JP2000344861A - Flame-retardant resin composition, and prepreg and laminate using the same - Google Patents
Flame-retardant resin composition, and prepreg and laminate using the sameInfo
- Publication number
- JP2000344861A JP2000344861A JP11156621A JP15662199A JP2000344861A JP 2000344861 A JP2000344861 A JP 2000344861A JP 11156621 A JP11156621 A JP 11156621A JP 15662199 A JP15662199 A JP 15662199A JP 2000344861 A JP2000344861 A JP 2000344861A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- bisphenol
- resin
- type epoxy
- resin composition
- 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.)
- Granted
Links
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【０００１】[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、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。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having excellent flame retardancy without using a halogen-based flame retardant, a prepreg and a laminate using the same.
【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が検討されている。[0002] Thermosetting resins represented by epoxy resins are widely used for electric and electronic equipment parts due to their excellent characteristics, and are provided with flame retardancy to ensure fire safety. There are many. Conventionally, these resins have generally used a halogen-containing compound such as a brominated epoxy resin. Although these halogen-containing compounds have high flame retardancy, aromatic bromine compounds not only separate corrosive bromine and hydrogen bromide by thermal decomposition, but also have high toxicity when decomposed in the presence of oxygen. May form bromodibenzofuran and polydibromobenzooxin. Further, disposal of aging waste material containing bromine is extremely difficult. For these reasons, phosphorus compounds have been studied as flame retardants in place of bromine-containing flame retardants.
【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。[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, which has an insulating effect and an oxygen blocking effect, and as a result, prevents combustion. is there.
【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。[0004] However, phosphorus compounds have a drawback of easily absorbing water, so that it is difficult to add them in large amounts. For this reason, it is necessary to make the resin structure flame-retardant. In general, epoxy resins used for laminates are bisphenol A type epoxy resin and novolak epoxy resin. However, since novolak epoxy resin has a higher heat resistance and is less likely to burn, it is difficult to add a large amount of novolak epoxy resin component. Can burn. However, when the novolak epoxy resin component increases, there is a disadvantage that the adhesive strength is reduced and the solder heat resistance is significantly reduced.
【０００５】[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。DISCLOSURE OF THE INVENTION The present invention has been made in order to solve such a problem, and the present invention has shown that by using a phosphorus-containing compound, flame retardancy can be exhibited without using a halogen-containing compound. Another object of the present invention is to provide a resin composition having a high degree of flame retardancy, a prepreg, and a laminate obtained from the prepreg, with the object of developing sufficient adhesiveness and solder heat resistance.
【０００６】[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１５０〜２
００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。According to the present invention, there are provided (A) a non-halogenated bisphenol A type epoxy resin or a bisphenol F type epoxy resin having an epoxy equivalent of 1500 to 3000, and (B) an epoxy equivalent of 150 to 2
A non-halogenated liquid bisphenol A type epoxy resin or bisphenol F type epoxy resin, (C) novolak epoxy resin, (D) epoxy resin curing agent, and (E) phosphorus containing no halogen in the molecule. The present invention relates to a resin composition comprising a compound as an essential component. And, a prepreg characterized by impregnating a base material with the resin composition, and a laminate or a metal foil-clad laminate characterized in that one or more prepregs are stacked and heated and pressed. It is.
【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。The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, as an epoxy resin, a non-halogenated bisphenol A type epoxy resin or a bisphenol F type epoxy resin having an epoxy equivalent of 1500 to 3000. Adhesive strength and heat resistance by using a resin and a non-halogenated liquid bisphenol A type epoxy resin or a bisphenol F type epoxy resin having an epoxy equivalent of 150 to 200 and a novolak epoxy resin, and further using a phosphorus-containing compound. It has been found that these compounds simultaneously satisfy the properties and exhibit sufficient flame retardancy without using a halogen compound.
【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。By using a phosphorus-containing compound as described above, flame retardancy can be achieved without using a halogen compound.
However, when the phosphorus-containing compound is blended in a large amount, it becomes easy to absorb moisture, so that the solder heat resistance decreases. For this reason, it is necessary to make the resin structure difficult to burn and to reduce the amount of the phosphorus-containing compound added.
【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。Examples of the epoxy resin used for the laminated board and the like include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and novolak epoxy resin, and these are often used in combination. Of these, novolak epoxy resin has a high benzene ring content and is easily carbonized, and has high heat resistance, so that it is difficult to burn. For this reason,
Increasing the amount of novolak epoxy resin can improve flame retardancy. However, if the amount of the novolak epoxy resin is increased, the resin becomes brittle and the adhesion is reduced.
【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。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. The 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 that the cured product is very soft, hardly generates cracks and the like, and has excellent adhesion. .
【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１５０〜２
００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。The 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. When a non-halogenated liquid bisphenol A-type epoxy resin or bisphenol F-type epoxy resin having a viscosity of 150 to 200 is used in combination, the viscosity is reduced and the coating is facilitated. The epoxy equivalent is 150-2.
The bisphenol A type epoxy resin or the bisphenol F type epoxy resin of 00 has a small epoxy equivalent and a short distance between crosslink points, so that the crosslink density does not decrease and the heat resistance does not decrease.
【００１２】本発明で用いる（Ａ）エポキシ当量が１５
００〜３０００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。The epoxy equivalent (A) used in the present invention is 15
The non-halogenated bisphenol A type epoxy resin or bisphenol F type epoxy resin of 100 to 3000 is 10 to 10 parts by weight in the total amount of the epoxy resin.
Preferably it is 40 parts by weight. 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 reduced, and the resin tends to burn. The epoxy equivalent is preferably about 1500 in consideration of heat resistance, and the epoxy equivalent is preferably about 3000 in consideration of adhesion. 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】本発明で用いる（Ｂ）エポキシ当量が１５
０〜２００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。The epoxy equivalent (B) used in the present invention is 15
The non-halogenated liquid bisphenol A-type epoxy resin or bisphenol F-type epoxy resin of 0 to 200 is contained in 5 parts by weight of the total amount of the epoxy resin.
It is preferably from 30 to 30 parts by weight. If the amount is less than 5 parts by weight, the viscosity of the resin becomes high, and if it exceeds 30 parts by weight, the viscosity of the resin becomes low and the application becomes difficult, which is not preferable. 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】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。The novolak epoxy resin (C) used in the present invention is used in an amount of 30 to 30 parts by weight based on 100 parts by weight of the total amount of the epoxy resin.
Preferably, it is 60 parts by weight. If the amount is less than 30 parts by weight, the flame retardancy is not sufficient, and if it exceeds 60 parts by weight, the resin becomes hard and brittle, which is not preferable.
【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。The epoxy resin curing agent (D) used in the present invention includes 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 easily carbonizes, and has excellent heat resistance and adhesion.
【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。The (E) phosphorus-containing compound containing no halogen in the molecule includes trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, and the like.
Phosphoric acid esters such as tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tris (2,6 dimethylphenyl) phosphate, resorcinol diphenyl phosphate, dialkyl hydroxymethyl phosphonate And the like, but are not particularly limited thereto. In order not to impair the excellent properties of the epoxy resin, those which react with the epoxy resin are desirable, and in particular, 9,10-dihydro-9-oxa-10
-Phosphaphenanthrene-10-oxide is preferred.
【００１７】本発明の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。The flame-retardant resin composition of the present invention comprises: (A) a non-halogenated bisphenol A type epoxy resin or bisphenol F type epoxy resin having an epoxy equivalent of 1500 to 3000; Non-halogenated liquid bisphenol A type epoxy resin or bisphenol F having a molecular weight of 150 to 200
Type epoxy resin, (C) novolak epoxy resin,
(D) an epoxy resin curing agent and (E) a phosphorus-containing compound containing no halogen in the molecule are essential components, but other curing agents, curing accelerators, and couplings within a range not inconsistent with the object of the present invention. Agents and other components can be added.
【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。Although the epoxy resin composition of the present invention is used in various forms, a solvent is usually used when impregnating the substrate. The solvent used must have good solubility for a part of the composition, but a poor solvent may be used as long as it does not adversely affect the composition.
【００１９】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、積層板等に好適に使用されるものである。The varnish obtained by dissolving the flame-retardant resin composition of the present invention in a solvent is applied and impregnated to a substrate such as glass cloth, glass non-woven fabric, or cloth containing a component other than glass at 80 to 200 ° C. Thus, a prepreg for a printed wiring board can be obtained. The prepreg is used for manufacturing a printed wiring board by heating and pressing, and the flame-retardant resin composition of the present invention is a thermosetting resin composition having a high flame retardancy without adding a halogen compound. And a laminate plate.
【００２０】[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。The present invention will be specifically described below with reference to examples and comparative examples. Here, “parts” and “%” indicate “parts by weight” and “% by weight”.
【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ＸＬ
Ｃ−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。Example 1 32.8 parts of a bisphenol A type epoxy resin (Epicoat 1007 manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent: 2106) and a cresol novolak epoxy resin (Epiclon N-690 manufactured by Dainippon Ink and Chemicals, Inc .: epoxy) 210) 47.4 parts, bisphenol F type epoxy resin (Epicoat 807 manufactured by Yuka Shell Epoxy Co., Ltd .: epoxy equivalent 170) 19.8 parts, phenol aralkyl resin (Mirex XL manufactured by Mitsui Chemicals, Inc.)
C-LL) 58.7 parts by weight, and 9,10-dihydro-
Methylcellosolve was added to 29 parts by weight of 9-oxa-10-phosphaphenanthrene-10-oxide to prepare a varnish so as to have a nonvolatile content of 60%.
【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。
上記プリプレグを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１９
０℃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。得られた積層板の難燃性は、Ｕ
Ｌ−９４規格に従い垂直方により評価した。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。Using this varnish, 100 parts of a glass cloth (0.18 mm in thickness, manufactured by Nitto Boseki Co., Ltd.) is impregnated with 80 parts of a varnish solid and dried in a dryer at 150 ° C. for 5 minutes to obtain a resin. A prepreg having a content of 44.4% was prepared.
Six prepregs were stacked, and an electrolytic copper foil having a thickness of 35 μm was stacked on the upper and lower sides under a pressure of 40 kgf / cm 2 and a temperature of 19
Heat and pressure molding was performed at 0 ° C for 120 minutes to obtain a double-sided copper-clad laminate having a thickness of 1.2 mm. The flame retardancy of the obtained laminate is U
It was evaluated in the vertical direction according to the L-94 standard. Solder heat resistance and peel strength were measured in accordance with JIS C 6481. Solder heat resistance was measured for the appearance of abnormalities after immersion in a 260 ° C. solder bath for 120 seconds after performing a moisture absorption treatment for 2 hours after boiling. Examined. Table 1 shows the formulation and results.
【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。(Examples 2 to 4 and Comparative Examples 1 to 4)
Except for this, the double-sided copper-clad laminate was prepared in the same manner as in Example 1 except for the formulation shown in (Example) and Table 2 (Comparative Example). The evaluation results are shown in Tables 1 and 2.
In the examples shown in Table 1, it can be seen that the peel strength is high and the flame resistance is excellent.
【００２４】[0024]
【表１】 [Table 1]
【００２５】[0025]
【表２】 [Table 2]
【００２６】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−６９
０、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４７８Notes to Tables 1 and 2 (1) Yuko Shell Epoxy Epicoat 1007, epoxy equivalent 2105 (2) Yuka Shell Epoxy Epicoat 4007, epoxy equivalent 2050 (3) Dainippon Ink & Chemicals, Inc. Epicron N-69
0, epoxy equivalent 210 (4) Yuka Shell Epoxy Epicoat 828, epoxy equivalent 190 (5) Yuka Shell Epoxy Epicoat 807, epoxy equivalent 170 (6) Mitsui Chemicals, Inc. Millex XLC-LL, hydroxyl group Equivalent 175 (7) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (8) Epicoat 1001 manufactured by Yuka Shell Epoxy Co., Ltd. Epoxy equivalent 475 (9) Epicoat 4001 manufactured by Yuka Shell Epoxy , Epoxy equivalent 478
【００２７】[0027]
【発明の効果】本発明の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。The flame-retardant resin composition of the present invention has a high degree of flame retardancy without adding a halogen compound, and provides a novel thermosetting resin composition as a non-halogen material required in the future. It is.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｋ 5/49 Ｃ０８Ｋ 5/49 Ｃ０８Ｌ 63/00 Ｃ０８Ｌ 63/00 Ｂ Ｃ Ｆターム(参考） 4F072 AA05 AA07 AB09 AB28 AD23 AE07 AF16 AG03 AG17 AG19 AH02 AH21 AJ04 AL12 4F100 AB01B AB33B AG00A AH03A AH07A AK33A AK33H AK53A BA01 BA02 CA02A DG11A DH01A EJ82A GB43 JJ03 4J002 CD05W CD05X CD06Y CE004 EW006 FD136 FD144 GF00 4J036 AA01 AA02 FA04 FB07 JA08──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C08K 5/49 C08K 5/49 C08L 63/00 C08L 63/00 B CF term (Reference) 4F072 AA05 AA07 AB09 AB28 AD23 AE07 AF16 AG03 AG17 AG19 AH02 AH21 AJ04 AL12 4F100 AB01B AB33B AG00A AH03A AH07A AK33A AK33H AK53A BA01 BA02 CA02A DG11A DH01A EJ82A GB43 JJ03 4J002 CD05W CD05X CD06A04 EA04A04
Claims (5)
０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難燃性樹脂組成物。(A) an epoxy equivalent of from 1500 to 300
0, a non-halogenated bisphenol A type epoxy resin or a bisphenol F type epoxy resin,
(B) Non-halogenated liquid bisphenol A type epoxy resin or bisphenol F type epoxy resin having an epoxy equivalent of 150 to 200, (C) novolak epoxy resin, (D) epoxy resin curing agent, and (E)
A flame-retardant resin composition comprising a phosphorus-containing compound containing no halogen in a molecule as an essential component.
ノールアラルキル樹脂であること請求項１記載の樹脂組
成物。2. The resin composition according to claim 1, wherein the epoxy resin curing agent (D) is a phenol aralkyl resin.
いリン含有化合物が９，１０−ジヒドロ−９−オキサ−
１０−ホスファフェナントレン−１０−オキシドである
請求項１又は２記載の樹脂組成物。3. The component (E) wherein the phosphorus-containing compound containing no halogen in the molecule is 9,10-dihydro-9-oxa-
3. The resin composition according to claim 1, which is 10-phosphaphenanthrene-10-oxide.
基材に含浸させてなることを特徴とするプリプレグ。4. A prepreg comprising a substrate impregnated with the resin composition according to claim 1, 2 or 3.
複数枚重ね合わせ、加熱加圧成形してなることを特徴と
する積層板又は金属箔張積層板。5. A laminate or a metal foil-clad laminate obtained by laminating one or more prepregs according to claim 4 and subjecting them to heat and pressure molding.
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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000344861A true JP2000344861A (en) | 2000-12-12 |
| JP3645745B2 JP3645745B2 (en) | 2005-05-11 |
Family
ID=15631724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15662199A Expired - Fee Related JP3645745B2 (en) | 1999-06-03 | 1999-06-03 | Flame retardant resin composition, prepreg and laminate using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3645745B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7601775B2 (en) | 2002-05-24 | 2009-10-13 | 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 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102111600B1 (en) * | 2013-05-31 | 2020-05-15 | 엘지이노텍 주식회사 | Epoxy resin composite and printed circuit board using the same |
-
1999
- 1999-06-03 JP JP15662199A patent/JP3645745B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7601775B2 (en) | 2002-05-24 | 2009-10-13 | 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 |
| WO2022152851A1 (en) * | 2021-01-15 | 2022-07-21 | Rembrandtin Coatings Gmbh | Composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3645745B2 (en) | 2005-05-11 |
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