JP3645745B2 - 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積層板用難燃性樹脂組成物、これを用いた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ムジベンゾフラン、及びポリブロモジ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が検討されている。
【０００３】
前述のように、リン化合物によって難燃化を実現できる。その機構は、リン化合物の分解および熱縮合によってポリリン酸が生成し、そのポリリン酸がエポキシ樹脂の表面に被膜を生成し、断熱効果、酸素遮断効果を生じ、その結果、燃焼を防ぐというものである。
【０００４】
しかしながら、リン化合物は吸水しやすい欠点があるため、多量に添加することは困難である。このため樹脂構造を難燃化する必要がある。一般に積層板に用いられるエポキシ樹脂はビスフェノールＡ型エポキシ樹脂とノボラックエポキシ樹脂であるが、ノボラックエポキシ樹脂の方が耐熱性も高く燃焼しにくい構造であるため、ノボラックエポキシ樹脂成分を多く添加すれば難燃化できる。しかしながらノボラックエポキシ樹脂成分が多くなれば密着力が低下し、半田耐熱性が著しく低下する欠点がある。
【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結果なされたものであり、リン含有化合物を用いることによってハロゲン含有化合物を使用しないで難燃性を発現させ、かつ十分な密着性と半田耐熱性を発現させることを目的とするもので、高度な難燃性を有する積層板用難燃性樹脂組成物、プリプレグ及びそのプリプレグから得られた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）エポキシ当量が１５００〜３０００であるハロゲン化されていないビスフェノールＡ型エポキシ樹脂又はビスフェノールＦ型エポキシ樹脂、（Ｂ）エポキシ当量が１５０〜２００であるハロゲン化されていない液状のビスフェノールＡ型エポキシ樹脂又はビスフェノールＦ型エポキシ樹脂、（Ｃ）ノボラックエポキシ樹脂、（Ｄ）エポキシ樹脂硬化剤、及び（Ｅ）分子内にハロゲンを含まないリン含有化合物を必須成分としてなることを特徴とする積層板用難燃性樹脂組成物に関するものである。そして、前記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、さらに前記プリプレグを１枚以上重ね合わせ加熱加圧してなることを特徴とする積層板又は金属箔張積層板に関するものである。
【０００７】
本発明者は、上記の課題を解決するために鋭意研究を重ねた結果、エポキシ樹脂として、エポキシ当量が１５００〜３０００であるハロゲン化されていないビスフェノールＡ型エポキシ樹脂又はビスフェノールＦ型エポキシ樹脂とエポキシ当量が１５０〜２００であるハロゲン化されていない液状のビスフェノールＡ型エポキシ樹脂又はビスフェノールＦ型エポキシ樹脂とノボラックエポキシ樹脂を併用し、さらにリン含有化合物を使用することで、密着力と耐熱性を同時に満足し、かつハロゲン化合物を使用しないで十分な難燃性を発現することを見いだした。
【０００８】
前述のようにリン含有化合物を使用することで、ハロゲン化合物を使用しなくても難燃化できる。しかしリン含有化合物を多量に配合すると吸湿しやすくなるため半田耐熱性が低下する。このため樹脂構造を燃焼しにくい構造にし、リン含有化合物の添加量を減少させる必要がある。
【０００９】
積層板等に使用されるエポキシ樹脂としてはビスフェノールＡ型エポキシ樹脂又はビスフェノールＦ型エポキシ樹脂、あるいはノボラックエポキシ樹脂があげられ、これらを併用することが多い。このうちノボラックエポキシ樹脂はベンゼン環含有率が高く炭化しやすく、また耐熱性も高いため燃焼しにくい。このため、ノボラックエポキシ樹脂の添加量を多くすれば難燃性を向上できる。しかしながらノボラックエポキシ樹脂の添加量を多くすれば、樹脂が脆くなり密着性が低下する。
【００１０】
密着性の低下を防ぐためには、用いるビスフェノールＡ型エポキシ樹脂又はビスフェノールＦ型エポキシ樹脂のエポキシ当量を大きくすればよい。エポキシ当量が１５００〜３０００であるハロゲン化されていないビスフェノールＡ型エポキシ樹脂又はビスフェノールＦ型エポキシ樹脂は鎖長が非常に長いため硬化物は非常に軟らかく、クラック等を生じにくく密着性に優れている。
【００１１】
エポキシ当量が１５００〜３０００であるハロゲン化されていないビスフェノールＡ型エポキシ樹脂又はビスフェノールＦ型エポキシ樹脂は粘度が非常に高くガラスクロス等の基材への塗布が困難であるが、エポキシ当量が１５０〜２００であるハロゲン化されていない液状ビスフェノールＡ型エポキシ樹脂又はビスフェノールＦ型エポキシ樹脂を併用することで粘度が下がり、塗布が容易となる。またエポキシ当量が１５０〜２００であるビスフェノールＡ型エポキシ樹脂又はビスフェノールＦ型エポキシ樹脂はエポキシ当量が小さく架橋点間距離が短いため架橋密度を低下させず、耐熱性が低下しない。
【００１２】
本発明で用いる（Ａ）エポキシ当量が１５００〜３０００であるハロゲン化されていないビスフェノールＡ型エポキシ樹脂又はビスフェノールＦ型エポキシ樹脂はエポキシ樹脂の合計量１００重量部中、１０〜４０重量部であることが好ましい。１０重量部未満では樹脂の密着力が十分でなく、４０重量部を越えると耐熱性が低下するようになり、また燃焼しやすくなる。耐熱性を考慮するとエポキシ当量は１５００程度が好ましく、密着力を考慮するとエポキシ当量は３０００程度が好ましい。耐熱性を考慮するとビスフェノールＡ型エポキシ樹脂が好ましく、耐燃性を考慮するとビスフェノールＦ型エポキシ樹脂が好ましい。
【００１３】
本発明で用いる（Ｂ）エポキシ当量が１５０〜２００であるハロゲン化されていない液状のビスフェノールＡ型エポキシ樹脂又はビスフェノールＦ型エポキシ樹脂は、エポキシ樹脂の合計量１００重量部中、５〜３０重量部であることが好ましい。５重量部未満では樹脂の粘度が高くなり、３０重量部を越えると樹脂の粘度が低くなりともに塗布が困難となるため好ましくない。耐熱性を考慮するとビスフェノールＡ型エポキシ樹脂が好ましく、耐燃性を考慮するとビスフェノールＦ型エポキシ樹脂が好ましい。
【００１４】
本発明で用いる（Ｃ）ノボラックエポキシ樹脂は、エポキシ樹脂の合計量１００重量部中、３０〜６０重量部であることが好ましい。３０重量部未満では難燃性が十分でなく、６０重量部を越えると樹脂が堅く脆くなり好ましくない。
【００１５】
本発明で用いる（Ｄ）エポキシ樹脂硬化剤は、芳香族アミン化合物、酸無水物、ノボラック樹脂などがあげられる。樹脂の難燃化を考慮するとフェノールアラルキル樹脂が炭化しやすい構造であり、また優れた耐熱性及び密着性を有することから好ましい。
【００１６】
本発明で用いる（Ｅ）分子内にハロゲンを含まないリン含有化合物としては、トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェート、トリ−２−エチルヘキシルホスフェート、トリブトキシエチルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、クレジルジフェニルホスフェート、キシレニルジフェニルホスフェート、２−エチルヘキシルジフェニルホスフェート、トリス（２、６ジメチルフェニル）ホスフェート、レゾルシンジフェニルホスフェート等のリン酸エステル、ジアルキルヒドロキシメチルホスホネート等の縮合リン酸エステル等が例示されるが、特にこれらに限定されるものではない。エポキシ樹脂の優れた特性を損なわないためには、エポキシ樹脂と反応するものが望ましく、特に、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシドが望ましい。
【００１７】
本発明の積層板用難燃性樹脂組成物は、上述した（Ａ）エポキシ当量が１５００〜３０００であるハロゲン化されていないビスフェノールＡ型エポキシ樹脂又はビスフェノールＦ型エポキシ樹脂、（Ｂ）エポキシ当量が１５０〜２００であるハロゲン化されていない液状のビスフェノールＡ型エポキシ樹脂又はビスフェノールＦ型エポキシ樹脂、（Ｃ）ノボラックエポキシ樹脂、（Ｄ）エポキシ樹脂硬化剤、及び（Ｅ）分子内にハロゲンを含まないリン含有化合物を必須成分とするが、本発明の目的に反しない範囲において、その他の硬化剤、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。
【００１８】
本発明のエポキシ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が使用される。用いられる溶剤は組成の一部に対して良好な溶解性を示すことが必要であるが、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。
【００１９】
本発明の積層板用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クロス、ガラス不織布、あるいはガラス以外を成分とする布等の基材に塗布、含浸させ、８０〜２００℃で乾燥させることによりプリント配線板用プリプレグを得ることが出来る。プリプレグは加熱加圧してプリント配線板を製造することに用いられるが、本発明の積層板用難燃性樹脂組成物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する熱硬化性樹脂組成物であり、積層板に好適に使用されるものである。
【００２０】
【実施例】
以下、本発明について実施例及び比較例により具体的に説明する。ここで、「部」及び「％」は「重量部」及び「重量％」を示す。
【００２１】
（実施例１）
ビスフェノールＡ型エポキシ樹脂（油化シェルエポキシ社製エピコート１００７：エポキシ当量２１０６）３２．８部、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社製エピクロンＮ−６９０：エポキシ当量２１０）４７．４部、ビスフェノールＦ型エポキシ樹脂（油化シェルエポキシ社製エピコート８０７：エポキシ当量１７０）１９．８部、フェノールアラルキル樹脂（三井化学社製ミレックスＸＬＣ−ＬＬ）５８．７重量部、及び９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド２９重量部にメチルセルソルブを加え、不揮発分濃度６０％となるようにワニスを調製した。
【００２２】
このワニスを用いて、ガラスクロス（厚さ０．１８ｍｍ、日東紡績（株）製）１００部にワニス固形分で８０部含浸させて、１５０℃の乾燥機で５分間乾燥させ、樹脂含有量４４．４％のプリプレグを作成した。上記プリプレグ６枚を重ね、上下に厚さ３５μｍの電解銅箔を重ねて、圧力４０ｋｇｆ／ｃｍ２、温度１９０℃で１２０分間加熱加圧成形を行い、厚さ１．２ｍｍの両面銅張積層板を得た。得られた積層板の難燃性は、ＵＬ−９４規格に従い垂直法により評価した。半田耐熱性、ピール強度についてはＪＩＳ Ｃ ６４８１に準じて測定し、半田耐熱性は煮沸２時間の吸湿処理を行った後、２６０℃の半田槽に１２０秒間浸漬した後の外観の異常の有無を調べた。配合処方及び結果を表１に示す。
【００２３】
（実施例２〜４、及び比較例１〜４）
表１（実施例）及び表２（比較例）に示した配合処方により、これ以外は全て実施例１と同様の方法で両面銅張積層板を作成した。評価結果を併せ表１及び表２に示す。表１に示す実施例では、いずれもピール強度が強く、かつ耐燃性に優れていることがわかる。
【００２４】
【表１】
【表２】
表１及び表２の注
（１）油化シェルエポキシ社製エピコート１００７、エポキシ当量２１０５
（２）油化シェルエポキシ社製エピコート４００７、エポキシ当量２０５０
（３）大日本インキ化学工業社製エピクロンＮ−６９０、エポキシ当量２１０
（４）油化シェルエポキシ社製エピコート８２８、エポキシ当量１９０
（５）油化シェルエポキシ社製エピコート８０７、エポキシ当量１７０
（６）三井化学(株)製ミレックスＸＬＣ−ＬＬ、水酸基当量１７５
（７）９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシド
（８）油化シェルエポキシ社製エピコート１００１、エポキシ当量４７５
（９）油化シェルエポキシ社製エピコート４００１、エポキシ当量４７８
【００２７】
【発明の効果】
本発明の積層板用難燃性樹脂組成物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、今後要求されるノンハロゲン材料として新規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 flame retardant resin composition for laminates having excellent flame retardancy without using a halogen-based flame retardant, a prepreg and a laminate using the flame retardant resin composition.
[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 polybromodibenzoxine . Also, it is extremely difficult to dispose of obsolete waste containing bromine. For these reasons, phosphorus compounds 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. The mechanism is that polyphosphoric acid is generated by the decomposition and thermal condensation of the phosphorus compound, and the polyphosphoric acid forms a film on the surface of the epoxy resin, resulting in an adiabatic effect and an oxygen blocking effect, thereby preventing combustion. is there.
[0004]
However, it is difficult to add a large amount of a phosphorus compound because it has a drawback of easily absorbing water. For this reason, it is necessary to make the resin structure flame-retardant. In general, epoxy resins used for laminated boards are bisphenol A type epoxy resin and novolac epoxy resin, but novolac epoxy resin is more heat resistant and less flammable, so it is difficult to add more novolac epoxy resin components. Can burn. However, when the novolac epoxy resin component is increased, the adhesion strength is lowered, and the solder heat resistance is significantly lowered.
[0005]
[Problems to be solved by the invention]
The present invention has been made in order to solve such a problem. By using a phosphorus-containing compound, the present invention exhibits flame retardancy without using a halogen-containing compound, and has sufficient adhesion and solder heat resistance. The present invention provides a flame retardant resin composition for laminates having a high degree of flame retardancy, a prepreg, and a laminate obtained from the prepreg.
[0006]
[Means for Solving the Problems]
The present invention includes (A) an unhalogenated bisphenol A type epoxy resin or bisphenol F type epoxy resin having an epoxy equivalent of 1500 to 3000, and (B) an unhalogenated liquid having an epoxy equivalent of 150 to 200. A bisphenol A type epoxy resin or a bisphenol F type epoxy resin, (C) a novolac epoxy resin, (D) an epoxy resin curing agent, and (E) a phosphorus-containing compound containing no halogen in the molecule are essential components. The present invention relates to a flame retardant resin composition for laminates . Further, the present invention relates to a prepreg obtained by impregnating a base material with the resin composition, and further, a laminate or a metal foil-clad laminate obtained by heating and pressing one or more of the prepregs. It is.
[0007]
As a result of intensive research in order to solve the above-mentioned problems, the present inventor, as an epoxy resin, an epoxy resin having an epoxy equivalent of 1500 to 3000, an unhalogenated bisphenol A type epoxy resin or a bisphenol F type epoxy resin and an epoxy By using a non-halogenated liquid bisphenol A type epoxy resin or bisphenol F type epoxy resin and a novolac epoxy resin having an equivalent weight of 150 to 200, and further using a phosphorus-containing compound, adhesion and heat resistance can be simultaneously achieved. It was found that satisfactory flame retardancy was developed without using a halogen compound.
[0008]
By using a phosphorus-containing compound as described above, flame retardancy can be achieved without using a halogen compound. However, when a large amount of a phosphorus-containing compound is blended, it becomes easy to absorb moisture and solder heat resistance is lowered. For this reason, it is necessary to make the resin structure difficult to burn and reduce the amount of phosphorus-containing compound added.
[0009]
Examples of the epoxy resin used for the laminated plate include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and novolac epoxy resin, and these are often used in combination. Of these, the novolac epoxy resin has a high benzene ring content and is easily carbonized, and also has high heat resistance, so it is difficult to burn. For this reason, if the addition amount of a novolak epoxy resin is increased, flame retardancy can be improved. However, if the addition amount of the novolac epoxy resin is increased, the resin becomes brittle and the adhesion is lowered.
[0010]
In order to prevent a decrease in adhesion, the epoxy equivalent of the bisphenol A type epoxy resin or bisphenol F type epoxy resin to be used may be increased. Non-halogenated bisphenol A type epoxy resin or bisphenol F type epoxy resin having an epoxy equivalent of 1500 to 3000 has a very long chain length, so the cured product is very soft and does not easily cause cracks and has excellent adhesion. .
[0011]
Non-halogenated bisphenol A type epoxy resin or bisphenol F type epoxy resin having an epoxy equivalent of 1500 to 3000 has a very high viscosity and is difficult to apply to a substrate such as a glass cloth, but has an epoxy equivalent of 150 to 3000. By using together the non-halogenated liquid bisphenol A type epoxy resin or bisphenol F type epoxy resin which is 200, the viscosity is lowered and the coating becomes easy. In addition, bisphenol A type epoxy resin or bisphenol F type epoxy resin having an epoxy equivalent of 150 to 200 has a low epoxy equivalent and a short distance between cross-linking points, so that the cross-linking density is not lowered and the heat resistance is not lowered.
[0012]
The non-halogenated bisphenol A type epoxy resin or bisphenol F type epoxy resin (A) having an epoxy equivalent of 1500 to 3000 used in the present invention is 10 to 40 parts by weight in a total amount of 100 parts by weight of the epoxy resin. Is preferred. If the amount is less than 10 parts by weight, the adhesive strength of the resin is not sufficient, and if it exceeds 40 parts by weight, the heat resistance is lowered and combustion tends to occur. In consideration of heat resistance, the epoxy equivalent is preferably about 1500, and in consideration of adhesion, the epoxy equivalent is preferably about 3000. In consideration of heat resistance, bisphenol A type epoxy resin is preferable, and in consideration of flame resistance, bisphenol F type epoxy resin is preferable.
[0013]
(B) The non-halogenated liquid bisphenol A type epoxy resin or bisphenol F type epoxy resin having an epoxy equivalent of 150 to 200 used in the present invention is 5 to 30 parts by weight in a total amount of 100 parts by weight of the epoxy resin. It is preferable that If it is less than 5 parts by weight, the viscosity of the resin is high, and if it exceeds 30 parts by weight, the viscosity of the resin is low and it becomes difficult to apply the resin. In consideration of heat resistance, bisphenol A type epoxy resin is preferable, and in consideration of flame resistance, bisphenol F type epoxy resin is preferable.
[0014]
The (C) novolac epoxy resin used in the present invention is preferably 30 to 60 parts by weight in 100 parts by weight of the total amount of the epoxy resin. If it is less than 30 parts by weight, the flame retardancy is not sufficient, and if it exceeds 60 parts by weight, the resin is not preferable because it is hard and brittle.
[0015]
Examples of the (D) epoxy resin curing agent used in the present invention include aromatic amine compounds, acid anhydrides, and novolak resins. Considering the flame retardancy of the resin, the phenol aralkyl resin is preferable because it has a structure that is easily carbonized and has excellent heat resistance and adhesion.
[0016]
The phosphorus-containing compound containing no halogen in the molecule (E) used in the present invention includes trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, Phosphoric esters such as trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tris (2,6 dimethylphenyl) phosphate, resorcin diphenyl phosphate, condensed phosphoric acid such as dialkylhydroxymethylphosphonate Examples include esters, but are not particularly limited thereto. In order not to impair the excellent properties of the epoxy resin, those that react with the epoxy resin are desirable, and in particular, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is desirable.
[0017]
The flame retardant resin composition for laminates of the present invention has the above-mentioned (A) non-halogenated bisphenol A type epoxy resin or bisphenol F type epoxy resin having an epoxy equivalent of 1500 to 3000, and (B) an epoxy equivalent of 150-200 non-halogenated liquid bisphenol A type epoxy resin or bisphenol F type epoxy resin, (C) novolac epoxy resin, (D) epoxy resin curing agent, and (E) no halogen in the molecule The phosphorus-containing compound is an essential component, but other curing agents, curing accelerators, coupling agents, and other components may be added within a range not departing from the object of the present invention.
[0018]
Although the epoxy resin composition of the present invention is used in various forms, a solvent is usually used when impregnating the base material. The solvent to be used needs to exhibit good solubility with respect to a part of the composition, but a poor solvent may be used as long as it does not adversely affect the composition.
[0019]
The varnish obtained by dissolving the flame retardant resin composition for laminates of the present invention in a solvent is coated and impregnated on a substrate such as glass cloth, glass nonwoven fabric, or cloth containing components other than glass, and 80 to 200 ° C. A prepreg for a printed wiring board can be obtained by drying with. Although the prepreg is used for producing a printed wiring board by heating and pressing, the flame retardant resin composition for laminated boards of the present invention is a thermosetting resin composition having high flame retardancy without adding a halogen compound. It is a thing and is used suitably for a laminated board .
[0020]
【Example】
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. Here, “parts” and “%” indicate “parts by weight” and “% by weight”.
[0021]
(Example 1)
32.8 parts of bisphenol A type epoxy resin (Epicoat 1007 manufactured by Yuka Shell Epoxy Co., Ltd .: epoxy equivalent 2106), 47.4 parts of cresol novolac epoxy resin (Epicron N-690 manufactured by Dainippon Ink and Chemicals, Inc. 210), 19.8 parts of bisphenol F type epoxy resin (Epicoat 807 manufactured by Yuka Shell Epoxy Co., Ltd .: epoxy equivalent 170), 58.7 parts by weight of phenol aralkyl resin (Millex XLC-LL manufactured by Mitsui Chemicals), and 9,10-dihydro- Methyl cellosolve was added to 29 parts by weight of 9-oxa-10-phosphaphenanthrene-10-oxide, and a varnish was prepared so as to have a nonvolatile content concentration of 60%.
[0022]
Using this varnish, a glass cloth (thickness 0.18 mm, manufactured by Nitto Boseki Co.) in 100 parts by impregnating 80 parts varnish solids, dried for 5 minutes at a 0.99 ° C. dryer resin content A 44.4% prepreg was made. Overlapping the prepreg six, overlapping the electrolytic copper foil having a thickness of 35μm up and down, pressure 40 kgf / cm 2, subjected to 120 minutes hot pressing at a temperature 190 ° C., a thickness of 1.2mm copper clad laminate I got a plate. The flame retardancy of the obtained laminate was evaluated by the vertical method according to the UL-94 standard. Solder heat resistance, measured according to JIS C 6481 for peel strength, after the performing the moisture absorption treatment of boiling 2 hours solder heat resistance, presence or absence of abnormality in appearance after immersion for 120 seconds in a solder bath at 260 ° C. I investigated. The formulation and results are shown in Table 1.
[0023]
(Examples 2 to 4 and Comparative Examples 1 to 4)
A double-sided copper-clad laminate was prepared in the same manner as in Example 1 except for the formulation described in Table 1 (Example) and Table 2 (Comparative Example). The evaluation results are shown in Table 1 and Table 2. In the examples shown in Table 1, it can be seen that the peel strength is strong and the flame resistance is excellent.
[0024]
[Table 1]
[Table 2]
Notes to Table 1 and Table 2 (1) Epicoat 1007, Epoxy equivalent 2105 manufactured by Yuka Shell Epoxy
(2) Epicoat 4007 made by Yuka Shell Epoxy, epoxy equivalent 2050
(3) Dainippon Ink & Chemicals, Inc. Epicron N-690, epoxy equivalent 210
(4) Yuko Shell Epoxy Epicoat 828, epoxy equivalent 190
(5) Epicoat 807 manufactured by Yuka Shell Epoxy, epoxy equivalent 170
(6) Millex XLC-LL, hydroxyl equivalent 175 manufactured by Mitsui Chemicals, Inc.
(7) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (8) Epicoat 1001 made by Yuka Shell Epoxy, epoxy equivalent 475
(9) Yuko Shell Epoxy Epicoat 4001, epoxy equivalent 478
[0027]
【The invention's effect】
The flame-retardant resin composition for laminates of the present invention has a high flame retardancy without adding a halogen compound, and provides a novel thermosetting resin composition as a non-halogen material that will be required in the future. .
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15662199A JP3645745B2 (en) | 1999-06-03 | 1999-06-03 | Flame retardant resin composition, prepreg and laminate using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15662199A JP3645745B2 (en) | 1999-06-03 | 1999-06-03 | Flame retardant resin composition, prepreg and laminate using the same |
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| Publication Number | Publication Date |
|---|---|
| JP2000344861A JP2000344861A (en) | 2000-12-12 |
| JP3645745B2 true JP3645745B2 (en) | 2005-05-11 |
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| JP (1) | JP3645745B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140141270A (en) * | 2013-05-31 | 2014-12-10 | 엘지이노텍 주식회사 | Epoxy resin composite and printed circuit board using the same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2003228106A1 (en) | 2002-05-24 | 2003-12-12 | Nippon Shokubai Co., Ltd. | Fire retardant resin composition, method of its production, shaped articles comprising the same, and silica |
| EP4029895A1 (en) * | 2021-01-15 | 2022-07-20 | Rembrandtin Coatings GmbH | Compound |
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1999
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140141270A (en) * | 2013-05-31 | 2014-12-10 | 엘지이노텍 주식회사 | Epoxy resin composite and printed circuit board using the same |
| KR102111600B1 (en) | 2013-05-31 | 2020-05-15 | 엘지이노텍 주식회사 | Epoxy resin composite and printed circuit board using the same |
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| Publication number | Publication date |
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| JP2000344861A (en) | 2000-12-12 |
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