低応力化剤
（Ｉ）両末端カルボキシル基イソプレン−スチレン共重
合体水添物（以下ＨＣＴＩＳと略記する）（カルボキシ
ル基当量２４００、スチレン含量１７．０モル％、分子
量５１００．粘度２．２００Ｆ、ヨウ素価３２）
（ＩＩ ）両末端カルボキシル基ブタジェン−アクリロ
ニトリル（以下ＣＴＢＮと略記する）（カルボキシル基
当量１９００．アクリロニトリル含量１７．０モル％、
分子量３９９０、粘度１０５０Ｆ）
（４）硬化促進剤
トリフェニルホスフィン
（５）充填剤
溶融シリカ
（８）ＩＩ型剤
カルナバワックス
（７）カップリング剤
γ−グリシドキシプロビルトリメトキシシラン（８）難
燃助剤
三酸化アンチモン
（９） 、ｉｉ−色剤
カーボンブラック
［ＨＣＴｒＳ変性エポキシ樹脂の合成］攪拌機付きの４
つロフラスコに、第１表に示した所定量のＨＣＴＩＳと
エポキシ樹脂およびトリフェニルホスフィンを加え、窒
素気流中１４０℃で攪拌しながら３時間反応させて、Ｈ
ＣＴＩＳ変性エポキシ樹脂を得た。(1) Epoxy resin (I) Orthocresol novolac type epoxy resin (epoxy equivalent: 197. Softening point: 73°C) (■) Brominated phenol novolac type epoxy resin (epoxy equivalent: 275.
Softening point: 84°C) (2) Epoxy resin curing agent Phenol novolac resin (hydroxyl equivalent: 108, softening point: 96°C) (3) Stress reducing agent (I) Hydrogenated isoprene-styrene copolymer with carboxyl groups at both terminals ( (hereinafter abbreviated as HCTIS) (carboxyl group equivalent 2400, styrene content 17.0 mol%, molecular weight 5100, viscosity 2.200F, iodine value 32) (II) Both terminal carboxyl groups butadiene-acrylonitrile (hereinafter abbreviated as CTBN) ( Carboxyl group equivalent: 1900. Acrylonitrile content: 17.0 mol%.
Molecular weight: 3990, viscosity: 1050 F Combustion aid antimony trioxide (9), ii-Coloring agent carbon black [Synthesis of HCTrS modified epoxy resin] 4 with a stirrer
A predetermined amount of HCTIS shown in Table 1, an epoxy resin, and triphenylphosphine were added to a two-glass flask, and the mixture was reacted with stirring at 140°C in a nitrogen stream for 3 hours.
A CTIS modified epoxy resin was obtained.
［ＣＴＢＮ変性エポキシ樹脂の合成］
上記と同様の操作で、トリフェニルホスフィンを硬化促
進剤として、ＣＴＢＮとエポキシ樹脂を反応させ、ＣＴ
ＢＮ変性エポキシ樹脂を得た。[Synthesis of CTBN-modified epoxy resin] In the same manner as above, CTBN and epoxy resin are reacted using triphenylphosphine as a curing accelerator.
A BN-modified epoxy resin was obtained.
第１表
実施例１．２および比較例１．２
第２表に示す材料を混合し、加熱ロールにより混線、冷
却後粉砕してエポキシ樹脂成形材料を調整した。これら
の成形材料を、１７５℃×３分の成形条件で試験片を作
成し、１７５℃×６時間後硬化をした後、諸物件を評価
した。この結果を第３表に示した。Table 1 Example 1.2 and Comparative Example 1.2 The materials shown in Table 2 were mixed, mixed with a heating roll, cooled and crushed to prepare an epoxy resin molding material. Test pieces were prepared from these molding materials under molding conditions of 175° C. for 3 minutes, and after curing at 175° C. for 6 hours, various objects were evaluated. The results are shown in Table 3.
（以下余白） − 第２表 ｗＩＪ３表 ※ＩＪＩＳ Ｋ６９１１にて測定した。(Margin below) − Table 2 wIJ3 table *Measured using IJIS K6911.
※２ ＴＭＡ法蜆碇した。*2 TMA law was established.
※３内部応力の目安として示した。*3 Indicated as a guideline for internal stress.
Claims (3)
は、末端に官能基を有するイソプレン／スチレン共重合
体の水添物からなることを特徴とするエポキシ樹脂組成
物。(1) a) Multifunctional epoxy resin b) Curing agent for epoxy resin c) Curing accelerator d) Inorganic filler e) Hydrogenated product of polyisoprene having a functional group at the end or isoprene having a functional group at the end/ An epoxy resin composition comprising a hydrogenated styrene copolymer.
たは、末端に官能基を有するイソプレン／スチレン共重
合体の水添物が、ヨウ素価が１２０以下、分子量が１，
０００〜５０，０００、スチレン含量が３０モル％以下
である特許請求の範囲第１項記載のエポキシ樹脂組成物
。(2) Hydrogenated polyisoprene having a functional group at the end or hydrogenated isoprene/styrene copolymer having a functional group at the end has an iodine value of 120 or less, a molecular weight of 1,
000 to 50,000, and the styrene content is 30 mol% or less.
たは、末端に官能基を有するイソプレン／スチレン共重
合体の水添物が、末端にカルボキシル基、エポキシ基、
水酸基、アミノ基、チオール基、およびビニル基のいず
れかを有する特許請求の範囲第１項記載のエポキシ樹脂
組成物。(3) Hydrogenated polyisoprene having a functional group at the end or hydrogenated isoprene/styrene copolymer having a functional group at the end has a carboxyl group, an epoxy group at the end,
The epoxy resin composition according to claim 1, which has any one of a hydroxyl group, an amino group, a thiol group, and a vinyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10622287A JPS63273624A (en) | 1987-05-01 | 1987-05-01 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10622287A JPS63273624A (en) | 1987-05-01 | 1987-05-01 | Epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63273624A true JPS63273624A (en) | 1988-11-10 |
Family
ID=14428112
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10622287A Pending JPS63273624A (en) | 1987-05-01 | 1987-05-01 | Epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63273624A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02189326A (en) * | 1989-01-18 | 1990-07-25 | Mitsubishi Petrochem Co Ltd | Epoxy resin composition for sealing electronic component |
| DE4138411A1 (en) * | 1991-11-22 | 1993-05-27 | Bosch Gmbh Robert | HARDENING POWERS |
| JP2007204738A (en) * | 2005-12-29 | 2007-08-16 | Corning Inc | Low out-gassing room temperature curable rubber-like polymer, preparation thereof and device comprising the same |
-
1987
- 1987-05-01 JP JP10622287A patent/JPS63273624A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02189326A (en) * | 1989-01-18 | 1990-07-25 | Mitsubishi Petrochem Co Ltd | Epoxy resin composition for sealing electronic component |
| DE4138411A1 (en) * | 1991-11-22 | 1993-05-27 | Bosch Gmbh Robert | HARDENING POWERS |
| JP2007204738A (en) * | 2005-12-29 | 2007-08-16 | Corning Inc | Low out-gassing room temperature curable rubber-like polymer, preparation thereof and device comprising the same |
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