JPWO2008143309A1 - Novel flame-retardant epoxy resin, epoxy resin composition containing the epoxy resin as an essential component, and cured product thereof - Google Patents

Novel flame-retardant epoxy resin, epoxy resin composition containing the epoxy resin as an essential component, and cured product thereof Download PDF

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JPWO2008143309A1
JPWO2008143309A1 JP2009515267A JP2009515267A JPWO2008143309A1 JP WO2008143309 A1 JPWO2008143309 A1 JP WO2008143309A1 JP 2009515267 A JP2009515267 A JP 2009515267A JP 2009515267 A JP2009515267 A JP 2009515267A JP WO2008143309 A1 JPWO2008143309 A1 JP WO2008143309A1
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epoxy resin
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一男 石原
一男 石原
中西　哲也
哲也 中西
典子 岸
典子 岸
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Nippon Steel Chemical and Materials Co Ltd
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    • H01—ELECTRIC ELEMENTS
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    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

難燃性で高耐熱性・高反応性である電子回路基板に用いられる銅張積層板や電子部品に用いられる封止材・成形材・注型材・接着剤・電気絶縁塗料用材料などに適した新規難燃性エポキシ樹脂、該エポキシ樹脂を必須成分とするエポキシ樹脂組成物及びその硬化物を提供することを目的とする。特定の一般式で示される窒素とリンを含有する新規難燃性エポキシ樹脂及び、該難燃性エポキシ樹脂を必須成分とする新規難燃性エポキシ樹脂組成物、更に該新規難燃性エポキシ樹脂組成物を加熱硬化してなる新規難燃性エポキシ樹脂硬化物である。Suitable for copper-clad laminates used for electronic circuit boards that are flame retardant, high heat resistance, and high reactivity, and for sealing materials, molding materials, casting materials, adhesives, and electrical insulating paint materials used in electronic components Another object of the present invention is to provide a novel flame-retardant epoxy resin, an epoxy resin composition containing the epoxy resin as an essential component, and a cured product thereof. A novel flame retardant epoxy resin containing nitrogen and phosphorus represented by a specific general formula, a novel flame retardant epoxy resin composition containing the flame retardant epoxy resin as an essential component, and the novel flame retardant epoxy resin composition It is a novel flame retardant epoxy resin cured product obtained by heating and curing a product.

Description

本発明は、電子回路基板に用いられる銅張積層板、フィルム材、樹脂付き銅箔などを製造する樹脂組成物や電子部品に用いられる封止材・成形材・注型材・接着剤・電気絶縁塗料用材料などとして有用な新規な難燃性エポキシ樹脂、エポキシ樹脂組成物及びその硬化物に関する。   The present invention relates to a resin composition for producing a copper clad laminate, a film material, a resin-coated copper foil, etc. used for an electronic circuit board, and a sealing material, a molding material, a casting material, an adhesive, and an electrical insulation used for an electronic component. The present invention relates to a novel flame-retardant epoxy resin useful as a coating material, an epoxy resin composition and a cured product thereof.

エポキシ樹脂は接着性、耐熱性、成形性に優れていることから電子部品、電気機器、自動車部品、ＦＲＰ、スポーツ用品などに広範囲に使用されている。なかでも電子部品、電気機器に使用される銅張積層板や封止材には火災の防止・遅延といった安全性が強く要求されていることから、これまでこれらの特性を有する臭素化エポキシ樹脂などが使用されている。比重が大きいという問題を有しているものの、エポキシ樹脂にハロゲン、特に臭素を導入することにより難燃性が付与されることと、エポキシ基は高反応性を有し優れた硬化物が得られることから、臭素化エポキシ樹脂類は有用な電子、電気材料として位置づけられている。
しかし、最近の電気機器を見るといわゆる軽薄短小を最重要視する傾向が次第に強くなってきている。このような社会的要求下において比重の大きいハロゲン化物は最近の軽量化傾向の観点からは好ましくない材料であり、また、高温で長期にわたって使用した場合、ハロゲン化物の解離が起こり、これによって配線腐食の発生の恐れがある。更に使用済みの電子部品、電気機器の燃焼の際にハロゲン化物などの有害物質を発生し、環境安全性の視点からハロゲンの利用が問題視されるようになり、これに代わる材料が研究されるようになった。本発明者はこの課題に鋭意取り組み、電子機器の軽薄短小化や配線腐食の問題、有害なハロゲン化物の発生の無いリン含有エポキシ樹脂を発明した。（特許文献１〜２）しかし、硬化物の耐熱性向上や難燃性の向上などが更に求められている。
特開平１１−１６６０３５ 特開平１１−２７９２５８ Epoxy resins are widely used in electronic parts, electrical equipment, automobile parts, FRP, sports equipment and the like because of their excellent adhesiveness, heat resistance and moldability. In particular, copper-clad laminates and encapsulants used in electronic parts and electrical equipment are strongly required to have safety such as fire prevention and delay. Brominated epoxy resins having these characteristics have been used so far. Is used. Although it has the problem of high specific gravity, flame resistance is imparted by introducing halogen, especially bromine, into the epoxy resin, and the epoxy group has high reactivity and an excellent cured product can be obtained. Thus, brominated epoxy resins are positioned as useful electronic and electrical materials.
However, when looking at recent electrical equipment, the tendency to place the highest importance on so-called lightness and thinness is becoming increasingly strong. Under such social demands, halides with a large specific gravity are undesirable materials from the viewpoint of recent light weight trends, and when used at high temperatures for a long period of time, halides dissociate, which causes corrosion of wiring. There is a risk of occurrence. Furthermore, when used electronic parts and electrical equipment are burned, harmful substances such as halides are generated, and the use of halogens has become a problem from the viewpoint of environmental safety, and alternative materials are studied. It became so. The present inventor has eagerly addressed this problem and invented a phosphorus-containing epoxy resin free from light and thin electronic devices, wiring corrosion problems, and generation of harmful halides. (Patent Documents 1 and 2) However, there is a further demand for improvement in heat resistance and flame retardancy of cured products.
JP-A-11-166035 JP-A-11-279258

本発明者は、ハロゲンを使用しないで難燃性を付与したリン含有エポキシ樹脂の、更なる耐熱性向上や難燃性の向上を達成すべく鋭意研究し、リンと窒素を含有した新規難燃性エポキシ樹脂により耐熱性向上や難燃性の向上ができることを見いだし、本発明を完成するに至ったものであり、電子回路基板に用いられる銅張積層板や電子部品に用いられる封止材・成形材・注型材・接着剤・電気絶縁塗料用材料・電気絶縁フィルムなどに適した、新規難燃性エポキシ樹脂、新規難燃性エポキシ樹脂組成物及びその硬化物を提供することを目的とする。
即ち、本発明の要旨は、一般式（１）で示される窒素とリンを含有する新規難燃性エポキシ樹脂および該エポキシ樹脂を必須成分としてなる新規難燃性エポキシ樹脂組成物及びその硬化物である。
具体的には、一般式（１）：

Figure 2008143309
（式中、Ｘは後記一般式（２）〜（５）からなる群から選ばれる少なくとも１つの化学構造を示し、
Ｙは後記一般式（６）〜（９）からなる群から選ばれる少なくとも１つの化学構造を示し、そして
ｎは１〜１０の整数を表す）
で示される特定の構造を有する窒素とリンを含有する新規な難燃性エポキシ樹脂を提供する。
上に引用した一般式（２）〜（２８）は下記の構造を有する。
一般式（２）：
Figure 2008143309
（式中、Ｒ１は水素又は炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐状又は環状であってもよく、そして
ａは０，１，２，３，４又は５の整数を表す）；
一般式（３）：
Figure 2008143309
（式中、Ｒ１は水素又は炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐状又は環状であってもよく、
ａは０，１，２，３，４又は５の整数を示し、そして
Ｚはメチレン、酸素、硫黄、ベンゼン、ナフタレン、アントラセン、フェナントレン、ビフェニル、または後記一般式（１０）〜（１９）のいずれかを示す）；
一般式（４）：
Figure 2008143309
（式中、Ｒ１は水素又は炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐状又は環状であってもよく、そして
ａは０，１，２，３，４又は５の整数を表す）；
一般式（５）：
Figure 2008143309
（式中、Ｒ１は水素又は炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐状又は環状であってもよく、そして
ｂは０，１，２，３，４，５，６又は７の整数を表す）；
一般式（６）：
Figure 2008143309
（式中、Ｒ２は水素又は炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐状又は環状であってもよく、
ｃは０，１，２，３又は４の整数を表し、
Ｇは後記一般式（２０）〜（２３）のいずれかを示し、１分子中に少なくとも１個は式（２１）または後記一般式（２２）を示し、
ｄは１，２，３，４又は５の整数を表し、そして
ｃ＋ｄ≦５である）；
一般式（７）：
Figure 2008143309
（式中、Ｒ２は水素又は炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐状又は環状であってもよく、
ｃ１及びｃ２は０，１，２，３又は４の整数を表し、
ｄは１，２，３，４又は５の整数を表し、
ｅは０，１，２，３又は４の整数を表し、
ｃ１＋ｅ≦４であり、
ｃ２＋ｄ≦５であり、そして
Ｇは後記一般式（２０）〜（２３）のいずれかを示し、１分子中に少なくとも１個は後記一般式（２１）または後記一般式（２２）を示す）、
一般式（８）：
Figure 2008143309
（式中、Ｒ２は水素又は炭化水素基を示し、各々は異なっていても同一でも良く、直鎖状、分岐状又は環状であってもよく、
ｃ１及びｃ２は０，１，２，３又は４の整数を表し、
ｅは０，１，２，３又は４の整数を表し、
ｆは１，２，３又は４の整数を表し、
ｃ１＋ｅ≦４であり、
ｃ２＋ｆ≦４であり、
Ｇは後記一般式（２０）〜（２３）のいずれかを示し、１分子中に少なくとも１個は後記一般式（２１）または（２２）を示し、
Ｚはメチレン、酸素、硫黄、ベンゼン、ナフタレン、アントラセン、フェナントレン、ビフェニル、または後記一般式（１０）〜（１９）のいずれかを示し、そして
ｍは１，２，３・・・の整数を表す）；
一般式（９）：
Figure 2008143309
（式中、Ｒ２は水素又は炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐状又は環状であってもよく、
Ｇは後記一般式（２０）〜（２２）のいずれかを示し、１分子中に少なくとも１個は後記一般式（２１）または（２２）を示し、
ｇは０，１，２，３，４，５又は６の整数を表し、
ｈ１及びｈ２は０，１，２，３，４又は５の整数を表し、
ｉは１，２，３，４，５又は６の整数を表し、
ｇ＋ｈ１≦６であり、
ｉ＋ｈ２≦６であり、
Ｚはメチレン、酸素、硫黄、ベンゼン、ナフタレン、アントラセン、フェナントレン、ビフェニル、または後記式（１０）〜（１９）のいずれかを示し、そして
ｌは１，２，３・・・の整数を表す）；
一般式（１０）；
Figure 2008143309
一般式（１１）；
Figure 2008143309
一般式（１２）；
Figure 2008143309
一般式（１３）；
Figure 2008143309
一般式（１４）；
−ＳＯ− （１４）
一般式（１５）；
Figure 2008143309
一般式（１６）；
Figure 2008143309
一般式（１７）；
−ＣＨ２−（Ｄ）−ＣＨ２− （１７）
（式中、Ｄはベンゼン、ナフタレン、アントラセン、フェナントレン又はビフェニルを示す）
一般式（１８）；
Figure 2008143309
（式中、ｑは０，１，２，３・・・の整数を表す）
一般式（１９）；
Figure 2008143309
（式中、Ｗはメチレン、硫黄、ベンゼン、ナフタレン、アントラセン、フェナントレン、ビフェニル、または一般式（１０）〜（１７）のいずれかを示す）；
一般式（２０）；
Figure 2008143309
一般式（２１）：
Figure 2008143309
（式中、ｊは０又は１であり、そして
Ｒ３及びＲ４は水素又は炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐鎖状又は環状であってもよく、或いはＲ３とＲ４が結合し、環状構造となっていてもよい）；
一般式（２２）：
Figure 2008143309
（式中、ｊは０又は１であり、
Ｒ３及びＲ４は水素又は炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐鎖状又は環状であっても良く、或いはＲ３とＲ４が結合し、環状構造となっていてもよく、
Ｂはベンゼン、ナフタレン、アントラセン、フェナントレン及びこれらの炭化水素置換体を示し、そして
Ｙは一般式（６）〜（９）のいずれかを示す）；
一般式（２３）：
Figure 2008143309
（式中、ｒは０，１，２，３…の整数を表わし、
Ｅはベンゼン、ナフタレン、アントラセン、フェナントレン、ビフェニル及びこれらの炭化水素置換体、一般式（２５）又は（２４）を示し、そして
Ｙは一般式（６）〜（９）のいずれかを示す）；
一般式（２４）：
Figure 2008143309
（式中、Ｒ２は水素又は炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐状又は環状であってもよく、
ｃ１及びｃ２は０，１，２，３又は４の整数を表し、
Ｚはメチレン、酸素、硫黄、ベンゼン、ナフタレン、アントラセン、フェナントレン、ビフェニル、または一般式（１０）〜（１９）のいずれかを示し、そして
ｍは１，２，３・・・の整数を表す）；
一般式（２５）：
Figure 2008143309
（式中、Ｒ２は水素又は炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐状又は環状であってもよく、
ｈ１及びｈ２は０，１，２，３，４又は５の整数を表し、
Ｚはメチレン、酸素、硫黄、ベンゼン、ナフタレン、アントラセン、フェナントレン、ビフェニル、または一般式（１０）〜（１９）のいずれかを示し、そして
ｌは１，２，３・・・の整数を表す）。
本発明はまた、一般式（２６）で示されるアミン化合物とエポキシ樹脂類と一般式（２７）及び／又は一般式（２８）で示される有機リン化合物類とを反応して得られる請求項１記載の化合物を含む新規難燃性エポキシ樹脂を提供する。ここで、一般式（２６）〜（２８）は下記の式により表される。
一般式（２６）：
Figure 2008143309
（式中、Ｘは一般式（２）〜（５）のいずれかを示し、そして
ｎは１，２，３，・・・の整数を表す）；
一般式（２７）：
Figure 2008143309
（式中、ｊは０又は１であり、そして
Ｒ３及びＲ４は水素又は炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐鎖状又は環状であってもよく、或いはＲ３とＲ４が結合し、環状構造となっていてもよい）；
一般式（２８）：
Figure 2008143309
（式中、ｊは０又は１であり、
Ｒ３及びＲ４は水素又は炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐鎖状又は環状であってもよく、或いはＲ３とＲ４が結合し、環状構造となっていてもよく、そして
Ｂはベンゼン、ナフタレン、アントラセン、フェナントレン及びこれらの炭化水素置換体を示す）。
上記のエポキシ樹脂において、好ましくは、エポキシ当量は２００ｇ／ｅｑ〜１０００ｇ／ｅｑ、リン含有率は０．２％〜８．０％且つ窒素含有率は０．１％〜４．０％である。
本発明はまた、上記の新規難燃性エポキシ樹脂を必須成分とし、硬化剤を配合してなる新規難燃性エポキシ樹脂組成物を提供する。
本発明はまた、上記の新規難燃性エポキシ樹脂組成物を用いて得られるエポキシ樹脂積層板を提供する。
本発明はまた、上記の新規難燃性エポキシ樹脂組成物を用いて得られるエポキシ樹脂封止材を提供する。
本発明はまた、上記の新規難燃性エポキシ樹脂組成物を用いて得られるエポキシ樹脂注型材を提供する。
本発明はまた、上記の難燃性エポキシ樹脂組成物を硬化して得られる新規難燃性エポキシ樹脂硬化物を提供する。
前記新規難燃性エポキシ樹脂、エポキシ樹脂組成物及びその硬化物は、電子回路基板に用いられる銅張積層板の製造用樹脂組成物や電子部品に用いられる封止材、成形材、注型材、接着剤、電気絶縁塗料用材料などとして有用である。
発明の効果
後述の実施例及び比較例との対比から明らかなように、本発明の新規難燃性エポキシ樹脂、新規難燃性エポキシ樹脂組成物は低いリン含有率で難燃性を有し、併せて耐熱性・反応性等の物性が優れているため、特に電子回路基板に用いられる銅張積層板をはじめとする電気絶縁材料に最適であり、電子部品に用いられる封止材・成形材・注型材・接着剤・フィルム材に適しており、更に電気絶縁塗料用材料としても有効である。The present inventor has intensively studied to achieve further improvement in heat resistance and flame retardancy of a phosphorus-containing epoxy resin imparted with flame retardancy without using halogen, and a novel flame retardant containing phosphorus and nitrogen. It was found that heat-resistant improvement and flame retardance can be improved by the conductive epoxy resin, and has led to the completion of the present invention, and a sealing material used for copper-clad laminates and electronic parts used for electronic circuit boards An object is to provide a novel flame-retardant epoxy resin, a novel flame-retardant epoxy resin composition and a cured product thereof suitable for molding materials, casting materials, adhesives, materials for electrical insulation coatings, electrical insulation films, etc. .
That is, the gist of the present invention is a novel flame retardant epoxy resin containing nitrogen and phosphorus represented by the general formula (1), a novel flame retardant epoxy resin composition containing the epoxy resin as an essential component, and a cured product thereof. is there.
Specifically, the general formula (1) :
Figure 2008143309
(In the formula, X represents at least one chemical structure selected from the group consisting of the following general formulas (2) to (5);
Y represents at least one chemical structure selected from the group consisting of the following general formulas (6) to (9), and n represents an integer of 1 to 10)
A novel flame retardant epoxy resin containing nitrogen and phosphorus having a specific structure represented by
General formulas (2) to (28) cited above have the following structure.
General formula (2) :
Figure 2008143309
(Wherein R1 represents hydrogen or a hydrocarbon group, each may be different or the same, may be linear, branched or cyclic, and a is 0, 1, 2, 3, 4 Or an integer of 5);
General formula (3) :
Figure 2008143309
(Wherein R1 represents hydrogen or a hydrocarbon group, each may be different or the same, and may be linear, branched or cyclic;
a represents an integer of 0, 1, 2, 3, 4 or 5, and Z represents methylene, oxygen, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or any one of the following general formulas (10) to (19) Indicate)
General formula (4) :
Figure 2008143309
(Wherein R1 represents hydrogen or a hydrocarbon group, each may be different or the same, may be linear, branched or cyclic, and a is 0, 1, 2, 3, 4 Or an integer of 5);
General formula (5) :
Figure 2008143309
(Wherein R1 represents hydrogen or a hydrocarbon group, each may be different or the same, may be linear, branched or cyclic, and b is 0, 1, 2, 3, 4 , Represents an integer of 5, 6 or 7);
General formula (6) :
Figure 2008143309
(Wherein R2 represents hydrogen or a hydrocarbon group, each may be different or the same, and may be linear, branched or cyclic;
c represents an integer of 0, 1, 2, 3 or 4;
G represents any one of the following general formulas (20) to (23), and at least one of each molecule represents formula (21) or the following general formula (22);
d represents an integer of 1, 2, 3, 4 or 5 and c + d ≦ 5);
General formula (7) :
Figure 2008143309
(Wherein R2 represents hydrogen or a hydrocarbon group, each may be different or the same, and may be linear, branched or cyclic;
c1 and c2 represent an integer of 0, 1, 2, 3 or 4;
d represents an integer of 1, 2, 3, 4 or 5;
e represents an integer of 0, 1, 2, 3 or 4;
c1 + e ≦ 4,
c2 + d ≦ 5, and G represents any one of the following general formulas (20) to (23), and at least one in one molecule represents the following general formula (21) or the following general formula (22)):
Formula (8) :
Figure 2008143309
(Wherein R2 represents hydrogen or a hydrocarbon group, each may be different or the same, and may be linear, branched or cyclic;
c1 and c2 represent an integer of 0, 1, 2, 3 or 4;
e represents an integer of 0, 1, 2, 3 or 4;
f represents an integer of 1, 2, 3 or 4;
c1 + e ≦ 4,
c2 + f ≦ 4,
G represents any one of the following general formulas (20) to (23), and at least one in each molecule represents the following general formula (21) or (22);
Z represents methylene, oxygen, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or any one of the following general formulas (10) to (19), and m represents an integer of 1, 2, 3,. );
Formula (9) :
Figure 2008143309
(Wherein R2 represents hydrogen or a hydrocarbon group, each may be different or the same, and may be linear, branched or cyclic;
G represents any one of the following general formulas (20) to (22), and at least one in each molecule represents the following general formula (21) or (22);
g represents an integer of 0, 1, 2, 3, 4, 5 or 6;
h1 and h2 represent an integer of 0, 1, 2, 3, 4 or 5;
i represents an integer of 1, 2, 3, 4, 5 or 6,
g + h1 ≦ 6,
i + h2 ≦ 6,
Z represents methylene, oxygen, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or any one of the following formulas (10) to (19), and l represents an integer of 1, 2, 3,. ;
General formula (10) ;
Figure 2008143309
General formula (11) ;
Figure 2008143309
General formula (12) ;
Figure 2008143309
General formula (13) ;
Figure 2008143309
General formula (14) ;
-SO- (14)
General formula (15) ;
Figure 2008143309
General formula (16) ;
Figure 2008143309
General formula (17) ;
—CH 2 — (D) —CH 2 — (17)
(In the formula, D represents benzene, naphthalene, anthracene, phenanthrene or biphenyl)
General formula (18) ;
Figure 2008143309
(In the formula, q represents an integer of 0, 1, 2, 3,...)
General formula (19) ;
Figure 2008143309
(Wherein W represents methylene, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or any one of the general formulas (10) to (17));
General formula (20) ;
Figure 2008143309
Formula (21) :
Figure 2008143309
(Wherein j is 0 or 1, and R3 and R4 each represent hydrogen or a hydrocarbon group, each of which may be different or the same, and may be linear, branched or cyclic; Alternatively, R3 and R4 may be bonded to form a cyclic structure);
Formula (22) :
Figure 2008143309
(Wherein j is 0 or 1,
R3 and R4 each represent hydrogen or a hydrocarbon group, and each may be different or the same, and may be linear, branched or cyclic, or R3 and R4 are bonded to form a cyclic structure. You can,
B represents benzene, naphthalene, anthracene, phenanthrene and their hydrocarbon substitutes, and Y represents any one of the general formulas (6) to (9));
Formula (23) :
Figure 2008143309
(Wherein r represents an integer of 0, 1, 2, 3...
E represents benzene, naphthalene, anthracene, phenanthrene, biphenyl and their hydrocarbon substituents, general formula (25) or (24), and Y represents any one of general formulas (6) to (9));
General formula (24) :
Figure 2008143309
(Wherein R2 represents hydrogen or a hydrocarbon group, each may be different or the same, and may be linear, branched or cyclic;
c1 and c2 represent an integer of 0, 1, 2, 3 or 4;
Z represents methylene, oxygen, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or any one of the general formulas (10) to (19), and m represents an integer of 1, 2, 3,. ;
Formula (25) :
Figure 2008143309
(Wherein R2 represents hydrogen or a hydrocarbon group, each may be different or the same, and may be linear, branched or cyclic;
h1 and h2 represent an integer of 0, 1, 2, 3, 4 or 5;
Z represents methylene, oxygen, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or any one of the general formulas (10) to (19), and l represents an integer of 1, 2, 3,. .
The present invention is also obtained by reacting an amine compound represented by the general formula (26), an epoxy resin, and an organophosphorus compound represented by the general formula (27) and / or the general formula (28). Novel flame retardant epoxy resins comprising the described compounds are provided. Here, general formula (26)-(28) is represented by the following formula.
General formula (26) :
Figure 2008143309
(Wherein X represents any one of general formulas (2) to (5), and n represents an integer of 1, 2, 3,...);
Formula (27) :
Figure 2008143309
(Wherein j is 0 or 1, and R3 and R4 each represent hydrogen or a hydrocarbon group, each of which may be different or the same, and may be linear, branched or cyclic; Alternatively, R3 and R4 may be bonded to form a cyclic structure);
Formula (28) :
Figure 2008143309
(Wherein j is 0 or 1,
R3 and R4 each represent hydrogen or a hydrocarbon group, and each may be different or the same, may be linear, branched or cyclic, or R3 and R4 are bonded to form a cyclic structure. And B represents benzene, naphthalene, anthracene, phenanthrene and hydrocarbon substitutes thereof).
In the above epoxy resin, preferably, the epoxy equivalent is 200 g / eq to 1000 g / eq, the phosphorus content is 0.2% to 8.0%, and the nitrogen content is 0.1% to 4.0%.
The present invention also provides a novel flame retardant epoxy resin composition comprising the above novel flame retardant epoxy resin as an essential component and a curing agent.
The present invention also provides an epoxy resin laminate obtained using the above novel flame-retardant epoxy resin composition.
This invention also provides the epoxy resin sealing material obtained using said novel flame-retardant epoxy resin composition.
The present invention also provides an epoxy resin casting material obtained by using the novel flame retardant epoxy resin composition.
The present invention also provides a novel flame retardant epoxy resin cured product obtained by curing the flame retardant epoxy resin composition.
The novel flame-retardant epoxy resin, epoxy resin composition and cured product thereof are a resin composition for producing a copper-clad laminate used for an electronic circuit board and a sealing material used for an electronic component, a molding material, a casting material, It is useful as a material for adhesives and electrical insulating paints.
Effects of the Invention As will be apparent from comparison with Examples and Comparative Examples described later, the novel flame-retardant epoxy resin of the present invention, the novel flame-retardant epoxy resin composition has flame retardancy at a low phosphorus content, In addition, because of its excellent heat resistance and reactivity, it is particularly suitable for electrical insulation materials such as copper-clad laminates used in electronic circuit boards. Sealing materials and molding materials used in electronic components・ Suitable for casting materials, adhesives, and film materials, and is also effective as a material for electrical insulating paints.

図１は、実施例１において得られたエポキシ樹脂のＧＰＣ図を示す。
図２は、実施例１において得られたエポキシ樹脂のＦＴＩＲ図を示す。
図３は、実施例４において得られたエポキシ樹脂のＧＰＣ図を示す。
図４は、実施例４において得られたエポキシ樹脂のＦＴＩＲ図を示す。FIG. 1 shows a GPC diagram of the epoxy resin obtained in Example 1.
FIG. 2 shows an FTIR diagram of the epoxy resin obtained in Example 1.
FIG. 3 shows a GPC diagram of the epoxy resin obtained in Example 4.
FIG. 4 shows an FTIR diagram of the epoxy resin obtained in Example 4.

本発明について詳細に述べる。一般式（１）で示される新規エポキシ樹脂は同一分子内にリンと窒素を含有していることから難燃性が高くなっている。また、窒素の導入の効果として、耐熱性も高くなっており、反応性も著しく改良されている。この様な新規エポキシ樹脂を合成する方法としては一般式（２６）に示されるアミン化合物と、一般式（２７）及び／または一般式（２８）で示される有機リン含有化合物、エポキシ樹脂類を反応することで得ることが出来る。
本発明に用いる一般式（２６）に示されるアミン化合物の具体例としては、（Ｘ）が一般式（２）の例としてアニリン、フェニレンジアミン、トルイジン、キシリジン、ジエチルトルエンジアミン等が挙げられる。（Ｘ）が一般式（３）、（４）の例としてジアミノジフェニルメタン、ジアミノジフェニルエタン、ジアミノジフェニルプロパン、ジアミノジフェニルケトン、ジアミノジフェニルスルフィド、ジアミノジフェニルスルホン、ビス（アミノフェニル）フルオレン、ジアミノジエチルジメチルジフェニルメタン、ジアミノジフェニルエーテル、ジアミノベンズアニリド、ジアミノビフェニル、ジメチルジアミノビフェニル、ビフェニルテトラアミン、ビスアミノフェニルアントラセン、ビスアミノフェノキシベンゼン、ビスアミノフェノキシフェニルエーテル、ビスアミノフェノキシビフェニル、ビスアミノフェノキシフェニルスルホン、ビスアミノフェノキシフェニルプロパン等が挙げられる。（Ｘ）が一般式（５）の例としてジアミノナフタレン等が挙げられる。また、これらの炭化水素置換基を持った化合物や異性体等も挙げられる。また、これらに限定されるものではなく一般式（２６）で示されるアミン化合物全般を示す物であり２種類以上併用しても良い。
本発明に用いる一般式（２７）で示される有機リン類とは、キノン類やグリシジル基、ビニル基などの官能基と反応しうる活性な水素がリン原子に結合した有機リン化合物類であり、具体的にはＨＣＡ（三光化学株式会社製 ９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキサイド）、ジフェニルホスフィンオキシド、ＣＰＨＯ（日本化学工業株式会社製 シクロオクチレンホスフィンオキシド）等が挙げられる。
本発明に用いる一般式（２８）に示される有機リン化合物類とは、一般式（２７）に示される有機リン化合物類の活性な水素とキノン類とを反応して得られるリン含有フェノール化合物であり、具体的にはＨＣＡ−ＨＱ（三光化学株式会社製 １０−（２，５−ジヒドロキシフェニル）−１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキサイド）、１０−（２，７−ジヒドロキシナフチル）−１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキサイド、ＰＰＱ（北興化学工業株式会社 ジフェニルホスフィニルハイドロキノン）、ジフェニルホスフィニルナフトキノン、ＣＰＨＯ−ＨＱ（日本化学工業株式会社製 シクロオクチレンホスフィニル−１，４−ベンゼンジオール）、シクロオクチレンホスフィニル−１，４−ナフタレンジオール、特開２００２−２６５５６２で開示されているリン含有フェノール化合物等が挙げられる。本発明では一般式（２７）及び／又は一般式（２８）で示されるものであれば良く、これらに限定されるものではなく、また、２種類以上使用しても良い。
リン原子に結合した活性な水素とキノン類とを反応して得られるリン含有フェノール化合物は、例えば特開平５−２１４０６８号公報、ロシアの一般的な雑誌である（Ｚｈ．Ｏｂｓｈｃｈ．Ｋｈｉｍ．），４２（１１），第２４１５−２４１８頁（１９７２）や特開昭６０−１２６２９３号公報、特開昭６１−２３６７８７号公報、特開平５−３３１１７９号公報で示される方法により反応される。この際、生成した多官能のリン含有フェノール化合物だけを取り出すには精製や再結晶などの操作が必要である。しかし、活性な水素がリン原子に結合した有機リン化合物を適度に残存させるとその様な操作が不要となるばかりか、エポキシ樹脂のリン含有率を高めつつ反応後のエポキシ樹脂粘度を低下させることも出来る。
一般式（２６）に示されるアミン化合物と、一般式（２７）及び／または一般式（２８）で示される有機リン含有化合物と反応を行うエポキシ樹脂類はグリシジルエーテル基をもったものが望ましい。
具体的にはエポトート ＹＤＣ−１３１２、ＺＸ−１０２７（東都化成株式会社製 ハイドロキノン型エポキシ樹脂）、ＺＸ−１２５１（東都化成株式会社製 ビフェノール型エポキシ樹脂）、エポトート ＹＤ−１２７、エポトート ＹＤ−１２８、エポトート ＹＤ−８１２５、エポトート ＹＤ−８２５ＧＳエポトート ＹＤ−０１１、エポトート ＹＤ−９００、エポトート ＹＤ−９０１（東都化成株式会社製 ＢＰＡ型エポキシ樹脂）、エポトート ＹＤＦ−１７０、エポトート ＹＤＦ−８１７０、エポトート ＹＤＦ−８７０ＧＳ、エポトート ＹＤＦ−２００１（東都化成株式会社製 ＢＰＦ型エポキシ樹脂）、エポトート ＹＤＰＮ−６３８（東都化成株式会社製 フェノールノボラック型エポキシ樹脂）、エポトート ＹＤＣＮ−７０１（東都化成株式会社製 クレゾールノボラック型エポキシ樹脂）、ＺＸ−１２０１（東都化成株式会社製 ビスフェノールフルオレン型エポキシ樹脂）、ＮＣ−３０００（日本化薬株式会社製 ビフェニルアラルキルフェノール型エポキシ樹脂）、ＥＰＰＮ−５０１Ｈ、ＥＰＰＮ−５０２Ｈ（日本化薬株式会社製 多官能エポキシ樹脂）ＺＸ−１３５５（東都化成株式会社製 ナフタレンジオール型エポキシ樹脂）、ＥＳＮ−１５５、ＥＳＮ−１８５Ｖ、ＥＳＮ−１７５（東都化成株式会社製 βナフトールアラルキル型エポキシ樹脂）、ＥＳＮ−３５５、ＥＳＮ−３７５（東都化成株式会社製 ジナフトールアラルキル型エポキシ樹脂）、ＥＳＮ−４７５Ｖ、ＥＳＮ−４８５（東都化成株式会社製 αナフトールアラルキル型エポキシ樹脂）等が挙げられるが、これらに限定されるものではなく２種類以上併用しても良い。
エポキシ樹脂類と一般式（２６）に示されるアミン化合物と、一般式（２７）及び／または一般式（２８）で示される有機リン含有化合物との反応は公知の方法で行うことが可能であり、反応温度として１００℃〜２００℃より好ましくは１２０℃〜１８０℃で攪拌下行うことができる。エポキシ樹脂類とアミン化合物、あるいは有機リン化合物を反応させた後、残りのアミン化合物、あるいは有機リン化合物を反応しても良く、同時にエポキシ樹脂類とアミン化合物と有機リン化合物を同時に反応しても良い。
反応時間はエポキシ当量の測定を行って決定することが出来る。測定にはＪＩＳ Ｋ７２３６の方法により測定可能である。エポキシ樹脂類とアミン化合物、有機リン含有化合物との反応によりエポキシ当量は大きくなっていき、理論エポキシ当量との比較により反応終点を決定できる。
また、反応の速度が遅い場合、必要に応じて触媒を使用して生産性の改善を計ることができる。具体的には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、トリス（２，６−ジメトキシフェニル）ホスフィン等のホスフィン類、エチルトリフェニルホスホニウムブロマイド等のホスホニウム塩類、２メチルイミダゾール、２エチル４メチルイミダゾール等のイミダゾール類等各種触媒が使用可能である。
反応には本発明の物性を損なわない範囲に於いて多価フェノール類等の変性剤を同時に用いても良い。多価フェノール類としてはビスフェノールＡ、ビスフェノールＦ、ビスフェノールＣ、ビスフェノールＺ、ビスフェノールＳ、ビフェノール等の二価フェノール類、フェノールノボラック樹脂、クレゾールノボラック樹脂、ナフトールノボラック樹脂、ナフトールアラルキル樹脂、フェノールアラルキル樹脂などの多価フェノール類が挙げられる。
本発明組成物の硬化剤としては、フェノールノボラック樹脂を代表とする各種多価フェノール樹脂類や酸無水物類、ＤＩＣＹを代表とするアミン類、ヒドラジッド類、酸性ポリエステル類等の通常使用されるエポキシ樹脂用硬化剤を使用することができ、これらの硬化剤は１種類だけ使用しても２種類以上使用しても良い。
本発明組成物には必要に応じて第３級アミン、第４級アンモニウム塩、ホスフィン類、イミダゾール類等の硬化促進剤を配合することができる。また、必要に応じて無機充填剤やガラスクロス・アラミド繊維などの補強材、充填材、顔料等を配合しても良い。
本発明の新規難燃性エポキシ樹脂を使用して得られた積層板の特性評価を行った結果、難熱性が高く、耐熱性が高いことがわかった。このことからハロゲン化物を含有しないで難燃性であるエポキシ樹脂組成物、またその硬化物を得ることが可能であり、該エポキシ樹脂、エポキシ樹脂組成物及びその硬化物は、電子回路基板に用いられる銅張積層板の製造用樹脂組成物や電子部品に用いられる封止材、成形材、注型材、接着剤、フィルム材、電気絶縁塗料用材料などとして有用であることがわかった。The present invention will be described in detail. The novel epoxy resin represented by the general formula (1) has high flame retardancy because it contains phosphorus and nitrogen in the same molecule. Further, as an effect of introducing nitrogen, the heat resistance is also high, and the reactivity is remarkably improved. As a method of synthesizing such a novel epoxy resin, an amine compound represented by the general formula (26) is reacted with an organic phosphorus-containing compound represented by the general formula (27) and / or the general formula (28) and epoxy resins. You can get it.
Specific examples of the amine compound represented by the general formula (26) used in the present invention include aniline, phenylenediamine, toluidine, xylidine, diethyltoluenediamine and the like as examples of the general formula (2) in which (X) is general formula (2). (X) is an example of general formula (3), (4) diaminodiphenylmethane, diaminodiphenylethane, diaminodiphenylpropane, diaminodiphenyl ketone, diaminodiphenyl sulfide, diaminodiphenylsulfone, bis (aminophenyl) fluorene, diaminodiethyldimethyldiphenylmethane , Diaminodiphenyl ether, diaminobenzanilide, diaminobiphenyl, dimethyldiaminobiphenyl, biphenyltetraamine, bisaminophenylanthracene, bisaminophenoxybenzene, bisaminophenoxyphenyl ether, bisaminophenoxybiphenyl, bisaminophenoxyphenyl sulfone, bisaminophenoxyphenyl Examples include propane. Examples of (X) in general formula (5) include diaminonaphthalene. Also included are compounds and isomers having these hydrocarbon substituents. Moreover, it is not limited to these, It is a thing which shows the amine compound whole shown by General formula (26), and may use 2 or more types together.
The organic phosphorus represented by the general formula (27) used in the present invention is an organic phosphorus compound in which an active hydrogen capable of reacting with a functional group such as a quinone, a glycidyl group, or a vinyl group is bonded to a phosphorus atom. Specifically, HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide manufactured by Sanko Chemical Co., Ltd.), diphenylphosphine oxide, CPHO (cyclooctylene phosphine oxide manufactured by Nippon Chemical Industry Co., Ltd.) Etc.
The organophosphorus compounds represented by the general formula (28) used in the present invention are phosphorus-containing phenol compounds obtained by reacting the active hydrogen of the organophosphorus compounds represented by the general formula (27) with quinones. Yes, specifically HCA-HQ (10- (2,5-dihydroxyphenyl) -10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide manufactured by Sanko Chemical Co., Ltd.), 10- (2, 7-dihydroxynaphthyl) -10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, PPQ (Hokuko Chemical Co., Ltd. diphenylphosphinylhydroquinone), diphenylphosphinylnaphthoquinone, CPHO-HQ (Nippon Kagaku) Kogyo Co., Ltd. cyclooctylenephosphinyl-1,4-benzenediol), cyclooctile Phosphinyl-1,4-naphthalene diol, and a phosphorus-containing phenol compound such as disclosed in JP 2002-265562. In this invention, what is shown by General formula (27) and / or General formula (28) should just be shown, It is not limited to these, You may use 2 or more types.
A phosphorus-containing phenol compound obtained by reacting active hydrogen bonded to a phosphorus atom with quinones is, for example, Japanese Patent Application Laid-Open No. 5-21068, Russian general magazine (Zh. Obshch. Khim.), 42 (11), pages 2415-2418 (1972), and JP-A-60-126293, JP-A-61-223687, and JP-A-5-331179. At this time, in order to take out only the polyfunctional phosphorus-containing phenol compound produced, operations such as purification and recrystallization are required. However, if an organic phosphorus compound in which active hydrogen is bonded to a phosphorus atom is appropriately left, such an operation becomes unnecessary, and the viscosity of the epoxy resin after the reaction is lowered while increasing the phosphorus content of the epoxy resin. You can also.
Epoxy resins that react with the amine compound represented by the general formula (26) and the organic phosphorus-containing compound represented by the general formula (27) and / or the general formula (28) preferably have a glycidyl ether group.
Specifically, Epototo YDC-1312, ZX-1027 (Hydroquinone type epoxy resin manufactured by Toto Kasei Co., Ltd.), ZX-1251 (Biphenol type epoxy resin manufactured by Toto Kasei Co., Ltd.), Epototo YD-127, Epototo YD-128, Epototo YD-8125, Epototo YD-825GS Epototo YD-011, Epototo YD-900, Epototo YD-901 (BPA type epoxy resin manufactured by Tohto Kasei Co., Ltd.), Epototo YDF-170, Epototo YDF-8170, Epototo YDF-870S YDF-2001 (BPF type epoxy resin manufactured by Toto Kasei Co., Ltd.), Epototo YDPN-638 (Phenol novolac type epoxy resin manufactured by Toto Kasei Co., Ltd.), Epototo YDCN-701 (Toto Kasei) (Cresol novolac type epoxy resin manufactured by Seisaku Co., Ltd.), ZX-1201 (Bisphenol fluorene type epoxy resin manufactured by Toto Kasei Co., Ltd.), NC-3000 (Biphenylaralkylphenol type epoxy resin manufactured by Nippon Kayaku Co., Ltd.), EPPN-501H, EPPN -502H (Nippon Kayaku Co., Ltd. polyfunctional epoxy resin) ZX-1355 (Tohto Kasei Co., Ltd. naphthalenediol type epoxy resin), ESN-155, ESN-185V, ESN-175 (Toto Kasei Co., Ltd. β-naphthol aralkyl) Type epoxy resin), ESN-355, ESN-375 (manufactured by Toto Kasei Co., Ltd., dinaphthol aralkyl type epoxy resin), ESN-475V, ESN-485 (manufactured by Toto Kasei Co., Ltd., α-naphthol aralkyl type epoxy resin) and the like. But, Is not limited to these it may be used in combination of two or more.
The reaction between the epoxy resin, the amine compound represented by the general formula (26), and the organic phosphorus-containing compound represented by the general formula (27) and / or the general formula (28) can be performed by a known method. The reaction temperature may be 100 ° C to 200 ° C, more preferably 120 ° C to 180 ° C with stirring. After reacting the epoxy resin with the amine compound or the organophosphorus compound, the remaining amine compound or the organophosphorus compound may be reacted. At the same time, the epoxy resin, the amine compound and the organophosphorus compound may be reacted simultaneously. good.
The reaction time can be determined by measuring the epoxy equivalent. Measurement can be performed by the method of JIS K7236. The epoxy equivalent is increased by the reaction of the epoxy resins with the amine compound and the organic phosphorus-containing compound, and the end point of the reaction can be determined by comparison with the theoretical epoxy equivalent.
Further, when the reaction rate is slow, productivity can be improved by using a catalyst as necessary. Specifically, tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine, ethyltriphenylphosphonium Various catalysts such as phosphonium salts such as bromide and imidazoles such as 2methylimidazole and 2ethyl4methylimidazole can be used.
In the reaction, modifiers such as polyhydric phenols may be used at the same time as long as the physical properties of the present invention are not impaired. Polyhydric phenols such as bisphenol A, bisphenol F, bisphenol C, bisphenol Z, bisphenol S, biphenol, and the like, phenol novolac resins, cresol novolac resins, naphthol novolac resins, naphthol aralkyl resins, phenol aralkyl resins, etc. A polyhydric phenol is mentioned.
As the curing agent of the composition of the present invention, various polyhydric phenol resins represented by phenol novolac resins, acid anhydrides, amines represented by DICY, hydrazides, acidic polyesters and the like are usually used. Resin curing agents can be used, and these curing agents may be used alone or in combination of two or more.
Curing accelerators such as tertiary amines, quaternary ammonium salts, phosphines, and imidazoles can be blended in the composition of the present invention as necessary. Moreover, you may mix | blend a reinforcing material, filler, a pigment, etc., such as an inorganic filler and glass cloth and aramid fiber, as needed.
As a result of evaluating the characteristics of the laminate obtained using the novel flame-retardant epoxy resin of the present invention, it was found that the flame-retardant property was high and the heat resistance was high. Accordingly, it is possible to obtain an epoxy resin composition that is flame retardant without containing a halide, and a cured product thereof. The epoxy resin, the epoxy resin composition, and the cured product thereof are used for an electronic circuit board. It was found to be useful as a resin composition for producing a copper-clad laminate and a sealing material used for electronic parts, a molding material, a casting material, an adhesive, a film material, and an electrical insulating paint material.

一般的事項
実施例及び比較例を挙げて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。積層板は以下の条件により作成した。得られたエポキシ樹脂、硬化剤、必要に応じて硬化促進剤を用いて、表１に示す組成を有する樹脂ワニスを調製し、この樹脂ワニスをガラスクロス（日東紡績株式会社製 ＷＥＡ７６２８）に含浸させた後、１５０℃で５分間加熱することにより乾燥し、プリプレグを得た。
このプリプレグを４枚積層し、その両側に厚み３５μｍの銅箔（三井金属鉱業株式会社製 ３ＥＣ−ＩＩＩ）を配置して積層物を作製した。この積層物を１７０℃、２０ｋｇｆ／ｃｍ２の条件で７０分間、加熱加圧成形することにより積層板を作製した。難燃性はＵＬ（Ｕｎｄｅｒｗｒｉｔｅｒ Ｌａｂｏｒａｔｏｒｉｃｓ）規格に準じて測定を行った。銅箔剥離強さはＪＩＳ Ｃ ６４８１ ５．７に準じて測定した。また、硬化物のガラス転移温度はエスエスアイナノテクノロジー株式会社製 Ｅｘｓｔｅｒ６０００ ＤＳＣで１０℃／分の昇温速度で測定を行った。
実施例１．
攪拌装置、温度計、冷却管、窒素ガス導入装置を備えた４つ口のガラス製セパラブルフラスコに、ＹＤＰＮ−６３８ ５７５．５重量部、ＹＤＦ−１７０ ２５０．０重量部、ＨＣＡ １４０．０重量部、エタキュアー１００（エチルコーポレーション製 ジエチルトルエンジアミン）３４．５重量部を仕込み、窒素ガスを導入しながら攪拌を行い加熱して溶解した。トリフェニルホスフィンを０．１重量部添加して１５０℃で４時間反応した。得られたエポキシ樹脂のエポキシ当量は２７５．９ｇ／ｅｑ、リン含有率は２．０重量％であった。得られたエポキシ樹脂のＧＰＣ、ＦＴＩＲを図１，図２に示す。得られたエポキシ樹脂に表１に示した割合で硬化剤（ＤＩＣＹ）及び硬化促進剤（２Ｅ４ＭＺ）を添加し、実施例の一般的事項の項に記載した方法により積層板評価を行った。その積層板評価結果を表１に示す。
実施例２．
実施例１と同様な装置にＹＤ−１２８ ３００．０重量部、ＹＤＰＮ−６３８ ５００．４重量部、ＨＣＡ １５４．６重量部、ＢＰＡ（新日鐵科学株式会社製 ビスフェノールＡ）１５．０重量部、エタキュアー１００ ３０．０重量部，トリフェニルホスフィン ０．２重量部とした以外は実施例１と同じ操作を行った。得られたエポキシ樹脂のエポキシ当量は２９９．８ｇ／ｅｑ、リン含有率は２．２重量％であった。得られたエポキシ樹脂に表１に示した割合で硬化剤（ＤＩＣＹ）及び硬化促進剤（２Ｅ４ＭＺ）を添加し、実施例の一般的事項の項に記載した方法により積層板評価を行った。その積層板評価結果を表１に示す。
実施例３．
実施例１と同様な装置にＹＤ−１２８ ２９９．６重量部、ＹＤＰＮ−６３８ ５０４．５重量部、ＨＣＡ １４３．７重量部、ＨＣＡ−ＨＱ １６．０重量部、ＢＰＡ １５．０重量部、エタキュアー１００ ２１．２重量部，トリフェニルホスフィン ０．２重量部とした以外は実施例１と同じ操作を行った。得られたエポキシ樹脂のエポキシ当量は３０１．８ｇ／ｅｑ、リン含有率は２．２重量％であった。得られたエポキシ樹脂に表１に示した割合で硬化剤（ＤＩＣＹ）及び硬化促進剤（２Ｅ４ＭＺ）を添加し、実施例の一般的事項の項に記載した方法により積層板評価を行った。その積層板評価結果を表１に示す。
実施例４．
実施例１と同様な装置にＨＣＡ ４２．０重量部、トルエン９８．０重量部を仕込み加熱して溶解した。１，４−ナフトキノン ２７．７重量部を反応発熱に注意しながら分割して投入した。反応発熱がほとんど無くなってから昇温し、還流温度で２時間保持して反応を進めた。ＥＳＮ−４８５ ８９５．３重量部とＴＳＢ−ＨＢ（和歌山精化工業株式会社製 ３，３′−ジメチル−４，４′−ジアミノビフェニル）３５．０重量部を仕込み、溶剤を除去しながら溶融した。トリフェニルホスフィン ０．１重量部配合して１６０℃で４時間反応した。得られたエポキシ樹脂のエポキシ当量は４５８．３ｇ／ｅｑ、リン含有率は０．６重量％であった。得られたエポキシ樹脂のＧＰＣ、ＦＴＩＲを図３，図４に示す。得られたエポキシ樹脂に表１に示した割合で硬化剤（ＤＩＣＹ）及び硬化促進剤（２Ｅ４ＭＺ）を添加し、実施例の一般的事項の項に記載した方法により積層板評価を行った。その積層板評価結果を表１に示す。
比較例１．
実施例１と同様な装置にＹＤＦ−１７０ ２５０．０重量部、ＹＤＰＮ−６３８ ５４７．５重量部、ＨＣＡ １４０．０重量部、ＢＲＧ−５５７（昭和高分子株式会社製 フェノールノボラック樹脂）６２．５重量部、トリフェニルホスフィン ０．２重量部とした以外は実施例１と同じ操作を行った。得られたエポキシ樹脂のエポキシ当量は２９７．５ｇ／ｅｑ、リン含有率は２．０重量％であった。得られたエポキシ樹脂に表１に示した割合で硬化剤（ＤＩＣＹ）及び硬化促進剤（２Ｅ４ＭＺ）を添加し、実施例の一般的事項の項に記載した方法により積層板評価を行った。その積層板評価結果を表１に示す。
比較例２．
実施例１と同様な装置にＹＤＰＮ−６３８ ７６１．０重量部、ＨＣＡ ２０９．０重量部、ＢＰＡ ３０．０重量部、トリフェニルホスフィン ０．２重量部とした以外は実施例１と同じ操作を行った。得られたエポキシ樹脂のエポキシ当量は３２７．４ｇ／ｅｑ、リン含有率は３．０重量％であった。得られたエポキシ樹脂に表１に示した割合で硬化剤（ＤＩＣＹ）及び硬化促進剤（２Ｅ４ＭＺ）を添加し、実施例の一般的事項の項に記載した方法により積層板評価を行った。その積層板評価結果を表１に示す。
比較例３．
実施例１と同様な装置にＨＣＡ ４２．０重量部、トルエン９８．０重量部を仕込み加熱して溶解した。１，４−ナフトキノン ２７．７重量部を反応発熱に注意しながら分割して投入した。反応発熱がほとんど無くなってから昇温し、還流温度で２時間保持して反応を進めた。ＥＳＮ−４８５ ９３０．３重量部を仕込み、溶剤を除去しながら溶融した。トリフェニルホスフィン ０．１重量部配合して１６０℃で４時間反応した。得られたエポキシ樹脂のエポキシ当量は３１５．２ｇ／ｅｑ、リン含有率は０．６重量％であった。得られたエポキシ樹脂に表１に示した割合で硬化剤（ＤＩＣＹ）及び硬化促進剤（２Ｅ４ＭＺ）を添加し、実施例の一般的事項の項に記載した方法により積層板評価を行った。その積層板評価結果を表１に示す。

Figure 2008143309
以上、実施例及び比較例の試験結果及び、表１の比較例に記載されている物性値から明らかなように、本発明の新規難燃性エポキシ樹脂を使用することでリン含有が同等でも高い難燃性が得られ、耐熱性も高い。実施例１と比較例１の比較においてエタキュア１００を反応して得られる本発明エポキシ樹脂はリン含有率が変わらないにもかかわらず高い難燃性を有し、ガラス転移温度の比較から耐熱性も高くなっている。また、実施例４と比較例３においても同様にＴＳＢ−ＨＢを反応して得られる本発明エポキシ樹脂は難燃性、耐熱性とも著しく改良されている。
また、使用した硬化触媒２Ｅ４ＭＺの配合量で解るように本発明のエポキシ樹脂は反応性をも改良されていることが解る。この様に本発明の新規難燃性エポキシ樹脂、新規難燃性エポキシ樹脂組成物は低いリン含有率で難燃性を有し、併せて耐熱性・反応性等の物性が優れているため、特に電子回路基板に用いられる銅張積層板をはじめとする電気絶縁材料に最適であり、電子部品に用いられる封止材・成形材・注型材・接着剤・フィルム材に適しており、更に電気絶縁塗料用材料としても有効である。 General Items The present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited thereto. The laminate was prepared under the following conditions. Using the obtained epoxy resin, curing agent, and curing accelerator as necessary, a resin varnish having the composition shown in Table 1 was prepared, and this resin varnish was impregnated into a glass cloth (WEA7628 manufactured by Nitto Boseki Co., Ltd.). And then dried by heating at 150 ° C. for 5 minutes to obtain a prepreg.
Four prepregs were laminated, and a 35 μm thick copper foil (Mitsui Metal Mining Co., Ltd. 3EC-III) was placed on each side to produce a laminate. This laminate was heat-pressed for 70 minutes under the conditions of 170 ° C. and 20 kgf / cm 2 to produce a laminate. Flame retardancy was measured according to UL (Underwriter Laboratories) standards. The copper foil peel strength was measured according to JIS C 6481 5.7. Moreover, the glass transition temperature of hardened | cured material measured with the temperature increase rate of 10 degree-C / min by SS6000 nano DSC manufactured by SS nanotechnology.
Example 1.
In a four-necked glass separable flask equipped with a stirrer, thermometer, condenser, and nitrogen gas introducing device, YDPN-638 575.5 parts by weight, YDF-170 250.0 parts by weight, HCA 140.0 parts by weight Part, Etacure 100 (diethyltoluenediamine manufactured by Ethyl Corporation) 34.5 parts by weight was stirred and stirred while introducing nitrogen gas to dissolve. 0.1 parts by weight of triphenylphosphine was added and reacted at 150 ° C. for 4 hours. The epoxy equivalent of the obtained epoxy resin was 275.9 g / eq, and the phosphorus content was 2.0% by weight. GPC and FTIR of the obtained epoxy resin are shown in FIGS. A curing agent (DICY) and a curing accelerator (2E4MZ) were added to the obtained epoxy resin in the proportions shown in Table 1, and laminate evaluation was performed by the method described in the general item section of the examples. The laminated board evaluation results are shown in Table 1.
Example 2
In the same apparatus as Example 1, 300.0 parts by weight of YD-128, 500.4 parts by weight of YDPN-638, 154.6 parts by weight of HCA, 15.0 parts by weight of BPA (Bisphenol A manufactured by Nippon Steel Science Co., Ltd.) The same operation as in Example 1 was carried out except that 30.0 parts by weight of Etacure 100 and 0.2 parts by weight of triphenylphosphine were used. The epoxy equivalent of the obtained epoxy resin was 299.8 g / eq, and the phosphorus content was 2.2% by weight. A curing agent (DICY) and a curing accelerator (2E4MZ) were added to the obtained epoxy resin in the proportions shown in Table 1, and laminate evaluation was performed by the method described in the general item section of the examples. The laminated board evaluation results are shown in Table 1.
Example 3
In the same apparatus as in Example 1, 299.6 parts by weight of YD-128, 504.5 parts by weight of YDPN-638, 143.7 parts by weight of HCA, 16.0 parts by weight of HCA-HQ, 15.0 parts by weight of BPA, Etacure The same operation as in Example 1 was performed except that 21.2 parts by weight of 100 and 0.2 parts by weight of triphenylphosphine were used. The epoxy equivalent of the obtained epoxy resin was 301.8 g / eq, and the phosphorus content was 2.2% by weight. A curing agent (DICY) and a curing accelerator (2E4MZ) were added to the obtained epoxy resin in the proportions shown in Table 1, and laminate evaluation was performed by the method described in the general item section of the examples. The laminated board evaluation results are shown in Table 1.
Example 4
In the same apparatus as in Example 1, 42.0 parts by weight of HCA and 98.0 parts by weight of toluene were charged and dissolved by heating. 27.7 parts by weight of 1,4-naphthoquinone was added in portions while paying attention to the reaction exotherm. The temperature was raised after almost no reaction exotherm, and the reaction was continued at the reflux temperature for 2 hours. ESN-485 895.3 parts by weight and 35.0 parts by weight of TSB-HB (3,3'-dimethyl-4,4'-diaminobiphenyl manufactured by Wakayama Seika Kogyo Co., Ltd.) were charged and melted while removing the solvent. . Triphenylphosphine (0.1 part by weight) was mixed and reacted at 160 ° C. for 4 hours. The epoxy equivalent of the obtained epoxy resin was 458.3 g / eq, and the phosphorus content was 0.6% by weight. GPC and FTIR of the obtained epoxy resin are shown in FIGS. A curing agent (DICY) and a curing accelerator (2E4MZ) were added to the obtained epoxy resin in the proportions shown in Table 1, and laminate evaluation was performed by the method described in the general item section of the examples. The laminated board evaluation results are shown in Table 1.
Comparative Example 1
In the same apparatus as in Example 1, 250.0 parts by weight of YDF-170, 547.5 parts by weight of YDPN-638, 140.0 parts by weight of HCA, BRG-557 (Phenol novolac resin manufactured by Showa Polymer Co., Ltd.) 62.5 The same operation as in Example 1 was performed except that 0.2 parts by weight of triphenylphosphine was used. The epoxy equivalent of the obtained epoxy resin was 297.5 g / eq, and the phosphorus content was 2.0% by weight. A curing agent (DICY) and a curing accelerator (2E4MZ) were added to the obtained epoxy resin in the proportions shown in Table 1, and laminate evaluation was performed by the method described in the general item section of the examples. The laminated board evaluation results are shown in Table 1.
Comparative Example 2
The same operation as in Example 1 was conducted except that YDPN-638 761.0 parts by weight, HCA 209.0 parts by weight, BPA 30.0 parts by weight, and triphenylphosphine 0.2 parts by weight were used in the same apparatus as in Example 1. went. The epoxy equivalent of the obtained epoxy resin was 327.4 g / eq, and the phosphorus content was 3.0% by weight. A curing agent (DICY) and a curing accelerator (2E4MZ) were added to the obtained epoxy resin in the proportions shown in Table 1, and laminate evaluation was performed by the method described in the general item section of the examples. The laminated board evaluation results are shown in Table 1.
Comparative Example 3
In the same apparatus as in Example 1, 42.0 parts by weight of HCA and 98.0 parts by weight of toluene were charged and dissolved by heating. 27.7 parts by weight of 1,4-naphthoquinone was added in portions while paying attention to the reaction exotherm. The temperature was raised after almost no reaction exotherm, and the reaction was continued at the reflux temperature for 2 hours. 930.3 parts by weight of ESN-485 was charged and melted while removing the solvent. Triphenylphosphine (0.1 part by weight) was mixed and reacted at 160 ° C. for 4 hours. The epoxy equivalent of the obtained epoxy resin was 315.2 g / eq, and the phosphorus content was 0.6% by weight. A curing agent (DICY) and a curing accelerator (2E4MZ) were added to the obtained epoxy resin in the proportions shown in Table 1, and laminate evaluation was performed by the method described in the general item section of the examples. The laminated board evaluation results are shown in Table 1.
Figure 2008143309
 As described above, as is clear from the test results of Examples and Comparative Examples and the physical property values described in Comparative Examples of Table 1, the use of the novel flame-retardant epoxy resin of the present invention is high even if the phosphorus content is equivalent. Flame retardancy is obtained and heat resistance is high. The epoxy resin of the present invention obtained by reacting Etacure 100 in the comparison between Example 1 and Comparative Example 1 has high flame retardancy despite the fact that the phosphorus content does not change, and also has heat resistance from the comparison of glass transition temperatures. It is high. Also in Example 4 and Comparative Example 3, the epoxy resin of the present invention obtained by reacting TSB-HB in the same manner is remarkably improved in both flame retardancy and heat resistance.
Moreover, it turns out that the reactivity of the epoxy resin of this invention is also improved so that it may understand with the compounding quantity of the used curing catalyst 2E4MZ. Thus, the novel flame retardant epoxy resin of the present invention, the novel flame retardant epoxy resin composition has flame retardance at a low phosphorus content, and also has excellent physical properties such as heat resistance and reactivity. It is particularly suitable for electrical insulation materials such as copper-clad laminates used for electronic circuit boards, and is suitable for sealing materials, molding materials, casting materials, adhesives, and film materials used for electronic components. It is also effective as a material for insulating paint.

本発明によって得られた新規難燃性エポキシ樹脂、新規難燃性エポキシ樹脂組成物は低いリン含有率で難燃性を有し、耐熱性・反応性等の物性が優れているため、特に電子回路基板に用いられる銅張積層板をはじめとする電気絶縁材料、電子部品に用いられる封止材・成形材・注型材・接着剤・フィルム剤として適しており、更に電気絶縁塗料用材料として適している。   The novel flame-retardant epoxy resin and novel flame-retardant epoxy resin composition obtained by the present invention have flame retardancy at a low phosphorus content and excellent physical properties such as heat resistance and reactivity. Suitable for electrical insulation materials such as copper-clad laminates used for circuit boards, sealing materials, molding materials, casting materials, adhesives and film materials used for electronic components, and also suitable for materials for electrical insulation paints ing.

Claims (8)

一般式（１）で示される特定の構造を有する窒素とリンを含有する新規な難燃性エポキシ樹脂：
一般式（１）：
Figure 2008143309
（式中、Ｘは後記一般式（２）〜（５）からなる群から選ばれる少なくとも１つの化学構造を示し、
Ｙは後記一般式（６）〜（９）からなる群から選ばれる少なくとも１つの化学構造を示し、そして
ｎは１〜１０の整数を表す）；
一般式（２）：
Figure 2008143309
（式中、Ｒ１は水素又は炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐状又は環状であってもよく、そして
ａは０，１，２，３，４又は５の整数を表す）；
一般式（３）：
Figure 2008143309
（式中、Ｒ１は水素又は炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐状又は環状であってもよく、
ａは０，１，２，３，４又は５の整数を示し、そして
Ｚはメチレン、酸素、硫黄、ベンゼン、ナフタレン、アントラセン、フェナントレン、ビフェニル、または後記一般式（１０）〜（１９）のいずれかを示す）；
一般式（４）：
Figure 2008143309
（式中、Ｒ１は水素又は炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐状又は環状であってもよく、そして
ａは０，１，２，３，４又は５の整数を表す）；
一般式（５）：
Figure 2008143309
（式中、Ｒ１は水素又は炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐状又は環状であってもよく、そして
ｂは０，１，２，３，４，５，６又は７の整数を表す）；
一般式（６）：
Figure 2008143309
（式中、Ｒ２は水素又は炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐状又は環状であってもよく、
ｃは０，１，２，３又は４の整数を表し、
Ｇは後記一般式（２０）〜（２３）のいずれかを示し、１分子中に少なくとも１個は式（２１）または後記一般式（２２）を示し、
ｄは１，２，３，４又は５の整数を表し、そして
ｃ＋ｄ≦５である）；
一般式（７）：
Figure 2008143309
（式中、Ｒ２は水素又は炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐状又は環状であってもよく、
ｃ１及びｃ２は０，１，２，３又は４の整数を表し、
ｄは１，２，３，４又は５の整数を表し、
ｅは０，１，２，３又は４の整数を表し、
ｃ１＋ｅ≦４であり、
ｃ２＋ｄ≦５であり、そして
Ｇは後記一般式（２０）〜（２３）のいずれかを示し、１分子中に少なくとも１個は後記一般式（２１）または後記一般式（２２）を示す）、
一般式（８）：
Figure 2008143309
（式中、Ｒ２は水素又は炭化水素基を示し、各々は異なっていても同一でも良く、直鎖状、分岐状又は環状であってもよく、
ｃ１及びｃ２は０，１，２，３又は４の整数を表し、
ｅは０，１，２，３又は４の整数を表し、
ｆは１，２，３又は４の整数を表し、
ｃ１＋ｅ≦４であり、
ｃ２＋ｆ≦４であり、
Ｇは後記一般式（２０）〜（２３）のいずれかを示し、１分子中に少なくとも１個は後記一般式（２１）または（２２）を示し、
Ｚはメチレン、酸素、硫黄、ベンゼン、ナフタレン、アントラセン、フェナントレン、ビフェニル、または後記一般式（１０）〜（１９）のいずれかを示し、そして
ｍは１，２，３・・・の整数を表す）；
一般式（９）：
Figure 2008143309
（式中、Ｒ２は水素又は炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐状又は環状であってもよく、
Ｇは後記一般式（２０）〜（２３）のいずれかを示し、１分子中に少なくとも１個は後記一般式（２１）または（２２）を示し、
ｇは０，１，２，３，４，５又は６の整数を表し、
ｈ１及びｈ２は０，１，２，３，４又は５の整数を表し、
ｉは１，２，３，４，５又は６の整数を表し、
ｇ＋ｈ１≦６であり、
ｉ＋ｈ２≦６であり、
Ｚはメチレン、酸素、硫黄、ベンゼン、ナフタレン、アントラセン、フェナントレン、ビフェニル、または後記式（１０）〜（１９）のいずれかを示し、そして
ｌは１，２，３・・・の整数を表す）；
一般式（１０）；
Figure 2008143309
一般式（１１）；
Figure 2008143309
一般式（１２）；
Figure 2008143309
一般式（１３）；
Figure 2008143309
一般式（１４）；
−ＳＯ− （１４）
一般式（１５）；
Figure 2008143309
一般式（１６）；
Figure 2008143309
一般式（１７）；
−ＣＨ２−（Ｄ）−ＣＨ２− （１７）
（式中、Ｄはベンゼン、ナフタレン、アントラセン、フェナントレン又はビフェニルを示す）
一般式（１８）；
Figure 2008143309
（式中、ｑは０，１，２，３・・・の整数を表す）
一般式（１９）；
Figure 2008143309
（式中、Ｗはメチレン、硫黄、ベンゼン、ナフタレン、アントラセン、フェナントレン、ビフェニル、または一般式（１０）〜（１７）のいずれかを示す）；
一般式（２０）；
Figure 2008143309
一般式（２１）：
Figure 2008143309
（式中、ｊは０又は１であり、そして
Ｒ３及びＲ４は水素又は炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐鎖状又は環状であってもよく、或いはＲ３とＲ４が結合し、環状構造となっていてもよい）；
一般式（２２）：
Figure 2008143309
（式中、ｊは０又は１であり、
Ｒ３及びＲ４は水素又は炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐鎖状又は環状であっても良く、或いはＲ３とＲ４が結合し、環状構造となっていてもよく、
Ｂはベンゼン、ナフタレン、アントラセン、フェナントレン及びこれらの炭化水素置換体を示し、そして
Ｙは一般式（６）〜（９）のいずれかを示す）；
一般式（２３）：
Figure 2008143309
（式中、ｒは０，１，２，３…の整数を表し、
Ｅはベンゼン、ナフタレン、アントラセン、フェナントレン、ビフェニル及びこれらの炭化水素置換体、一般式（２４）又は（２５）を示し、そして
Ｙは一般式（６）〜（９）のいずれかを示す）；
一般式（２４）：
Figure 2008143309
（式中、Ｒ２は水素又は炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐状又は環状であってもよく、
ｃ１及びｃ２は０，１，２，３又は４の整数を表し、
Ｚはメチレン、酸素、硫黄、ベンゼン、ナフタレン、アントラセン、フェナントレン、ビフェニル、または一般式（１０）〜（１９）のいずれかを示し、そして
ｍは１，２，３・・・の整数を表す）；
一般式（２５）：
Figure 2008143309
（式中、Ｒ２は水素又は炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐状又は環状であってもよく、
ｈ１及びｈ２は０，１，２，３，４又は５の整数を表し、
Ｚはメチレン、酸素、硫黄、ベンゼン、ナフタレン、アントラセン、フェナントレン、ビフェニル、または一般式（１０）〜（１９）のいずれかを示し、そして
ｌは１，２，３・・・の整数を表す）。Novel flame-retardant epoxy resin containing nitrogen and phosphorus having a specific structure represented by the general formula (1):
General formula (1) :
Figure 2008143309
(In the formula, X represents at least one chemical structure selected from the group consisting of the following general formulas (2) to (5);
Y represents at least one chemical structure selected from the group consisting of the following general formulas (6) to (9), and n represents an integer of 1 to 10);
General formula (2) :
Figure 2008143309
(Wherein R1 represents hydrogen or a hydrocarbon group, each may be different or the same, may be linear, branched or cyclic, and a is 0, 1, 2, 3, 4 Or an integer of 5);
General formula (3) :
Figure 2008143309
(Wherein R1 represents hydrogen or a hydrocarbon group, each may be different or the same, and may be linear, branched or cyclic;
a represents an integer of 0, 1, 2, 3, 4 or 5, and Z represents methylene, oxygen, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or any one of the following general formulas (10) to (19) Indicate)
General formula (4) :
Figure 2008143309
(Wherein R1 represents hydrogen or a hydrocarbon group, each may be different or the same, may be linear, branched or cyclic, and a is 0, 1, 2, 3, 4 Or an integer of 5);
General formula (5) :
Figure 2008143309
(Wherein R1 represents hydrogen or a hydrocarbon group, each may be different or the same, may be linear, branched or cyclic, and b is 0, 1, 2, 3, 4 , Represents an integer of 5, 6 or 7);
General formula (6) :
Figure 2008143309
(Wherein R2 represents hydrogen or a hydrocarbon group, each may be different or the same, and may be linear, branched or cyclic;
c represents an integer of 0, 1, 2, 3 or 4;
G represents any one of the following general formulas (20) to (23), and at least one of each molecule represents formula (21) or the following general formula (22);
d represents an integer of 1, 2, 3, 4 or 5 and c + d ≦ 5);
General formula (7) :
Figure 2008143309
(Wherein R2 represents hydrogen or a hydrocarbon group, each may be different or the same, and may be linear, branched or cyclic;
c1 and c2 represent an integer of 0, 1, 2, 3 or 4;
d represents an integer of 1, 2, 3, 4 or 5;
e represents an integer of 0, 1, 2, 3 or 4;
c1 + e ≦ 4,
c2 + d ≦ 5, and G represents any one of the following general formulas (20) to (23), and at least one in one molecule represents the following general formula (21) or the following general formula (22)):
Formula (8) :
Figure 2008143309
(Wherein R2 represents hydrogen or a hydrocarbon group, each may be different or the same, and may be linear, branched or cyclic;
c1 and c2 represent an integer of 0, 1, 2, 3 or 4;
e represents an integer of 0, 1, 2, 3 or 4;
f represents an integer of 1, 2, 3 or 4;
c1 + e ≦ 4,
c2 + f ≦ 4,
G represents any one of the following general formulas (20) to (23), and at least one in each molecule represents the following general formula (21) or (22);
Z represents methylene, oxygen, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or any one of the following general formulas (10) to (19), and m represents an integer of 1, 2, 3,. );
Formula (9) :
Figure 2008143309
(Wherein R2 represents hydrogen or a hydrocarbon group, each may be different or the same, and may be linear, branched or cyclic;
G represents any one of the following general formulas (20) to (23), and at least one in each molecule represents the following general formula (21) or (22);
g represents an integer of 0, 1, 2, 3, 4, 5 or 6;
h1 and h2 represent an integer of 0, 1, 2, 3, 4 or 5;
i represents an integer of 1, 2, 3, 4, 5 or 6,
g + h1 ≦ 6,
i + h2 ≦ 6,
Z represents methylene, oxygen, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or any one of the following formulas (10) to (19), and l represents an integer of 1, 2, 3,. ;
General formula (10) ;
Figure 2008143309
General formula (11) ;
Figure 2008143309
General formula (12) ;
Figure 2008143309
General formula (13) ;
Figure 2008143309
General formula (14) ;
-SO- (14)
General formula (15) ;
Figure 2008143309
General formula (16) ;
Figure 2008143309
General formula (17) ;
—CH 2 — (D) —CH 2 — (17)
(In the formula, D represents benzene, naphthalene, anthracene, phenanthrene or biphenyl)
General formula (18) ;
Figure 2008143309
(In the formula, q represents an integer of 0, 1, 2, 3,...)
General formula (19) ;
Figure 2008143309
(Wherein W represents methylene, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or any one of the general formulas (10) to (17));
General formula (20) ;
Figure 2008143309
Formula (21) :
Figure 2008143309
(Wherein j is 0 or 1, and R3 and R4 each represent hydrogen or a hydrocarbon group, each of which may be different or the same, and may be linear, branched or cyclic; Alternatively, R3 and R4 may be bonded to form a cyclic structure);
Formula (22) :
Figure 2008143309
(Wherein j is 0 or 1,
R3 and R4 each represent hydrogen or a hydrocarbon group, and each may be different or the same, and may be linear, branched or cyclic, or R3 and R4 are bonded to form a cyclic structure. You can,
B represents benzene, naphthalene, anthracene, phenanthrene and their hydrocarbon substitutes, and Y represents any one of the general formulas (6) to (9));
Formula (23) :
Figure 2008143309
(Wherein r represents an integer of 0, 1, 2, 3...
E represents benzene, naphthalene, anthracene, phenanthrene, biphenyl and their hydrocarbon substituents, general formula (24) or (25), and Y represents any one of general formulas (6) to (9));
General formula (24) :
Figure 2008143309
(Wherein R2 represents hydrogen or a hydrocarbon group, each may be different or the same, and may be linear, branched or cyclic;
c1 and c2 represent an integer of 0, 1, 2, 3 or 4;
Z represents methylene, oxygen, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or any one of the general formulas (10) to (19), and m represents an integer of 1, 2, 3,. ;
Formula (25) :
Figure 2008143309
(Wherein R2 represents hydrogen or a hydrocarbon group, each may be different or the same, and may be linear, branched or cyclic;
h1 and h2 represent an integer of 0, 1, 2, 3, 4 or 5;
Z represents methylene, oxygen, sulfur, benzene, naphthalene, anthracene, phenanthrene, biphenyl, or any one of the general formulas (10) to (19), and l represents an integer of 1, 2, 3,. . 一般式（２６）で示されるアミン化合物とエポキシ樹脂類と一般式（２７）及び／又は一般式（２８）で示される有機リン化合物類とを反応して得られる請求項１記載の化合物を含む新規難燃性エポキシ樹脂：
一般式（２６）：
Figure 2008143309
（式中、Ｘは一般式（２）〜（５）のいずれかを示し、そして
ｎは１，２，３，・・・の整数を表す）；
一般式（２７）：
Figure 2008143309
（式中、ｊは０又は１であり、そして
Ｒ３及びＲ４は水素又は炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐鎖状又は環状であってもよく、或いはＲ３とＲ４が結合し、環状構造となっていてもよい）；
一般式（２８）：
Figure 2008143309
（式中、ｊは０又は１であり、
Ｒ３及びＲ４は水素又は炭化水素基を示し、各々は異なっていても同一でもよく、直鎖状、分岐鎖状又は環状であってもよく、或いはＲ３とＲ４が結合し、環状構造となっていてもよく、そして
Ｂはベンゼン、ナフタレン、アントラセン、フェナントレン及びこれらの炭化水素置換体を示す）。The compound of Claim 1 obtained by reacting the amine compound and the epoxy resin represented by the general formula (26) with the organophosphorus compound represented by the general formula (27) and / or the general formula (28). New flame retardant epoxy resin:
General formula (26) :
Figure 2008143309
(Wherein X represents any one of general formulas (2) to (5), and n represents an integer of 1, 2, 3,...);
Formula (27) :
Figure 2008143309
(Wherein j is 0 or 1, and R3 and R4 each represent hydrogen or a hydrocarbon group, each of which may be different or the same, and may be linear, branched or cyclic; Alternatively, R3 and R4 may be bonded to form a cyclic structure);
Formula (28) :
Figure 2008143309
(Wherein j is 0 or 1,
R3 and R4 each represent hydrogen or a hydrocarbon group, and each may be different or the same, may be linear, branched or cyclic, or R3 and R4 are bonded to form a cyclic structure. And B represents benzene, naphthalene, anthracene, phenanthrene and hydrocarbon substitutes thereof). エポキシ当量が２００ｇ／ｅｑ〜１０００ｇ／ｅｑ、リン含有率が０．２％〜８．０％且つ窒素含有率が０．１％〜４．０％である請求項１又は２記載の新規難燃性エポキシ樹脂。 3. The novel flame retardant according to claim 1, wherein the epoxy equivalent is 200 g / eq to 1000 g / eq, the phosphorus content is 0.2% to 8.0%, and the nitrogen content is 0.1% to 4.0%. Epoxy resin. 請求項１，２又は３記載の新規難燃性エポキシ樹脂を必須成分とし、硬化剤を配合してなる新規難燃性エポキシ樹脂組成物。 A novel flame retardant epoxy resin composition comprising the novel flame retardant epoxy resin according to claim 1, 2 or 3 as an essential component and a curing agent. 請求項４記載の新規難燃性エポキシ樹脂組成物を用いて得られるエポキシ樹脂積層板。 An epoxy resin laminate obtained by using the novel flame-retardant epoxy resin composition according to claim 4. 請求項４記載の新規難燃性エポキシ樹脂組成物を用いて得られるエポキシ樹脂封止材。 The epoxy resin sealing material obtained using the novel flame-retardant epoxy resin composition of Claim 4. 請求項４記載の新規難燃性エポキシ樹脂組成物を用いて得られるエポキシ樹脂注型材。 An epoxy resin casting material obtained by using the novel flame-retardant epoxy resin composition according to claim 4. 請求項４〜７のいずれか１項記載の難燃性エポキシ樹脂組成物を硬化して得られる新規難燃性エポキシ樹脂硬化物。 A novel flame-retardant epoxy resin cured product obtained by curing the flame-retardant epoxy resin composition according to any one of claims 4 to 7.
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