JP4568937B2 - Flame retardant resin composition, prepreg and laminate using the same - Google Patents
Flame retardant resin composition, prepreg and laminate using the same Download PDFInfo
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Description
【0001】
【発明の属する技術分野】
本発明はハロゲン系難燃剤を使用しなくても優れた難燃性を有する樹脂組成物、プリプレグ及び積層板に関するものである。
【0002】
エポキシ樹脂等に代表される熱硬化性樹脂はその優れた特性から電気及び電子機器部品等に広く使用されており、火災に対する安全性を確保するため難燃性が付与されている場合が多い。これらの樹脂の難燃化は従来臭素化エポキシ樹脂等のハロゲン含有化合物を用いることが一般的であった。これらのハロゲン含有化合物は高度な難燃性を有するが、芳香族臭素化合物は熱分解で腐食性の臭素、臭化水素を分離するだけでなく、酸素存在下で分解した場合に毒性の高いポリブロモジベンゾフラン、及びポリジブロモベンゾオキシンを形成する可能性がある。
また、臭素を含有する老朽廃材の処分は極めて困難である。このような理由から臭素含有難燃剤に代わる難燃剤としてリン化合物や窒素化合物、及び無機充填材が検討されている。
【0003】
前述のように、リン化合物及び窒素化合物及び無機充填材によって難燃化を実現できる。その機構は、窒素化合物及びリン化合物は樹脂の炭化を促進し燃焼を防ぐというものであり、無機充填材は樹脂に添加することにより燃焼しやすい樹脂を低減でき、結果として燃焼しにくくなるというものである。また金属水酸化物などの無機充填材は燃焼時に水を放出し温度を低下させることにより燃焼を防ぐものである。ハロゲン化合物を使用せず、リン化合物及び窒素化合物及び無機充填材によって樹脂を難燃化することは、特開平10−195178号公報や特開平10−166501号公報等に見られるように周知の事実であり、またこれらの樹脂組成物を用いたプリプレグ及び積層板も実用化されている。
【0004】
積層板製造工程においては様々な薬液工程が行われ、デスメア工程では水酸化ナトリウムなどの塩基性化合物が用いられ、黒化処理などでは、酸化化合物が用いられる。一般に難燃剤として用いられるリン酸エステルなどのリン化合物や無機充填材はこれらの化合物と反応し不具合を生じる欠点がある。
【0005】
【発明が解決しようとする課題】
本発明は、このような問題を解決すべく検討した結果なされたものであり、リン系難燃剤として、耐加水分解性の強いホスフィンオキサイド化合物を使用することで、耐薬品性と耐燃性に優れた特性を有する樹脂組成物、プリプレグ及びこのプリプレグから得られる難燃性積層板を提供するものである。
【0006】
【課題を解決するための手段】
本発明は、(A)フェノールノボラックエポキシ樹脂、(B)ジシアンジアミド、及び(C)トリフェニルホスフィンオキサイドを必須成分として含有することを特徴とする積層板用難燃性樹脂組成物である。そして、本発明の積層板用難燃性樹脂組成物を基材に含浸させてなることを特徴とするプリプレグであり、さたに前記のプリプレグを1枚又は2枚以上重ね合わせ加熱加圧してなることを特徴とする銅張積層板である。
【0007】
前述のように、無機充填材はエポキシ樹脂あるいはエポキシ樹脂積層板の難燃剤として有用であるが、塩基性化合物や酸化化合物に対する耐薬品性がよくないものが多い。また一般的にリン系難燃剤として用いられるトリフェニルホスフェート、クレジルジフェニルホスフェートなどの添加型リン酸エステルは加水分解を受けやすく薬液中に溶出しやすい。このためこれらの化合物を難燃剤として使用した樹脂組成物は積層板に使用することには問題がある。
【0008】
ホスフィンオキサイド類はP−C結合をもち加水分解されにくい。このためP−O結合を有するリン酸エステル類と異なり、耐薬品性に優れている。また一般にリン含有率が高いため少量の添加で十分な難燃性を有し、無機充填材を使用する必要がない。
本発明の樹脂組成物は、リン系難燃剤として、耐加水分解性の強いホスフィンオキサイド化合物を使用することで、ハロゲン系化合物を使用しないで十分な難燃性と耐薬品性を発現させることを技術骨子とするものであり、無機充填材を使用しなくても十分な難燃性を有するものである。
【0009】
本発明で用いる(A)成分のエポキシ樹脂としては、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールA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、クレゾールノボラック型エポキシ樹脂、テトラキス(グリシジルオキシフェニル)エタンなどがあげられるが、これらに限定されるものではなく、また数種類を同時に用いても差し支えない。耐熱性を考慮すると、ビスフェノールA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、クレゾールノボラック型エポキシ樹脂などのノボラック型エポキシ樹脂が好ましい。
【0010】
本発明で用いる(B)成分の硬化剤としては、ノボラック樹脂、ジシアンジアミド、アミン化合物、酸無水物などがあげられる。ノボラック樹脂もしくはジシアンジアミドが耐熱性が高く好ましい。またノボラック樹脂としてトリアジンノボラックを用いると、窒素成分の効果により難燃性が向上し好ましい。
【0011】
本発明で用いる(C)成分のホスフィンオキサイドとしては、トリフェニルホスフィンオキサイド、トリクレジルホスフィンオキサイド、トリオクチルホスフィンオキサイド、オクチル(フェニル)−N,N‘−ジイソブチルカルバモイルメチルホスフィンオキサイド、トリス−(4−アミノフェニル)ホスフィンオキサイドなどがあげられるが、これらに限定されるものではない。汎用性などを考慮するとトリフェニルホスフィンオキサイドが好ましい。またトリス−(4−アミノフェニル)ホスフィンオキサイドを用いるとエポキシ樹脂と反応し樹脂骨格中に難燃剤を導入でき、耐熱性が上昇するため好ましい。
【0012】
本発明の難燃性樹脂組成物は、上述したエポキシ樹脂と硬化剤とホスフィンオキサイドを必須成分として含有するが、本発明の目的に反しない範囲において、その他の樹脂、硬化促進剤、カップリング剤、その他の成分を添加することは差し支えない。ただし、本発明においては、樹脂及び積層板としての特性、特に耐薬品性を低下させないために、無機充填材及び又はリン酸エステルを添加しないことが好ましく、また、添加しなくても優れた難燃性を発現するものである。
【0013】
本発明の難燃性樹脂組成物は種々の形態で利用されるが、基材に含浸する際には通常溶剤に溶解したワニスの形で使用される。用いられる溶剤は組成に対して良好な溶解性を示すことが望ましいが、悪影響を及ぼさない範囲で貧溶媒を使用しても構わない。
【0014】
本発明の難燃性樹脂組成物を溶剤に溶解して得られるワニスは、ガラス繊布、ガラス不繊布、あるいはガラス以外を成分とする繊布又は不繊布等の基材に塗布、含浸させ、80〜200℃で乾燥させることによりプリプレグを得ることが出来る。かかるプリプレグは加熱加圧して積層板又は銅張積層板を製造することに用いられる。本発明の難燃性樹脂組成物はハロゲン化合物を含有しなくとも高度な難燃性を有する熱硬化性樹脂組成物であり、特に、プリント配線板用の積層板等に好適に使用されるものである。
【0015】
【実施例】
以下、本発明を実施例により具体的に説明する。
【0016】
(参考例1)
クレゾールノボラックエポキシ樹脂(大日本インキ化学工業(株)製エピクロンN−690)100重量部、フェノールアラルキル樹脂(三井化学(株)製ミレックスXLC−LL)52重量部、トリアジン変性フェノールノボラック樹脂(大日本インキ化学工業(株)製LA−7054)15重量部、及びトリフェニルホスフィンオキサイド38重量部にメチルセルソルブを加え、不揮発分濃度60重量%となるようにワニスを調製した。このときエポキシ樹脂、リン化合物及び硬化剤の合計100重量%に対し、リン成分が2.1重量%、窒素成分が0.9重量%となった。このワニスを用いて、ガラス繊布(厚さ0.18mm、日東紡績(株)製)100重量部にワニス固形分で80重量部含浸させて、150℃の乾燥機炉で5分乾燥させ、樹脂含有量44.4%のプリプレグを作製した。上記プリプレグを6枚重ね、上下に厚さ35μmの電解銅箔を重ねて、圧力40kgf/cm2 、温度190℃で120
分加熱加圧成形を行い、厚さ1.2mmの両面銅張積層板を得た。
【0017】
(実施例2)
フェノールノボラック型エポキシ樹脂(大日本インキ化学工業(株)製エピクロンN−770)100重量部、ジシアンジアミド5.5重量部、トリフェニルホスフィンオキサイド23重量部にジメチルホルムアミドを加え、不揮発分濃度60重量%となるようにワニスを調製した。このときエポキシ樹脂、リン化合物及び硬化剤の合計100重量%に対し、リン成分が2.0重量%、窒素成分が2.9重量%となった。
このワニスを用いて、ガラス繊布(厚さ0.18mm、日東紡績(株)製)100重量部にワニス固形分で80重量部含浸させて、150℃の乾燥機炉で5分乾燥させ、樹脂含有量44.4%のプリプレグを作製した。
上記プリプレグを6枚重ね、上下に厚さ35μmの電解銅箔を重ねて、圧力40kgf/cm2 、温度190℃で120分加熱加圧成形を行い、厚さ1.2mmの両面銅張積層板を得た。
【0018】
(実施例3、参考例4、及び比較例1〜3)
表1に示した配合処方で、これ以外は全て実施例1及び実施例2と同様の方法で両面銅張積層板を作成した。
【0019】
得られた銅張積層板については、難燃性、半田耐熱性、及びピール強度を測定した。評価結果を表1及び表2に示す。実施例に示す銅張積層板はいずれも耐燃性、及び耐薬品性に優れている。
【0020】
【表1】
【0021】
【表2】
【0022】
(測定方法)
1. .難燃性:UL−94規格に従い垂直法により評価した。
2. .半田耐熱性、ピール強度:JISC6481に準じて測定した。
3.半田耐熱性:煮沸2時間の吸湿処理を行った後、260℃の半田槽に120秒浸漬した後の外観の異常の有無を観察した。
4.耐薬品性:80℃の水酸化ナトリウム20%水溶液に10分浸漬したときの重量減少率と、70℃の過硫酸カリウム20%水溶液に96時間浸漬したときの重量減少率を求めた。
【0023】
表の注
(1)大日本インキ化学工業(株)製 エピクロンN−690、エポキシ当量=210
(2)大日本インキ化学工業(株)製 エピクロンN−770、エポキシ当量=190
(3)三井化学(株)性 ミレックスXLC−LL、水酸基当量=175
(4)大日本インキ化学工業(株)製 LA−7054、水酸基当量=125、窒素含有率=12重量%
(5)80℃の水酸化ナトリウム20重量%水溶液に10分浸漬したときの重量減少率
(6)70℃の過硫酸カリウム20重量%水溶液に96時間浸漬したときの重量減少率
【0024】
【発明の効果】
本発明の難燃性樹脂組成物、これを用いたプリプレグ及び積層板は、ハロゲン化合物を添加することなく高度な難燃性を有し、半田耐熱性等の特性も優れており、かつ十分な耐薬品性を有する。従って今後要求される非ハロゲン材料として新規で有用な熱硬化性樹脂組成物を提供するものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resin composition, a prepreg and a laminate having excellent flame retardancy without using a halogen-based flame retardant.
[0002]
Thermosetting resins typified by epoxy resins and the like are widely used for electrical and electronic equipment parts due to their excellent characteristics, and are often provided with flame retardancy in order to ensure safety against fire. Conventionally, flame retardants of these resins have been made using halogen-containing compounds such as brominated epoxy resins. Although these halogen-containing compounds have a high degree of flame retardancy, aromatic bromine compounds not only separate corrosive bromine and hydrogen bromide by thermal decomposition, but also are highly toxic when decomposed in the presence of oxygen. May form bromodibenzofuran and polydibromobenzoxine.
Also, it is extremely difficult to dispose of obsolete waste containing bromine. For these reasons, phosphorus compounds, nitrogen compounds, and inorganic fillers have been studied as flame retardants to replace bromine-containing flame retardants.
[0003]
As described above, flame retardancy can be realized by a phosphorus compound, a nitrogen compound, and an inorganic filler. The mechanism is that nitrogen compounds and phosphorus compounds promote carbonization of the resin and prevent combustion, and inorganic fillers can be added to the resin to reduce flammable resin, resulting in difficulty in burning. It is. Also, inorganic fillers such as metal hydroxides prevent combustion by releasing water during combustion and lowering the temperature. It is a well-known fact that a resin is flame-retarded with a phosphorus compound, a nitrogen compound and an inorganic filler without using a halogen compound, as seen in JP-A-10-195178 and JP-A-10-166501. In addition, prepregs and laminates using these resin compositions have been put into practical use.
[0004]
In the laminated plate manufacturing process, various chemical processes are performed, in the desmear process, a basic compound such as sodium hydroxide is used, and in the blackening process, an oxidized compound is used. In general, phosphorus compounds such as phosphoric acid esters and inorganic fillers used as flame retardants have the disadvantage of reacting with these compounds and causing defects.
[0005]
[Problems to be solved by the invention]
The present invention has been made as a result of studies to solve such problems, and has excellent chemical resistance and flame resistance by using a phosphine oxide compound having high hydrolysis resistance as a phosphorus-based flame retardant. The present invention provides a resin composition having the above characteristics, a prepreg, and a flame retardant laminate obtained from the prepreg.
[0006]
[Means for Solving the Problems]
The present invention is a flame retardant resin composition for laminates, comprising (A) a phenol novolac epoxy resin, (B) dicyandiamide, and (C) triphenylphosphine oxide as essential components . And it is the prepreg characterized by making a base material impregnate the flame-retardant resin composition for laminated boards of this invention, and also the said prepreg is piled up 1 sheet or 2 sheets or more, and heat-pressed. copper-clad laminate characterized by comprising.
[0007]
As described above, inorganic fillers are useful as flame retardants for epoxy resins or epoxy resin laminates, but many have poor chemical resistance against basic compounds and oxidized compounds. In addition, additive-type phosphate esters such as triphenyl phosphate and cresyl diphenyl phosphate, which are generally used as phosphorus flame retardants, are easily hydrolyzed and easily eluted in a chemical solution. For this reason, the resin composition which uses these compounds as a flame retardant has a problem in using for a laminated board.
[0008]
Phosphine oxides have a P—C bond and are not easily hydrolyzed. For this reason, it is excellent in chemical resistance unlike phosphate esters having a P—O bond. In general, since the phosphorus content is high, the addition of a small amount has sufficient flame retardancy, and there is no need to use an inorganic filler.
The resin composition of the present invention uses a phosphine oxide compound having strong hydrolysis resistance as a phosphorus flame retardant, and exhibits sufficient flame resistance and chemical resistance without using a halogen compound. It is the technical outline and has sufficient flame retardancy without using inorganic fillers.
[0009]
As the epoxy resin of component (A) used in the present invention, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol A novolak type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, tetrakis (glycidyloxyphenyl) ) Ethane and the like are mentioned, but the ethane is not limited to these, and several types may be used simultaneously. In view of heat resistance, novolak type epoxy resins such as bisphenol A novolak type epoxy resin, phenol novolak type epoxy resin, and cresol novolak type epoxy resin are preferable.
[0010]
Examples of the curing agent for the component (B) used in the present invention include novolak resins, dicyandiamide, amine compounds, and acid anhydrides. A novolac resin or dicyandiamide is preferable because of its high heat resistance. Further, it is preferable to use triazine novolac as the novolak resin because the flame retardancy is improved by the effect of the nitrogen component.
[0011]
As the phosphine oxide of component (C) used in the present invention, triphenylphosphine oxide, tricresylphosphine oxide, trioctylphosphine oxide, octyl (phenyl) -N, N′-diisobutylcarbamoylmethylphosphine oxide, tris- (4 -Aminophenyl) phosphine oxide and the like, but are not limited thereto. Considering versatility, triphenylphosphine oxide is preferable. Tris- (4-aminophenyl) phosphine oxide is preferable because it can react with an epoxy resin to introduce a flame retardant into the resin skeleton and heat resistance is increased.
[0012]
The flame-retardant resin composition of the present invention contains the above-described epoxy resin, curing agent, and phosphine oxide as essential components. However, other resins, curing accelerators, and coupling agents are used as long as they do not contradict the purpose of the present invention. It is possible to add other components. However, in the present invention, it is preferable not to add an inorganic filler and / or phosphate ester in order not to deteriorate the properties as a resin and a laminate, particularly chemical resistance, and excellent difficulty even without the addition. It exhibits flammability.
[0013]
The flame-retardant resin composition of the present invention is used in various forms. When impregnating a base material, it is usually used in the form of a varnish dissolved in a solvent. Although it is desirable that the solvent used has good solubility in the composition, a poor solvent may be used as long as it does not adversely affect the composition.
[0014]
A varnish obtained by dissolving the flame-retardant resin composition of the present invention in a solvent is coated and impregnated on a substrate such as a glass fabric, a glass fabric, or a fabric or fabric containing other than glass as a component. A prepreg can be obtained by drying at 200 ° C. Such a prepreg is used for producing a laminate or a copper clad laminate by heating and pressing. The flame retardant resin composition of the present invention is a thermosetting resin composition having a high degree of flame retardancy without containing a halogen compound, and is particularly suitable for use in laminated boards for printed wiring boards. It is.
[0015]
【Example】
Hereinafter, the present invention will be specifically described by way of examples.
[0016]
( Reference Example 1 )
Cresol novolac epoxy resin (Epiclon N-690, manufactured by Dainippon Ink & Chemicals, Inc.), phenol aralkyl resin (Mirex XLC-LL, manufactured by Mitsui Chemicals, Inc.) 52 parts by weight, triazine-modified phenol novolac resin (Dainippon) Methyl Cellosolve was added to 15 parts by weight of LA-7054 (Ink Chemical Industry Co., Ltd.) and 38 parts by weight of triphenylphosphine oxide, and a varnish was prepared so as to have a nonvolatile content concentration of 60% by weight. At this time, the phosphorus component was 2.1% by weight and the nitrogen component was 0.9% by weight with respect to the total of 100% by weight of the epoxy resin, the phosphorus compound and the curing agent. Using this varnish, 100 parts by weight of glass fiber cloth (thickness 0.18 mm, manufactured by Nitto Boseki Co., Ltd.) was impregnated with 80 parts by weight of varnish solids, and dried in a dryer oven at 150 ° C. for 5 minutes to obtain a resin. A prepreg having a content of 44.4% was produced. Six prepregs are stacked, and 35 μm thick electrolytic copper foil is stacked on the top and bottom, and the pressure is 40 kgf / cm 2 and the temperature is 190 ° C. and 120 ° C.
Minute heating and pressure molding was performed to obtain a double-sided copper-clad laminate having a thickness of 1.2 mm.
[0017]
(Example 2)
Dimethylformamide is added to 100 parts by weight of a phenol novolac type epoxy resin (Epiclon N-770, manufactured by Dainippon Ink and Chemicals, Inc.), 5.5 parts by weight of dicyandiamide, and 23 parts by weight of triphenylphosphine oxide, and the nonvolatile content concentration is 60% by weight. A varnish was prepared so that At this time, the phosphorus component was 2.0% by weight and the nitrogen component was 2.9% by weight with respect to the total of 100% by weight of the epoxy resin, the phosphorus compound and the curing agent.
Using this varnish, 100 parts by weight of glass fiber cloth (thickness 0.18 mm, manufactured by Nitto Boseki Co., Ltd.) was impregnated with 80 parts by weight of varnish solid, and dried in a dryer oven at 150 ° C. for 5 minutes to obtain a resin. A prepreg having a content of 44.4% was produced.
6 sheets of the above prepregs, 35 μm thick electrolytic copper foils are stacked on the top and bottom, and heat-pressed for 120 minutes at a pressure of 40 kgf / cm 2 and a temperature of 190 ° C., and a 1.2 mm thick double-sided copper-clad laminate Got.
[0018]
(Example 3 , Reference Example 4 , and Comparative Examples 1-3)
A double-sided copper-clad laminate was prepared in the same manner as in Example 1 and Example 2 except for the formulation shown in Table 1.
[0019]
About the obtained copper clad laminated board, the flame retardance, solder heat resistance, and peel strength were measured. The evaluation results are shown in Tables 1 and 2. The copper clad laminates shown in the examples are all excellent in flame resistance and chemical resistance.
[0020]
[Table 1]
[0021]
[Table 2]
[0022]
(Measuring method)
1. . Flame retardancy: Evaluated by vertical method according to UL-94 standard.
2. . Solder heat resistance, peel strength: measured in accordance with JISC6481.
3. Solder heat resistance: After performing a moisture absorption treatment for 2 hours after boiling, the presence or absence of abnormal appearance was observed after being immersed in a solder bath at 260 ° C. for 120 seconds.
4). Chemical resistance: The weight loss rate when immersed in a 20% aqueous solution of sodium hydroxide at 80 ° C. for 10 minutes and the weight decrease rate when immersed in a 20% aqueous solution of potassium persulfate at 70 ° C. for 96 hours were determined.
[0023]
Notes to Table (1) Daikoku Ink Chemical Industries, Ltd. Epicron N-690, Epoxy Equivalent = 210
(2) manufactured by Dainippon Ink & Chemicals, Inc. Epicron N-770, epoxy equivalent = 190
(3) Mitsui Chemicals Co., Ltd. Millex XLC-LL, hydroxyl group equivalent = 175
(4) Dainippon Ink & Chemicals, Inc. LA-7054, hydroxyl equivalent = 125, nitrogen content = 12% by weight
(5) Weight reduction rate when immersed in a 20% by weight aqueous solution of sodium hydroxide at 80 ° C. for 10 minutes (6) Weight reduction rate when immersed in a 20% by weight aqueous solution of potassium persulfate at 70 ° C. for 96 hours
【The invention's effect】
The flame retardant resin composition of the present invention, a prepreg and a laminate using the same, have high flame retardancy without adding a halogen compound, have excellent properties such as solder heat resistance, and sufficient Has chemical resistance. Accordingly, the present invention provides a novel and useful thermosetting resin composition as a non-halogen material required in the future.
Claims (3)
Priority Applications (9)
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JP2000007515A JP4568937B2 (en) | 2000-01-17 | 2000-01-17 | Flame retardant resin composition, prepreg and laminate using the same |
TW89116711A TW587094B (en) | 2000-01-17 | 2000-08-18 | Flame-retardant resin composition comprising no halogen-containing flame retardant, and prepregs and laminates using such composition |
US09/642,156 US6551714B1 (en) | 2000-01-17 | 2000-08-21 | Flame-retardant resin composition, and prepregs and laminates using such composition |
SG200004757A SG92734A1 (en) | 2000-01-17 | 2000-08-22 | Flame-retardant resin composition, and prepregs and laminates using such composition |
MYPI20003881A MY120855A (en) | 2000-01-17 | 2000-08-23 | Flame-retardant resin composition, and prepregs and laminates using such composition. |
KR1020000050089A KR100701839B1 (en) | 2000-01-17 | 2000-08-28 | Flame-retardant resin composition, and prepregs and laminates using such composition |
EP20000118672 EP1116774B1 (en) | 2000-01-17 | 2000-08-29 | Flame-retardant resin composition, and prepregs and laminates using such composition |
DE2000621344 DE60021344T2 (en) | 2000-01-17 | 2000-08-29 | Flame retardant resin composition and prepregs and laminates made therefrom |
CNB001260979A CN1174046C (en) | 2000-01-17 | 2000-08-31 | Fire resistance resin compsns. and presoaking material and laminated products using same |
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JP4581599B2 (en) * | 2004-09-27 | 2010-11-17 | 住友ベークライト株式会社 | Resin composition, prepreg and laminate |
KR20110018938A (en) | 2008-06-11 | 2011-02-24 | 미쓰비시 쥬시 가부시끼가이샤 | Flame-retardant adhesive composition and laminated film |
JP5476284B2 (en) * | 2010-09-27 | 2014-04-23 | 積水化学工業株式会社 | Epoxy resin material and multilayer substrate |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS6079063A (en) * | 1983-10-07 | 1985-05-04 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and production thereof |
JPS6395223A (en) * | 1986-10-09 | 1988-04-26 | Asahi Denka Kogyo Kk | Phosphorus-containing epoxy resin composition |
JPH0439324A (en) * | 1990-06-04 | 1992-02-10 | Nippon Chem Ind Co Ltd | Epoxy resin hardener and phosphorus-containing epoxy resin composition produced by using the same |
JPH04306254A (en) * | 1990-12-12 | 1992-10-29 | American Cyanamid Co | Flame-retardant epoxy resin composition |
JPH08253557A (en) * | 1995-03-16 | 1996-10-01 | Dainippon Ink & Chem Inc | Epoxy resin composition |
JPH09255851A (en) * | 1996-03-22 | 1997-09-30 | Toshiba Chem Corp | Flame-retardant epoxy resin composition |
JPH09324108A (en) * | 1996-06-07 | 1997-12-16 | Sumitomo Bakelite Co Ltd | Flame-retarded resin composition and laminated board made thereof |
JP2000336243A (en) * | 1999-05-28 | 2000-12-05 | Toray Ind Inc | Epoxy resin composition and semiconductor device |
Family Cites Families (3)
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JP2757938B2 (en) * | 1987-09-14 | 1998-05-25 | 日東電工株式会社 | Semiconductor device |
JP3645694B2 (en) * | 1997-07-25 | 2005-05-11 | 住友ベークライト株式会社 | Flame retardant resin composition |
JP5139608B2 (en) * | 1999-11-18 | 2013-02-06 | Dic株式会社 | Epoxy resin composition |
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Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS6079063A (en) * | 1983-10-07 | 1985-05-04 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and production thereof |
JPS6395223A (en) * | 1986-10-09 | 1988-04-26 | Asahi Denka Kogyo Kk | Phosphorus-containing epoxy resin composition |
JPH0439324A (en) * | 1990-06-04 | 1992-02-10 | Nippon Chem Ind Co Ltd | Epoxy resin hardener and phosphorus-containing epoxy resin composition produced by using the same |
JPH04306254A (en) * | 1990-12-12 | 1992-10-29 | American Cyanamid Co | Flame-retardant epoxy resin composition |
JPH08253557A (en) * | 1995-03-16 | 1996-10-01 | Dainippon Ink & Chem Inc | Epoxy resin composition |
JPH09255851A (en) * | 1996-03-22 | 1997-09-30 | Toshiba Chem Corp | Flame-retardant epoxy resin composition |
JPH09324108A (en) * | 1996-06-07 | 1997-12-16 | Sumitomo Bakelite Co Ltd | Flame-retarded resin composition and laminated board made thereof |
JP2000336243A (en) * | 1999-05-28 | 2000-12-05 | Toray Ind Inc | Epoxy resin composition and semiconductor device |
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