JPS5952907B2 - Resin composition for flame-retardant laminates - Google Patents

Description

【発明の詳細な説明】 本発明は難燃性の優れた積層板用樹脂組成物に関するも
ので、その目的とするところは乾性油変性フェノール樹
脂の有する優れた低温打抜加工性を損うことなく、難燃
性を付与し、且耐熱性、電気特性の優れた安価な積層板
を提供しうる樹脂組成物を提供すること、更には貯蔵安
定性を向上せしめた前記積層板用のプリプレグを提供し
うる樹脂組成物を提供することにある。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition for laminates with excellent flame retardancy, and its purpose is to prevent the excellent low-temperature punching processability of the drying oil-modified phenolic resin from being impaired. To provide a resin composition capable of providing an inexpensive laminate that is flame retardant and has excellent heat resistance and electrical properties, and furthermore to provide a prepreg for the laminate that has improved storage stability. The object of the present invention is to provide a resin composition that can be used.

従来、乾性油変性フェノール樹脂を繊維素基材に含浸せ
しめて得たプリプレグを使用した積層板は低温打抜き加
工性が優れたものとして広く実用に供されてきた。Conventionally, laminates using prepregs obtained by impregnating a cellulose base material with a drying oil-modified phenolic resin have been widely put to practical use because of their excellent low-temperature punching workability.

ところが近年、需要分野の拡大に伴い低温打抜加工性が
優れ、且難燃性の優れた・積層板の要望が著しく増大し
ている。この点より乾性油変性フェノール樹脂の低温打
抜き加工性を損わない範囲で種々の難燃剤を添加して必
要な難燃化を達成しようとする検討が種々なされている
。例えば、（１）難燃剤としてハロゲン化フェノール類
、例えばテトラブロモビスフェノールＡを桐油変性フェ
ノール樹脂に含有せしめた樹脂組成物を基材に含浸して
得たプリプレグを使用し積層板を製造する方法。However, in recent years, with the expansion of demand fields, the demand for laminates with excellent low-temperature punching workability and flame retardancy has increased significantly. From this point of view, various studies have been made in an attempt to achieve the necessary flame retardancy by adding various flame retardants within a range that does not impair the low-temperature punching processability of the drying oil-modified phenolic resin. For example, (1) a method of manufacturing a laminate using a prepreg obtained by impregnating a base material with a resin composition in which a tung oil-modified phenol resin contains a halogenated phenol, such as tetrabromobisphenol A, as a flame retardant.

フ この場合、テトラブロモビスフェノールＡは安価で
ブロム含有率が高く比較的少量の添加で優れた難燃効果
を示すが、分子中のフェノール性ＯＨ基とハロゲンの相
互作用により高温積層成形工程時にハロゲンの解離を起
こし易く、積７ 層板の変色やふくれの惧れがある。In this case, tetrabromobisphenol A is inexpensive, has a high bromine content, and exhibits an excellent flame retardant effect even when added in a relatively small amount. It is easy to cause dissociation, and there is a risk of discoloration and blistering of the 7-layer board.

また、得られた積層板も耐熱性、電気特性が著しく低く
、更に積層板中に比較的低分子のテトラブロモビスフエ
ノールＡが他の化合物と結合することなく単分子で存在
している為に打抜き加工時の最適温度幅が狭く、若千の
加熱で急激に積層板の硬さが低下し、打抜き時に粉落ち
や目白が発生する問題があつた。（２）難燃性のエポキ
シ樹脂、例えばテトラプロモビスフエノールＡのジグリ
シジルエーテルを桐油変性フエノール樹脂に含有せしめ
た樹脂組成物も知られている。In addition, the resulting laminate also has extremely low heat resistance and electrical properties, and furthermore, the relatively low molecular weight tetrabromobisphenol A exists in the laminate as a single molecule without bonding with other compounds. The optimal temperature range during punching was narrow, and the hardness of the laminate rapidly decreased when heated to a certain temperature, causing problems such as powder falling and whitening during punching. (2) A resin composition in which a flame-retardant epoxy resin, for example diglycidyl ether of tetrapromobisphenol A, is contained in a tung oil-modified phenolic resin is also known.

この樹脂組成物は反応性に富み得られる積層板は耐熱性
、強度が優れているが著しく硬く、所要の難燃性（ＵＬ
−９４Ｖ−（１）と打抜き加工性（低温領域６０〜８０
℃で打抜き可能なこと）のバランスが困難であり、他の
添加型の難燃可塑剤（有機リン酸エステル類）を必要と
し、この場合耐熱性の低下や打抜き加工時の目白が発生
し易い欠点がある。This resin composition is highly reactive, and the resulting laminate has excellent heat resistance and strength, but is extremely hard and has the required flame retardancy (UL).
-94V-(1) and punching workability (low temperature range 60-80
It is difficult to strike a balance between the following: (can be punched at ℃), and other additive flame-retardant plasticizers (organic phosphate esters) are required; in this case, heat resistance decreases and whitening is likely to occur during the punching process. There are drawbacks.

更に大きな欠点としては、前記樹脂組成物を繊維素基材
に含浸して得たプリプレグの貯蔵安定性（ポツトライフ
）が劣り、積層板の市場提供が困難な点である。また所
要の難燃性を得るためには可成りの難燃性エポキシ樹脂
を必要とし、コストが高くなる欠点を有していた。本発
明はかかる欠点を改良するためになされたもので、両末
端エポキシ基をもつビスフエノールＡ型エポキシ樹脂化
合物とハロゲン化ビスフエノールＡを予め反応せしめた
反応混合物に一般式 Ｒ：ＨまたはＣＨ３，Ｃ４Ｈ， Ｘ：Ｂｒｎ＝１〜２ で示されるモノグリシジルエーテルを前記反応混合物に
対して１０〜８０重量％添加し反応せしめた混合物を乾
性油変性フエノール樹脂に該樹脂に対し２０〜５０重量
％含有せしめて、難燃積層板用樹脂組成物を得んとする
ものである。A further major drawback is that the prepreg obtained by impregnating a fiber base material with the resin composition has poor storage stability (pot life), making it difficult to market the laminate. Furthermore, in order to obtain the required flame retardancy, a considerable amount of flame retardant epoxy resin is required, which has the disadvantage of increasing costs. The present invention was made in order to improve such drawbacks, and a reaction mixture obtained by reacting a bisphenol A type epoxy resin compound having epoxy groups at both ends and a halogenated bisphenol A in advance, with the general formula R:H or CH3, A mixture obtained by adding 10 to 80% by weight of a monoglycidyl ether represented by C4H, At the very least, the aim is to obtain a resin composition for flame-retardant laminates.

即ち、安価でＢｒ含有率の高い難燃効果の優れたハロゲ
ン化ビスフエノールＡと耐熱及び電気特性の優れた積層
板を与える両末端にエポキシ基をもつビスフエノールＡ
型エポキシ樹脂を反応させて、前者単独の場合の欠点で
ある耐熱性の改良と後者単独の場合の欠点であるプリプ
レグの貯蔵安定性の改良をなすものである。Namely, halogenated bisphenol A is inexpensive and has a high Br content and has an excellent flame retardant effect, and bisphenol A has an epoxy group at both ends that provides a laminate with excellent heat resistance and electrical properties.
By reacting the type epoxy resin, the heat resistance, which is a drawback when the former is used alone, is improved, and the storage stability of the prepreg, which is a drawback when the latter is used alone, is improved.

しかし、前記ハロゲン化ビスフエノールＡと前記ビスフ
エノールＡ門型エポキシ樹脂との配合比を変えても、ま
たこの両者の反応混合物と乾性油変性フエノール樹脂の
配合比を変えても所要の難燃性と打抜き加工性及びプリ
プレグの貯蔵安定性のバランスをとることは困難である
。然るに、前記反応混合物に１官能０性のモノグリシジ
ルエーテルを配合し反応に関与させることによつて得た
反応混合物を乾性油変性フエノール樹脂に含有せしめる
ことによつて初めて所望の難燃性、打抜き加工性、耐熱
性及びプリプレグの貯蔵安定性のバランスをとることが
出来夕る。これは前記のモノグリシジルエーテルが前記
のハロゲン化ビスフエノールＡとビスフエノールＡ型エ
ポキシ樹脂の反応混合物中のエポキシ基の開環により生
じた０Ｈ基や末端のフエノール性０Ｈ基と反応し、架橋
に関与する官能基を減少せフしめ、乾性油変性フエノー
ル樹脂と混合した場合の硬さの上昇を防ぎ、且貯蔵安定
性を向上さたものと推定出来る。本発明を実施するに当
り、両末端にエポキシ基をもつビスフエノールＡ型エポ
キシ樹脂化合物は阿テトラプロモビスフエノールＡのジ
グリシジルエーテル、ビスフエノールＡのジグリシジル
エーテル等があり、ハロゲン化ビスフエノールＡとして
はテトラプロモビスフエノールＡ、トリプロモビスフエ
ノールＡ１ジプロモビスフエノールＡ等で″あり、特に
難燃性の点からテトラプロモビスフエノールＡが望まし
い。However, even if the blending ratio of the halogenated bisphenol A and the bisphenol A portal epoxy resin is changed, or the blending ratio of the reaction mixture of the two and the drying oil-modified phenolic resin is changed, the desired flame retardance cannot be maintained. It is difficult to strike a balance between punching processability and storage stability of the prepreg. However, the desired flame retardancy and punching properties can only be achieved by incorporating a reaction mixture obtained by blending a monofunctional and zero-functional monoglycidyl ether into the reaction mixture and allowing it to participate in the reaction. It is possible to balance processability, heat resistance and storage stability of the prepreg. This is because the monoglycidyl ether reacts with the OH group generated by ring opening of the epoxy group in the reaction mixture of the halogenated bisphenol A and bisphenol A type epoxy resin and the terminal phenolic OH group, resulting in crosslinking. It can be assumed that this reduces the number of functional groups involved, prevents an increase in hardness when mixed with a dry oil-modified phenolic resin, and improves storage stability. In carrying out the present invention, bisphenol A type epoxy resin compounds having epoxy groups at both ends include diglycidyl ether of tetrapromobisphenol A, diglycidyl ether of bisphenol A, etc., and halogenated bisphenol A Examples include tetrapromobisphenol A, tripromobisphenol A1, dipromobisphenol A, etc., and tetrapromobisphenol A is particularly preferred from the viewpoint of flame retardancy.

尚、１官能性のハロゲン化フエノール類は耐熱性に乏し
い。ここで、ビスフエノールＡ型エポキシ樹脂化合物と
ハロゲン化ビスフエノールＡの反応はその配合量が前者
１モルに対し後者０．３〜１モルの範囲で、触媒として
第３級アミンを用いるのが好ましい。ハロゲン化ビスフ
エノールＡが０．３モル以下ではプリプレグの貯蔵安定
性が充分でなく、且所望の難燃性を得るためには多量の
反応混合物を乾性油変性樹脂に添加する必要があり高コ
ストになる。一方、１モルを越えると残存する未反応ハ
ロゲン化ビスフエノールＡが多くなり、耐熱性が問題に
なる。上記で得られた反応混合物に反応させるモノグリ
シジルエーテルは一般式 Ｒ：Ｈまたは０Ｈ３，Ｃ４Ｈ９ Ｘ：Ｂｒｎ二１〜２ で示されるもので、ジプロモクレジルモノグリシジルエ
ーテル、ジプロモフエニルモノグリシジルｌエーテル、
ジプロモブチルフエニルモノグリシジルエーテル、モノ
プロモクレジルモノグリシジルエーテル等が使用できる
。Note that monofunctional halogenated phenols have poor heat resistance. Here, in the reaction between the bisphenol A type epoxy resin compound and the halogenated bisphenol A, it is preferable to use a tertiary amine as a catalyst in a range of 0.3 to 1 mol of the latter per 1 mol of the former. . If the amount of halogenated bisphenol A is less than 0.3 mole, the prepreg will not have sufficient storage stability, and in order to obtain the desired flame retardancy, it will be necessary to add a large amount of the reaction mixture to the drying oil-modified resin, resulting in high costs. become. On the other hand, if the amount exceeds 1 mole, a large amount of unreacted halogenated bisphenol A remains, and heat resistance becomes a problem. The monoglycidyl ether to be reacted with the reaction mixture obtained above is represented by the general formula R:H or 0H3,C4H9 ,
Dipromobutylphenyl monoglycidyl ether, monopromocresyl monoglycidyl ether, etc. can be used.

このモノグリシジルエーテルの添加量は前記のビスフエ
ノールＡ型エポキシ樹脂化合物とハロゲン化ビスフエノ
ールＡ（７）１反応混合物に対して１０〜８０重量％の
範囲内が好ましく、１０重量％未満ではプリプレグの貯
蔵安定性の向上、積層板の良好な低温打抜き加工性は得
られず、８０重量％を越えると積層板の耐熱性や耐湿性
が低下する。また、モノグリシジルエーテルの２添加時
期は前記のビスフエノールＡ型エポキシ樹脂化合物とハ
ロゲン化ビスフエノールＡの反応が平衡に達した時点が
望ましく、当初から３者を混合反応させるとモノグリシ
ジルエーテルとハロゲン化ビスフエノールＡの反応が促
進され低分子の，難燃樹脂組成物しか得られず所要の耐
熱性のある電気特性の優れた積層板を与える反応混合物
が得られない。モノグリシジルエーテルを加えた反応混
合物を添加する乾性油変性フエノール樹脂は、フエノー
ル類１００重量部に対し１０〜５０重量部の乾性油、例
えば桐油を酸性触媒下に反応させ、その後アミン触媒下
にホルムテルデヒドと反応させて得る公知のものである
。The amount of monoglycidyl ether added is preferably within the range of 10 to 80% by weight based on the reaction mixture of the bisphenol A type epoxy resin compound and halogenated bisphenol A (7) 1, and if it is less than 10% by weight, the prepreg Improvement in storage stability and good low-temperature punching processability of the laminate cannot be obtained, and if it exceeds 80% by weight, the heat resistance and moisture resistance of the laminate decrease. Furthermore, it is desirable to add the two monoglycidyl ethers at the time when the reaction between the bisphenol A type epoxy resin compound and the halogenated bisphenol A has reached equilibrium. The reaction of bisphenol A is accelerated, and only a low-molecular, flame-retardant resin composition is obtained, and a reaction mixture that provides a laminate with the required heat resistance and excellent electrical properties cannot be obtained. A drying oil-modified phenolic resin to which a reaction mixture containing a monoglycidyl ether is added is produced by reacting 10 to 50 parts by weight of a drying oil, such as tung oil, with 100 parts by weight of phenols under an acidic catalyst, and then reacting with a form under an amine catalyst. This is a known product obtained by reacting with teldehyde.

前記モノグリシジルエーテルを加えた反応混合物の乾性
油変性フエノール樹脂への添加量は、要求される難燃性
（例えばＵＬ規格で規定する９４−１．９４Ｖ−０）に
応じて増減させることが出来るが本発明の目的である良
好なる低温打抜き加工性、電気特性、耐熱性をもつ積層
板を得るためには乾性油変性フエノール樹脂に対して２
０〜５０重量％の範囲が望ましく、２０重量％未満では
所要の難燃性が充分でなく、５０重量％を越えると乾性
油変性の特徴である低温打抜き加工性が減じられる。本
発明の樹脂組成物を用いて積層品を製造する場合、本発
明の樹脂組成物を溶解したワニスに難燃助剤として三酸
化アンチモンを加えても良い。The amount of the reaction mixture added with the monoglycidyl ether added to the dry oil-modified phenolic resin can be increased or decreased depending on the required flame retardance (for example, 94-1.94V-0 specified by UL standards). However, in order to obtain a laminate with good low-temperature punching workability, electrical properties, and heat resistance, which is the objective of the present invention, the drying oil-modified phenolic resin should be
A range of 0 to 50% by weight is desirable; if it is less than 20% by weight, the required flame retardance is insufficient, and if it exceeds 50% by weight, the low temperature punching processability, which is a characteristic of drying oil modification, is reduced. When manufacturing a laminate using the resin composition of the present invention, antimony trioxide may be added as a flame retardant aid to a varnish in which the resin composition of the present invention is dissolved.

このようにして得た樹脂組成物のワニスを繊維素基材に
含浸、乾燥してプリプレグとした後、該プリプレグの必
要枚数を積層し、加熱加圧成形する。以下実施例によつ
て本発明を更に具体的に説明する。A fiber base material is impregnated with the varnish of the resin composition thus obtained and dried to form a prepreg, and then the required number of sheets of the prepreg are laminated and molded under heat and pressure. The present invention will be explained in more detail below using Examples.

実施例 １ 両末端にエポキシ基をもつビスフエノールＡ型エポキシ
樹脂化合物であるテトラプロモビスフエノールＡのジグ
リシジルエーテルを４００重量部、テトラプロモビスフ
エノールＡを１００重量部及びトルエンを加えて６０重
量％溶液にした後この溶液にベンジルジメチルアミンを
１重量部加え１００℃で４時間反応させ、更にジプロモ
クレジルモノグリシジルエーテルを２００重量部追加混
合して、１００℃で２時間反応させ（系中のエポキシ基
の濃度が平衡）、トルエンを加えて不揮発分６０重量％
の反応混合物（Ａ）を得た。Example 1 400 parts by weight of diglycidyl ether of tetrapromobisphenol A, which is a bisphenol A type epoxy resin compound having epoxy groups at both ends, 100 parts by weight of tetrapromobisphenol A, and toluene were added to make 60% by weight. After making a solution, 1 part by weight of benzyl dimethylamine was added to this solution and reacted at 100°C for 4 hours. Furthermore, 200 parts by weight of dibromocresyl monoglycidyl ether was added and reacted at 100°C for 2 hours ( Equilibrium concentration of epoxy groups), non-volatile content 60% by weight by adding toluene
A reaction mixture (A) was obtained.

一方、桐油変性フエノール樹脂を次のようにして調製し
た。On the other hand, tung oil-modified phenolic resin was prepared as follows.

フエノール２００重量部、クレゾール３００重量部、桐
油２００重量部及びパラトルエンスルホン酸の１０％水
溶液を５重量部を加えて１２０℃で３時間反応後、冷却
して３７％ホルマリン５００重量部、２５％アンモニア
水１５従量部を加えて還流下に９０分反応させた。Add 200 parts by weight of phenol, 300 parts by weight of cresol, 200 parts by weight of tung oil, and 5 parts by weight of a 10% aqueous solution of para-toluenesulfonic acid, react at 120°C for 3 hours, cool, and prepare 500 parts by weight of 37% formalin, 25% 15 parts of aqueous ammonia were added, and the mixture was reacted under reflux for 90 minutes.

その後脱水処理し、メタノール−トルエン（１：１）混
合溶剤を加えて不揮発分６０重量％のワニス（Ｂ）を調
製した。このように調製したワニス（Ｂ）にワニス（Ｂ
）に対して前記の反応混合物（４）が固形分換算で３０
重量％になるように配合し、次いで難燃助剤として三酸
化アンチモンを全ワニス固形分に対して２重量％添加し
て、基材含浸用樹脂組成物のワニスを調整した。Thereafter, it was dehydrated and a methanol-toluene (1:1) mixed solvent was added to prepare a varnish (B) with a non-volatile content of 60% by weight. Add varnish (B) to varnish (B) prepared in this way.
), the reaction mixture (4) has a solid content of 30
% by weight, and then 2% by weight of antimony trioxide was added as a flame retardant aid based on the total solid content of the varnish to prepare a varnish for the resin composition for impregnating a base material.

このワニスを厚さ１０ミルスのクラフト紙に含浸し乾燥
して樹脂含量５０重量％のプリプレグを得フた。This varnish was impregnated into kraft paper having a thickness of 10 mils and dried to obtain a prepreg having a resin content of 50% by weight.

該プリプレグを９枚重ねて積層成形（１００ｋｇ／Ｃｎ
ｌ２、１６０℃で５０分間）し１．６ｍ／ｍ厚の積層板
を得た。また、これとは別に３５μ銅箔を貼着した銅張
積層板をも得た。実施例 ２ テトラプロモビスフエノールＡのジグリシジルニーテル
を４００重量部、テトラプロモビスフエノールＡを２５
０重量部及びトルエンを加えて６０重量％溶液にした後
この溶液にベンジルジメチルアミンを１．３重量部加え
、１００℃で４時間反応させた。Nine sheets of the prepreg were layered and laminated (100 kg/Cn).
12 at 160° C. for 50 minutes) to obtain a laminate with a thickness of 1.6 m/m. Separately, a copper-clad laminate with 35μ copper foil attached was also obtained. Example 2 400 parts by weight of diglycidyl niter of tetrapromobisphenol A, 25 parts by weight of tetrapromobisphenol A
After adding 0 parts by weight and toluene to make a 60% by weight solution, 1.3 parts by weight of benzyldimethylamine was added to this solution, and the mixture was reacted at 100°C for 4 hours.

更にジプロモクレジルモノグリシジルエーテルを１００
重量部追加混合して１００℃で２時間反応させトルエン
を加えて不揮発分６０重量％の反応混合物（Ｃ）を得た
。実施例１で調製したワニス（Ｂ）にワニス（Ｂ）．に
対して反応混合物（６）が固形分換算で２０重量％にな
るように配合し、次いで難燃助剤として三酸化アンチモ
ンを全ワニス固形分に対して２重量％添加して基材含浸
用樹脂組成物のワニスを調製した。以下実施例１と同様
の方法で１．６ｍ／ｍ厚の積・層板を得た。比較例 １ テトラプロモビスフエノールＡを実施例１のワニス（Ｂ
）にワニス（Ｂ）に対して固形分換算で２５重量％添加
（２５重量％で所要の難燃Ｖ−０が出る）し、実施例１
と同様の方法で１．６ｍ／ｍ厚の積層板を得た。Furthermore, 100% dibromocresyl monoglycidyl ether
Parts by weight were added and reacted at 100° C. for 2 hours, and toluene was added to obtain a reaction mixture (C) with a nonvolatile content of 60% by weight. Varnish (B) was added to the varnish (B) prepared in Example 1. The reaction mixture (6) was blended so as to have a solid content of 20% by weight, and then antimony trioxide was added as a flame retardant aid at 2% by weight based on the total varnish solid content to impregnate the base material. A resin composition varnish was prepared. Thereafter, a laminated plate having a thickness of 1.6 m/m was obtained in the same manner as in Example 1. Comparative Example 1 Tetrapromobisphenol A was added to the varnish of Example 1 (B
) was added to varnish (B) in an amount of 25% by weight in terms of solid content (at 25% by weight, the required flame retardant V-0 was achieved), and Example 1
A laminate with a thickness of 1.6 m/m was obtained in the same manner as above.

比較例 ２ テトラプロモビスフエノールＡのジグリシジルエーテル
を実施例１のワニス８にワニス（Ｂ）に対して固形分換
算で４０重量％添加（３０重量％では所要の難燃性が得
られない）し、実施例１と同様の方法で１．６ｍ／ｍ厚
の積層板を得た。Comparative Example 2 Addition of diglycidyl ether of tetrapromobisphenol A to varnish 8 of Example 1 at 40% by weight in terms of solid content based on varnish (B) (30% by weight does not provide the required flame retardancy) Then, in the same manner as in Example 1, a laminate with a thickness of 1.6 m/m was obtained.

比較例 ３ テトラプロモビスフエノールＡのジグリシジルエーテル
とテトラプロモビスフエノールＡを実施例２と同様に反
応させて得た反応混合物（ジプロモクレジルモノグリシ
ジルエーテルは反応させない）を実施例１のワニス８に
ワニス（３）に対し固形分換算で３０重量％添加し、実
施例１と同様の方法で１．６ｍ／ｍ厚の積層板を得た。Comparative Example 3 A reaction mixture obtained by reacting diglycidyl ether of tetrapromobisphenol A and tetrapromobisphenol A in the same manner as in Example 2 (dipromocresyl monoglycidyl ether was not reacted) was used as Varnish 8 of Example 1. To the varnish (3), 30% by weight was added in terms of solid content, and a laminate with a thickness of 1.6 m/m was obtained in the same manner as in Example 1.

比較例 ４ ジプロモクレジルモノグリシジルエーテルを実施例１の
ワニス（Ｂ）にワニス（Ｂ）に対し固形分換算で４０重
量％添加（３０重量％では所要の難燃性が得られない）
し、実施例１と同様の方法で１．６ｍ／ｍ厚の積層板を
得た。Comparative Example 4 Dibromocresyl monoglycidyl ether was added to the varnish (B) of Example 1 in an amount of 40% by weight in terms of solid content (30% by weight does not provide the required flame retardancy)
Then, in the same manner as in Example 1, a laminate with a thickness of 1.6 m/m was obtained.

以上の実施例および比較例で得た積層板につき特性試験
を行い第１表の結果を得た。Characteristic tests were conducted on the laminates obtained in the above Examples and Comparative Examples, and the results shown in Table 1 were obtained.

第１表の結果から明らかなように、本発明の樹脂組成物
のワニスを基材に含浸したプリプレグを成形して得られ
る積層板は、耐熱性、電気絶縁性に優れ、且乾性油変性
フエノール樹脂の特徴である低温領域（６０〜８０℃）
での良好な打抜加工性が保持され、また単分子で存在す
る難燃剤が減少したことにより８０〜１００℃の温度領
域に於ても目白は発生せず、粉落ちの量も著しく減少し
た。As is clear from the results in Table 1, the laminate obtained by molding the prepreg in which the base material is impregnated with the varnish of the resin composition of the present invention has excellent heat resistance and electrical insulation properties, and also has excellent heat resistance and electrical insulation properties. Low temperature range (60-80℃) which is a characteristic of resin
Good punching workability was maintained, and because the amount of flame retardant present as a single molecule was reduced, whitening did not occur even in the temperature range of 80 to 100 degrees Celsius, and the amount of powder falling off was significantly reduced. .

特に、本発明は難燃性のエポキシ樹脂化合物を乾性油変
性フエノール樹脂に使用した際、積層板が硬くなつて打
抜き加工性が低下する点及びプリプレグの貯蔵安定性の
低下する点を改良したものであり、また耐熱性の低下や
打抜き時の目白の発生の惧れのある他の添加型の可撓性
難燃剤（例えば有機リン酸エステル類）や可塑剤を使用
する必要もなく比較的低コストで実用性の高い難燃積層
板が提供できる点、極めて工業的価値の大なるものであ
る。In particular, the present invention improves the problem that when a flame-retardant epoxy resin compound is used in a drying oil-modified phenolic resin, the laminate becomes hard and the punching workability decreases, and the storage stability of the prepreg decreases. In addition, there is no need to use other additive-type flexible flame retardants (e.g. organic phosphate esters) or plasticizers, which may reduce heat resistance or cause white spots during punching. It is of great industrial value in that it can provide a highly practical flame-retardant laminate at a low cost.

Claims (1)

【特許請求の範囲】 １ 両末端にエポキシ基をもつビスフェノールＡ型エポ
キシ樹脂化合物とハロゲン化ビスフェノールＡの反応混
合物に一般式 ▲数式、化学式、表等があります▼ Ｒ：ＨまたはＣＨ＿３、Ｃ＿４Ｈ＿０ Ｘ：Ｂｒｎ＝１〜２ で示されるモノグリシジルエーテルを前記反応混合物に
対して１０〜８０重量％添加し反応せしめた混合物を乾
性油変性フェノール樹脂に該樹脂に対し２０〜５０重量
％含有せしめてなる難燃積層板用樹脂組成物。 ２ 両末端にエポキシ基をもつビスフェノールＡ型のエ
ポキシ樹脂化合物がテトラブロモビスフェノールＡのジ
グリシジルエーテルである特許請求の範囲第１項記載の
難燃積層板用樹脂組成物。 ３ ハロゲン化ビスフェノールＡの配合量が両末端にエ
ポキシ基をもつビスフェノールＡ型エポキシ樹脂化合物
１モルに対して０．３〜１モルである特許請求の範囲第
１項記載の難燃積層板用樹脂組成物。[Claims] 1. A reaction mixture of bisphenol A type epoxy resin compound having epoxy groups at both ends and halogenated bisphenol A has the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ R: H or CH_3, C_4H_0 X: Brn = 1 to 2 A monoglycidyl ether represented by 1 to 2 is added to the reaction mixture in an amount of 10 to 80% by weight, and a mixture obtained by reacting the mixture is added to a drying oil-modified phenolic resin in an amount of 20 to 50% by weight based on the resin. Resin composition for flame laminates. 2. The resin composition for a flame-retardant laminate according to claim 1, wherein the bisphenol A type epoxy resin compound having epoxy groups at both ends is diglycidyl ether of tetrabromobisphenol A. 3. The resin for flame-retardant laminates according to claim 1, wherein the amount of halogenated bisphenol A is 0.3 to 1 mole per mole of bisphenol A type epoxy resin compound having epoxy groups at both ends. Composition.