JP2002012655A - Flame retardant epoxy resin composition, prepreg and laminated product - Google Patents
Flame retardant epoxy resin composition, prepreg and laminated productInfo
- Publication number
- JP2002012655A JP2002012655A JP2000200540A JP2000200540A JP2002012655A JP 2002012655 A JP2002012655 A JP 2002012655A JP 2000200540 A JP2000200540 A JP 2000200540A JP 2000200540 A JP2000200540 A JP 2000200540A JP 2002012655 A JP2002012655 A JP 2002012655A
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- Japan
- Prior art keywords
- epoxy resin
- resin composition
- halogen
- prepreg
- laminate
- 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.)
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- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ハロゲンフリーの
難燃性エポキシ樹脂組成物、それを含浸したプリプレグ
並びに積層板、銅張積層板及びプリント配線板の積層製
品に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a halogen-free flame-retardant epoxy resin composition, a prepreg impregnated with the composition, and a laminate product of a laminate, a copper-clad laminate and a printed wiring board.
【０００２】[0002]
【従来の技術】近年、世界的な環境問題、人体に対する
安全性についての関心の高まりに伴なって、電気・電子
機器については、従来からの難燃性に加えて、より少な
い有害性、より高い安全性という要求が増大している。
すなわち、電気・電子機器は、単に燃えにくいだけでな
く、有害ガスや発煙などの発生が少ないことが要望され
ている。従来、電気・電子部品を搭載するガラス基材エ
ポキシ樹脂のプリント配線板は、エポキシ樹脂として、
難燃剤の臭素を含有する臭素化エポキシ樹脂、特にテト
ラブロモビスフェノールＡ型エポキシ樹脂が一般に使用
されている。2. Description of the Related Art In recent years, as environmental concerns around the world and concerns about safety for the human body have increased, electric and electronic devices have become less hazardous in addition to the conventional flame retardancy. The demand for high security is increasing.
That is, it is demanded that electric / electronic devices not only hardly burn, but also generate less harmful gas and smoke. Conventionally, printed wiring boards made of glass-based epoxy resin on which electrical and electronic components are mounted
Brominated epoxy resins containing bromine as a flame retardant, especially tetrabromobisphenol A type epoxy resins, are commonly used.
【０００３】このような臭素化エポキシ樹脂は、良好な
難燃性を有するものの、燃焼時に有害なハロゲン化水素
（臭化水素）ガスを発生することや、ブロモ化ダイオキ
シン、フラン類を発生する可能性があるため、その使用
が抑制されつつある。[0003] Such brominated epoxy resins have good flame retardancy, but can generate harmful hydrogen halide (hydrogen bromide) gas upon combustion, and can also generate brominated dioxins and furans. Therefore, its use is being suppressed.
【０００４】そこで、リン化合物を配合した種々のエポ
キシ樹脂組成物が開発されているが、例えば、リン変性
エポキシやリン酸エステル等である。しかし、これらに
記載の化合物を使用した積層製品は、機械特性（層間引
き剥がし強度等）が低く、ガラス転移点が低いという問
題があつた。Accordingly, various epoxy resin compositions containing a phosphorus compound have been developed, and examples thereof include phosphorus-modified epoxy and phosphate esters. However, laminated products using the compounds described above have problems in that mechanical properties (such as peeling strength between layers) are low and the glass transition point is low.
【０００５】また、エポキシ樹脂の硬化剤としてアミノ
変性のノボラックフェノール樹脂を使用した組成物が開
発されている。例えば、トリアジン変性ノボラックフェ
ノール樹脂のＬＡ−７０５１（大日本インキ化学工業社
製、商品名）がそれである。しかし、この組成物を使用
した積層品は、上記機械特性は向上するが、ガラス転移
点の向上に限界があった。Further, a composition using an amino-modified novolak phenol resin as a curing agent for an epoxy resin has been developed. For example, it is LA-7051 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) of a triazine-modified novolak phenol resin. However, a laminate using this composition has improved mechanical properties, but has a limit in improving the glass transition point.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、ハロ
ゲンを含まずに良好な難燃性を示す（ハロゲンフリー）
とともに、上記従来技術の機械特性、ガラス転移点の低
下などの欠点を解消した難燃性エポキシ樹脂組成物を提
供することにある。An object of the present invention is to exhibit good flame retardancy without halogen (halogen free).
Another object of the present invention is to provide a flame-retardant epoxy resin composition which has solved the above-mentioned drawbacks such as the mechanical properties and the lowering of the glass transition point of the prior art.
【０００７】さらに、本発明は、そのような難燃性エポ
キシ樹脂組成物で含浸されたプリプレグ、並びにこれら
プリプレグを用いて製造された積層板、銅張積層板およ
びプリント配線板を提供することをも目的とする。Further, the present invention provides a prepreg impregnated with such a flame-retardant epoxy resin composition, and a laminate, a copper-clad laminate and a printed wiring board manufactured using these prepregs. Also aim.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、上記の目
的を達成しようと鋭意研究を重ねた結果、樹脂組成物
に、前記化３に示すリン含有エポキシ樹脂を主とした主
剤と前記化４に示すメラミン変性ノボラック型フェノー
ル樹脂をその硬化剤として用いるという新規な配合によ
って、ハロゲンを含まずに良好な難燃性を示すととも
に、機械特性を向上し、ガラス転移点の低下を抑制し、
上記目的が達成されることを見いだし、本発明を完成さ
せたものである。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that a resin composition containing a main agent mainly containing a phosphorus-containing epoxy resin represented by Chemical Formula 3 and The novel formulation of using a melamine-modified novolak-type phenol resin shown in Chemical formula 4 as a curing agent shows good flame retardancy without containing halogen, improves mechanical properties, and suppresses a decrease in glass transition point. ,
The inventors have found that the above-mentioned object is achieved, and have completed the present invention.
【０００９】即ち、本発明は、（Ａ）下記一般式に示す
リン含有エポキシ樹脂、That is, the present invention provides (A) a phosphorus-containing epoxy resin represented by the following general formula:
【化５】 （但し、式中、Ｒは水素原子又はメチル基を表す） （Ｂ）ハロゲンを含まないポリエポキシド化合物および
（Ｃ）下式に示すメラミン変性ノボラック型フェノール
硬化剤Embedded image (Wherein, R represents a hydrogen atom or a methyl group) (B) a polyepoxide compound containing no halogen and (C) a melamine-modified novolak-type phenol curing agent represented by the following formula
【化６】 を必須成分とすることを特徴とするハロゲンフリー積層
板用の難燃性エポキシ樹脂組成物である。また、上記難
燃性エポキシ樹脂組成物で含浸されたガラス基材プリプ
レグ、並びに上記プリプレグを用いて製造された積層
板、銅張積層板およびプリント配線板である。Embedded image And a flame-retardant epoxy resin composition for a halogen-free laminate. Also, a glass substrate prepreg impregnated with the above flame-retardant epoxy resin composition, and a laminate, a copper-clad laminate and a printed wiring board manufactured using the prepreg.
【００１０】以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
【００１１】本発明に用いる（Ａ）リン含有エポキシ樹
脂は、前記一般式化５に示される化合物である。この化
合物は、下記一般式に示すThe (A) phosphorus-containing epoxy resin used in the present invention is a compound represented by the aforementioned general formula (5). This compound is represented by the following general formula:
【化７】 １０−（２，５−ジヒドロキシフェニル）−１０−ハイ
ドロ−９−オキサ−１０−ホスファフェナントレン−１
０−オキサイドまたはその誘導体とビフェノールＡ型エ
ポキシ樹脂又はビスフェノールＦ型エポキシ樹脂とを第
３級アミン、第４級アンモニウム塩、ホスフィン類、ホ
スホニウム塩類、イミダゾール類等の触媒の存在下で反
応させて合成される。Embedded image 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-1
Synthesis by reacting 0-oxide or a derivative thereof with a biphenol A type epoxy resin or a bisphenol F type epoxy resin in the presence of a catalyst such as a tertiary amine, a quaternary ammonium salt, a phosphine, a phosphonium salt or an imidazole. Is done.
【００１２】本発明に用いる（Ｂ）ハロゲンを含まない
ポリエポキシド化合物としては、グリシジルエーテル系
エポキシ樹脂が好適である。これには、ビスフェノール
Ａ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、
ノボラック型エポキシ樹脂等が挙げられ、これらは単独
又は２種以上混合して使用することができる。また、こ
のエポキシ樹脂には、グリシジルエーテル系の変性エポ
キシ樹脂も含む。変性エポキシ樹脂として例えば、ＢＴ
樹脂などを使用することができる。As the halogen-free polyepoxide compound (B) used in the present invention, a glycidyl ether epoxy resin is preferred. This includes bisphenol A epoxy resin, bisphenol F epoxy resin,
Novolak type epoxy resins and the like can be mentioned, and these can be used alone or in combination of two or more. The epoxy resin also includes a glycidyl ether-based modified epoxy resin. As a modified epoxy resin, for example, BT
Resin or the like can be used.
【００１３】本発明に用いる（Ｃ）メラミン変性ノボラ
ック型フェノール硬化剤としては、前記化６に示すメラ
ミン変性ノボラック型フェノール樹脂である。製造条件
により、化６の他にメラミン１分子に対し２分子のフェ
ノールが結合したもの、メラミンとフェノールがさらに
結合したもの等もある。製造時のメラミンとフェノール
の比率に特に制限はないが、最低でもメラミン１分子に
対して２分子以上のフェノールを含まないとポットライ
フに悪影響を及ぼす。望ましくはメラミン１分子に対し
てフェノール３分子となるように配合する。The melamine-modified novolak type phenol curing agent (C) used in the present invention is a melamine-modified novolak type phenol resin represented by the above formula (6). Depending on the production conditions, in addition to Chemical Formula 6, there are also those in which two molecules of phenol are bonded to one molecule of melamine, those in which melamine and phenol are further bonded, and the like. The ratio of melamine to phenol at the time of production is not particularly limited, but if at least two or more phenols are not contained per melamine molecule, the pot life is adversely affected. Desirably, it is blended so that one molecule of melamine becomes three molecules of phenol.
【００１４】本発明に用いる（Ｄ）無機充填剤として
は、難燃性などの補助添加剤として使用する無機充填剤
であり、樹脂含浸性等の樹脂特性を阻害しない範囲で可
能である。これらの充填剤には、タルク、シリカ、アル
ミナ、水酸化アルミニウム、水酸化マグネシウム等が挙
げられ、これらは単独又は２種以上混合して使用するこ
とができる。好ましい添加量は、樹脂固形分中の３０重
量％以下であり、これ以上添加すると機械特性が低下す
るため好ましくない。The inorganic filler (D) used in the present invention is an inorganic filler used as an auxiliary additive such as flame retardancy, and can be in a range not impairing resin properties such as resin impregnation. These fillers include talc, silica, alumina, aluminum hydroxide, magnesium hydroxide and the like, and these can be used alone or in combination of two or more. A preferable addition amount is 30% by weight or less based on the resin solid content, and if it is more than this, the mechanical properties are deteriorated, which is not preferable.
【００１５】本発明においては、必要に応じて、硬化促
進剤を用いる。硬化促進剤としては、通常のエポキシ樹
脂用硬化促進剤として用いられる第３アミン、イミダゾ
ール、芳香族アミンのうちの少なくとも一種を用いるこ
とができる。In the present invention, a curing accelerator is used if necessary. As the curing accelerator, at least one of tertiary amines, imidazoles, and aromatic amines used as ordinary curing accelerators for epoxy resins can be used.
【００１６】本発明のエポキシ樹脂組成物は、これをプ
ロピレングリコールモノメチルエーテル等の好適な有機
溶剤で希釈してワニスとなし、これをガラス不織布、ガ
ラス織布等の多孔質ガラス基材に塗布、含浸させ、加熱
するという通常の方法によりプリプレグを製造すること
ができる。また、このプリプレグを複数枚重ね合わせ、
その積層構造の片面又は両面に銅箔を重ね合わせた後、
これを通常の条件で加熱・加圧してガラスエポキシ銅張
積層板を得ることができる。この時、銅箔を用いなけれ
ば積層板が得られる。多層板は、銅張積層板（内層板）
に回路を形成し、ついで銅箔表面をエッチング処理した
後、内層板の少なくとも片面にプリプレグおよび銅箔を
重ね合わせ、これを例えば、１７０℃，４ＭＰａの圧力
で６０分間加熱・加圧するという通常の方法により製造
することができる。さらに、プリント配線板は、銅張積
層板もしくは多層板にスルーホールを形成し、スルーホ
ールメッキを行った後、所定の回路を形成するという通
常の方法により製造することができる。The epoxy resin composition of the present invention is diluted with a suitable organic solvent such as propylene glycol monomethyl ether to form a varnish, which is applied to a porous glass substrate such as a glass nonwoven fabric or a glass woven fabric. The prepreg can be manufactured by a usual method of impregnating and heating. Also, multiple prepregs are stacked,
After laminating copper foil on one or both sides of the laminated structure,
This is heated and pressed under normal conditions to obtain a glass epoxy copper clad laminate. At this time, a laminate can be obtained without using a copper foil. Multilayer board is copper-clad laminate (inner board)
After forming a circuit on the surface of the copper foil and then etching the surface of the copper foil, a prepreg and a copper foil are overlaid on at least one surface of the inner layer plate, and this is heated and pressed at a pressure of, for example, 170 ° C. and 4 MPa for 60 minutes. It can be manufactured by a method. Further, the printed wiring board can be manufactured by a usual method of forming a through hole in a copper-clad laminate or a multilayer board, performing through-hole plating, and then forming a predetermined circuit.
【００１７】[0017]
【発明の実施の形態】以下、本発明を実施例により説明
するが、本発明はこれらの実施例によって限定されるも
のではない。以下の実施例および比較例において「部」
とは「重量部」を意味する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. "Part" in the following Examples and Comparative Examples
Means "parts by weight".
【００１８】実施例１ 次式に示すリン含有エポキシ樹脂（リン含有量３重量
％、樹脂固形分７０重量％）３３部、Example 1 33 parts of a phosphorus-containing epoxy resin (phosphorus content: 3% by weight, resin solid content: 70% by weight) represented by the following formula:
【化８】 クレゾールノボラックエポキシ樹脂（エポキシ当量２１
５、樹脂固形分７０重量％）３３部、前記した式化６に
示すメラミン変性ノボラック型フェノール樹脂（水酸基
当量１４８、樹脂固形分６０重量％、窒素含有量２０
％）３４部、水酸化アルミニウム１８部からなる混合物
に溶媒としてプロピレングリコールモノメチルエーテル
を加えて樹脂固形分６５重量％のエポキシ樹脂組成物を
調製した。Embedded image Cresol novolak epoxy resin (epoxy equivalent 21
5. 33 parts of melamine-modified novolak-type phenol resin (hydroxyl equivalent: 148, resin solid content: 60% by weight, nitrogen content: 20)
%) Propylene glycol monomethyl ether as a solvent was added to a mixture consisting of 34 parts and 18 parts of aluminum hydroxide to prepare an epoxy resin composition having a resin solid content of 65% by weight.
【００１９】実施例２ 実施例１で使用した化８のリン含有エポキシ樹脂（リン
含有量３重量％、樹脂固形分７０重量％）３３部、フェ
ノールノボラック型エポキシ樹脂（エポキシ当量１８
２、樹脂固形分７０重量％）３３部、前記した式化６に
示すメラミン変性ノボラック型フェノール樹脂（水酸基
当量１４８、樹脂固形分６０重量％、窒素含有量２０
％）３４部、水酸化アルミニウム１８部からなる混合物
に溶媒としてプロピレングリコールモノメチルエーテル
を加えて樹脂固形分６５重量％のエポキシ樹脂組成物を
調製した。Example 2 33 parts of the phosphorus-containing epoxy resin of the formula 8 used in Example 1 (phosphorus content: 3% by weight, resin solid content: 70% by weight), phenol novolak type epoxy resin (epoxy equivalent: 18)
2, 33 parts of melamine-modified novolak-type phenolic resin (hydroxyl equivalent: 148, resin solids: 60% by weight, nitrogen content: 20)
%) Propylene glycol monomethyl ether as a solvent was added to a mixture consisting of 34 parts and 18 parts of aluminum hydroxide to prepare an epoxy resin composition having a resin solid content of 65% by weight.
【００２０】実施例３ 実施例１で使用した化８のリン含有エポキシ樹脂（リン
含有量３重量％、樹脂固形分７０重量％）３３部、ビス
フェノールＡ型液状エポキシ樹脂（エポキシ当量１８
０）２０部、前記した式化６に示すメラミン変性ノボラ
ック型フェノール樹脂（水酸基当量１４８、樹脂固形分
６０重量％、窒素含有量２０％）３４部、水酸化アルミ
ニウム１８部からなる混合物に溶媒としてプロピレング
リコールモノメチルエーテルを加えて樹脂固形分６５重
量％のエポキシ樹脂組成物を調製した。Example 3 33 parts of the phosphorus-containing epoxy resin of the formula 8 used in Example 1 (phosphorus content 3% by weight, resin solid content 70% by weight), bisphenol A type liquid epoxy resin (epoxy equivalent 18
0) As a solvent, a mixture of 20 parts, 34 parts of the melamine-modified novolak type phenol resin represented by the above formula 6 (hydroxyl equivalent 148, resin solid content 60% by weight, nitrogen content 20%), and 18 parts of aluminum hydroxide was used as a solvent. Propylene glycol monomethyl ether was added to prepare an epoxy resin composition having a resin solid content of 65% by weight.
【００２１】比較例１ 実施例１で使用した化８のリン含有エポキシ樹脂（リン
含有量３重量％、樹脂固形分７０重量％）３３部、クレ
ゾールノボラック型エポキシ樹脂（エポキシ当量２１
５、樹脂固形分７０重量％）３３部、トリアジン変性ノ
ボラック型フェノール樹脂ＬＡ−７０５１（大日本イン
キ化学工業社製商品名、水酸基当量１２４、樹脂固形分
７０重量％、窒素含有量５％）２１部、水酸化アルミニ
ウム１８部からなる混合物に溶媒としてプロピレングリ
コールモノメチルエーテルを加えて樹脂固形分６５重量
％のエポキシ樹脂組成物を調製した。Comparative Example 1 33 parts of the phosphorus-containing epoxy resin of Chemical formula 8 (phosphorus content: 3% by weight, resin solid content: 70% by weight) used in Example 1, cresol novolak type epoxy resin (epoxy equivalent: 21)
5, triazine-modified novolak-type phenol resin LA-7051 (trade name of Dainippon Ink and Chemicals, hydroxyl equivalent 124, resin solids 70% by weight, nitrogen content 5%) 21 And propylene glycol monomethyl ether as a solvent were added to a mixture consisting of 18 parts of aluminum hydroxide and 18 parts of aluminum hydroxide to prepare an epoxy resin composition having a resin solid content of 65% by weight.
【００２２】比較例２ 実施例１で使用した化８のリン含有エポキシ樹脂（リン
含有量３重量％、樹脂固形分７０重量％）３３部、クレ
ゾールノボラック型エポキシ樹脂（エポキシ当量２１
５、樹脂固形分７０重量％）３３部、ジシアンジアミド
（日本カーバイト社製）３部、水酸化アルミニウム１８
部からなる混合物に溶媒としてプロピレングリコールモ
ノメチルエーテルを加えて樹脂固形分６５重量％のエポ
キシ樹脂組成物を調製した。Comparative Example 2 33 parts of the phosphorus-containing epoxy resin of the formula 8 used in Example 1 (phosphorus content 3% by weight, resin solid content 70% by weight), cresol novolak type epoxy resin (epoxy equivalent 21
5, 70 parts by weight of resin solids) 33 parts, dicyandiamide (manufactured by Nippon Carbide Co., Ltd.) 3 parts, aluminum hydroxide 18
Propylene glycol monomethyl ether as a solvent was added to the mixture of parts to prepare an epoxy resin composition having a resin solid content of 65% by weight.
【００２３】比較例３ ビスフェノールＡ型エポキシ樹脂のエピクロン１０５１
−７５Ｍ（大日本インキ化学社製商品名、エポキシ当量
４７３、樹脂固形分７５重量％）３３部、クレゾールノ
ボラック型エポキシ樹脂（エポキシ当量２１５、樹脂固
形分７０重量％）３３部、前記した式化６に示すメラミ
ン変性ノボラック型フェノール樹脂（水酸基当量１４
８、樹脂固形分６０重量％、窒素含有量２０％）３４
部、水酸化アルミニウム１８部からなる混合物に溶媒と
してプロピレングリコールモノメチルエーテルを加えて
樹脂固形分６５重量％のエポキシ樹脂組成物を調製し
た。Comparative Example 3 Epicron 1051 of bisphenol A type epoxy resin
33 parts of -75M (trade name, manufactured by Dainippon Ink and Chemicals, epoxy equivalent 473, resin solid content 75% by weight), 33 parts of cresol novolac type epoxy resin (epoxy equivalent 215, resin solid content 70% by weight), Melamine-modified novolak type phenol resin (having a hydroxyl equivalent of 14
8, resin solid content 60% by weight, nitrogen content 20%) 34
And propylene glycol monomethyl ether as a solvent were added to a mixture consisting of 18 parts of aluminum hydroxide and 18 parts of aluminum hydroxide to prepare an epoxy resin composition having a resin solid content of 65% by weight.
【００２４】比較例４ ビスフェノールＡ型エポキシ樹脂のエピクロン１０５１
−７５Ｍ（大日本インキ化学社製商品名、エポキシ当量
４７３、樹脂固形分７５重量％）２７部、フェノールノ
ボラック型エポキシ樹脂エピクロン−７７０−７０Ｍ
（大日本インキ化学社製商品名、エポキシ当量１９０、
樹脂固形分７０重量％）２０部、トリアジン変性ノボラ
ック型フェノール樹脂ＬＡ７０５１（大日本インキ化学
社製商品名、水酸基価１２４、樹脂固形分７０重量％）
２１部、縮合型リン酸エステルＰＸ−２００（大八化学
社製商品名、リン含有量９％）１２部、水酸化アルミニ
ウム２０部からなる混合物に溶媒としてプロピレングリ
コールモノメチルエーテルを加えて樹脂固形分６５重量
％のエポキシ樹脂組成物を調製した。Comparative Example 4 Epicron 1051 of a bisphenol A type epoxy resin
27 parts of -75M (trade name, manufactured by Dainippon Ink and Chemicals, epoxy equivalent: 473, resin solid content: 75% by weight), phenol novolak type epoxy resin Epicron-770-70M
(Dai Nippon Ink Chemical Co., Ltd., epoxy equivalent 190,
20 parts of triazine-modified novolak type phenol resin LA7051 (trade name, manufactured by Dainippon Ink and Chemicals, hydroxyl value 124, resin solid content 70% by weight)
To a mixture consisting of 21 parts, 12 parts of condensed phosphate ester PX-200 (trade name, manufactured by Daihachi Chemical Co., phosphorus content 9%) and 20 parts of aluminum hydroxide, propylene glycol monomethyl ether was added as a solvent to obtain a resin solid content. An epoxy resin composition of 65% by weight was prepared.
【００２５】実施例１〜３および比較例１〜４で得たエ
ポキシ樹脂組成物に硬化促進剤として２−エチル−４−
メチル−イミダゾールを添加してゲルタイム２１０秒に
設定し、各々をガラス織布に連続的に塗布・含浸させ、
１６０℃の温度で乾燥してプリプレグを製造した。こう
して得られた１８０μｍガラス織布を用いたプリプレグ
８枚を重ね合わせて、この積層体の両面に厚さ１８μｍ
の銅箔を重ね合わせて１７０℃の温度、４Ｍｐａの圧力
で１００分間加熱・加圧し、厚さ１．６ｍｍのガラスエ
ポキシ銅張積層板を得た。得られた銅張積層板および使
用したプリプレグについての特性評価結果を表１に示
す。The epoxy resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 4 were added with 2-ethyl-4- as a curing accelerator.
Methyl-imidazole was added to set the gel time to 210 seconds, and each was continuously applied and impregnated on a glass woven fabric,
It dried at the temperature of 160 degreeC, and manufactured the prepreg. Eight prepregs using 180 μm glass woven fabric obtained in this manner are superimposed, and a 18 μm thick
Were heated and pressed at a temperature of 170 ° C. and a pressure of 4 Mpa for 100 minutes to obtain a 1.6 mm thick glass epoxy copper clad laminate. Table 1 shows the results of evaluating the properties of the obtained copper-clad laminate and the prepreg used.
【００２６】また、同じプリプレグを重ね合わせ、その
両面に厚さ３５μｍの銅箔を重ね合わせて同様に加熱・
加圧して板厚０．８ｍｍの内層板を製造した。この内層
板に回路を形成し、銅箔表面を酸化処理した後、その両
面に上記プリプレグを重ね合わせ、その上にそれぞれ厚
さ１８μｍの銅箔を重ね合わせて同様に加熱・加圧して
板厚１．６ｍｍの多層板を製造した。得られた多層板に
ついての特性評価結果を表２に示す。Further, the same prepreg is superimposed, and a copper foil having a thickness of 35 μm is superimposed on both surfaces thereof.
Pressing produced an inner layer plate having a thickness of 0.8 mm. After forming a circuit on this inner layer plate and oxidizing the surface of the copper foil, the prepreg is superimposed on both surfaces thereof, and a copper foil having a thickness of 18 μm is superimposed on each of the prepregs. A 1.6 mm multilayer board was produced. Table 2 shows the results of evaluating the characteristics of the obtained multilayer board.
【００２７】[0027]
【表１】 ＊１：ＪＩＳ−Ｃ−６４８１に準じて測定した。[Table 1] * 1: Measured according to JIS-C-6481.
【００２８】＊２：ＵＬ９４難燃性試験に準じて測定し
た。* 2: Measured according to the UL94 flame retardancy test.
【００２９】＊３：ＪＩＳ−Ｃ−６４８１に準じて２６
０℃の半田浴中に８分間サンプルを浮かべ、フクレの有
無を観察した。◎印…全部なし、○印…一部あり。* 3: 26 according to JIS-C-6481
The sample was floated in a solder bath at 0 ° C. for 8 minutes, and the presence or absence of blisters was observed. ◎: none, ○: some.
【００３０】＊４：表層のガラスクロス１枚を剥がし、
ＪＩＳ−Ｃ−６４８１に準じて測定した。* 4: One glass cloth on the surface layer was peeled off.
It measured according to JIS-C-6481.
【００３１】＊５：ＪＩＳ−Ｃ−６４８１に準じて測定
した。* 5: Measured according to JIS-C-6481.
【００３２】[0032]
【表２】 ＊１：ＪＩＳ−Ｃ−６４８１に準じて測定した。[Table 2] * 1: Measured according to JIS-C-6481.
【００３３】＊２：ＵＬ９４難燃性試験に準じて測定し
た。* 2: Measured according to the UL94 flame retardancy test.
【００３４】＊３：５０×５０ｍｍに切断したサンプル
を４時間煮沸し、２６０℃の半田浴中に３０秒間サンプ
ルを浮かべ、フクレの有無を観察した。◎印…全部な
し、○印…一部あり。* 3: The sample cut to 50 × 50 mm was boiled for 4 hours, the sample was floated in a solder bath at 260 ° C. for 30 seconds, and the presence or absence of blisters was observed. ◎: none, ○: some.
【００３５】[0035]
【発明の効果】以上の説明および表１〜２から明らかな
ように、本発明によれば、ハロゲンを含有しないで優れ
た難燃性を示し、しかも機械特性に優れ、ガラス転移温
度の高いガラスエポキシ積層製品を与えるエポキシ樹脂
組成物が提供される。このようなガラスエポキシ銅張積
層板を用いれば、良好な環境特性を付与し、かつ種々の
特性に優れたプリント配線板を製造することができる。As is clear from the above description and Tables 1 and 2, according to the present invention, a glass which exhibits excellent flame retardancy without containing halogen, has excellent mechanical properties, and has a high glass transition temperature. An epoxy resin composition is provided that provides an epoxy laminate product. By using such a glass epoxy copper clad laminate, it is possible to produce a printed wiring board that imparts good environmental characteristics and is excellent in various characteristics.
─────────────────────────────────────────────────────
────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成１２年１０月３日（２０００．１０．
３）[Submission date] October 3, 2000 (2000.10.
3)
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】特許請求の範囲[Correction target item name] Claims
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【特許請求の範囲】[Claims]
【化１】 （但し、式中、Ｒは水素原子又はメチル基を表す） （Ｂ）ハロゲンを含まないポリエポキシド化合物および
（Ｃ）下式に示すメラミン変性ノボラック型フェノール
硬化剤 Embedded image (Wherein, R represents a hydrogen atom or a methyl group) (B) a polyepoxide compound containing no halogen and (C) a melamine-modified novolak-type phenol curing agent represented by the following formula
【化２】 を必須成分とすることを特徴とするハロゲンフリー積層
板用の難燃性エポキシ樹脂組成物。 Embedded image And a flame-retardant epoxy resin composition for a halogen-free laminate.
【化３】 （但し、式中、Ｒは水素原子又はメチル基を表す） （Ｂ）ハロゲンを含まないポリエポキシド化合物、
（Ｃ）下式に示すメラミン変性ノボラック型フェノール
硬化剤および Embedded image (Wherein, R represents a hydrogen atom or a methyl group) (B) a halogen-free polyepoxide compound,
(C) a melamine-modified novolak-type phenol curing agent represented by the following formula and
【化４】 （Ｄ）無機充填剤を必須成分とすることを特徴とするハ
ロゲンフリー積層板用の難燃性エポキシ樹脂組成物。 Embedded image (D) A flame-retardant epoxy resin composition for a halogen-free laminate, comprising an inorganic filler as an essential component.
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００９[Correction target item name] 0009
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００９】即ち、本発明は、（Ａ）下記一般式に示す
リン含有エポキシ樹脂、That is, the present invention provides (A) a phosphorus-containing epoxy resin represented by the following general formula:
【化５】 （但し、式中、Ｒは水素原子又はメチル基を表す） （Ｂ）ハロゲンを含まないポリエポキシド化合物および
（Ｃ）下式に示すメラミン変性ノボラック型フェノール
硬化剤 Embedded image (Wherein, R represents a hydrogen atom or a methyl group) (B) a polyepoxide compound containing no halogen and (C) a melamine-modified novolak-type phenol curing agent represented by the following formula
【化６】 を必須成分とすることを特徴とするハロゲンフリー積層
板用の難燃性エポキシ樹脂組成物である。また、上記難
燃性エポキシ樹脂組成物で含浸されたガラス基材プリプ
レグ、並びに上記プリプレグを用いて製造された積層
板、銅張積層板およびプリント配線板である。 Embedded image And a flame-retardant epoxy resin composition for a halogen-free laminate. Also, a glass substrate prepreg impregnated with the above flame-retardant epoxy resin composition, and a laminate, a copper-clad laminate and a printed wiring board manufactured using the prepreg.
【手続補正３】[Procedure amendment 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１３[Correction target item name] 0013
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１３】本発明に用いる（Ｃ）メラミン変性ノボラ
ック型フェノール硬化剤としては、前記化６に示すメラ
ミン変性ノボラック型フェノール樹脂である。製造条件
により、メラミン１分子に対し２分子のフェノールが結
合したもの、メラミンとフェノールがさらに結合したも
の等もある。このうち、メラミン１分子に対し３分子以
上のフェノールが結合したものが樹脂中に９０％以上含
まれているものが硬化物のガラス転位点が高くなるので
より好ましい。 The melamine-modified novolak type phenol curing agent (C) used in the present invention is a melamine-modified novolak type phenol resin represented by the above formula (6). The production conditions, those to melamine 1 molecule phenol 2 molecules bound, also like those melamine and phenol was further bonded. Of these, three or more molecules per melamine molecule
More than 90% of the above phenol bonded to the resin
What is rare is that the glass transition point of the cured product increases
More preferred.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１８[Correction target item name] 0018
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１８】実施例１ 次式に示すリン含有エポキシ樹脂（リン含有量３重量
％、樹脂固形分７０重量％）３３部、Example 1 33 parts of a phosphorus-containing epoxy resin (phosphorus content: 3% by weight, resin solid content: 70% by weight) represented by the following formula:
【化８】 クレゾールノボラックエポキシ樹脂（エポキシ当量２１
５、樹脂固形分７０重量％）３３部、前記した式化６に
示すメラミン変性ノボラック型フェノール樹脂（油化シ
ェル社製ＹＬＨ８２８：水酸基当量１４８、樹脂固形分
６０重量％、窒素含有量２０％）３４部、水酸化アルミ
ニウム１８部からなる混合物に溶媒としてプロピレング
リコールモノメチルエーテルを加えて樹脂固形分６５重
量％のエポキシ樹脂組成物を調製した。Embedded image Cresol novolak epoxy resin (epoxy equivalent 21
5, a resin solid content of 70% by weight) 33 parts, a melamine-modified novolak-type phenol resin represented by the above-mentioned formula ( 6)
YLH828 manufactured by Jell Co., Ltd .: propylene glycol monomethyl ether as a solvent was added to a mixture consisting of 34 parts of a hydroxyl equivalent of 148, a resin solid content of 60% by weight, and a nitrogen content of 34 parts) and 18 parts of aluminum hydroxide to obtain a resin solid content of 65% by weight. Was prepared.
【手続補正５】[Procedure amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１９[Correction target item name] 0019
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１９】実施例２ 実施例１で使用した化８のリン含有エポキシ樹脂（リン
含有量３重量％、樹脂固形分７０重量％）３３部、フェ
ノールノボラック型エポキシ樹脂（エポキシ当量１８
２、樹脂固形分７０重量％）３３部、前記した式化６に
示すメラミン変性ノボラック型フェノール樹脂（油化シ
ェル社製ＹＬＨ８２８：水酸基当量１４８、樹脂固形分
６０重量％、窒素含有量２０％）３４部、水酸化アルミ
ニウム１８部からなる混合物に溶媒としてプロピレング
リコールモノメチルエーテルを加えて樹脂固形分６５重
量％のエポキシ樹脂組成物を調製した。Example 2 33 parts of the phosphorus-containing epoxy resin of the formula 8 used in Example 1 (phosphorus content: 3% by weight, resin solid content: 70% by weight), phenol novolak type epoxy resin (epoxy equivalent: 18)
2. 33 parts of melamine-modified novolak-type phenol resin ( oiled silicone)
YLH828 manufactured by Jell Co., Ltd .: propylene glycol monomethyl ether as a solvent was added to a mixture consisting of 34 parts of a hydroxyl equivalent of 148, a resin solid content of 60% by weight, and a nitrogen content of 34 parts) and 18 parts of aluminum hydroxide to obtain a resin solid content of 65% by weight. Was prepared.
【手続補正６】[Procedure amendment 6]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２０[Correction target item name] 0020
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００２０】実施例３ 実施例１で使用した化８のリン含有エポキシ樹脂（リン
含有量３重量％、樹脂固形分７０重量％）３３部、ビス
フェノールＡ型液状エポキシ樹脂（エポキシ当量１８
０）２０部、前記した式化６に示すメラミン変性ノボラ
ック型フェノール樹脂（油化シェル社製ＹＬＨ８２８：
水酸基当量１４８、樹脂固形分６０重量％、窒素含有量
２０％）３４部、水酸化アルミニウム１８部からなる混
合物に溶媒としてプロピレングリコールモノメチルエー
テルを加えて樹脂固形分６５重量％のエポキシ樹脂組成
物を調製した。Example 3 33 parts of the phosphorus-containing epoxy resin of the formula 8 used in Example 1 (phosphorus content 3% by weight, resin solid content 70% by weight), bisphenol A type liquid epoxy resin (epoxy equivalent 18
0) 20 parts, melamine-modified novolak-type phenolic resin represented by the above formula 6 ( YLH828 manufactured by Yuka Shell Co., Ltd.):
Propylene glycol monomethyl ether is added as a solvent to a mixture consisting of 34 parts of a hydroxyl equivalent 148, a resin solid content of 60% by weight, a nitrogen content of 20%) and aluminum hydroxide of 18 parts to obtain an epoxy resin composition having a resin solid content of 65% by weight. Prepared.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０５Ｋ 1/03 ６１０ Ｈ０５Ｋ 1/03 ６１０Ｌ ６１０Ｒ (72)発明者 神谷 博輝 神奈川県川崎市川崎区千鳥町９番２号 東 芝ケミカル株式会社川崎工場内 Ｆターム(参考） 4F072 AA02 AA04 AA07 AB09 AB28 AB29 AD15 AD18 AD23 AD32 AE01 AE06 AF03 AG03 AH21 AL12 AL13 4J002 CC07Y CD00X CD05X CD06X CD11W DE076 DE146 DJ016 DJ046 DL007 FA047 FD016 FD150 GF00 4J036 AA02 AA05 AC01 AC05 AC09 AC20 AD08 AF06 FA03 FA05 FB08 JA08 JA11 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) H05K 1/03 610 H05K 1/03 610L 610R (72) Inventor Hiroki Kamiya 9 Chidoricho, Kawasaki-ku, Kawasaki-shi, Kawasaki, Kanagawa Prefecture. No. 2 Toshiba Chemical Corporation Kawasaki Factory F-term (reference) 4F072 AA02 AA04 AA07 AB09 AB28 AB29 AD15 AD18 AD23 AD32 AE01 AE06 AF03 AG03 AH21 AL12 AL13 4J002 CC07Y CD00X CD05X CD06X CD11W DE076 DE146 DJ016 DJ046 DL007 FA047 AA02 AA05 AC01 AC05 AC09 AC20 AD08 AF06 FA03 FA05 FB08 JA08 JA11
Claims (6)
シ樹脂、 【化１】 （但し、式中、Ｒは水素原子又はメチル基を表す） （Ｂ）ハロゲンを含まないポリエポキシド化合物および
（Ｃ）下式に示すメラミン変性ノボラック型フェノール
硬化剤 【化２】 を必須成分とすることを特徴とするハロゲンフリー積層
板用の難燃性エポキシ樹脂組成物。(A) a phosphorus-containing epoxy resin represented by the following general formula: (Wherein, R represents a hydrogen atom or a methyl group) (B) a halogen-free polyepoxide compound and (C) a melamine-modified novolak-type phenol curing agent represented by the following formula: And a flame-retardant epoxy resin composition for a halogen-free laminate.
シ樹脂、 【化３】 （但し、式中、Ｒは水素原子又はメチル基を表す） （Ｂ）ハロゲンを含まないポリエポキシド化合物、
（Ｃ）下式に示すメラミン変性ノボラック型フェノール
硬化剤および 【化４】 （Ｄ）無機充填剤を必須成分とすることを特徴とするハ
ロゲンフリー積層板用の難燃性エポキシ樹脂組成物。(A) a phosphorus-containing epoxy resin represented by the following general formula: (Wherein, R represents a hydrogen atom or a methyl group) (B) a halogen-free polyepoxide compound,
(C) a melamine-modified novolak-type phenol curing agent represented by the following formula: (D) A flame-retardant epoxy resin composition for a halogen-free laminate, comprising an inorganic filler as an essential component.
脂組成物によってガラス基材が含浸されたことを特徴と
するプリプレグ。3. A prepreg, wherein a glass substrate is impregnated with the epoxy resin composition according to claim 1 or 2.
項３記載のプリプレグからなることを特徴とする積層
板。4. A laminate comprising the prepreg according to claim 3, wherein the epoxy resin composition is cured.
項３記載のプリプレグからなる基板および該基板の少な
くとも片面に接合された銅箔を備えたことを特徴とする
銅張積層板。5. A copper-clad laminate comprising a substrate made of the prepreg according to claim 3, wherein the epoxy resin composition has been cured, and a copper foil bonded to at least one surface of the substrate.
項３記載のプリプレグからなる基板および該基板の少な
くとも片面に形成された銅箔回路を備えたことを特徴と
するプリント配線板。6. A printed wiring board comprising a substrate made of the prepreg according to claim 3, wherein the epoxy resin composition is cured, and a copper foil circuit formed on at least one surface of the substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2000200540A JP3500465B2 (en) | 2000-07-03 | 2000-07-03 | Flame retardant epoxy resin composition, prepreg and laminated product |
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| JP2000200540A JP3500465B2 (en) | 2000-07-03 | 2000-07-03 | Flame retardant epoxy resin composition, prepreg and laminated product |
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| JP2002012655A true JP2002012655A (en) | 2002-01-15 |
| JP3500465B2 JP3500465B2 (en) | 2004-02-23 |
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| JP2002201364A (en) * | 2001-01-05 | 2002-07-19 | Fujitsu Ltd | Flame-retardant resin composition and build-up substrate using the same |
| JP2005187800A (en) * | 2003-12-01 | 2005-07-14 | Hitachi Chem Co Ltd | Resin composition, and prepreg, metal-clad laminated sheet, and printed-wiring board using the composition |
| KR100589096B1 (en) * | 2003-07-11 | 2006-06-14 | 히다치 가세고교 가부시끼가이샤 | Phenol Resin Composition and Phenol Resin Copper-Clad Laminate |
| JP2007182544A (en) * | 2005-12-07 | 2007-07-19 | Hitachi Chem Co Ltd | Halogen-free resin composition, and prepreg and printed wiring board by using the same |
| JP2008007575A (en) * | 2006-06-27 | 2008-01-17 | Matsushita Electric Works Ltd | Epoxy resin composition, resin film, prepreg and multilayer printed wiring board |
| JP2008074929A (en) * | 2006-09-20 | 2008-04-03 | Matsushita Electric Works Ltd | Flame retardant epoxy resin composition, resin film, prepreg and multilayered printed circuit board |
| JP2008095105A (en) * | 2006-10-11 | 2008-04-24 | Samsung Electro Mech Co Ltd | Flame-retardant resin composition for use in printed circuit board, and printed circuit board using it |
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| JP2010540724A (en) * | 2007-09-28 | 2010-12-24 | ダウ グローバル テクノロジーズ インコーポレイティド | Epoxy resin composition |
| JP2011213830A (en) * | 2010-03-31 | 2011-10-27 | Ube Industries Ltd | Phosphorus-containing phenol novolak resin and manufacturing method therefor |
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| JP2002201364A (en) * | 2001-01-05 | 2002-07-19 | Fujitsu Ltd | Flame-retardant resin composition and build-up substrate using the same |
| KR100589096B1 (en) * | 2003-07-11 | 2006-06-14 | 히다치 가세고교 가부시끼가이샤 | Phenol Resin Composition and Phenol Resin Copper-Clad Laminate |
| JP2005187800A (en) * | 2003-12-01 | 2005-07-14 | Hitachi Chem Co Ltd | Resin composition, and prepreg, metal-clad laminated sheet, and printed-wiring board using the composition |
| JP2007182544A (en) * | 2005-12-07 | 2007-07-19 | Hitachi Chem Co Ltd | Halogen-free resin composition, and prepreg and printed wiring board by using the same |
| JP4600359B2 (en) * | 2006-06-27 | 2010-12-15 | パナソニック電工株式会社 | Epoxy resin composition, resin film, prepreg, and multilayer printed wiring board |
| JP2008007575A (en) * | 2006-06-27 | 2008-01-17 | Matsushita Electric Works Ltd | Epoxy resin composition, resin film, prepreg and multilayer printed wiring board |
| JP2008074929A (en) * | 2006-09-20 | 2008-04-03 | Matsushita Electric Works Ltd | Flame retardant epoxy resin composition, resin film, prepreg and multilayered printed circuit board |
| JP2008095105A (en) * | 2006-10-11 | 2008-04-24 | Samsung Electro Mech Co Ltd | Flame-retardant resin composition for use in printed circuit board, and printed circuit board using it |
| US8840967B2 (en) | 2006-10-11 | 2014-09-23 | Samsung Electro-Mechanics Co., Ltd. | Method for manufacturing printed circuit board including flame retardant insulation layer |
| JP2009067987A (en) * | 2007-09-13 | 2009-04-02 | Samsung Electro Mech Co Ltd | Nonflammable resin composition for printed circuit board, printed circuit board using nonflammable resin composition, and manufacturing method for nonflammable resin composition |
| JP2010540724A (en) * | 2007-09-28 | 2010-12-24 | ダウ グローバル テクノロジーズ インコーポレイティド | Epoxy resin composition |
| JP2014159566A (en) * | 2007-09-28 | 2014-09-04 | Dow Global Technologies Llc | Epoxy resin compositions |
| KR101520131B1 (en) * | 2007-09-28 | 2015-05-13 | 다우 글로벌 테크놀로지스 엘엘씨 | Epoxy resin formulations |
| JP2011213830A (en) * | 2010-03-31 | 2011-10-27 | Ube Industries Ltd | Phosphorus-containing phenol novolak resin and manufacturing method therefor |
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