JPS6239607B2 - - Google Patents
Info
- Publication number
- JPS6239607B2 JPS6239607B2 JP8330982A JP8330982A JPS6239607B2 JP S6239607 B2 JPS6239607 B2 JP S6239607B2 JP 8330982 A JP8330982 A JP 8330982A JP 8330982 A JP8330982 A JP 8330982A JP S6239607 B2 JPS6239607 B2 JP S6239607B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- brominated
- bisphenol
- type epoxy
- epoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000003822 epoxy resin Substances 0.000 claims description 34
- 229920000647 polyepoxide Polymers 0.000 claims description 34
- 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 claims description 24
- 229920003986 novolac Polymers 0.000 claims description 21
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 239000006082 mold release agent Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 239000012756 surface treatment agent Substances 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 description 8
- 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 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 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 6
- 238000004132 cross linking Methods 0.000 description 4
- 239000012778 molding material Substances 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 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
- 229920001342 Bakelite® Polymers 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Description
本発明は、耐熱性に優れる難燃性エポキシ樹脂
組成物に係るものであり、その特徴は難燃性樹脂
としてビスフエノールＡをノボラツク骨格に持つ
臭素化エポキシ樹脂を用いるところにある。
近年、金属部品がセラミツク部品類のプラスチ
ツク化は驚異的な速さで進行していることは衆知
の事実である。プラスチツクとしてはフエノール
樹脂、ポリエステル樹脂、エポキシ樹脂等が使わ
れ、絶縁性が耐湿性の要求が厳しいもの例えば電
子部品用等にはエポキシ樹脂が用いられている。
又、近年、部品類の難燃化が必要とされるように
なりプラスチツクも難燃性（UL規格94V−Ｏ
等）を付与することが通常となつている。エポキ
シ樹脂系プラスチツクもその難燃対策として三酸
化アンチモンといつた難燃性を使用すると共に樹
脂の難燃化も行つている。通常用いられるものは
臭素化ビスフエノール型エポキシ樹脂（臭素率10
〜50重量％、エポキシ当量385〜2000）である。
商品名としては、ESB−400・700（住友化学工
業）、エピクロン152といつたものを挙げることが
できる。
しかし、この樹脂はエポキシ当量が大きいため
架橋密度が高くならず比較的低温で分解する即ち
耐熱性が劣るという欠点を持つていた。このため
耐熱性を強く要求する用途例えば電子部品封止用
成形材料には臭素化フエノールノボラツク型エポ
キシ樹脂（臭素率35重量％、エポキシ当量225）
が用いられている。
しかしながら市場では、さらに耐熱性向上の要
求が強い。
本発明は下記の平均構造式を有するビスフエノ
ールＡをノボラツク骨格に持つ臭素化エポキシ樹
脂並びにエポキシ樹脂、硬化促進剤等より成るエ
ポキシ樹脂組成物である。
〔平均構造式〕
ｎ＝０〜３
臭素含有率 10〜50重量％、
エポキシ当量 240〜400ｇ／eq、
この樹脂は、ビスフエノールA1分子毎にエポ
キシ基が２コついており、この２コのエポキシ基
が互いに反対方向にのびているため、反応する確
率が高いだけでなく三次元的架橋が必ず達成され
る。このため高架橋密度が得られ熱分解温度が高
くなる即ち耐熱性が向上するという長所が得られ
た。
本発明でいうエポキシ樹脂組成物は、ビスフエ
ノールＡをノボラツク骨格を持つ臭素化エポキシ
樹脂（以下、臭素化ビスフエノールＡノボラツク
型エポキシ樹脂を称する）及びエポキシ樹脂、硬
化促進剤、通常さらに硬化剤・充填剤・離型剤・
表面処理剤等より構成される。エポキシ樹脂はエ
ポキシ基を有するもの全搬をいい、ビスフエノー
ル型エポキシ・フエノールノボラツク型エポキ
シ・クレゾールノボラツク型エポキシ等を挙げる
ことができる。硬化促進剤は、エポキシ樹脂を架
橋させるための触媒全搬のことをいい、イミダゾ
ール類・３級アミン類・有機ホスフイン化合物・
有機アルミニウム化合物等を挙げることができ
る。臭素化ビスフエノールＡノボラツク型エポキ
シ樹脂は１重量％以上組成中に含まれることが望
ましい。１％未満では難燃化効果が期待しにく
い。さらに他の臭素化エポキシ樹脂を併用しても
良いが、耐熱性は悪くなる。併用する場合は、臭
素化ビスフエノールＡノボラツク型エポキシ樹脂
を半分以上使用することが好ましい。以下、実験
例によつて説明を行う。
＜臭素化ビスフエノールＡノボラツク型エポキシ
樹脂＞
臭素化ビスフエノールＡ（臭素含有率12.5％）
460ｇを37％ホルマリン65ｇ、蓚酸２ｇを２時間
還流反応させる。水酸カルシウムで中和後150℃
まで昇温しノボラツク化した。この後エピクロル
ヒドリン261ｇと30％水酸化ナトリウム1.5ｇを加
え90℃で８時間環流反応させた。この後さらに30
％水酸化ナトリウム60ｇを加え環化反応を行な
い、さらに水洗精製し臭素化ビスフエノールＡノ
ボラツク型エポキシ樹脂480ｇを得た。（臭素含有
率10％、エポキシ当量240）
＜臭素化ビスフエノールＡノボラツク型エポキシ
樹脂＞
臭素含有率44％の臭素化ビスフエノールA540
ｇを上記と同条件で反応させ得た。収量500ｇ
（臭素含有率40％、エポキシ当量350）
〔基礎検討例〕
臭素化ビスフエノールＡノボラツク型エポキシ
樹脂と臭素化ビスフエノール型エポキシ樹脂
（ESB−700 住友化学工業）及び臭素化フエノー
ルノボラツク型エポキシ樹脂（BREN日本化薬）
各100重量部と２メチル−イミダゾール１重量部
を微粉砕混合し示差熱分析を行つた。この結果熱
分解温度は、が373℃、ESB−700が284℃、
BRENが341℃であつた。臭素化ビスフエノール
Ａノボラツク型エポキシ樹脂が耐熱性で最も優れ
る。
〔成形材料への応用例〕
オルソクレゾールノボラツク型エポキシ樹脂
（エピクロンＮ−670 大日本インキ化学工業Q22
部、フエノールノボラツク（住友ベークライト）
６部、結晶シリカ（クリスタライトSKS 龍森）
70部、シランカツプリング剤（Ａ−187 日本ユ
ニカー）１部、硬化促進剤（2P4MZ 四国化
成）0.5部、離型剤（ヘキストOP ヘキストジヤ
パン）１部及び臭素化エポキシ樹脂２部を120℃
の熱ロールで３分混練し（臭素化エポキシ樹脂の
タイプを変えた）成形材料４種を得た。これら材
緑と臭素化エポキシ樹脂を加えていない材料計５
種の示差熱分析における硬化反応後の重量減開始
温度及び圧力釜による成形材料抽出水の臭素量増
大時間は表−１の通りである。臭素化ビスフエノ
ールＡノボラツク型エポキシ樹脂が最も熱分
解しにくく耐熱性で優れる。
The present invention relates to a flame-retardant epoxy resin composition having excellent heat resistance, and its feature lies in the use of a brominated epoxy resin having bisphenol A in its novolak skeleton as the flame-retardant resin. It is a well-known fact that in recent years, metal parts and ceramic parts are being replaced with plastic at an astonishing rate. Phenol resins, polyester resins, epoxy resins, etc. are used as plastics, and epoxy resins are used for materials with strict requirements for insulation and moisture resistance, such as for electronic parts.
In addition, in recent years, it has become necessary to make parts flame retardant, and plastics are also flame retardant (UL standard 94V-O).
etc.) is the norm. Epoxy resin plastics also use flame retardants such as antimony trioxide as flame retardant measures, and the resin is also made flame retardant. The commonly used epoxy resin is brominated bisphenol type epoxy resin (bromine ratio 10).
~50% by weight, epoxy equivalent weight 385~2000).
Product names include ESB-400/700 (Sumitomo Chemical) and Epicron 152. However, since this resin has a large epoxy equivalent weight, it does not have a high crosslinking density and has the disadvantage that it decomposes at a relatively low temperature, that is, it has poor heat resistance. For this reason, brominated phenol novolac type epoxy resin (bromine content: 35% by weight, epoxy equivalent: 225) is used for applications that strongly require heat resistance, such as molding materials for encapsulating electronic components.
is used. However, there is a strong demand in the market for further improvement in heat resistance. The present invention is an epoxy resin composition comprising a brominated epoxy resin having a novolak skeleton containing bisphenol A having the following average structural formula, an epoxy resin, a curing accelerator, and the like. [Average structural formula] n = 0 to 3 Bromine content 10 to 50% by weight, Epoxy equivalent 240 to 400 g/eq, This resin has two epoxy groups per molecule of bisphenol A, and these two epoxy groups are in opposite directions. Because it extends over a wide area, not only is there a high probability of reaction, but three-dimensional crosslinking is always achieved. This has the advantage that a high crosslinking density can be obtained and the thermal decomposition temperature can be increased, that is, the heat resistance can be improved. The epoxy resin composition in the present invention includes bisphenol A, a brominated epoxy resin having a novolak skeleton (hereinafter referred to as brominated bisphenol A novolak type epoxy resin), an epoxy resin, a curing accelerator, and usually a curing agent. Filler, mold release agent,
Consists of surface treatment agents, etc. Epoxy resins include all those having an epoxy group, including bisphenol epoxy, phenol novolak epoxy, cresol novolak epoxy, and the like. Curing accelerators refer to all catalysts for crosslinking epoxy resins, and include imidazoles, tertiary amines, organic phosphine compounds,
Examples include organic aluminum compounds. It is desirable that the brominated bisphenol A novolak type epoxy resin is contained in the composition in an amount of 1% by weight or more. If it is less than 1%, it is difficult to expect a flame retardant effect. Furthermore, other brominated epoxy resins may be used in combination, but the heat resistance will deteriorate. When used together, it is preferable to use brominated bisphenol A novolak type epoxy resin for half or more. The following is an explanation using experimental examples. <Brominated bisphenol A novolak type epoxy resin> Brominated bisphenol A (bromine content 12.5%)
460 g was refluxed with 65 g of 37% formalin and 2 g of oxalic acid for 2 hours. 150℃ after neutralization with calcium hydroxide
The temperature rose to 100%, and it became a novolak. Thereafter, 261 g of epichlorohydrin and 1.5 g of 30% sodium hydroxide were added, and the mixture was refluxed at 90° C. for 8 hours. 30 more after this
% sodium hydroxide was added to carry out a cyclization reaction, and the mixture was further washed and purified to obtain 480 g of a brominated bisphenol A novolak type epoxy resin. (Bromine content 10%, epoxy equivalent 240) <Brominated bisphenol A novolak type epoxy resin> Brominated bisphenol A540 with bromine content 44%
g could be reacted under the same conditions as above. Yield 500g
(Bromine content 40%, epoxy equivalent 350) [Basic study example] Brominated bisphenol A novolak type epoxy resin, brominated bisphenol type epoxy resin (ESB-700 Sumitomo Chemical) and brominated phenol novolak type epoxy resin (BREN Nippon Kayaku)
100 parts by weight of each and 1 part by weight of 2-methyl-imidazole were pulverized and mixed and subjected to differential thermal analysis. As a result, the thermal decomposition temperature was 373℃, ESB-700 was 284℃,
BREN was 341℃. Brominated bisphenol A novolac type epoxy resin has the best heat resistance. [Example of application to molding materials] Orthocresol novolak type epoxy resin (Epicron N-670 Dainippon Ink & Chemicals Q22
Department, Phenol Novolac (Sumitomo Bakelite)
Part 6, Crystalline Silica (Crystallite SKS Ryumori)
70 parts of silane coupling agent (A-187 Nippon Unicar), 0.5 part of curing accelerator (2P4MZ Shikoku Kasei), 1 part of mold release agent (Hoechst OP Hoechst Japan) and 2 parts of brominated epoxy resin at 120°C.
The mixture was kneaded for 3 minutes using hot rolls to obtain four types of molding materials (with different types of brominated epoxy resins). Total of 5 materials without adding green and brominated epoxy resin
Table 1 shows the temperature at which weight loss begins after the curing reaction and the time for increase in the amount of bromine in the water extracted from the molding material using the pressure cooker in the differential thermal analysis of the seeds. Brominated bisphenol A novolak type epoxy resin is the most difficult to thermally decompose and has excellent heat resistance.
【表】
はオルソクレゾールノボラツク型エポキシ
樹脂の熱分解前までには熱分解しない。
臭素量増大時間もが長く、安定であること
を示している。[Table] does not thermally decompose before the thermal decomposition of orthocresol novolak type epoxy resin. The bromine content increase time was also long, indicating stability.
Claims (1)
をノボラツク骨格に持つ臭素化エポキシ樹脂と、
エポキシ樹脂並びに硬化剤、硬化促進剤、充填
剤、離型剤及び表面処理剤等の選ばれた添加剤と
から成るエポキシ樹脂組成物。 〔平均構造式〕 ｎ＝０〜３ 臭素含有率 10〜50重量％、 エポキシ当量 240〜400ｇ／eq、[Claims] 1. Bisphenol A having the following average structural formula:
A brominated epoxy resin having a novolak skeleton,
An epoxy resin composition comprising an epoxy resin and selected additives such as a curing agent, a curing accelerator, a filler, a mold release agent, and a surface treatment agent. [Average structural formula] n=0-3 Bromine content 10-50% by weight, Epoxy equivalent 240-400g/eq,
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8330982A JPS58201819A (en) | 1982-05-19 | 1982-05-19 | Flame-retardant epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8330982A JPS58201819A (en) | 1982-05-19 | 1982-05-19 | Flame-retardant epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58201819A JPS58201819A (en) | 1983-11-24 |
| JPS6239607B2 true JPS6239607B2 (en) | 1987-08-24 |
Family
ID=13798811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8330982A Granted JPS58201819A (en) | 1982-05-19 | 1982-05-19 | Flame-retardant epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58201819A (en) |
-
1982
- 1982-05-19 JP JP8330982A patent/JPS58201819A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58201819A (en) | 1983-11-24 |
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