JP2003221430A - Epoxy resin composition, prepreg and laminated board - Google Patents
Epoxy resin composition, prepreg and laminated boardInfo
- Publication number
- JP2003221430A JP2003221430A JP2002024503A JP2002024503A JP2003221430A JP 2003221430 A JP2003221430 A JP 2003221430A JP 2002024503 A JP2002024503 A JP 2002024503A JP 2002024503 A JP2002024503 A JP 2002024503A JP 2003221430 A JP2003221430 A JP 2003221430A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- phosphorus
- resin composition
- prepreg
- formula
- 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
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ハロゲン化合物を
使用しなくても優れた難燃性を有する硬化物が得られる
エポキシ樹脂組成物、これを用いたプリプレグ及びこの
プリプレグを用いた積層板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition capable of obtaining a cured product having excellent flame retardancy without using a halogen compound, a prepreg using the same, and a laminate using the prepreg. .
【０００２】[0002]
【従来の技術】エポキシ樹脂組成物はその優れた特性か
ら、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。エポキシ樹脂組成物の難燃化は、従来臭素化エポ
キシ樹脂等のハロゲン化合物を用いることが一般的であ
った。ハロゲン化合物は、難燃性を付与する機能は優れ
るが、燃焼した際に人体に悪影響を及ぼす物質（例えば
ダイオキシン等）が生成するという、環境上の問題があ
ることが指摘されている。そこで、ハロゲン化合物を使
用しなくても優れた難燃性を有する硬化物が得られるエ
ポキシ樹脂組成物が検討され、例えば特開平１１−１６
６０３５号公報、特開平１１−２７９２５８号公報等に
は、前記式（１）で示されるリン化合物を用いてエポキ
シ樹脂を変性して得られたリン含有エポキシ樹脂と、硬
化剤と、溶剤とを含有してなるエポキシ樹脂組成物が提
案されている。2. Description of the Related Art Epoxy resin compositions are widely used in electronic equipment parts and the like due to their excellent properties, and are often provided with flame retardancy in order to ensure safety against fire. Conventionally, halogen compounds such as brominated epoxy resins have been generally used for making an epoxy resin composition flame-retardant. It has been pointed out that a halogen compound has an excellent problem of imparting flame retardancy, but it has an environmental problem that a substance (for example, dioxin) that adversely affects the human body is generated when burned. Therefore, an epoxy resin composition that can obtain a cured product having excellent flame retardancy without using a halogen compound has been investigated. For example, JP-A-11-16
JP-A-6035, JP-A-11-279258 and the like describe a phosphorus-containing epoxy resin obtained by modifying an epoxy resin with the phosphorus compound represented by the formula (1), a curing agent, and a solvent. An epoxy resin composition containing the same has been proposed.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、特開平
１１−１６６０３５号公報や特開平１１−２７９２５８
号公報で提案されているエポキシ樹脂組成物では、ハロ
ゲン化合物を使用しなくても優れた難燃性を有する硬化
物を得ることはできるが、プリプレグを積層成形して製
造する積層板に使用した場合に、積層板としての吸湿性
が大きく、そのため、長時間吸湿後の耐熱性等が劣る問
題があった。また、吸湿性を改善するために、硬化剤と
してフェノールノボラック樹脂を使用するようにする
と、積層板としたときの接着性が低下するという新たな
問題が生じていた。そのため、ハロゲン化合物を使用し
なくても優れた難燃性を有する硬化物を得ることがで
き、且つ、硬化物としたときの吸湿性及び接着性が共に
良好であるエポキシ樹脂組成物が求められているのが現
状である。However, JP-A-11-166035 and JP-A-11-279258.
In the epoxy resin composition proposed in the publication, a cured product having excellent flame retardancy can be obtained without using a halogen compound, but it was used for a laminated plate produced by laminating a prepreg. In this case, there is a problem that the laminated plate has a large hygroscopic property, and therefore the heat resistance after long-term hygroscopicity is poor. In addition, when a phenol novolac resin is used as a curing agent to improve hygroscopicity, a new problem arises in that the adhesiveness of a laminated board is reduced. Therefore, an epoxy resin composition capable of obtaining a cured product having excellent flame retardancy without using a halogen compound, and having good hygroscopicity and adhesiveness when the cured product is demanded. Is the current situation.
【０００４】本発明は、上記の事情に鑑みて成されたも
のであり、その目的とする所は、ハロゲン化合物を使用
しなくても優れた難燃性を有する硬化物を得ることがで
き、且つ、硬化物としたときの吸湿性及び接着性が共に
良好であるエポキシ樹脂組成物を提供することにある。
さらには、このエポキシ樹脂組成物を用いたプリプレグ
及びこのプリプレグを用いた積層板を提供することが本
発明の目的である。The present invention has been made in view of the above circumstances, and an object thereof is to obtain a cured product having excellent flame retardancy without using a halogen compound. Another object of the present invention is to provide an epoxy resin composition having good hygroscopicity and adhesiveness when made into a cured product.
Further, it is an object of the present invention to provide a prepreg using the epoxy resin composition and a laminated board using the prepreg.
【０００５】[0005]
【課題を解決するための手段】請求項１に係る発明のエ
ポキシ樹脂組成物は、リン含有エポキシ樹脂と、芳香族
ジアミンと、溶剤とを含有してなるエポキシ樹脂組成物
であって、リン含有エポキシ樹脂が下記式（１）で示さ
れるリン化合物を用いてエポキシ樹脂を変性して得られ
たリン含有エポキシ樹脂であり、芳香族ジアミンが分子
内にベンゼン環を３〜６個有する化合物であることを特
徴とするエポキシ樹脂組成物である。The epoxy resin composition of the invention according to claim 1 is an epoxy resin composition containing a phosphorus-containing epoxy resin, an aromatic diamine, and a solvent. The epoxy resin is a phosphorus-containing epoxy resin obtained by modifying the epoxy resin with the phosphorus compound represented by the following formula (1), and the aromatic diamine is a compound having 3 to 6 benzene rings in the molecule. It is an epoxy resin composition characterized by the above.
【０００６】[0006]
【化２】 [Chemical 2]
【０００７】請求項２に係る発明のエポキシ樹脂組成物
は、リン含有エポキシ樹脂のリン含有量が１．５〜３．
０質量％であることを特徴とする請求項１記載のエポキ
シ樹脂組成物である。In the epoxy resin composition of the second aspect of the present invention, the phosphorus content of the phosphorus-containing epoxy resin is 1.5 to 3.
It is 0 mass%, It is an epoxy resin composition of Claim 1 characterized by the above-mentioned.
【０００８】請求項３に係る発明のエポキシ樹脂組成物
は、リン含有エポキシ樹脂が、式（１）で示されるリン
化合物とキノン類とを反応させて得られた反応物と、エ
ポキシ樹脂とを反応させて得たリン含有エポキシ樹脂で
あることを特徴とする請求項１又は請求項２記載のエポ
キシ樹脂組成物である。In the epoxy resin composition of the invention according to claim 3, a phosphorus-containing epoxy resin comprises a reaction product obtained by reacting a phosphorus compound represented by the formula (1) with a quinone, and an epoxy resin. It is a phosphorus-containing epoxy resin obtained by making it react, It is the epoxy resin composition of Claim 1 or Claim 2 characterized by the above-mentioned.
【０００９】請求項４に係る発明のプリプレグは、請求
項１〜請求項３の何れかに記載のエポキシ樹脂組成物
を、基材に含浸、乾燥させてなるプリプレグである。The prepreg of the invention according to claim 4 is a prepreg obtained by impregnating a base material with the epoxy resin composition according to any one of claims 1 to 3 and drying.
【００１０】請求項５に係る発明のプリプレグは、基材
として、アラミド繊維で構成した基材を用いることを特
徴とする請求項４記載のプリプレグである。The prepreg of the invention according to claim 5 is the prepreg according to claim 4, characterized in that a base material made of aramid fiber is used as the base material.
【００１１】請求項６に係る発明の積層板は、請求項４
又は請求項５記載のプリプレグを成形してなる積層板で
ある。The laminated plate of the invention according to claim 6 is the same as claim 4.
Alternatively, it is a laminated plate formed by molding the prepreg according to claim 5.
【００１２】[0012]
【発明の実施の形態】まず、エポキシ樹脂組成物に係る
発明について説明する。BEST MODE FOR CARRYING OUT THE INVENTION First, the invention relating to an epoxy resin composition will be described.
【００１３】本発明のエポキシ樹脂組成物は、リン含有
エポキシ樹脂と、硬化剤である芳香族ジアミンと、溶剤
とを含有している。リン含有エポキシ樹脂は式（１）で
示されるリン化合物を用いてエポキシ樹脂を変性して得
られたリン含有エポキシ樹脂である。具体的には、例え
ば式（１）で示されるリン化合物（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）と、ノボラック型エポキシ樹脂等のエポキシ
樹脂とを反応させて得られたものや、式（１）で示され
るリン化合物と、１，４−ナフトキノン、１，４−ベン
ゾキノン、１，２−ベンゾキノン等のキノン類とを反応
させ、さらにこの反応物とノボラック型エポキシ樹脂等
のエポキシ樹脂とを反応させて得られたもの等を用いる
ことができる。式（１）で示されるリン化合物のリン原
子に直結した活性水素と、エポキシ樹脂のエポキシ基と
は反応するので、式（１）で示されるリン化合物とエポ
キシ樹脂とを直接反応させることで、式（１）で示され
るリン化合物に由来する構造を分子内に有するエポキシ
樹脂を得るこができる。また、特開平１１−２７９２５
８号公報にも記載されているように、式（１）で示され
るリン化合物とキノン類とが反応したものは、エポキシ
樹脂のエポキシ基と反応するヒドロキシル基を有するも
のとなるので、式（１）で示されるリン化合物とキノン
類とが反応したものとエポキシ樹脂とを反応させること
でも、式（１）で示されるリン化合物に由来する構造を
分子内に有するエポキシ樹脂を得ることができる。な
お、式（１）で示されるリン化合物とキノン類との反応
物を用いてエポキシ樹脂を変性して得たリン含有エポキ
シ樹脂をエポキシ樹脂組成物で用いるようにすると、キ
ノン類との反応を全く行わずに式（１）で示されるリン
化合物のみとエポキシ樹脂とを反応させて得たリン含有
エポキシ樹脂を用いる場合に比べて、得られる硬化物の
耐熱性が向上する利点がある。また、式（１）で示され
るリン化合物とキノン類とを反応させる場合には、キノ
ン類の式（１）で示されるリン化合物に対するモル比を
０より大きく、１未満とすることが好ましい。このよう
にすると、式（１）で示されるリン化合物とキノン類と
を反応させて得られる反応物中に、未反応のキノン類は
残存せず、未反応の式（１）で示されるリン化合物を残
存するようにできるからである。未反応のキノン類が反
応物中に残存すると、最終的にエポキシ樹脂組成物の硬
化物の性能を低下する傾向があるので、未反応のキノン
類が反応物中に残存しないように製造条件を設定するこ
とが好ましい。The epoxy resin composition of the present invention contains a phosphorus-containing epoxy resin, an aromatic diamine as a curing agent, and a solvent. The phosphorus-containing epoxy resin is a phosphorus-containing epoxy resin obtained by modifying the epoxy resin with the phosphorus compound represented by the formula (1). Specifically, for example, a phosphorus compound represented by the formula (1) (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-
Oxide) and an epoxy resin such as a novolac type epoxy resin, or a phosphorus compound represented by the formula (1), 1,4-naphthoquinone, 1,4-benzoquinone, 1,2- It is possible to use a product obtained by reacting a quinone such as benzoquinone and then reacting the reaction product with an epoxy resin such as a novolac type epoxy resin. Since the active hydrogen directly bonded to the phosphorus atom of the phosphorus compound represented by the formula (1) reacts with the epoxy group of the epoxy resin, by directly reacting the phosphorus compound represented by the formula (1) with the epoxy resin, An epoxy resin having a structure derived from the phosphorus compound represented by the formula (1) in the molecule can be obtained. Also, JP-A-11-27925
As described in Japanese Patent Publication No. 8, a reaction of the phosphorus compound represented by the formula (1) with a quinone has a hydroxyl group that reacts with the epoxy group of the epoxy resin, and therefore the formula ( An epoxy resin having a structure derived from the phosphorus compound represented by the formula (1) in the molecule can also be obtained by reacting a reaction product of the phosphorus compound represented by 1) with a quinone with an epoxy resin. . When the phosphorus-containing epoxy resin obtained by modifying the epoxy resin with the reaction product of the phosphorus compound represented by the formula (1) and the quinones is used in the epoxy resin composition, the reaction with the quinones is caused. Compared with the case where a phosphorus-containing epoxy resin obtained by reacting only the phosphorus compound represented by the formula (1) with an epoxy resin is used at all, there is an advantage that the heat resistance of the obtained cured product is improved. When the phosphorus compound represented by the formula (1) is reacted with the quinones, the molar ratio of the quinone to the phosphorus compound represented by the formula (1) is preferably more than 0 and less than 1. In this way, unreacted quinones do not remain in the reaction product obtained by reacting the phosphorus compound represented by formula (1) with quinones, and the unreacted phosphorus represented by formula (1) This is because the compound can remain. When unreacted quinones remain in the reaction product, the performance of the cured product of the epoxy resin composition tends to be finally reduced.Therefore, the production conditions should be set so that the unreacted quinones do not remain in the reaction product. It is preferable to set.
【００１４】このように、式（１）で示されるリン化合
物を用いてエポキシ樹脂を変性して得られたものとは、
式（１）で示されるリン化合物を直接エポキシ樹脂と反
応させて得られたものでもよく、また、式（１）で示さ
れるリン化合物と例えばキノン類等のエポキシ樹脂以外
の成分と反応させて得られた反応物を、さらにエポキシ
樹脂と反応させて得られたものであってもよい。すなわ
ち、本発明でいうリン含有エポキシ樹脂は少なくとも式
（１）で示されるリン化合物に由来する構造を分子内に
有するように変性したエポキシ樹脂である。そして、本
発明のエポキシ樹脂組成物では、式（１）で示されるリ
ン化合物を用いてエポキシ樹脂を変性して得られたリン
含有エポキシ樹脂に加えて、ノボラック型エポキシ樹脂
やビスフェノール型エポキシ樹脂等の他のエポキシ樹脂
を併用することもできる。As described above, the product obtained by modifying the epoxy resin with the phosphorus compound represented by the formula (1) is
It may be obtained by directly reacting the phosphorus compound represented by the formula (1) with an epoxy resin, or by reacting the phosphorus compound represented by the formula (1) with a component other than the epoxy resin such as quinones. It may be one obtained by further reacting the obtained reaction product with an epoxy resin. That is, the phosphorus-containing epoxy resin referred to in the present invention is an epoxy resin modified so as to have at least a structure derived from the phosphorus compound represented by the formula (1) in the molecule. Then, in the epoxy resin composition of the present invention, in addition to the phosphorus-containing epoxy resin obtained by modifying the epoxy resin with the phosphorus compound represented by the formula (1), a novolac type epoxy resin, a bisphenol type epoxy resin, etc. Other epoxy resins can also be used together.
【００１５】また、リン含有エポキシ樹脂を得るため
に、式（１）で示されるリン化合物を用いて変性するエ
ポキシ樹脂については、特に限定はなく、例えば、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、ビスフェノールノボラック型エポキ
シ樹脂等のノボラック型エポキシ樹脂、ビスフェノール
型エポキシ樹脂、ビフェニル型エポキシ樹脂等を使用す
ることができる。式（１）で示されるリン化合物を用い
てエポキシ樹脂を変性する方法としては、例えば１００
〜２００℃で攪拌下で反応させる方法等によって行うこ
とができる。エポキシ樹脂を変性する際には、必要に応
じて触媒を使用する。この場合の触媒としては、例え
ば、ベンジルジメチルアミン等の第３級アミン類、テト
ラメチルアンモニウムクロライド等の第４級アンモニウ
ム塩類、トリフェニルホスフィン等のホスフィン類、２
メチルイミダゾール等のイミダゾール類等を使用するこ
とができる。The epoxy resin modified with the phosphorus compound represented by the formula (1) to obtain the phosphorus-containing epoxy resin is not particularly limited, and examples thereof include phenol novolac type epoxy resin and cresol novolac type epoxy resin. Resins, novolak type epoxy resins such as bisphenol novolac type epoxy resins, bisphenol type epoxy resins, biphenyl type epoxy resins and the like can be used. Examples of the method for modifying the epoxy resin with the phosphorus compound represented by the formula (1) include 100
It can be carried out by a method such as reacting at ~ 200 ° C under stirring. When modifying the epoxy resin, a catalyst is used if necessary. Examples of the catalyst in this case include tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, phosphines such as triphenylphosphine, and 2
Imidazoles such as methylimidazole can be used.
【００１６】式（１）で示されるリン化合物を用いてエ
ポキシ樹脂を変性して得られたリン含有エポキシ樹脂
は、製造後にそのエポキシ当量を測定することが望まし
い。このように、エポキシ当量を測定しておくことによ
って、エポキシ樹脂組成物を配合する際のエポキシ樹脂
と硬化剤との当量関係についての比率を所望の比率にす
ることが可能となる。また、本発明で使用するリン含有
エポキシ樹脂は、特に限定するものではないが、リン含
有量が１．５〜３．０質量％の範囲内であることが好ま
しい。なぜならば、１．５質量％未満では十分な難燃性
が得にくく、３．０質量％を越えると得られる硬化物の
耐熱性等の物性が低下する傾向があるからである。この
ように、本発明のエポキシ樹脂組成物では、式（１）で
示されるリン化合物を単に配合するのではなく、このリ
ン化合物を用いてエポキシ樹脂を変性して得られたリン
含有エポキシ樹脂を使用するので、リン化合物を単に配
合する場合に比べて、得られる硬化物の耐熱性等の物性
が優れたものとなる。It is desirable to measure the epoxy equivalent of the phosphorus-containing epoxy resin obtained by modifying the epoxy resin with the phosphorus compound represented by the formula (1) after production. As described above, by measuring the epoxy equivalent, it becomes possible to set the ratio regarding the equivalent relationship between the epoxy resin and the curing agent when the epoxy resin composition is blended to a desired ratio. The phosphorus-containing epoxy resin used in the present invention is not particularly limited, but the phosphorus content is preferably within the range of 1.5 to 3.0% by mass. This is because if it is less than 1.5% by mass, it is difficult to obtain sufficient flame retardancy, and if it exceeds 3.0% by mass, physical properties such as heat resistance of the obtained cured product tend to deteriorate. As described above, in the epoxy resin composition of the present invention, the phosphorus-containing epoxy resin obtained by modifying the epoxy resin with the phosphorus compound is not merely blended with the phosphorus compound represented by the formula (1). Since it is used, the obtained cured product has excellent physical properties such as heat resistance as compared with the case where the phosphorus compound is simply added.
【００１７】本発明のエポキシ樹脂組成物では、硬化剤
として芳香族ジアミンを含有していて、且つ、この芳香
族ジアミンは分子内にベンゼン環を３〜６個有する化合
物であることが、重要である。分子内にベンゼン環を３
〜６個有する芳香族ジアミンを硬化剤として使用するこ
とによって、ハロゲン化合物を使用しなくても優れた難
燃性を有する硬化物を得ることができ、且つ、硬化物と
したときの吸湿性及び接着性が共に良好であるエポキシ
樹脂組成物とすることができるからである。分子内に有
するベンゼン環の個数が２個以下の場合には、硬化物と
したときの吸湿性が大きく、また分子内に有するベンゼ
ン環の個数が７個以上のものは入手が困難であるという
問題がある。そして、本発明のエポキシ樹脂組成物で
は、エポキシ樹脂組成物中の１エポキシ当量の全エポキ
シ樹脂（リン含有エポキシ樹脂を含む使用している全エ
ポキシ樹脂）に対して、芳香族ジアミンを０．８〜１．
０活性水素当量の割合で配合することが好ましい。この
範囲内とすることによって、硬化物としたときの吸湿性
及び接着性が共に良好であるエポキシ樹脂組成物とする
ことがより確実になるからである。なお、エポキシ樹脂
組成物を配合する際に使用しているエポキシ樹脂がリン
含有エポキシ樹脂のみの場合には、このリン含有エポキ
シ樹脂が全エポキシ樹脂に相当する。It is important that the epoxy resin composition of the present invention contains an aromatic diamine as a curing agent, and the aromatic diamine is a compound having 3 to 6 benzene rings in the molecule. is there. 3 benzene rings in the molecule
By using an aromatic diamine having 6 to 6 as a curing agent, a cured product having excellent flame retardancy can be obtained without using a halogen compound, and a hygroscopic property when the cured product is obtained. This is because it is possible to obtain an epoxy resin composition having good adhesiveness. If the number of benzene rings in the molecule is 2 or less, the hygroscopic property of the cured product is high, and if the number of benzene rings in the molecule is 7 or more, it is difficult to obtain. There's a problem. In the epoxy resin composition of the present invention, aromatic diamine is added to 0.8 with respect to 1 epoxy equivalent of all epoxy resins in the epoxy resin composition (all epoxy resins used including phosphorus-containing epoxy resin). ~ 1.
It is preferable to mix it at a ratio of 0 active hydrogen equivalent. This is because by setting it within this range, it becomes more reliable to obtain an epoxy resin composition having both good hygroscopicity and adhesiveness when made into a cured product. When the epoxy resin used when blending the epoxy resin composition is only a phosphorus-containing epoxy resin, this phosphorus-containing epoxy resin corresponds to all epoxy resins.
【００１８】分子内にベンゼン環を３〜６個有する芳香
族ジアミンの具体例としては、１，３−ビス（４−アミ
ノフェノキシ）ベンゼン、１，４−ビス（４−アミノフ
ェノキシ）ベンゼン、４，４’−ビス（４−アミノフェ
ノキシ）ビフェニル、２，２−ビス〔４−（４−アミノ
フェノキシ）フェニル〕プロパン、ビス〔４−（４−ア
ミノフェノキシ）フェニル〕スルホン、ビス〔４−（３
−アミノフェノキシ）フェニル〕スルホン等が例示でき
る。Specific examples of the aromatic diamine having 3 to 6 benzene rings in the molecule include 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene and 4 , 4'-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- ( Three
Examples include -aminophenoxy) phenyl] sulfone.
【００１９】なお、本発明のエポキシ樹脂組成物では、
上記の分子内にベンゼン環を３〜６個有する芳香族ジア
ミンと共に、各種のアミン類、フェノール樹脂類、酸無
水物類、ヒドラジッド類等を併用することができる。In the epoxy resin composition of the present invention,
Various amines, phenolic resins, acid anhydrides, hydrazides and the like can be used together with the aromatic diamine having 3 to 6 benzene rings in the molecule.
【００２０】また、本発明のエポキシ樹脂組成物は、必
須成分としてトルエン、メチルエチルケトン、メチルセ
ロソルブ、ジメチルホルムアミド等の溶剤を含有するよ
うにしている。このように本発明のエポキシ樹脂組成物
は、溶剤を含有しているので、プリプレグを製造する際
のエポキシ樹脂組成物の粘度調整を溶剤の添加割合で容
易に調整することが可能となる利点がある。また、本発
明のエポキシ樹脂組成物には、必要に応じて、硬化促進
剤、無機充填材、顔料等の各種添加剤を添加することが
できる。Further, the epoxy resin composition of the present invention contains a solvent such as toluene, methyl ethyl ketone, methyl cellosolve or dimethylformamide as an essential component. Thus, since the epoxy resin composition of the present invention contains a solvent, there is an advantage that it is possible to easily adjust the viscosity adjustment of the epoxy resin composition when producing a prepreg by the addition ratio of the solvent. is there. In addition, various additives such as a curing accelerator, an inorganic filler, and a pigment can be added to the epoxy resin composition of the present invention, if necessary.
【００２１】次に、プリプレグに係る発明について説明
する。Next, the invention relating to the prepreg will be described.
【００２２】本発明のプリプレグは、上述した本発明の
エポキシ樹脂組成物を、基材に含浸、乾燥させてなるプ
リプレグであり、ハロゲン化合物を使用しなくても優れ
た難燃性を有する積層板を得ることができ、且つ、積層
板としたときの吸湿性及び接着性が共に良好であるプリ
プレグとなる。The prepreg of the present invention is a prepreg obtained by impregnating a substrate with the above-mentioned epoxy resin composition of the present invention and drying the prepreg, which has excellent flame retardancy without using a halogen compound. And a prepreg having good hygroscopicity and adhesiveness when formed into a laminated plate.
【００２３】エポキシ樹脂組成物を、基材に含浸、乾燥
させる方法については特に限定はなく、例えば液状のエ
ポキシ樹脂組成物中に基材を浸漬した後、加熱して溶剤
の除去及びエポキシ樹脂組成物を半硬化させる等の方法
で行うことができる。なお、乾燥後のエポキシ樹脂組成
物の含有量が、プリプレグ全体の質量に対して３０〜７
０質量％となるように含浸すると、電気特性が優れる積
層板が得られるので好ましい。エポキシ樹脂組成物を含
浸する基材としては、ガラスクロス、アラミドクロス、
ポリエステルクロス、ガラス不織布、アラミド不織布、
各種の紙等が挙げられる。ガラスクロスを用いると、機
械的強度が優れる積層板が得られるので好ましい。ま
た、アラミドクロス、アラミド不織布等のアラミド繊維
で構成した基材を用いると、ガラス繊維に比べてレーザ
ーの照射で容易に分解除去されるため、レーザーを用い
た穴加工が容易にできる利点があり、好ましい。The method of impregnating the base material with the epoxy resin composition and drying is not particularly limited. For example, after the base material is dipped in the liquid epoxy resin composition, it is heated to remove the solvent and the epoxy resin composition. It can be performed by a method of semi-curing the product. The content of the epoxy resin composition after drying is 30 to 7 with respect to the mass of the entire prepreg.
It is preferable to impregnate so that the content of the resin is 0% by mass because a laminated plate having excellent electrical characteristics can be obtained. As the base material impregnated with the epoxy resin composition, glass cloth, aramid cloth,
Polyester cloth, glass non-woven fabric, aramid non-woven fabric,
Examples include various types of paper. It is preferable to use glass cloth because a laminated plate having excellent mechanical strength can be obtained. In addition, when a base material composed of aramid fibers such as aramid cloth and aramid non-woven fabric is used, it can be easily decomposed and removed by laser irradiation as compared with glass fibers, so that there is an advantage that hole processing using laser can be easily performed ,preferable.
【００２４】次に、積層板に係る発明について説明す
る。本発明の積層板は、上述した本発明のプリプレグを
１枚又は複数枚重ねたものを成形して製造する。なお、
プリプレグと共に金属箔（銅箔、アルミ箔等）、内層
材、外層材等を同時に重ねて成形して、金属箔張り積層
板や多層板等とすることも可能である。本発明の積層板
は、ハロゲン化合物を使用しなくても優れた難燃性を有
する積層板であって、且つ、吸湿性及び接着性が共に良
好である積層板となる。Next, the invention relating to the laminated plate will be described. The laminated board of the present invention is manufactured by molding one or a plurality of the above-mentioned prepregs of the present invention which are stacked. In addition,
It is also possible to form a metal foil-clad laminate or a multilayer board by simultaneously stacking and molding a metal foil (copper foil, aluminum foil, etc.), an inner layer material, an outer layer material and the like together with the prepreg. The laminated plate of the present invention is a laminated plate having excellent flame retardancy without using a halogen compound, and has good hygroscopicity and adhesiveness.
【００２５】[0025]
【実施例】次に実施例及び比較例をあげて本発明を具体
的に説明する。EXAMPLES Next, the present invention will be specifically described with reference to Examples and Comparative Examples.
【００２６】（リン含有エポキシ樹脂Ａ、Ｂ、Ｃの合
成）攪拌装置、温度計、冷却管、窒素ガス導入装置を備
えた四つ口のガラス製セパラブルフラスコに、式（１）
で示されるリン化合物（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：
三光化学株式会社製の品番ＨＣＡ）とトルエンを表１に
示す配合量だけ仕込み、加熱して溶解した。次いで１，
４−ナフトキノンを反応熱による昇温に注意しながら表
１に示す配合量だけ分割投入して、式（１）で示される
リン化合物と１，４−ナフトキノンとの反応を行った。
反応終了後、表１に示す配合量のクレゾールノボラック
型エポキシ樹脂（東都化成株式会社製の品番ＹＤＣＮ−
７０１）を投入し、窒素ガスを導入しながら、１２０℃
で攪拌、溶解した。次いで、表１に示す配合量の、触媒
であるトリフェニルホスフィンを添加し、１５０℃で４
時間反応させた後、トルエン等の揮発成分を除去して、
リン含有エポキシ樹脂Ａ、Ｂ、Ｃを得た。各リン含有エ
ポキシ樹脂Ａ、Ｂ、Ｃのエポキシ当量を測定した結果を
表１に示す。また、配合量から算出した各リン含有エポ
キシ樹脂Ａ、Ｂ、Ｃ中のリン含有量を表１に示す。(Synthesis of Phosphorus-Containing Epoxy Resins A, B, and C) A four-neck glass separable flask equipped with a stirrer, a thermometer, a cooling pipe, and a nitrogen gas introducing device was charged with the formula (1).
A phosphorus compound (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide:
Sanko Chemical Co., Ltd. product number HCA) and toluene were charged in the amounts shown in Table 1, and heated to dissolve. Then 1,
4-naphthoquinone was dividedly charged by the blending amount shown in Table 1 while paying attention to the temperature rise due to the heat of reaction, and the phosphorus compound represented by the formula (1) was reacted with 1,4-naphthoquinone.
After completion of the reaction, the cresol novolac type epoxy resin having the compounding amount shown in Table 1 (product number YDCN- manufactured by Tohto Kasei Co., Ltd.
701), and while introducing nitrogen gas, 120 ° C
It was stirred and dissolved. Then, triphenylphosphine as a catalyst in the compounding amount shown in Table 1 was added, and the mixture was heated at 150 ° C.
After reacting for a time, volatile components such as toluene are removed,
Phosphorus-containing epoxy resins A, B and C were obtained. Table 1 shows the results of measuring the epoxy equivalents of the phosphorus-containing epoxy resins A, B, and C. Table 1 shows the phosphorus content in each of the phosphorus-containing epoxy resins A, B, and C calculated from the blended amount.
【００２７】[0027]
【表１】 [Table 1]
【００２８】（実施例１〜５、比較例１、２）上記で得
られたリン含有エポキシ樹脂と、下記に示す各種硬化剤
と、硬化促進剤である２エチル４メチルイミダゾール
（四国化成株式会社製の品番２Ｅ４ＭＺ）と、溶剤であ
るジメチルホルムアミド又はメチルエチルケトンとを、
表２に示す配合量で配合し、混合して実施例１〜５及び
比較例１、２について、それぞれのエポキシ樹脂組成物
を得た。各エポキシ樹脂組成物における、硬化剤の配合
割合は、１エポキシ当量あたり硬化剤が１当量となるよ
うに配合した。なお、硬化剤の当量は、芳香族ジアミン
については活性水素当量に基き、フェノールノボラック
樹脂については水酸基当量に基いて決定している。ま
た、得られた各エポキシ樹脂組成物について、ワニスゲ
ルタイムを測定した結果を表２に示す。なお、ワニスゲ
ルタイムは、ワニス（エポキシ樹脂組成物）１０ｍｇが
１７０℃のキュアープレート上でゲル化するまでの時間
を測定した値である。(Examples 1 to 5, Comparative Examples 1 and 2) The phosphorus-containing epoxy resin obtained above, various curing agents shown below, and 2 ethyl 4 methyl imidazole (Shikoku Kasei Co., Ltd.) as a curing accelerator. Manufactured by product number 2E4MZ) and dimethylformamide or methylethylketone as a solvent,
The epoxy resin compositions of Examples 1 to 5 and Comparative Examples 1 and 2 were obtained by mixing and mixing in the amounts shown in Table 2. The mixing ratio of the curing agent in each epoxy resin composition was such that the curing agent was 1 equivalent per 1 epoxy equivalent. The equivalent of the curing agent is determined based on the active hydrogen equivalent for the aromatic diamine and the hydroxyl equivalent for the phenol novolac resin. Table 2 shows the results of measuring the varnish gel time of each of the obtained epoxy resin compositions. The varnish gel time is a value obtained by measuring the time required for 10 mg of the varnish (epoxy resin composition) to gel on a cure plate at 170 ° C.
【００２９】使用した硬化剤
硬化剤Ｄ：４，４’−ビス（４−アミノフェノキシ）ビ
フェニル〔和歌山精化株式会社製の品番ＢＡＰＢ〕
硬化剤Ｅ：１，３−ビス（４−アミノフェノキシ）ベン
ゼン〔和歌山精化株式会社製の品番ＴＰＥ−Ｒ〕
硬化剤Ｆ：４，４’メチレン−ビス（２，５−エチルア
ニリン）〔日本化薬株式会社製の商品名カヤボンドＣ−
３００Ｓ〕
硬化剤Ｇ：フェノールノボラック樹脂〔大日本インキ化
学工業株式会社製の商品名フェノライトＴＤ−２１３
１〕
なお、使用した芳香族ジアミンが分子内に有するベンゼ
ン環の個数は表２に示すとおりである。Hardener used Hardener D: 4,4'-bis (4-aminophenoxy) biphenyl [Product number BAPB manufactured by Wakayama Seika Co., Ltd.] Hardener E: 1,3-bis (4-aminophenoxy) Benzene [Product No. TPE-R manufactured by Wakayama Seika Co., Ltd.] Curing agent F: 4,4'methylene-bis (2,5-ethylaniline) [Kayabond C-, trade name manufactured by Nippon Kayaku Co., Ltd.]
300S] Curing agent G: Phenol novolac resin [trade name Phenolite TD-213 manufactured by Dainippon Ink and Chemicals, Inc.
1] The number of benzene rings contained in the molecule of the aromatic diamine used is as shown in Table 2.
【００３０】上記で得られたエポキシ樹脂組成物（ワニ
ス）を表２に示す基材に含浸し、加熱・乾燥して、プリ
プレグを得た。表２に示すアラミド不織布としてはデュ
ポン帝人アドバンスドペーパー株式会社製の品番Ｎ−７
１８＃１００を使用し、ガラス布としては日東紡績株式
会社製の品番１１６ＥＳ１３６を使用した。そして、基
材にアラミド不織布を使用したプリプレグ（実施例１〜
４、比較例１、２）における樹脂含有率は５８質量％、
基材にガラス布を使用したプリプレグ（実施例５）にお
ける樹脂含有率は４５質量％とした。The epoxy resin composition (varnish) obtained above was impregnated into the base material shown in Table 2 and heated and dried to obtain a prepreg. As the aramid nonwoven fabric shown in Table 2, product number N-7 manufactured by DuPont Teijin Advanced Paper Co., Ltd.
18 # 100 was used, and as the glass cloth, product number 116ES136 manufactured by Nitto Boseki Co., Ltd. was used. Then, a prepreg using an aramid nonwoven fabric as a base material (Examples 1 to 1
4, the resin content in Comparative Examples 1 and 2) is 58% by mass,
The resin content of the prepreg (Example 5) using glass cloth as the base material was 45% by mass.
【００３１】上記で得られたプリプレグを６枚又は８枚
数重ね、さらにその上下に厚さ１８μｍの銅箔を配した
ものを、温度２００℃、圧力３０ＭＰａの条件で６０分
間、加熱・加圧して成形後の厚さが０．６ｍｍと０．８
ｍｍの両面銅張積層板を、実施例１〜５及び比較例１、
２のそれぞれにおいて作製した。Six or eight prepregs obtained as described above were stacked, and copper foil having a thickness of 18 μm was placed on the upper and lower sides of the prepreg, and the mixture was heated and pressurized for 60 minutes at a temperature of 200 ° C. and a pressure of 30 MPa. Thickness after molding is 0.6mm and 0.8
mm double-sided copper clad laminates were tested in Examples 1-5 and Comparative Example 1,
It was prepared in each of the two.
【００３２】上記で得たプリプレグ及び両面銅張積層板
を用いて、下記の評価方法で、難燃性、接着性、吸湿
性、レーザー加工対応性について評価し、評価結果を表
２に示した。
（評価方法）
難燃性試験：ＵＬ規格に基いて、厚さが０．８ｍｍの両
面銅張積層板から銅箔を除去したものから試験片を作製
し、垂直燃焼試験を行い、難燃性を評価し、評価結果を
Ｖ−０又はＶ−１として表２に示した。なお、ＵＬ規格
では、Ｖ−０の方がＶ−１より難燃性の程度は優れてい
る。Using the prepreg and the double-sided copper clad laminate obtained above, flame retardancy, adhesiveness, hygroscopicity, and laser processing compatibility were evaluated by the following evaluation methods, and the evaluation results are shown in Table 2. . (Evaluation method) Flame retardance test: Based on the UL standard, a test piece was prepared from a 0.8-mm-thick double-sided copper-clad laminate with the copper foil removed, and a vertical combustion test was performed to confirm flame retardancy. Was evaluated, and the evaluation results are shown in Table 2 as V-0 or V-1. According to the UL standard, V-0 is superior in flame retardancy to V-1.
【００３３】接着性試験：厚さが０．８ｍｍの両面銅張
積層板（銅箔厚さ１８μｍ）について、ＪＩＳ Ｃ−６
４８１に準拠して銅箔引き剥がし強さを測定し、測定結
果を表２に示した。Adhesion test: For a double-sided copper clad laminate having a thickness of 0.8 mm (copper foil thickness 18 μm), JIS C-6
The peel strength of the copper foil was measured according to 481 and the measurement results are shown in Table 2.
【００３４】吸湿性試験：厚さが０．６ｍｍの両面銅張
積層板から銅箔をエッチング除去した、５０ｍｍ×５０
ｍｍの試験片について、飽和蒸気（温度１２１℃、相対
湿度１００％）中に２０時間保持する吸湿処理を施すと
共に、処理前後の試験片の重量を測定する。そして、重
量変化から、吸湿処理による吸湿率（質量％）を算出
し、得られた結果を表２に示した。
レーザー加工対応性試験：プリプレグ１枚を試験片と
し、これに炭酸ガスレーザーをマスク径２．１ｍｍ、加
工エネルギー２４．２ｍＪ／Ｐ、パルス幅１５μｓ、シ
ョット数１ショットの条件で照射し、直径１００μｍの
穴あけ加工を行う。次いで、穴あけ加工をしたプリプレ
グを樹脂に埋めこみ、埋めこんだプリプレグの断面を顕
微鏡で観察することにより、穴内壁の表面粗度を測定
し、表面凹凸の高低差が１０μｍ以下のものを「○」、
１０μｍを越えると共に３０μｍ以下のものを「△」、
３０μｍを越えるものを「×」と評価して、評価結果を
表２に示した。Hygroscopicity test: 50 mm × 50, where copper foil was removed by etching from a double-sided copper clad laminate having a thickness of 0.6 mm
The mm test piece is subjected to a moisture absorption treatment in which it is held in saturated steam (temperature 121 ° C., relative humidity 100%) for 20 hours, and the weight of the test piece before and after the treatment is measured. Then, the moisture absorption rate (mass%) by the moisture absorption treatment was calculated from the weight change, and the obtained results are shown in Table 2. Laser processing compatibility test: One prepreg was used as a test piece, and a carbon dioxide gas laser was irradiated on this with a mask diameter of 2.1 mm, a processing energy of 24.2 mJ / P, a pulse width of 15 μs, and a shot number of 1 shot, and a diameter of 100 μm Drilling process. Then, the prepreg that has been subjected to the drilling process is embedded in a resin, and the cross section of the embedded prepreg is observed with a microscope to measure the surface roughness of the hole inner wall. ,
"△" when the thickness exceeds 10 μm and is less than 30 μm,
Those having a thickness of more than 30 μm were evaluated as “x”, and the evaluation results are shown in Table 2.
【００３５】[0035]
【表２】 [Table 2]
【００３６】表２の結果から明かなように、本発明の実
施例では、ハロゲン化合物を使用しなくても優れた難燃
性を有する硬化物を得ることができていて、且つ、比較
例に比べて、吸湿性及び接着性が共に良好である積層板
が得られていることが確認された。As is clear from the results shown in Table 2, in the examples of the present invention, cured products having excellent flame retardancy could be obtained without using a halogen compound, and in comparative examples. In comparison, it was confirmed that a laminate having good hygroscopicity and adhesiveness was obtained.
【００３７】また、アラミド不織布を用いたもの方が、
ガラス布を用いたもの（実施例５）よりレーザー加工対
応性が優れることも確認できた。Further, the one using the aramid non-woven fabric is
It was also confirmed that the laser processing compatibility was superior to that using the glass cloth (Example 5).
【００３８】[0038]
【発明の効果】請求項１〜請求項３に係る発明のエポキ
シ樹脂組成物は、（１）で示されるリン化合物を用いて
エポキシ樹脂を変性して得られたリン含有エポキシ樹脂
と、分子内にベンゼン環を３〜６個有する芳香族ジアミ
ンを含有しているので、ハロゲン化合物を使用しなくて
も優れた難燃性を有する硬化物を得ることができ、且
つ、硬化物としたときの吸湿性及び接着性が共に良好で
あるエポキシ樹脂組成物となる。EFFECTS OF THE INVENTION The epoxy resin compositions of the inventions according to claims 1 to 3 are a phosphorus-containing epoxy resin obtained by modifying an epoxy resin with a phosphorus compound represented by (1), and an intramolecular compound. Since it contains an aromatic diamine having 3 to 6 benzene rings, a cured product having excellent flame retardancy can be obtained without using a halogen compound, and when a cured product is obtained, The epoxy resin composition has good hygroscopicity and adhesiveness.
【００３９】請求項４及び請求項５に係る発明のプリプ
レグは、請求項１〜請求項３の何れかに記載のエポキシ
樹脂組成物を、基材に含浸、乾燥させてなるプリプレグ
であるので、ハロゲン化合物を使用しなくても優れた難
燃性を有する積層板を得ることができ、且つ、積層板と
したときの吸湿性及び接着性が共に良好であるプリプレ
グとなる。Since the prepreg of the invention according to claims 4 and 5 is a prepreg obtained by impregnating a substrate with the epoxy resin composition according to any one of claims 1 to 3 and drying the prepreg. It is possible to obtain a laminated plate having excellent flame retardancy without using a halogen compound, and the prepreg has good hygroscopicity and adhesiveness when formed into a laminated plate.
【００４０】請求項５に係る発明の積層板は、請求項４
又は請求項５記載のプリプレグを成形してなる積層板で
あるので、ハロゲン化合物を使用しなくても優れた難燃
性を有する積層板であって、且つ、吸湿性及び接着性が
共に良好である積層板となる。The laminated plate of the invention according to claim 5 is the same as claim 4.
Alternatively, since it is a laminate obtained by molding the prepreg according to claim 5, it is a laminate having excellent flame retardancy without using a halogen compound, and has good hygroscopicity and adhesiveness. It becomes a certain laminated board.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 藤木 智之 大阪府門真市大字門真1048番地松下電工株 式会社内 Ｆターム(参考） 4F072 AA07 AB03 AB05 AB06 AB09 AB28 AB29 AD32 AD33 AE01 AF14 AF28 AG03 AH31 AJ04 AK02 AL09 4J036 AD07 AD08 AF06 AF08 CA13 CC02 DC03 DC10 DC11 DD04 DD05 JA11 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Tomoyuki Fujiki 1048, Kadoma, Kadoma-shi, Osaka Matsushita Electric Works Co., Ltd. Inside the company F-term (reference) 4F072 AA07 AB03 AB05 AB06 AB09 AB28 AB29 AD32 AD33 AE01 AF14 AF28 AG03 AH31 AJ04 AK02 AL09 4J036 AD07 AD08 AF06 AF08 CA13 CC02 DC03 DC10 DC11 DD04 DD05 JA11
Claims (6)
ンと、溶剤とを含有してなるエポキシ樹脂組成物であっ
て、リン含有エポキシ樹脂が下記式（１）で示されるリ
ン化合物を用いてエポキシ樹脂を変性して得られたリン
含有エポキシ樹脂であり、芳香族ジアミンが分子内にベ
ンゼン環を３〜６個有する化合物であることを特徴とす
るエポキシ樹脂組成物。 【化１】 1. An epoxy resin composition comprising a phosphorus-containing epoxy resin, an aromatic diamine, and a solvent, wherein the phosphorus-containing epoxy resin is an epoxy compound using a phosphorus compound represented by the following formula (1). An epoxy resin composition, which is a phosphorus-containing epoxy resin obtained by modifying a resin, wherein the aromatic diamine is a compound having 3 to 6 benzene rings in the molecule. [Chemical 1]
１．５〜３．０質量％であることを特徴とする請求項１
記載のエポキシ樹脂組成物。2. The phosphorus content of the phosphorus-containing epoxy resin is 1.5 to 3.0% by mass.
The epoxy resin composition described.
されるリン化合物とキノン類とを反応させて得られた反
応物と、エポキシ樹脂とを反応させて得たリン含有エポ
キシ樹脂であることを特徴とする請求項１又は請求項２
記載のエポキシ樹脂組成物。3. A phosphorus-containing epoxy resin is a phosphorus-containing epoxy resin obtained by reacting a reaction product obtained by reacting a phosphorus compound represented by formula (1) with a quinone with an epoxy resin. Claim 1 or claim 2 characterized in that
The epoxy resin composition described.
ポキシ樹脂組成物を、基材に含浸、乾燥させてなるプリ
プレグ。4. A prepreg obtained by impregnating a base material with the epoxy resin composition according to claim 1 and drying the base material.
材を用いることを特徴とする請求項４記載のプリプレ
グ。5. The prepreg according to claim 4, wherein a base material made of aramid fiber is used as the base material.
を成形してなる積層板。6. A laminated plate formed by molding the prepreg according to claim 4 or 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002024503A JP3912125B2 (en) | 2002-01-31 | 2002-01-31 | Prepreg and laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002024503A JP3912125B2 (en) | 2002-01-31 | 2002-01-31 | Prepreg and laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003221430A true JP2003221430A (en) | 2003-08-05 |
| JP3912125B2 JP3912125B2 (en) | 2007-05-09 |
Family
ID=27746929
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002024503A Expired - Fee Related JP3912125B2 (en) | 2002-01-31 | 2002-01-31 | Prepreg and laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3912125B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005179598A (en) * | 2003-12-22 | 2005-07-07 | Chin Yee Chemical Industries Co Ltd | Flame-retardant epoxy resin and flame-retardant epoxy resin composition |
| US20120088863A1 (en) * | 2010-10-12 | 2012-04-12 | Hexcel Corporation | Solvent resistant thermoplastic toughened epoxy |
| WO2012128313A1 (en) | 2011-03-24 | 2012-09-27 | 三菱瓦斯化学株式会社 | Resin composition, prepreg and resin sheet, and metal foil-clad laminate |
| WO2013146302A1 (en) | 2012-03-29 | 2013-10-03 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, resin sheet, and metal foil-clad laminate |
| KR20160130227A (en) | 2014-03-06 | 2016-11-10 | 미츠비시 가스 가가쿠 가부시키가이샤 | Resin composition, prepreg, resin sheet, metal-foil-clad laminated plate, and printed wiring board |
-
2002
- 2002-01-31 JP JP2002024503A patent/JP3912125B2/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005179598A (en) * | 2003-12-22 | 2005-07-07 | Chin Yee Chemical Industries Co Ltd | Flame-retardant epoxy resin and flame-retardant epoxy resin composition |
| US20120088863A1 (en) * | 2010-10-12 | 2012-04-12 | Hexcel Corporation | Solvent resistant thermoplastic toughened epoxy |
| US9068040B2 (en) | 2010-10-12 | 2015-06-30 | Hexcel Corporation | Solvent resistant thermoplastic toughened epoxy |
| WO2012128313A1 (en) | 2011-03-24 | 2012-09-27 | 三菱瓦斯化学株式会社 | Resin composition, prepreg and resin sheet, and metal foil-clad laminate |
| US9318402B2 (en) | 2011-03-24 | 2016-04-19 | Mitsubishi Gas Chemical Company, Inc. | Resin composition, prepreg and resin sheet and metal foil-clad laminate |
| WO2013146302A1 (en) | 2012-03-29 | 2013-10-03 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, resin sheet, and metal foil-clad laminate |
| KR20140146589A (en) | 2012-03-29 | 2014-12-26 | 미츠비시 가스 가가쿠 가부시키가이샤 | Resin composition, prepreg, resin sheet, and metal foil-clad laminate |
| US9394439B2 (en) | 2012-03-29 | 2016-07-19 | Mitsubishi Gas Chemical Company, Inc. | Resin composition, prepreg, resin sheet, and metal foil-clad laminate |
| KR20160130227A (en) | 2014-03-06 | 2016-11-10 | 미츠비시 가스 가가쿠 가부시키가이샤 | Resin composition, prepreg, resin sheet, metal-foil-clad laminated plate, and printed wiring board |
| US10370536B2 (en) | 2014-03-06 | 2019-08-06 | Mitsubishi Gas Chemical Company, Inc. | Resin composition, prepreg, resin sheet, metal foil-clad laminate, and printed wiring board |
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| Publication number | Publication date |
|---|---|
| JP3912125B2 (en) | 2007-05-09 |
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