JPH021725A - Flame-retardant resin composition for sealing electronic part or lamination - Google Patents
Flame-retardant resin composition for sealing electronic part or laminationInfo
- Publication number
- JPH021725A JPH021725A JP19827188A JP19827188A JPH021725A JP H021725 A JPH021725 A JP H021725A JP 19827188 A JP19827188 A JP 19827188A JP 19827188 A JP19827188 A JP 19827188A JP H021725 A JPH021725 A JP H021725A
- Authority
- JP
- Japan
- Prior art keywords
- flame
- epoxy resin
- resin composition
- curing accelerator
- retardant resin
- 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
- 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 title claims description 9
- 239000003063 flame retardant Substances 0.000 title claims description 9
- 239000011342 resin composition Substances 0.000 title claims description 9
- 238000007789 sealing Methods 0.000 title claims description 4
- 238000003475 lamination Methods 0.000 title 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 claims abstract description 18
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 11
- 150000003003 phosphines Chemical class 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 8
- 238000010030 laminating Methods 0.000 claims description 5
- 150000002989 phenols Chemical class 0.000 claims description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 4
- 239000004843 novolac epoxy resin Substances 0.000 claims description 3
- 229920003986 novolac Polymers 0.000 abstract description 21
- 239000003822 epoxy resin Substances 0.000 abstract description 17
- 229920000647 polyepoxide Polymers 0.000 abstract description 17
- -1 (substituted) phenol Chemical class 0.000 abstract description 10
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 11
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 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 3
- 239000004593 Epoxy Substances 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 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 3
- 238000000034 method Methods 0.000 description 3
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000009529 body temperature measurement Methods 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000002648 laminated material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000002253 acid 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
- 238000004458 analytical method Methods 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
- 229940006460 bromide ion Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000000725 suspension 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
- 238000012546 transfer Methods 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Laminated Bodies (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、′電子部品の封止又は積層用の材料として有
用な難燃性の樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a flame-retardant resin composition useful as a material for sealing or laminating electronic components.
［従来の技術］
エポキシ樹脂はその硬化物の電気的、機械的、熱的に優
れた特性を生かして種々の材料に使われているが、近年
、半導体の封止材料又は電子部品用の積層材料としても
広く使われるに至っている。[Prior Art] Epoxy resins are used in various materials by taking advantage of the excellent electrical, mechanical, and thermal properties of their cured products. It has come to be widely used as a material.
これら封止材料あるいは積層材料は火災による危険性を
防止づるために難燃性を付与することが要求される場合
が多く、この為に臭素を含有するエポキシ化合物が離燃
剤として多く用いられている。These encapsulating materials or laminated materials are often required to be flame retardant to prevent the risk of fire, and for this reason bromine-containing epoxy compounds are often used as flame release agents. .
［発明が解決しようどする課題］
このような封止材料あるいは積層材料として用いられる
場合、紺み込まれた電子部品の耐久性を増すために、そ
の材料中に含まれる加水分解性ハロゲンの螢を極力少な
くすることが要求されている。この耐久性に関する加水
分解性ハロゲンとしては、臭素イオン、塩素イオンが考
えられているが、近年、特に塩素イオンの軽減化法に関
する特許が多数提示されている。[Problems to be Solved by the Invention] When used as such a sealing material or a laminated material, in order to increase the durability of electronic components embedded with deep blue, the hydrolyzable halogen fireflash contained in the material is used. It is required to reduce the amount as much as possible. Bromine ions and chlorine ions are considered as hydrolyzable halogens related to this durability, and in recent years, many patents have been proposed, particularly regarding methods for reducing chlorine ions.
しかしながら、臭素イオンの軽減化に関しては未だ充分
とはいえない。従って難燃性を付与するために臭素化エ
ポキシ樹脂を使用した場合、その分子中に結合した臭素
原子のうち、比較的弱い結合をしている臭素原子が通常
のプレッシャー・クツカー・テスト（ＰＣＴ）の条件に
おいて加水分解され臭素イオンとして定量されることが
考えられる。事実、通常用いられている臭素化ビスフェ
ノール系あるいは臭素化ノボラック系の難燃性エポキシ
樹脂を配合し、通常使用されているイミダゾール系の硬
化促進剤によって得られた硬化物では、ＰＣＴにおいて
２００ｐｐｍ程度（ＰＣＴ時の硬化物に対する端）ある
いはそれ以Ｆの臭素イオンが検出され、しかもＰＣＴを
長時間実ＩＪｌ！することにより、更に臭素イオンの脱
離聞が大巾に増加する。However, the reduction of bromine ions is still not sufficient. Therefore, when a brominated epoxy resin is used to impart flame retardancy, among the bromine atoms bonded in the molecule, the bromine atoms with relatively weak bonds undergo the normal pressure Kutzker test (PCT). It is thought that it is hydrolyzed and quantified as bromide ion under these conditions. In fact, a cured product obtained by blending commonly used brominated bisphenol-based or brominated novolac-based flame-retardant epoxy resins with a commonly used imidazole-based curing accelerator has a PCT concentration of about 200 ppm ( Bromine ions (edge) or higher than F for the cured product during PCT are detected, and PCT is actually carried out for a long time! By doing so, the number of bromine ions desorbed is greatly increased.
［課題を解決するための手段］
本発明者らはこの問題を解決する為、鋭意検討を進めた
結果、臭素を含有するノボラック型エボ４−シ樹脂及び
フェノールノボラック型１ボキシ樹脂と硬化剤を硬化促
進剤を用いて硬化せしめる際、特定の硬化促進剤を用い
ることによって高イ、１頼性の硬化物を得ることができ
ることを見い出し本発明を完成するにｆつだ。[Means for Solving the Problem] In order to solve this problem, the present inventors have carried out extensive studies and have developed a method using a bromine-containing novolac type Evo 4-cy resin, a phenol novolac type 1 boxy resin, and a curing agent. When curing using a curing accelerator, the present invention was completed by discovering that a cured product with high reliability can be obtained by using a specific curing accelerator.
即ら、本発明は臭素を含有するノボラックＪｐｌエボギ
シ樹脂及び置換又は無置換フェノールノボラック型エポ
キシ樹脂と硬化剤を合む組成物であって、硬化促進剤と
して少なくともホスフィン類を含有してなる電子部品封
止又は積層用難燃性樹脂組成物に関する。That is, the present invention relates to a composition comprising a bromine-containing novolac JPL epoxy resin, a substituted or unsubstituted phenol novolac type epoxy resin, and a curing agent, and an electronic component comprising at least a phosphine as a curing accelerator. The present invention relates to a flame-retardant resin composition for sealing or lamination.
本発明によれば硬化促進剤としてホスフィン類を使用す
れば、ＰＣＴによって加水分解される臭素イオンの邑が
軽減され、しかも、長時間のＰＣＴにおいても臭素イオ
ンの脱離がほとんど増加しないという驚くべき利点を有
するものである。According to the present invention, by using phosphines as a curing accelerator, the amount of bromide ions hydrolyzed by PCT can be reduced, and moreover, the desorption of bromide ions hardly increases even during long-term PCT, which is surprising. It has advantages.
また、硬化促進剤としてホスフィン類を使用した場合に
は、最終硬化物のガラス転移温度（Ｔ（＋）が若干低下
する場合があるが、これは硬化促進剤としてイミダゾー
ル類の少なくとも１つを前記ホスフィン類と併用するこ
とで解決し得ることが本発明において知見された。Furthermore, when a phosphine is used as a curing accelerator, the glass transition temperature (T(+)) of the final cured product may be slightly lowered. It has been found in the present invention that the problem can be solved by using it in combination with phosphines.
本発明に係わる臭素を含有するノボラック型エポキシ樹
脂は臭素化ノボラック型エポキシ樹脂であり、置換又は
無置換フェノールノボラック型エポキシ樹脂はフェノー
ル、クレゾール等のノボラック型エポキシ樹脂等が挙げ
られ、硬化剤はフェノール、クレゾール等のフェノール
系化合物のノボラック型樹脂およびジシアンジアミド等
が挙げられる。又、本発明にとって・ｎ要な成分である
硬化促進剤のホスフィン類としては、１−リフェニルホ
スフィン、ジエチルフ１ニルホスフィン、ジフェニルホ
スフィン、トリーｎ−ブチルホスフィン雪の有機ホスフ
ィン化合物が挙げられるが、特にトリフェニルホスフィ
ンが好ましい。また、ホスフィン類と併用し得るイミダ
ゾール類化合物としては、２−メチルイミダゾール、２
−フェニルイミダゾール、２−ニブ′ルー ４−メチル
イミダゾール等が挙げられる。The bromine-containing novolak epoxy resin according to the present invention is a brominated novolak epoxy resin, and the substituted or unsubstituted phenol novolak epoxy resin includes novolak epoxy resins such as phenol and cresol.The curing agent is phenol. , novolac type resins of phenolic compounds such as cresol, and dicyandiamide. In addition, examples of phosphines as curing accelerators, which are essential components for the present invention, include organic phosphine compounds such as 1-liphenylphosphine, diethylph1-nylphosphine, diphenylphosphine, and tri-n-butylphosphine. Particularly preferred is triphenylphosphine. In addition, as imidazole compounds that can be used in combination with phosphines, 2-methylimidazole, 2-methylimidazole,
-phenylimidazole, 2-nibu-4-methylimidazole, and the like.
又、臭素化ノボラック型エポキシ樹脂（ａ）と置換又は
無置換フェノールノボラック型エポキシ樹脂（ｂ）の混
合割合は樹脂（ｂ）に対して樹脂（ａ）が５重重％以上
であることが好ましい。樹脂（ａ）がこれ以下では、難
燃性の付与を十分に達成しにくくなる。又、硬化剤はノ
ボラック型樹脂においては樹脂（ａ）と樹脂（ｂ）に含
まれるエボギシ樋１個に対してフェノール性水酸褪が０
．５〜１，５個となる範囲で用いるのが好ましく、特に
０．８〜１，２個となる範囲で用いるのが好ましい。又
、ジシアンジアミドにおいては、樹脂（ａ）ど樹脂（ｂ
）に台上れるエポキシ基１個に対して活性水素０．５〜
１．０個となる範υＭで使用するのが好ましい。又、本
発明の硬化促進剤は樹脂（ａ）と樹脂（ｂ）の合計１０
０巾吊部に対して０．１〜５重ｆｉ１部用いるのが好ま
しく、特に０．３〜３■串部用いるのが好ましい。ホス
フィン類とイミダゾール類とを硬化促進剤とし−Ｕ ０
１用する場合、その使用割合はホスフィン類が８０〜２
０車ｆｆ１ｋ％、イミダゾール類が２０〜８唖１％とな
るように用いるのが好ましく、特に、ホスフィン類が７
０〜３０重量％、イミダゾール類が３０〜１０唄吊％と
なるように用いるのが好ましい。Further, the mixing ratio of the brominated novolac type epoxy resin (a) and the substituted or unsubstituted phenol novolac type epoxy resin (b) is preferably 5% by weight or more of the resin (a) with respect to the resin (b). If the amount of resin (a) is less than this, it becomes difficult to sufficiently impart flame retardancy. In addition, in the case of novolak type resins, the curing agent has 0 phenolic hydroxyl loss per 1 piece of evogishi gutter contained in resin (a) and resin (b).
．． It is preferably used in a range of 5 to 1.5 pieces, particularly preferably 0.8 to 1.2 pieces. In addition, in dicyandiamide, resin (a), resin (b)
) active hydrogen 0.5 to 1 epoxy group
It is preferable to use the range υM in which the number is 1.0. Further, the curing accelerator of the present invention has a total of 10% of resin (a) and resin (b).
It is preferable to use 1 part of 0.1 to 5 fold fi for the 0 width hanging part, and it is particularly preferable to use the 0.3 to 3 inch skewer part. Using phosphines and imidazoles as curing accelerators - U 0
When using 1, the ratio of phosphines used is 80 to 2
It is preferable to use so that the amount of imidazole is 20 to 1%, and especially the amount of phosphine is 7%.
It is preferable to use it in an amount of 0 to 30% by weight, and an amount of imidazoles of 30 to 10% by weight.
この発明の樹脂組成物は、上述の臭素化ノボラック型エ
ポキシ樹脂、ノボラック型エボ１ニジ樹脂、硬化剤およ
び硬化促進剤を含むものであるが、必要に応じて公知の
添加剤を配合することによっても、本発明の効果を損な
わない。添加剤として、例えば、シリカ、アルミナ、タ
ルク、ガレスｍ維等の無１ｆｉＹｆｆ充填剤、シランカ
ップリング剤のような充噴剤の表面処理剤、！ｔｌ型剤
、顔料等が挙げられる。又、本発明の組成物は一般的な
成形法、例えば、トランスファー成形によつＣ好適に使
用される。これによって得られる本発明の硬化物はＰＣ
Ｔで加水分解される臭素イオン頃を大幅に軽減した高信
頼性の電子部品を供するものである。The resin composition of the present invention contains the above-mentioned brominated novolac type epoxy resin, novolac type Evo 1 resin, curing agent, and curing accelerator, but it can also be prepared by adding known additives as necessary. This does not impair the effects of the present invention. As additives, for example, non-1fiYff fillers such as silica, alumina, talc, and Galeth fiber, surface treatment agents for fillers such as silane coupling agents, etc. Examples include tl type agents and pigments. Further, the composition of the present invention can be suitably used by common molding methods, such as transfer molding. The cured product of the present invention obtained in this way is PC
This provides highly reliable electronic components in which the amount of bromide ions hydrolyzed by T is significantly reduced.
［実施例１ 以下、本発明を実施例により説明する。[Example 1 The present invention will be explained below using examples.
実施例１．２，３．４
重版の奥累化フェノールノボラックエボキシ樹脂（日本
生薬■ＢＲＥＮ−８：エボキシ当吊２７８゜軟化点８４
℃） １００重＆１部、クレゾールノボラックエポキ
シ樹脂（日本生薬■Ｅ ＯＣＮ １０２０ ：エポキシ
当量２０１．軟化点７１℃）３０■■部、フェノールノ
ボラック樹脂（日本化薬■；水ｗｉ基当市１０６、軟化
点８４℃） ２０Ｏｔｌａｉ部及びトリフェニルホス
フィンを表−１に示す重量部で配合し、７０〜８０℃で
１５分間ロール混練した後、冷却、粉砕して目的の樹脂
組成物を得Ｉ；。Examples 1.2, 3.4 Reprinted deep-graded phenol novolac epoxy resin (Japanese crude drug ■BREN-8: Epoxy suspension 278° Softening point 84
°C) 100 weight & 1 part, cresol novolak epoxy resin (Nippon Kayaku ■E OCN 1020: epoxy equivalent 201. Softening point 71℃) 30 parts, phenol novolac resin (Nippon Kayaku ■; water wi base 106, softened Point 84°C) 200 parts and triphenylphosphine were blended in the parts by weight shown in Table 1, roll-kneaded at 70 to 80°C for 15 minutes, cooled and pulverized to obtain the desired resin composition.
各組成物を１５０℃、５（Ｈｇ／、Ｊ、３分間の条件で
トランスファー成形してＰＣＴ用試判を作成した。Each composition was transfer molded under the conditions of 150° C., 5 (Hg/, J, 3 minutes) to prepare PCT test samples.
得られた成形物を１８０’Ｃｘ １３時間、後硬化を行
った。ＰＣＴ用試料として、後硬化後、粉砕して６０メ
ツシユ〜１００メツシユの粒径の硬化物を得た。The obtained molded product was post-cured at 180'Cx for 13 hours. After post-curing, the sample was crushed to obtain a cured product having a particle size of 60 mesh to 100 mesh as a sample for PCT.
硬化物の評価結果を表−１に示した。The evaluation results of the cured product are shown in Table-1.
なお、ＰＣＦの評価条件は次の通り。The evaluation conditions for PCF are as follows.
ＰＣＴの条件
硬化物５ｇ（粉砕品：６０メツシユ〜１００メツシユ）
イオン交換水５０ｇ
温度１８０℃
分析条件
イオンクロマト：横河北辰゛眉気
（カラム；５ＡＸ１）
溶離液； ４ｍＭ−Ｎａ２Ｃｏ３／ ４ｍＭ −Ｎ
ａ ＨＣＯ３
除去ｍ ： ０．０５Ｍ・ドデシルベンピンスルホン酸
検 出；電気伝導度計
比較例１．２
トリフェニルホスフィンの代りに２−メヂルイミタソー
ル、２−フェニルイミダゾールを表−１に示ず割合で配
合した以外は実施例１ど同様の操作を行って硬化物の評
価を実流した。硬化物の評価結果を表−１に示した。Conditions for PCT: 5 g of cured product (pulverized product: 60 meshes to 100 meshes) 50 g of ion-exchanged water Temperature: 180°C Analysis conditions: Ion chromatography: Yokogawa Hokutatsu Meiji (column: 5AX1) Eluent: 4mM-Na2Co3/4mM-N
a HCO3 removal m: 0.05M dodecylbenpinesulfonic acid detection; electrical conductivity meter comparative example 1.2 Table 1 shows 2-medylimitasol and 2-phenylimidazole instead of triphenylphosphine. The same operation as in Example 1 was carried out except that the mixture was blended in the proportion of The evaluation results of the cured product are shown in Table-1.
実施例５．６
トリフェニルホスフィン、２−メチルイミダゾールより
なる硬化促進剤２重＠部を表−２に示す混合割合で使用
し、トランスファー成形によりＰＣＴ用試料及びガラス
転移温度測定用試片を作成した以外は実施例１と同様の
操作を行って成形物を得、後硬化を行った。Example 5.6 PCT samples and specimens for glass transition temperature measurement were prepared by transfer molding using a double curing accelerator consisting of triphenylphosphine and 2-methylimidazole in the mixing ratio shown in Table 2. A molded product was obtained by performing the same operations as in Example 1 except for the following steps, and post-curing was performed.
ＰＣＴ用試料として、後硬化慢粉砕して６０メツシ１〜
１００メツシユの粒径の硬化物を得た。As a sample for PCT, after hardening and grinding, 60 mesh 1 ~
A cured product with a particle size of 100 mesh was obtained.
ＰＣＴの評価条件は実施例１と同じであるが、加熱時間
を１８０℃で２０時間とした。The PCT evaluation conditions were the same as in Example 1, but the heating time was 20 hours at 180°C.
ガラス転移温度の評価はガラス転移温度測定用試片を使
用し、次の条件下で行なった。Evaluation of the glass transition temperature was carried out under the following conditions using a sample for glass transition temperature measurement.
ガラス転移温度
熱機械測定装＠（ＴＭＡ）：真空理工（株）Ｔ Ｍ −
７０００
昇温速度； ２℃／ｍｉｎ
硬化物の評価結果を表−２に示した。Glass transition temperature thermomechanical measuring instrument @ (TMA): Shinku Riko Co., Ltd. TM -
7000 Temperature increase rate: 2°C/min The evaluation results of the cured product are shown in Table-2.
実施例７．８
トリフェニルホスフィン、２−メチルイミダゾールより
なる硬化促進剤４重量部を表−３に示す混合割合で使用
した以外は実施例５と同様の操作を行って硬化物の評価
を実施した。硬化物の評価結果を表−３に示した。Example 7.8 Evaluation of the cured product was carried out in the same manner as in Example 5, except that 4 parts by weight of a curing accelerator consisting of triphenylphosphine and 2-methylimidazole was used at the mixing ratio shown in Table 3. did. The evaluation results of the cured product are shown in Table 3.
実施例９，１０
トリフェニルホスフィン、２−メチルイミダゾールより
なる硬化だ通則８ｆｉｆｆｉ部を表−４に示す混合割合
で使用した以外は実施例５ど同様の操作を行って硬化物
の評価を実施した。硬化物の評価結果を表−４に示した
。Examples 9 and 10 The cured products were evaluated by performing the same operations as in Example 5, except that 8 fiffi parts of the cured product consisting of triphenylphosphine and 2-methylimidazole were used at the mixing ratio shown in Table 4. . The evaluation results of the cured product are shown in Table 4.
比較例３〜５
２−メチルイミダゾールを表−２〜表−４に示すように
それぞれ単独で使用した以外は実施例５と同様の操作を
行って硬化物の評価を実施した。Comparative Examples 3 to 5 The cured products were evaluated in the same manner as in Example 5, except that 2-methylimidazole was used alone as shown in Tables 2 to 4.
硬化物の評価結果を表−２〜表−４に示した。The evaluation results of the cured products are shown in Tables 2 to 4.
実施例１１
実施例５〜１０において２−メチルイミダゾールの代り
に２−フェニルイミダゾール又は２−エチル−４−メチ
ルイミダゾールを用い、その他は実施例５〜１０と同様
の操作を行って硬化物の評価を行ったところ、いずれの
場合も実施例５〜１０と同様な結果が得られた。Example 11 In Examples 5 to 10, 2-phenylimidazole or 2-ethyl-4-methylimidazole was used instead of 2-methylimidazole, and the same operations as in Examples 5 to 10 were performed except for the evaluation of the cured product. When conducted, the same results as Examples 5 to 10 were obtained in all cases.
［発明の効果］
表−１〜４の結果から明らかなように、本発明によれば
ボスフーｆン類の硬化促進剤を使用することによって、
Ｆ’ ＣＴでの臭素イオンの発生を抑えた高信頼性の電
子部品を得ることかぐきる。また、ホスフィン類とイミ
ダゾール類とを併用した硬化促進剤の使用により、耐熱
性の指標である高いガラス転移温度を保持することがで
きる。[Effects of the Invention] As is clear from the results in Tables 1 to 4, according to the present invention, by using a hardening accelerator such as Bossfung,
It is possible to obtain highly reliable electronic components that suppress the generation of bromide ions in F' CT. Furthermore, by using a curing accelerator containing phosphines and imidazoles in combination, a high glass transition temperature, which is an index of heat resistance, can be maintained.
Claims (4)
換又は無置換フェノールノボラック型エポキシ樹脂と硬
化剤を含む組成物であって、硬化促進剤として少なくと
もホスフィン類を含有してなる電子部品封止又は積層用
難燃性樹脂組成物。(1) A composition containing a bromine-containing novolac epoxy resin, a substituted or unsubstituted phenol novolac epoxy resin, and a curing agent, and containing at least phosphine as a curing accelerator, for sealing or laminating electronic components. Flame retardant resin composition for use.
項１に記載の電子部品封止又は積層用難燃性樹脂組成物
。(2) The flame-retardant resin composition for encapsulating or laminating electronic components according to claim 1, wherein the curing accelerator is triphenylphosphine.
ミダゾール類との混合物である請求項１に記載の電子部
品封止又は積層用難燃性樹脂組成物。(3) The flame-retardant resin composition for encapsulating or laminating electronic components according to claim 1, wherein the curing accelerator is a mixture of phosphines and at least one imidazole.
ール類との混合物である請求項３に記載の電子部品封止
又は積層用難燃性樹脂組成物。(4) The flame-retardant resin composition for encapsulating or laminating electronic components according to claim 3, wherein the curing accelerator is a mixture of triphenylphosphine and imidazoles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19827188A JPH021725A (en) | 1988-03-09 | 1988-08-09 | Flame-retardant resin composition for sealing electronic part or lamination |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-53558 | 1988-03-09 | ||
| JP5355888 | 1988-03-09 | ||
| JP19827188A JPH021725A (en) | 1988-03-09 | 1988-08-09 | Flame-retardant resin composition for sealing electronic part or lamination |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH021725A true JPH021725A (en) | 1990-01-08 |
Family
ID=26394272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19827188A Pending JPH021725A (en) | 1988-03-09 | 1988-08-09 | Flame-retardant resin composition for sealing electronic part or lamination |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH021725A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4110219A1 (en) * | 1991-03-28 | 1992-10-01 | Huels Troisdorf | METHOD FOR PRODUCING PREPREGS WITH SOLVENT-FREE EPOXY RESIN |
| JP2002226555A (en) * | 2001-01-31 | 2002-08-14 | Dainippon Ink & Chem Inc | Flame-retardant epoxy resin composition |
| JP2009521562A (en) * | 2005-12-22 | 2009-06-04 | ダウ グローバル テクノロジーズ インコーポレイティド | Curable epoxy resin composition containing mixed catalyst system and laminate made therefrom |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5592757A (en) * | 1979-01-09 | 1980-07-14 | Toray Ind Inc | Flame-retardant epoxy resin for reinforcing with carbon fiber |
| JPS57184241A (en) * | 1981-05-08 | 1982-11-12 | Toshiba Corp | Resin sealing type semiconductor device |
| JPS60202118A (en) * | 1984-03-26 | 1985-10-12 | Toshiba Corp | Sealing epoxy resin composition and semiconductor device sealed therewith |
| JPS6181426A (en) * | 1984-09-28 | 1986-04-25 | Toshiba Corp | Epoxy resin composition for encapsulatingj semiconductor |
| JPS6354419A (en) * | 1986-08-26 | 1988-03-08 | Mitsubishi Gas Chem Co Inc | Thermosetting resin composition |
-
1988
- 1988-08-09 JP JP19827188A patent/JPH021725A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5592757A (en) * | 1979-01-09 | 1980-07-14 | Toray Ind Inc | Flame-retardant epoxy resin for reinforcing with carbon fiber |
| JPS57184241A (en) * | 1981-05-08 | 1982-11-12 | Toshiba Corp | Resin sealing type semiconductor device |
| JPS60202118A (en) * | 1984-03-26 | 1985-10-12 | Toshiba Corp | Sealing epoxy resin composition and semiconductor device sealed therewith |
| JPS6181426A (en) * | 1984-09-28 | 1986-04-25 | Toshiba Corp | Epoxy resin composition for encapsulatingj semiconductor |
| JPS6354419A (en) * | 1986-08-26 | 1988-03-08 | Mitsubishi Gas Chem Co Inc | Thermosetting resin composition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4110219A1 (en) * | 1991-03-28 | 1992-10-01 | Huels Troisdorf | METHOD FOR PRODUCING PREPREGS WITH SOLVENT-FREE EPOXY RESIN |
| JP2002226555A (en) * | 2001-01-31 | 2002-08-14 | Dainippon Ink & Chem Inc | Flame-retardant epoxy resin composition |
| JP2009521562A (en) * | 2005-12-22 | 2009-06-04 | ダウ グローバル テクノロジーズ インコーポレイティド | Curable epoxy resin composition containing mixed catalyst system and laminate made therefrom |
| JP2013166959A (en) * | 2005-12-22 | 2013-08-29 | Dow Global Technologies Llc | Curable epoxy resin composition having mixed catalyst system and laminate made therefrom |
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