JPS59182815A - Oil-modified phenolic resin and electrical laminated board using the same - Google Patents

Abstract

PURPOSE:The titled resin, obtained by reacting a phenol with a vegetable oil and then formaldehyde, and further reacting the resultant reaction product with a precondensate of a phenolic resin, etc., having improved punchability, and capable of giving electrical laminated boards rich in flexibility. CONSTITUTION:One mole vegetable oil, e.g. tung oil, is reacted with preferably 2-5mol phenol and then preferably 2-6mol formaldehyde to give a reaction product, which is reacted with a precondensate obtained by reacting phenol with formaldehyde and hexamine in a solvent, e.g. methanol, preferably at 30-110 deg.C to afford the aimed oil-modified phenolic resin. The resultant oil-modified phenolic resin is then impregnated into a base material for a laminated board and dried to give a prepreg. Sheets of the resultant prepreg in a necessary number are laminated, hot-pressed and molded to afford the aimed electrical laminated board.

Description

【発明の詳細な説明】 〔技術分野〕 本発明は産業］幾器用、電子部品用、電気機器用の電気
用積層板及びそれに用いる油変性フェノ−）Ｖ樹脂に関
するものである。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to an electrical laminate for industrial use, electronic parts, and electrical equipment, and an oil-modified phenol-V resin used therein.

〔背景技術〕[Background technology]

従来、産業機器用、電子部品用、′１ホ気（蔑器用の電
気用積層板はＩＣ，）ランジスタ等の゛虫気部品を装着
せしめる為に１Ｓ気用積／？々仮に装着用穴を多数設け
る必要があり装着用穴をパンチング等で作成時に電気用
Ｒ層板にワレ、クラックを発生することが多かった。更
に難燃化の要求に対応するため積層板用樹脂に難燃剤を
多量に混入することかありワレ、クラックの発生を益々
多発させていたものである。Conventionally, 1S air/? It is necessary to temporarily provide a large number of mounting holes, and when the mounting holes are created by punching or the like, cracks and cracks often occur in the electrical R-layer board. Furthermore, in order to meet the demand for flame retardancy, a large amount of flame retardant was mixed into the resin for the laminate, which caused cracks and cracks to occur more frequently.

〔発明の目的〕[Purpose of the invention]

本発明の目的とするところは、可撓性にホむユ；１気用
ｆ＃層板訃よびそれに用いる油変性フェノール樹脂を安
価に提供することにある。An object of the present invention is to provide a flexible F# layer plate for one-time use and an oil-modified phenolic resin used therein at a low cost.

〔発明の開示〕[Disclosure of the invention]

本発明は上記欠点を解決するもので、フェノ−）ｖ類と
植物油とを反応させた後、ホルムアルテヒＶ類と反応さ
せた反応物に、フェノール系、Ｈ１脂初旬」縮合物と溶
剤とへキサミンとを添加し反応させることによって可撓
性に優れた油変性フェノール樹脂を高収工で得ることが
でき、該油変性フェノール樹脂を積層４反用樹脂として
用することにより可撓性に優れた′電気用積層板を安価
ＩＣ得ることかできたものである。The present invention solves the above-mentioned drawbacks, and after reacting phenol-V and vegetable oil, the reaction product reacted with formaltech V is added with phenol-based, H1 fat condensate and a solvent. By adding and reacting with xamine, oil-modified phenolic resin with excellent flexibility can be obtained with high yield, and by using this oil-modified phenolic resin as a laminated 4-layer resin, it has excellent flexibility. In addition, it was possible to obtain inexpensive ICs using electrical laminates.

次に本発明の詳細な説明する。本発明に用いるフェノ−
／Ｌ／類はフェノール、クレゾール、ギシレノール及び
フェノール類と変性用能な糖蜜、リグニン、キシレン、
ナフタリン、石油系芳香族炭化水ぶ樹脂等とフェノ−）
Ｖ類との混合物をも含むものである。植物油としては桐
油、大豆油、ヒマシ油、アマニ油等の植物油全般を用い
ることかできる。ホルムアルデヒド知としてはホルマリ
ン、バラホルムアルデヒド等を用粘る。フェノール果樹
）危初期縮合物としては、上記のフェノール類とホルム
アルデヒド４頃とを酸性又はアルカリ性下ｔこお一へて
反応させた初期縮合物である。７η剤表してはメチフレ
アルコール、アセトン、トルエン等のようにフェノール
糸樹脂初４４Ａｉ；ｉ合物と相浴注のある溶剤であるな
らばよく時に限足するものではなり０フェノール頌と植
物油との反応は植物油１モルに対しフェノールＶ類２〜
５モルをパラトルエンヌルホン酸等の酸性触媒下に５０
〜゛１２０　　℃の温度で反応させた後、ホルムアルデ
ヒド褪２〜６モルと反応させて反応物を得、次に該反応
物にフェノール頑とホルムアルデヒド類とを酸性又はア
ルカリ性下において反応させたフェノール糸、耐脂初期
縮合物と溶剤とへキサミンとを添加し３０〜１１０Ｃで
反応させて油変性フェノール撓脂を得るものである。仄
に、積層シ反用基相としては、ガラス、アスベヌト寺の
勲機繊維やポリエステル、ポリアミド、ポリビニルアル
コール、アクリル等の有峨合成葎維や木綿等の天然漆維
からなる織布、不織布、マット或は紙又はこれらの紬合
せ基材を用い、上記油変性フェノ−１ｖ樹脂を、積層板
用基材に含浸、乾燥させて得たプリプレグを所要枚数オ
β層した積層体を、或は必要に応じて該積層体の最外側
に、接着剤付銅箔の接着剤側を積増体側に対向させて載
置してから加熱加圧成形して電気用積層板を得るもので
ある。Next, the present invention will be explained in detail. Phenol used in the present invention
/L/ types include phenol, cresol, gyclenol, molasses capable of modification with phenols, lignin, xylene,
naphthalene, petroleum-based aromatic hydrocarbon resin, etc., and phenol)
It also includes mixtures with Group V. As the vegetable oil, all vegetable oils such as tung oil, soybean oil, castor oil, and linseed oil can be used. As for formaldehyde, formalin, rose formaldehyde, etc. are used. The precondensation product (phenol fruit tree) is an initial condensation product obtained by reacting the above-mentioned phenols with formaldehyde in an acidic or alkaline environment. In terms of 7η agents, if it is a solvent that is compatible with phenolic thread resin first 44Ai;i compounds such as metifle alcohol, acetone, toluene, etc., it may not be necessary to add it only once in a while. The reaction is 2 to 1 mole of vegetable oil to phenol V
5 moles under an acidic catalyst such as para-toluene sulfonic acid
Phenol thread obtained by reacting at a temperature of ~120°C, then reacting with 2 to 6 moles of formaldehyde to obtain a reactant, and then reacting the reactant with phenol and formaldehyde under acidic or alkaline conditions. , a fat-resistant initial condensate, a solvent, and hexamine are added and reacted at 30 to 110C to obtain an oil-modified phenol resin. In addition, the base materials for lamination include glass, woven fabrics made of Asbenuto fibers, synthetic fibers such as polyester, polyamide, polyvinyl alcohol, and acrylic, and natural lacquer fibers such as cotton, non-woven fabrics, A laminate in which the required number of prepregs obtained by impregnating the oil-modified pheno-1v resin into the laminate board base material and drying the above-mentioned oil-modified phenol-1v resin using a mat or paper or a pongee combination base material of these materials is laminated with the required number of sheets, or If necessary, an electrical laminate is obtained by placing an adhesive-coated copper foil on the outermost side of the laminate with the adhesive side facing the laminate side, and then heating and press-forming the foil.

以下本発明を’ＩＪ　ｈｇ例にもとすいて説明する。The present invention will be explained below using an example of 'IJhg.

実施例 桐油１モルに対しフェノール３モルを加えてからパラト
ルエンスルホン酸２．１６ｆを加え８５℃で１７５分間
反応させた後、ホルムアルデヒド４モルを３７％ホルマ
リンで加え、アンモニア水でアルカリ性にした後、還流
温度で６０分間反応させてル応物ヲ得だ。別にフェノ−
）Ｖ１モルに対しホルムアルデヒド１６５モルを３７係
ホルマリンで加え、アンモニア水でアルカリ性にしてか
ら連流温度で６０分間反応させてフェノール樹脂初期縮
合物を得、該フェノ−）ｖオケ脂初Ｍ縄合物１００　”
Ｉｇ、　□３４１部（以下哨に部と記す）とメチルアル
コ−）ｖ２０部とへキサミンＩｌｌ　’ｊｌｓとを上記
反応物１００部に鍋加し４０℃で４０分間Ｊ又尾；させ
、メチルアルコール 以下．１に％と記す）に調整した油変性フェノールＡＲ
脂を得た。次に厚さ０．２闘のクラフト紙に付着１、ｊ
：力（５０４になるように上記油変性フェノ−）ｖ　ｊ
ｔＮ脂を含浸、乾燥させてプリプレグを得、このプリプ
レグ８枚を積層し更にその上下面に厚さ０．０３５＋ｕ
の接着剤性％ｌ　ｆＭを接着剤側をプリプレグ側に対向
させて夫々載置してから金型プレートに挾んで成形圧力
１ｏｏ　Ｋｇ／ｃＡ　　、成形温度１６０’ｃで６０分
間成形して両面＠張積層板を得だ。Example: Add 3 moles of phenol to 1 mole of tung oil, then add 2.16 f of para-toluenesulfonic acid, react at 85°C for 175 minutes, then add 4 moles of formaldehyde with 37% formalin, and make alkaline with ammonia water. The reaction product was obtained by reacting at reflux temperature for 60 minutes. Separately pheno
) Add 165 moles of formaldehyde to 1 mole of V with 37% formalin, make it alkaline with aqueous ammonia, and react at continuous flow temperature for 60 minutes to obtain a phenol resin initial condensate, and the phenol resin initial condensate is obtained. 100 things”
341 parts of Ig (hereinafter referred to as "parts"), 20 parts of methyl alcohol) and hexamine were added to 100 parts of the above reaction mixture in a pot and heated at 40°C for 40 minutes, and methyl alcohol was added. below. Oil-modified phenol AR adjusted to
I got fat. Next, attach it to kraft paper with a thickness of 0.2 mm.
: Force (the above oil-modified phenol so that it becomes 504) v j
Impregnated with tN resin and dried to obtain prepreg, stacked 8 sheets of this prepreg, and further coated the top and bottom surfaces with a thickness of 0.035+u.
The adhesive properties of %l fM were each placed with the adhesive side facing the prepreg side, and then sandwiched between mold plates and molded for 60 minutes at a molding pressure of 10 Kg/cA and a molding temperature of 160'C, and both sides @ I got a stretched laminate.

従来例１ フェノ−）Ｖ　１モルに対しホルムアルデヒド１．５を
３７チホルマリンで加えてからアルカリ性下、還流温度
で６０分間反応させてから樹脂量５０％になるようにメ
チルアルコールで希釈してフェノール樹脂を得、該フェ
ノール樹脂を用い、実施例と同様に処理して両面絹張１
７　）ｉ４板を得だ。Conventional Example 1 1.5% of formaldehyde was added to 1 mole of phenol V in 37 diformalin, reacted under alkaline conditions at reflux temperature for 60 minutes, and then diluted with methyl alcohol to make the resin amount 50%. A resin was obtained, and the phenolic resin was treated in the same manner as in Example to obtain double-sided silk-covered 1
7) I got an i4 board.

従来例２ 桐油１モルに対しフェノ−）Ｖ１０モルを加えてからバ
ラトルソエンスル瞭２．１６ｇを加え８５　Ｃで１７５
分間反応させた後、ホルムアルデヒド６七ルヲ３フ係ホ
ルマリンで加え、アンモニア水でアルカリ性にした後、
還流温度で６０分間反応させてから拉脂Ｊ５０％になる
ようにメチルアルコールで希釈してフエノール樹脂を得
、識°フェノ−Ｉし槓１１旨を用い実施例と同様に処ル
して画面銅張積層板を得た。Conventional Example 2 To 1 mole of tung oil, add 10 moles of pheno-)V, then add 2.16 g of balatorsoensul and heat at 85C to 175%.
After reacting for minutes, 67% formaldehyde and 3% formalin were added, and after making it alkaline with aqueous ammonia,
After reacting at reflux temperature for 60 minutes, diluted with methyl alcohol to give a concentration of 50% phenol resin, the phenol resin was treated in the same manner as in Example using a phenol-I resin and a 11-piece filter to obtain screen copper. A stretched laminate was obtained.

〔発明の効果〕〔Effect of the invention〕

失施例と従来例１汐び２のフェノールＡ９［脂の収率及
び積層板のパンチング加工１生はイ３１．＆で明らかな
ように本発明の油斐注フェノ−）Ｖ　４３４脂の収率及
びパンチング加工性はよく本発明の伝れてｂることを確
＋ｚ、写シた。Lost Example and Conventional Example 1 Phenol A9 [Fast yield and punching process of laminate 1] As is clear from the figures, the yield and punching processability of the oil-injected phenol V434 fat of the present invention were confirmed to be well-performed by the present invention.

第１表 注・γ　パンチング用金型ＣごてパンチングＥ　Ｍｔを
おこないそのケｌＦ観判・、Ｃによる。Notes to Table 1: γ Punching die C with trowel Punching E Mt was performed and the results were observed according to C.

Claims (2)

【特許請求の範囲】[Claims] （１）　　フェノ−ＪＶ類と植物油とを反応させた後、
ホルムアルデヒド類と反応させた反応物に、フェノール
系、ＩＮ脂初期縮合物と溶剤とへキサミンとを添加し反
応させてなることを特徴とする清貧性フエ　ノ　−−ル
右汀脂。(1) After reacting the pheno-JVs with vegetable oil,
1. A lean phenol starch fat, which is produced by adding and reacting a phenol-based IN fat initial condensate, a solvent, and hexamine to a reaction product reacted with formaldehyde. （２）　　フェノ−）Ｖ類と植物油とを反応させた後、
ホルムアルデヒド類と反応させた反応物に、フェノール
系１列脂初期縮金物と溶剤とへギサミンとを添加し反応
させてなる油変性フェノール４Ｘｊｆ　崩を、檜加板用
基＋Ａ’　ｒこ含浸、乾燥させて得たプリプレグを所要
枚数ｆｒｒＦ　１ｙ９した積層体を、或は史に必・ｌ拝
に応じて該積層体の最外側に接若剤付蛎箔を・成ＨＬ／
て別懇側圧成形したことを特徴とする電気用、Ｒ１層板
。(2) After reacting pheno-)V with vegetable oil,
An oil-modified phenol 4Xjf mixture obtained by adding and reacting a phenolic single-series resin initial shrinkage product, a solvent, and hegisamine to a reaction product reacted with formaldehyde is impregnated with a base for cypress plating + A'r, and dried. A laminate made of the required number of prepregs (frrF 1y9), or, depending on historical needs, a laminate foil with an electromagnetic agent on the outermost side of the laminate.
An R1-layer board for electrical use, which is characterized by being separately lateral pressure-formed.