JPS5952905B2 - Flame retardant phenolic resin composition - Google Patents

Description

【発明の詳細な説明】 本発明は難燃性が優れ且扛抜き加工性の優れた積層品用
の難燃性フェノール樹脂組成物に関し、その目的とする
ところは、優れた難燃性と優れた打抜き加工性を併せ持
ち、且耐熱性、電気特性を充分保持した積層板を提供し
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 flame-retardant phenolic resin composition for laminates that has excellent flame retardancy and excellent striping processability. The object of the present invention is to provide a resin composition that can provide a laminate that has good punching workability and sufficiently maintains heat resistance and electrical properties.

近年の電気電子機器の発展に伴い、これ等の分野で使用
される紙基材積層板には安全性の点より難燃性であるこ
と、また部品の自動挿入化の発達により打抜穴密度の増
加や打抜き品の寸法変化を出来るだけ少くするために低
温打抜き加工の出来る積層板の要望が著しく増大してい
る。With the recent development of electrical and electronic equipment, the paper-based laminates used in these fields are required to be flame retardant for safety reasons, and due to the development of automatic parts insertion, the density of punched holes has increased. Demand for laminates that can be punched at low temperatures is increasing significantly in order to minimize the increase in the number of sheets and the dimensional changes in the punched products.

この点に鑑み、従来、積層板に難燃性と打抜き加工性を
兼ね備えさせる方法が種々検討されている。例えば、難
燃剤としてハロゲン化エポキシ樹脂の一つであるテトラ
ブロモビスフェノールＡのジグリシジルエーテルを所要
の難燃性（ＵＬ−９４Ｖ−Ｏ）を得るに必要な量だけ、
低温打抜き加工性が良い（６０〜８０℃で打抜性良好、
クラックや自白が発生しない）と言われる乾性油変性フ
ェノール樹脂組成物或はアルキルフェノールを併用した
フェノール樹脂組成物に添加した難燃性樹脂組成物が知
られている。In view of this point, conventionally, various methods have been studied to provide a laminate with both flame retardancy and punching workability. For example, diglycidyl ether of tetrabromobisphenol A, which is one of the halogenated epoxy resins, is used as a flame retardant in the amount necessary to obtain the required flame retardancy (UL-94V-O).
Good low-temperature punching workability (good punching workability at 60-80℃,
A flame-retardant resin composition added to a drying oil-modified phenol resin composition or a phenol resin composition containing an alkylphenol is known, which is said to cause no cracking or whitening.

これら樹脂組成物を繊維素基材に含浸して得たプリプレ
グを加熱加工下に積層成型して得られる積層板は、前記
工程間にエポキシ樹脂とフェノール樹脂の架橋反応が進
行し、耐熱性は優れているが非常に硬くて、良好な低温
打抜き加工性は得られない。低温打抜き加工性を得よう
とすると乾性油或はアルキルフェノールの割合を増加さ
せざるを得ず、逆に難燃性が得られない。このように難
燃性と低温打抜き加工性のバランスをとることは非常に
困難であつた。また、前記のプリプレグは常温下に貯蔵
した場合使用可能時間が短かく、積層板の市場提供に支
障があつた。その他の方法として、ハロゲン化フェノー
ル類或はリン酸エステル類を添加する方法等があるが、
いずれも耐熱性が不充分であり且電気特性も良くない欠
点があつた。本発明はかかる欠点を改良するためになさ
れたもので、分子中に２個のエポキシ基を有するハロ、
ゲン化エポキシ樹脂と一般式 式中 Ｒ，Ｒ″はＣｌ６〜Ｃｌ８の不飽和炭化水素（Ｒ
，Ｒ″は同じ場合もある）で示される不飽和高級脂肪酸
のアミド、イミノ基を含む化合物との反応付加物を２０
〜５０重量％、レゾール型フエノール樹脂を５０〜８０
重量％、三酸化アンチモンを１〜３重量％含有してなる
積層品用の難燃性フエノール樹脂組成物である。The laminate obtained by laminating and molding the prepreg obtained by impregnating a fiber base material with these resin compositions under heat processing undergoes a crosslinking reaction between the epoxy resin and the phenol resin during the above process, and the heat resistance is low. Although it is excellent, it is very hard and does not have good low-temperature punching workability. In order to obtain low-temperature punching processability, the proportion of drying oil or alkylphenol must be increased, and flame retardancy cannot be obtained. In this way, it has been extremely difficult to strike a balance between flame retardancy and low-temperature punching workability. In addition, the above-mentioned prepreg has a short usable time when stored at room temperature, which has hindered the provision of laminates on the market. Other methods include adding halogenated phenols or phosphate esters, etc.
All of them had drawbacks of insufficient heat resistance and poor electrical properties. The present invention was made to improve such drawbacks, and includes halo, which has two epoxy groups in the molecule,
In the general formula, R and R″ are unsaturated hydrocarbons of Cl6 to Cl8 (R
, R'' may be the same) is a reaction adduct of an unsaturated higher fatty acid represented by 20
~50% by weight, 50~80% resol type phenolic resin
This is a flame-retardant phenolic resin composition for laminates containing 1 to 3% by weight of antimony trioxide.

本発明を実施するに当り、分子中に２個のエポキシ基を
有するハロゲン化エポキシ樹脂としては、一般に反応性
の難燃性付与剤として知られてい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、ジブロモネオペン
チルグリコールジグリシジルエーテル等が使用できる。In carrying out the present invention, halogenated epoxy resins having two epoxy groups in the molecule include diglycidyl ether of tetrapromobisphenol A, dibromobisphenol A, which is generally known as a reactive flame retardant imparting agent; Neopentyl glycol diglycidyl ether and the like can be used.

また、前記一般式で示される不飽和高級脂肪酸のアミド
、イミノ基を含む化合物は不飽和脂肪酸とポリアルキレ
ンポリアミンを脱水縮合して得たものであり、長鎖の不
飽和炭化水素とエポキシ基との反応に関５与出来る２個
の（−ＮＨ−）結合をもつものである。ハロゲン化エポ
キシ樹脂と前記一般式で示される化合物との反応は両者
を化学量論的に等モル量若しくは後者を若干過剰に用い
るのが好ましい。後者の量が少い場合は可撓性が充分で
なくま，たプリプレグの使用可能期間の延長効果も小さ
い。また、後者の量が著しく多い場合は、所要の難燃性
を得るために大量の両者の反応付加物をレゾール型フエ
ノール樹脂に加えなければならず、積層板にしたときの
層間密着力が減少し、打抜き．穴周囲に目白が発生し易
い。更に吸湿時の電気特性の低下も大きい。尚、前記一
般式で示される化合物中の不飽和基は、ハロゲン化合物
の熱分解抑制効果をもち耐熱性向上に役立つものである
。レゾール型フエノール樹脂としては、フエノ一・ル、
クレゾール、ノニルフエノール等のフエノール類をアン
モニア水、エチレンジアミン等のアルカリ触媒でホルム
アルデヒドと反応させて得た公知のものである。前記一
般式で示される化合物とハロゲン化エポキシ樹脂との反
応付加物をレゾール型フエノール樹脂と混合するとき前
記反応付加物は２０〜５０重量％含有されるのが望まし
い。In addition, the compound containing an amide or imino group of an unsaturated higher fatty acid represented by the above general formula is obtained by dehydration condensation of an unsaturated fatty acid and a polyalkylene polyamine, and is a compound containing a long-chain unsaturated hydrocarbon and an epoxy group. It has two (-NH-) bonds that can participate in the reaction. In the reaction between the halogenated epoxy resin and the compound represented by the above general formula, it is preferable to use stoichiometrically equimolar amounts of both or a slight excess of the latter. If the latter amount is small, the flexibility will not be sufficient and the effect of extending the usable period of the prepreg will be small. Additionally, if the amount of the latter is significantly large, a large amount of reactive adducts of both must be added to the resol-type phenolic resin in order to obtain the required flame retardancy, resulting in a decrease in interlayer adhesion when formed into a laminate. Then, punch out. White spots tend to appear around the holes. Furthermore, the electrical properties deteriorate significantly when moisture is absorbed. The unsaturated group in the compound represented by the above general formula has the effect of suppressing thermal decomposition of the halogen compound and is useful for improving heat resistance. Examples of resol type phenolic resins include phenol,
It is a known product obtained by reacting phenols such as cresol and nonylphenol with formaldehyde using an alkali catalyst such as aqueous ammonia or ethylenediamine. When the reaction adduct of the compound represented by the general formula and the halogenated epoxy resin is mixed with the resol type phenolic resin, it is desirable that the reaction adduct be contained in an amount of 20 to 50% by weight.

２０重量％以下の場合所要の難燃性を得ることが出来ず
、また良好な低温打抜き加工性も得られない。If it is less than 20% by weight, the required flame retardancy cannot be obtained and good low-temperature punching workability cannot be obtained.

一方、５０重量％を越えるとフエノール樹脂本来の耐熱
性や層間接着力が低下して積層板として必要な機械的強
度も不足する。三酸化アンチモンは難燃補助剤として所
要の難燃性が得られるよう１〜３重量％の範囲で含有さ
れるのが望ましい。On the other hand, if it exceeds 50% by weight, the inherent heat resistance and interlayer adhesion of the phenolic resin will decrease, and the mechanical strength required for a laminate will also be insufficient. Antimony trioxide is preferably contained as a flame retardant auxiliary agent in an amount of 1 to 3% by weight in order to obtain the required flame retardancy.

但し、３重量％を越えると含浸工程時の三酸化アンチモ
ンの分散性、積層板にした場合の外観不良等の問題があ
る。上記本発明の難燃性フエノール樹脂組成物は、ハロ
ゲン化エポキシ樹脂の難燃性を有効に生かし、且これを
レゾール型フエノール樹脂に添加した場合の欠点である
プリプレグの不安定性、積層板の硬さ等の改良を前記一
般式で示される化合物を使用したことにより初めて達成
出来るものである。However, if it exceeds 3% by weight, there will be problems such as poor dispersibility of antimony trioxide during the impregnation process and poor appearance when made into a laminate. The flame-retardant phenolic resin composition of the present invention effectively takes advantage of the flame retardancy of halogenated epoxy resins, and also eliminates the disadvantages of instability of prepregs and hardness of laminates when added to resol-type phenolic resins. This improvement can only be achieved by using the compound represented by the above general formula.

尚、前記のハロゲン化エポキシ樹脂に前記一般式で示さ
れる化合物を単に加えたものをレゾール型フエノール樹
脂と併用し基材に含浸して得たプリプレグは前記のハロ
ゲン化エポキシ樹脂を単独で使用したときより更にプリ
プレグの使用可能時間が短かくまた得られた積層板の低
温打抜き加工性も良くない。本発明の如く付加物として
利用することにより初めて目的を達成することができる
のである。以下実施例によつて本発明を更に具体的に説
明する。Incidentally, the prepreg obtained by simply adding the compound represented by the above general formula to the above halogenated epoxy resin in combination with a resol type phenolic resin and impregnating the base material is obtained by using the above halogenated epoxy resin alone. The usable time of the prepreg is even shorter than before, and the low-temperature punching processability of the obtained laminate is also poor. The purpose can only be achieved by using it as an additive as in the present invention. 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４００重量部にＲ，Ｒ″はリ
ノレイン酸基を３２０重量部及びトルエンを加えて６０
重量％溶液にした後、８０℃にて４時間反応（エポキシ
基の減少が平衡）させて付加物を含むワニス（Ａ）を得
た。Example 1 To 400 parts by weight of diglycidyl ether of tetrapromobisphenol A having epoxy groups at both ends, 320 parts by weight of linoleic acid group and toluene (R, R'') were added to give 60 parts by weight.
After making it into a weight% solution, it was reacted at 80° C. for 4 hours (balanced reduction of epoxy groups) to obtain a varnish (A) containing the adduct.

別途、レゾール型フエノール樹脂は、フエノｌール３０
０重量部、ノニルフエノール２００重量部、８５％パラ
ホルムアルデヒド１５０重量部、２５％アンモニア水１
０ｇを１００℃にて３時間反応させ脱水処理を行つた後
、メタノールを加えて不揮発分６０重量％のワニス（Ｂ
）を得た。 １次いで、前記付加
物を含むワニス（Ａ）が固形物換算で４０重量部、レゾ
ール型フエノール樹脂のワニス（Ｂ）が固形物換算で５
７重量部、三酸化アンチモンが３重量部からなる紙基材
含浸用の難燃性フエノール樹脂組成物のワニスを調製し
た。こ２のワニスを厚さ１０ミルスのクラフト紙に含浸
、乾燥し樹脂含量５０重量％のプリプレグを得た。この
プリプレグを９枚重ねて積層成形（１００ｋｇ／ＣＩｎ
２、１６０℃で５０分間）し、１．６ｍ／ｍ厚の積層板
を得た。尚これとは別に３５μ銅箔を貼着した銅張積層
２板を得た。実施例 ２ 両末端にエポキシ基をもつジブロモネオペンチルグリコ
ールジグリシジルエーテル３２０重量部に実施例１と同
じ化学式で示される化合物を３２０重，゛量部及びトル
コンを加えて６０重量％溶液にした後８０℃にて４時間
反応させて付加物を含むワニス（Ｃ）を得た。Separately, the resol type phenolic resin is Phenol 30.
0 parts by weight, 200 parts by weight of nonylphenol, 150 parts by weight of 85% paraformaldehyde, 1 part by weight of 25% ammonia water
0g was reacted at 100°C for 3 hours and dehydrated, then methanol was added to make a varnish (B
) was obtained. 1 Next, the varnish (A) containing the adduct was 40 parts by weight in terms of solids, and the resol type phenolic resin varnish (B) was 5 parts by weight in terms of solids.
A varnish of a flame-retardant phenolic resin composition for impregnating a paper base material was prepared, containing 7 parts by weight and 3 parts by weight of antimony trioxide. Kraft paper with a thickness of 10 mils was impregnated with this 2 varnish and dried to obtain a prepreg having a resin content of 50% by weight. Laminate molding by stacking 9 sheets of this prepreg (100kg/CIn
2, 50 minutes at 160° C.) to obtain a laminate with a thickness of 1.6 m/m. Separately, two copper-clad laminates with 35 μm copper foil attached were obtained. Example 2 To 320 parts by weight of dibromoneopentyl glycol diglycidyl ether having epoxy groups at both ends, 320 parts by weight of a compound represented by the same chemical formula as in Example 1 and Torcon were added to make a 60% solution by weight. The mixture was reacted at 80° C. for 4 hours to obtain a varnish (C) containing the adduct.

該ワニス（Ｃ）が固形分換算で４０重量部、実施例１で
調製したレゾール型フエノール樹脂のワニ．ス（Ｂ）が
固形分換算で５７重量部、三酸化アンモンが３重量部か
らなる紙基材含浸用のワニスを調製した。The varnish (C) was 40 parts by weight in terms of solid content, and the resol type phenolic resin varnish prepared in Example 1 was used. A varnish for impregnating a paper base material was prepared, containing 57 parts by weight of base (B) and 3 parts by weight of ammonium trioxide in terms of solid content.

このワニスにより実施例１と同様の方法で１．６ｍ／ｍ
の積層板及び銅張積層板を得た。比較例 １テトラプロ
モンビスフエノールＡのジグリシジルエーテルが４０重
量部、実施例１で調製したレゾール型フエノール樹脂の
ワニス（Ｂ）が固形分換算で５７重量部、三酸化アンチ
モンが３重量部からなる紙基材含浸用のワニスを調整し
た。With this varnish, 1.6 m/m was obtained in the same manner as in Example 1.
A laminate and a copper-clad laminate were obtained. Comparative Example 1 40 parts by weight of diglycidyl ether of tetrapromone bisphenol A, 57 parts by weight of the resol type phenolic resin varnish (B) prepared in Example 1 in terms of solid content, and 3 parts by weight of antimony trioxide. A varnish for impregnating paper base material was prepared.

このワニスにより実施例１と同様の方法で１．６ｍ／ｍ
の積層板及び銅張積層板を得た。以上の実施例、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。With this varnish, 1.6 m/m was obtained in the same manner as in Example 1.
A laminate and a copper-clad laminate were obtained. Characteristic tests were conducted on the laminates obtained in the above Examples and Comparative Examples, and the results shown in Table 1 were obtained.

また、プリプレグの貯蔵可能期間も示した。第１表の結
果より明らかなように、本発明の難燃性フエノール樹脂
組成物のワニスを基材に含浸して成形して得られる積層
板は（ＵＬ９４，ＶＯ）を保持し、耐熱性、打抜き加工
性をも充分兼ね備えている。It also shows the shelf life of the prepreg. As is clear from the results in Table 1, the laminate obtained by impregnating a base material with the varnish of the flame-retardant phenolic resin composition of the present invention and molding it maintains (UL94, VO), has heat resistance, It also has sufficient punching workability.

特に本発明は、前記一般式で示される不飽和高級脂肪酸
のアミド、イミノ基を含む化合物とハロゲン化エポキシ
樹脂の反応付加体を利用することにより目的を達成する
ことが出来、従来の如く耐熱性や電気特性に問題のある
添加型の難燃可塑剤（例えば有機リン酸エステル類）を
使用する必要もなく、低コストで実用性の高い難燃積層
板が提供できる。In particular, the object of the present invention can be achieved by using a reaction adduct of a compound containing an amide or imino group of an unsaturated higher fatty acid represented by the above general formula and a halogenated epoxy resin, and the heat resistance There is no need to use additive-type flame-retardant plasticizers (such as organic phosphate esters) that have problems with electrical properties, and a highly practical flame-retardant laminate can be provided at low cost.

Claims (1)

【特許請求の範囲】 １ 分子中に２個のエポキシ基を有するハロゲン化エポ
キシ樹脂と一般式 ▲数式、化学式、表等があります▼ 式中Ｒ、Ｒ′はＣ＿１＿６〜Ｃ＿１＿８の不飽和炭化水
素基で示される不飽和高級脂肪酸のアミド、イミノ基を
含む化合物との反応付加物を２０〜５０重量％、レゾー
ル型フェノール樹脂を５０〜８０重量％、三酸化アンチ
モンを１〜３重量％の組成で含有してなる積層品用の難
燃性フェノール樹脂組成物。[Claims] 1. A halogenated epoxy resin having two epoxy groups in the molecule and a general formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ In the formula, R and R' are unsaturated hydrocarbon groups of C_1_6 to C_1_8 A composition of 20 to 50% by weight of a reaction adduct of an unsaturated higher fatty acid shown with a compound containing an amide or imino group, 50 to 80% by weight of a resol type phenolic resin, and 1 to 3% by weight of antimony trioxide. A flame-retardant phenolic resin composition for laminated products comprising: