JPH05318688A - Phenolic resin laminated plate - Google Patents
Phenolic resin laminated plateInfo
- Publication number
- JPH05318688A JPH05318688A JP4133897A JP13389792A JPH05318688A JP H05318688 A JPH05318688 A JP H05318688A JP 4133897 A JP4133897 A JP 4133897A JP 13389792 A JP13389792 A JP 13389792A JP H05318688 A JPH05318688 A JP H05318688A
- Authority
- JP
- Japan
- Prior art keywords
- phenols
- tung oil
- phenol
- resin
- reaction
- 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.)
- Pending
Links
Landscapes
- Laminated Bodies (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、樹脂成分と基材とから
なる積層板において、樹脂成分が、フェノール類が十分
に付加した桐油とフェノール類とホルムアルデヒド類と
を塩基性触媒存在下で反応せしめたレゾール型の変性フ
ェノール樹脂組成物であるフェノール樹脂積層板および
その製造方法に関するものであり、さらに打抜き加工
性、機械的特性、耐湿性、電気的特性に優れた印刷配線
板に好適なフェノール樹脂積層板およびその製造方法に
関するものである。BACKGROUND OF THE INVENTION The present invention relates to a laminated plate comprising a resin component and a base material, wherein the resin component reacts tung oil with sufficient addition of phenols, phenols and formaldehydes in the presence of a basic catalyst. The present invention relates to a phenol resin laminate, which is a modified resol-type modified phenol resin composition, and a method for producing the same, and is suitable for printed wiring boards having excellent punching workability, mechanical properties, moisture resistance, and electrical properties. The present invention relates to a resin laminated plate and a method for manufacturing the same.
【０００２】[0002]
【従来の技術】フェノール樹脂は耐熱性、電気的特性、
機械的特性が優れており、印刷配線板用積層板に用いら
れている。しかし、一般にフェノール樹脂は固くて脆い
欠点を有しているため、積層板に用いた場合、打抜き加
工性が劣る欠点がある。この欠点を改良する方法として
桐油、脱水ひまし油、カシューナット核油、ウルシオー
ル類などの植物油やアルキルフェノールなどで変性され
た可撓性を有するフェノール樹脂を用いる方法が知られ
ている。しかし最近、印刷配線板が益々高密度化される
に伴って、打抜き加工性、強靱性の一層優れた積層板が
必要となっており、従来の方法ではこれらの特性が不足
する欠点がある。2. Description of the Related Art Phenolic resin has heat resistance, electrical characteristics,
It has excellent mechanical properties and is used for laminated boards for printed wiring boards. However, in general, a phenol resin has a defect that it is hard and brittle, and therefore, when it is used for a laminated plate, it has a defect that the punching workability is poor. As a method for improving this drawback, there is known a method using a vegetable oil such as tung oil, dehydrated castor oil, cashew nut kernel oil, urushiols and a flexible phenol resin modified with an alkylphenol. However, recently, as the density of printed wiring boards has become higher and higher, a laminated board having more excellent punching workability and toughness is required, and the conventional methods have a drawback that these characteristics are insufficient.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、従来の方法
では得られない打抜き加工性と強靱性とを有するフェノ
ール樹脂積層板を得んとして研究した結果、従来知られ
ている桐油変性フェノール樹脂では、桐油とフェノール
類との反応が不十分であったために種々の欠点があり、
フェノール類が十分に付加した桐油とフェノール類とホ
ルムアルデヒド類とを塩基性触媒存在下で反応せしめた
変性フェノール樹脂組成物と基材とからなる積層板が打
抜き加工性、強靱性に極めて優れるとの知見を得、更に
この知見に基づき種々研究を進めて本発明を完成するに
至ったものである。その目的とするところは打抜き加工
性、機械的特性、耐水性、電気的特性の優れた極めて強
靱なフェノール樹脂積層板およびその製造方法を提供す
るにある。DISCLOSURE OF INVENTION Problems to be Solved by the Invention The present invention has been studied to obtain a phenol resin laminate having punching workability and toughness which cannot be obtained by the conventional method. Then, there were various drawbacks because the reaction between tung oil and phenols was insufficient,
A laminated plate composed of a base material and a modified phenolic resin composition obtained by reacting tung oil sufficiently added with phenols, phenols and formaldehydes in the presence of a basic catalyst is extremely excellent in punching workability and toughness. The present invention was completed by obtaining knowledge and further conducting various researches based on this knowledge. An object of the invention is to provide an extremely tough phenol resin laminate excellent in punching workability, mechanical properties, water resistance and electrical properties, and a method for producing the same.
【０００４】[0004]
【課題を解決するための手段】本発明は、樹脂成分を基
材に含浸・乾燥させ、所定量積層し、加熱加圧してなる
積層板において、樹脂成分が、反応可能な二重結合にフ
ェノール類が十分に付加した桐油とフェノール類とホル
ムアルデヒド類とが塩基性触媒存在下で反応せしめられ
た変性フェノール樹脂組成物であることを特徴とするフ
ェノール樹脂積層板であり、さらに変性フェノール樹脂
組成物が、フェノール類（Ａ）と桐油（Ｂ）とを重量比 Ｘ ＜ Ａ／Ｂ ＜ 10 Ｘ＝0.024×（ｆｗ−１）× Ｍ／ｆｎ （ｆｎはフェノール類の数平均官能数、ｆｗはフェノー
ル類の量平均官能数、Ｍはフェノール類の数平均分子量
である）で酸性触媒存在下で反応させ、フェノール類が
十分に付加した桐油とフェノール類とからなる反応組成
物を得、該反応組成物より未反応フェノール類の所定量
（Ｃ）を重量比 （Ａ−Ｃ）／Ｂ＝0.4〜1.3 となるように除去し、次いで塩基性触媒存在下でホルム
アルデヒド類と反応させて得られる変性フェノール樹脂
であるフェノール樹脂積層板である。According to the present invention, in a laminate obtained by impregnating and drying a resin component in a substrate, laminating a predetermined amount, and heating and pressurizing the resin component, the resin component forms a reactive double bond with phenol. A phenolic resin laminate characterized by being a modified phenolic resin composition obtained by reacting tung oil sufficiently added with phenols, phenols and formaldehydes in the presence of a basic catalyst, and further a modified phenolic resin composition. Is a weight ratio of phenols (A) and tung oil (B) X <A / B <10 X = 0.024 x (fw-1) x M / fn (fn is the number average functional number of phenols, fw is phenol) (The number average molecular weight of the phenols, M is the number average molecular weight of the phenols) in the presence of an acidic catalyst to obtain a reaction composition composed of tung oil and phenols to which phenols are sufficiently added. A modified phenol obtained by removing a predetermined amount (C) of unreacted phenols from the product so that the weight ratio (AC) /B=0.4 to 1.3, and then reacting with formaldehyde in the presence of a basic catalyst. It is a phenol resin laminated plate which is a resin.
【０００５】本発明における桐油とは、エレオステアリ
ン酸のグリセリンエステルを主成分とする天然に産する
桐油を言い、エレオステアリン酸基中にある共役した３
個の二重結合がフェノール類との反応性を有しており、
この内２個までフェノール類が通常の反応条件下で付加
し得る性質を有している。本発明におけるフェノール類
が十分に付加した桐油とは、上記エレオステアリン酸基
の反応性を有する２重結合のうちの２個の二重結合の殆
どないし全てがフェノール類のオルトまたはパラ位と化
学結合したものを言う。The tung oil in the present invention refers to naturally occurring tung oil mainly composed of glycerin ester of eleostearic acid, which is a conjugated 3 atom in the eleostearic acid group.
The double bond of each has reactivity with phenols,
Up to two of these phenols can be added under normal reaction conditions. The tung oil with sufficient addition of phenols in the present invention means that most or all of the two double bonds among the double bonds having reactivity of the eleostearic acid group are in the ortho or para position of the phenols. It refers to a chemically bonded substance.
【０００６】本発明において用いられるフェノール類
は、フェノール、クレゾール、キシレノール、P-t-ブチ
ルフェノール、ビスフェノールＡ、レゾルシンなどの１
価並びに２価のフェノール類およびそれらの置換体の１
種以上が用いられ、少なくとも３官能以上のフェノール
類を50モル％以上含有するフェノール類が用いられる。
好ましいフェノール類はフェノールおよびクレゾールで
ある。The phenols used in the present invention include phenol, cresol, xylenol, Pt-butylphenol, bisphenol A, resorcin and the like.
Of dihydric and dihydric phenols and their substitution products
Phenols containing at least 50 mol% of trifunctional or higher functional phenols are used.
Preferred phenols are phenol and cresol.
【０００７】本発明において用いられるホルムアルデヒ
ド類は、ホルマリン、パラホルムアルデヒドなどであ
る。The formaldehydes used in the present invention are formalin, paraformaldehyde and the like.
【０００８】本発明において、フェノール類が十分に付
加した桐油とフェノール類とホルムアルデヒド類とを塩
基性触媒存在下で反応せしめた変性フェノール樹脂組成
物の組成は、桐油に対し付加したものを含めた全フェノ
ール類が重量比で0.4〜1.3のものが好ましい。割合が1.
3以上では桐油成分の含有量が少なくなり積層板の打抜
き加工性が損なわれ、0.4以下では桐油成分が多くな
り、積層板の強度が低下する。In the present invention, the composition of the modified phenolic resin composition obtained by reacting tung oil sufficiently added with phenols, phenols and formaldehydes in the presence of a basic catalyst includes those added to tung oil. It is preferable that all phenols have a weight ratio of 0.4 to 1.3. The ratio is 1.
When it is 3 or more, the content of the tung oil component is small and the punching workability of the laminated plate is impaired. When it is 0.4 or less, the tung oil component is large and the strength of the laminated plate is lowered.
【０００９】本発明における塩基性触媒としては、アン
モニア、トリエチルアミン、エチレンジアミン、ヘキサ
メチレンテトラミン、トリエタノールアミン、水酸化バ
リウムなどのような触媒をあげることができる。Examples of the basic catalyst in the present invention include catalysts such as ammonia, triethylamine, ethylenediamine, hexamethylenetetramine, triethanolamine and barium hydroxide.
【００１０】本発明で用いられる基材としては、クラフ
ト紙、リンター紙のようなセルロースを主成分とする
紙、ガラス布、ガラス不織布物のようなガラス布、ポリ
エステル布、アラミド繊維布のような合成繊維布、帆布
などをあげることができ、またこれらが処理剤で処理さ
れた基材を用いることができる。処理剤としては、低縮
合のレゾール型フェノール樹脂、メラミン樹脂、シラン
カップリング剤などを例示することができる。Examples of the substrate used in the present invention include kraft paper, paper containing cellulose as a main component such as linter paper, glass cloth, glass cloth such as glass non-woven cloth, polyester cloth and aramid fiber cloth. Examples thereof include synthetic fiber cloth and canvas, and a base material obtained by treating these with a treating agent can be used. Examples of the treating agent include low-condensation resol-type phenol resin, melamine resin, and silane coupling agent.
【００１１】本発明においては、樹脂成分を基材に含浸
・乾燥させて得られるプリプレグを所定量積層し、必要
によりこれに銅箔、アルミニウム箔などを重ねて加熱加
圧積層成形を行なう。In the present invention, a predetermined amount of a prepreg obtained by impregnating a base material with a resin component and drying is laminated, and if necessary, a copper foil, an aluminum foil or the like is laminated on the prepreg to carry out heat pressure lamination molding.
【００１２】フェノール類が十分に付加した桐油とフェ
ノール類とホルムアルデヒド類とを塩基性触媒存在下で
反応せしめた変性フェノール樹脂組成物中の桐油に対す
るフェノール類の割合として、重量比で0.4〜1.3のもの
を得る場合、桐油に対してフェノール類を、重量比で0.
4〜1.3で混合して反応させる方法で得ることは困難であ
る。この範囲の重量比での反応では、桐油中のエレオス
テアリン酸基の二重結合にフェノール類が十分に付加す
る前にゲル化するので、付加が不十分の状態で反応を完
了し、これをホルムアルデヒドと塩基性触媒下で反応さ
せざるを得ず、その結果、得られる樹脂は結合が不完全
であるため、可撓性と強靭性とに限界があり、これを用
いたフェノール樹脂積層板は打抜き加工性と強靭性とを
さらに向上させることは困難である。The ratio of phenols to tung oil in a modified phenolic resin composition obtained by reacting tung oil with sufficient addition of phenols, phenols and formaldehydes in the presence of a basic catalyst is 0.4 to 1.3 by weight ratio. To obtain a product, phenols are added to tung oil in a weight ratio of 0.
It is difficult to obtain it by a method of mixing and reacting with 4 to 1.3. In the reaction in the weight ratio within this range, the phenol gels before the sufficient addition to the double bond of the eleostearic acid group in tung oil, so the reaction is completed in an insufficient addition state. Is forced to react with formaldehyde under a basic catalyst, and as a result, the resulting resin has incomplete bonding, so there is a limit to flexibility and toughness. It is difficult to further improve punching workability and toughness.
【００１３】本発明においては、フェノール類（Ａ）と
桐油（Ｂ）とを重量比 Ｘ ＜ Ａ／Ｂ ＜ 10 Ｘ＝0.024×（ｆｗ−１）× Ｍ／ｆｎ （ｆｎはフェノール類の数平均官能数、ｆｗはフェノー
ル類の量平均官能数、Ｍはフェノール類の数平均分子量
である）で酸性触媒存在下で反応させ、フェノール類が
十分に付加した桐油とフェノール類とからなる反応組成
物を得、該反応組成物より未反応フェノール類の所定量
（Ｃ）を重量比 （Ａ−Ｃ）／Ｂ＝0.4〜1.3 となるように除去し、次いで塩基性触媒存在下でホルム
アルデヒド類と反応させ、フェノール類が十分に付加し
た桐油とフェノール類とホルムアルデヒド類とを塩基性
触媒存在下で反応させて得られる変性フェノール樹脂組
成物を用いることにより、優れた打抜き加工性と高い強
靭性とを有するフェノール樹脂積層板を得ることができ
る。In the present invention, the weight ratio of phenols (A) and tung oil (B) is X <A / B <10 X = 0.024 x (fw-1) x M / fn (fn is the number average of phenols). (Functional number, fw is the amount average functional number of phenols, M is the number average molecular weight of phenols) and reacted in the presence of an acidic catalyst, and a reaction composition comprising tung oil and phenols with sufficient addition of phenols From the reaction composition, a predetermined amount (C) of unreacted phenols is removed so that the weight ratio (AC) /B=0.4 to 1.3, and then the reaction is performed with formaldehydes in the presence of a basic catalyst. By using a modified phenolic resin composition obtained by reacting tung oil sufficiently added with phenols, phenols and formaldehydes in the presence of a basic catalyst, excellent punching processability and high toughness are obtained. Existence It can be obtained that phenolic resin laminate.
【００１４】本発明のフェノール類の数平均官能数と
は、フェノール類のベンゼン核上の反応性位置（即ち、
フェノール類の官能基）の合計モル数をフェノール類の
合計モル数で除した数を言う。本発明のフェノール類の
量平均官能数とは、フェノール類の官能基数の二乗とフ
ェノール類のモル数との積の合計値を、フェノール類の
官能基の合計モル数で除した数を言う。本発明のフェノ
ール類の数平均分子量とは、フェノール類の合計重量を
フェノール類の合計モル数で除した数を言う。The number average functionality of the phenols of the present invention means the reactive position of the phenols on the benzene nucleus (ie,
The total number of moles of phenolic functional groups) is divided by the total number of moles of phenols. The amount average functional number of phenols of the present invention means the number obtained by dividing the total product of the square of the number of functional groups of phenols and the number of moles of phenols by the total number of moles of functional groups of phenols. The number average molecular weight of the phenols of the present invention means the number obtained by dividing the total weight of the phenols by the total number of moles of the phenols.
【００１５】本発明において、フェノール類（Ａ）と桐
油（Ｂ）との反応比は、重量比で（Ａ）／（Ｂ）＝Ｘ〜
10である。（Ａ）／（Ｂ）がＸより少ないと、桐油にフ
ェノール類が十分付加する前にゲル化してしまうか、著
しく粘度が増大し、桐油にフェノール類が十分に付加し
た反応組成物を得ることが困難となる。また10以上で
は、未反応フェノール類の除去量が増加し、経済的に不
利となる。好ましい反応比（Ａ）／（Ｂ）はＸ〜５であ
る。該反応によって、フェノール類が十分に付加した桐
油と未反応のフェノール類とからなる反応組成物が得ら
れる。In the present invention, the reaction ratio of the phenols (A) and tung oil (B) is (A) / (B) = X ~ by weight.
Is 10. When (A) / (B) is less than X, gelation occurs before the phenols are sufficiently added to the tung oil, or the viscosity is remarkably increased to obtain a reaction composition in which the phenols are sufficiently added to the tung oil. Becomes difficult. If it is 10 or more, the amount of unreacted phenols removed increases, which is economically disadvantageous. The preferred reaction ratio (A) / (B) is X-5. By the reaction, a reaction composition composed of tung oil sufficiently added with phenols and unreacted phenols is obtained.
【００１６】本発明において、フェノール類（Ａ）と桐
油（Ｂ）との反応に用いられる酸性触媒としては、パラ
トルエンスルホン酸、メタンスルホン酸、三弗化ほう
素、塩化第二錫、塩化第二鉄、パーフロロメタンスルホ
ン酸などのようなフリーデルクラフト形触媒をあげるこ
とができる。該酸性触媒の使用量は特に制限はないが、
反応物の合計量に対して0.01〜0.5重量％が好ましい。
また該反応は50〜120℃の温度で行なうのが好ましい。1
20℃以上では桐油のエステル結合が分解切断されるので
好ましくない。また、必要によりトルエンなどの溶媒中
で反応させてもよい。In the present invention, the acidic catalyst used in the reaction of the phenols (A) and tung oil (B) includes paratoluenesulfonic acid, methanesulfonic acid, boron trifluoride, stannic chloride, and stannic chloride. Friedel-Crafts type catalysts such as diiron, perfluoromethanesulfonic acid and the like can be mentioned. The amount of the acidic catalyst used is not particularly limited,
0.01 to 0.5% by weight, based on the total amount of reactants, is preferred.
The reaction is preferably carried out at a temperature of 50 to 120 ° C. 1
Above 20 ° C, ester bonds of tung oil are decomposed and cleaved, which is not preferable. If necessary, the reaction may be carried out in a solvent such as toluene.
【００１７】本発明において、フェノール類が十分に付
加した桐油とフェノール類とからなる反応組成物から未
反応フェノール類の所定量（Ｃ）が重量比で （Ａ−Ｃ）／Ｂ＝0.4〜1.3 となるように除去され、本発明の変性フェノール樹脂組
成物の好ましいフェノール類の割合に調節される。次い
で塩基性触媒存在下で反応させるホルムアルデヒド類の
量は、所定量の未反応フェノール類除去後の全フェノー
ル類１モルに対して、ホルムアルデヒドとして0.6〜1.5
モルである。該反応は前記塩基性触媒下で60〜100℃の
温度で行なうのが好ましい。必要によりトルエンなどの
溶媒中で反応させてもよい。In the present invention, a predetermined amount (C) of unreacted phenols is (A-C) /B=0.4 to 1.3 in a weight ratio from a reaction composition composed of tung oil sufficiently added with phenols and phenols. And the ratio of the preferred phenols in the modified phenolic resin composition of the present invention is adjusted. Then, the amount of formaldehyde to be reacted in the presence of a basic catalyst is 0.6 to 1.5 as formaldehyde based on 1 mol of all phenols after removal of a predetermined amount of unreacted phenols.
It is a mole. The reaction is preferably carried out under the above-mentioned basic catalyst at a temperature of 60 to 100 ° C. If necessary, the reaction may be carried out in a solvent such as toluene.
【００１８】本発明において、フェノール類（Ａ）と桐
油（Ｂ）との反応比の下限を表わすＸは次式 Ｘ＝0.024×（ｆｗ−１）× Ｍ／ｆｎ で表され、実験値とフローリーのゲル化条件式とにより
求めることができる。In the present invention, X, which represents the lower limit of the reaction ratio between the phenols (A) and tung oil (B), is represented by the following formula: X = 0.024 × (fw-1) × M / fn The gelling conditional expression of
【００１９】本発明のフェノール樹脂積層板は、該レゾ
ール型変性フェノール樹脂組成物の溶液をシート状基材
に含浸して乾燥し、３〜10枚積層して、２枚の熱板間で
加熱加圧し、樹脂を硬化させて１〜10mmの厚さの板状体
とすることにより得ることができる。含浸させる樹脂の
量としては、樹脂と基材の合計量に対して乾燥基準で30
〜70重量％である。加熱加圧条件としては、120〜180℃
の温度で、50〜150kg／cm2の圧力である。The phenol resin laminate of the present invention is obtained by impregnating a sheet-like base material with a solution of the resol-type modified phenol resin composition and drying the laminate, heating 3 to 10 sheets, and heating between two hot plates. It can be obtained by pressurizing and curing the resin to form a plate-shaped body having a thickness of 1 to 10 mm. The amount of resin to be impregnated is 30 on a dry basis with respect to the total amount of resin and substrate.
~ 70% by weight. As heating and pressurizing conditions, 120 to 180 ℃
At a pressure of 50-150 kg / cm 2 .
【００２０】本発明において、桐油の内の30重量％まで
を、脱水ひまし油、亜麻仁油などの他の乾性油で適宜置
き換えることができる。また、ロジン、アニリン、カシ
ュナット核油などの他の変性剤で20％以内で適宜変性す
ることができる。また、基材に含浸させる樹脂として
は、全樹脂の50重量％まで他のフェノール樹脂を適宜併
用することができる。In the present invention, up to 30% by weight of tung oil can be appropriately replaced with other drying oil such as dehydrated castor oil and linseed oil. Further, it can be appropriately modified within 20% with other modifiers such as rosin, aniline, and Kashnut kernel oil. As the resin with which the base material is impregnated, up to 50% by weight of the total resin can be appropriately used together with other phenol resins.
【００２１】[0021]
【実施例】以下実施例により本発明を例示する。The present invention will be illustrated by the following examples.
【００２２】（実施例１）フェノール類として、フェノ
ール（Ｉ）を準備した。フェノールの官能数は３、分子
量は94の単独成分である。したがって、その数平均およ
び量平均官能数は３であり、数平均分子量は94である。
Ｘは1.504である。５リットルの撹拌機付きフラスコに
フェノール（Ｉ）を2500ｇ、桐油（II）を800ｇ仕込み
｛重量比（Ｉ）／（II）＝3.125｝、適量のパラトルエ
ンスルホン酸を触媒として、100℃で桐油の官能基の反
応が完結するまで反応させた。反応に要した時間は４時
間であった。桐油の官能基の反応状態は核磁気共鳴スペ
クトルで追跡した。得られた反応組成物は、フェノール
が十分に付加した桐油が36重量％、未反応フェノールが
64重量％であった。この反応組成物をトリエタノールア
ミンで中和し、反応組成物中の未反応フェノールが34重
量％になるまで、真空下で未反応フェノールを蒸発除去
し、仕込み桐油に対し、結合フェノールも含めた全フェ
ノール成分の重量比が1.25の混合物を得た。この混合物
の蒸気圧平衡法で測定した平均分子量は253であった。
次いで、これに触媒としてアンモニアを適量、パラホル
ムアルデヒドを430ｇ、トルエンを500ｇ添加し、樹脂の
150℃の熱板上でのゲル化時間が６分になるまで80℃で
反応させた後、真空下で脱水、脱溶媒を行い、トルエン
とメタノールの１／１の混合溶剤を添加して冷却し、樹
脂分52重量％のレゾール型変性フェノール樹脂組成物
（樹脂１）を得た。Example 1 Phenol (I) was prepared as a phenol. Phenol is a single component having a functional number of 3 and a molecular weight of 94. Therefore, its number average and number average functional number is 3, and number average molecular weight is 94.
X is 1.504. Charge a flask (5 liters) equipped with a stirrer with 2500 g of phenol (I) and 800 g of tung oil (II) {weight ratio (I) / (II) = 3.125}, and tung oil at 100 ° C using an appropriate amount of paratoluene sulfonic acid as a catalyst. The reaction was continued until the reaction of the functional group of 1 was completed. The time required for the reaction was 4 hours. The reaction state of functional groups of tung oil was traced by nuclear magnetic resonance spectroscopy. The reaction composition obtained contained 36% by weight of tung oil with sufficient addition of phenol and unreacted phenol.
It was 64% by weight. The reaction composition was neutralized with triethanolamine, and the unreacted phenol was removed by evaporation under vacuum until the unreacted phenol in the reaction composition became 34% by weight, and the bound phenol was also included in the charged tung oil. A mixture having a weight ratio of all phenol components of 1.25 was obtained. The average molecular weight of this mixture measured by the vapor pressure equilibrium method was 253.
Then, to this, an appropriate amount of ammonia as a catalyst, 430 g of paraformaldehyde and 500 g of toluene were added to
After reacting at 80 ° C until gelling time on a hot plate at 150 ° C reaches 6 minutes, dehydration and desolvation are performed under vacuum, and a 1/1 mixed solvent of toluene and methanol is added to cool. Then, a resol type modified phenolic resin composition (resin 1) having a resin content of 52% by weight was obtained.
【００２３】また、フェノール1000ｇ、37％ホルマリン
9800ｇ、トリエチルアミン20ｇを混合して60℃で２時間
反応させ、次いで減圧下で濃縮し、これをメタノール／
水＝80／20の混合溶剤で希釈して樹脂分50重量％の水溶
性低分子フェノール樹脂溶液（樹脂２）を得た。次い
で、樹脂２をクラフト紙に含浸して乾燥し、樹脂分10.5
％の処理基材を得た。この処理基材に樹脂２を含浸して
乾燥し、全樹脂分56％のプリプレグを得た。これを８枚
積層し、片側に35μmの銅箔を重ね合わせ、積層板用プ
レスの２枚の熱板間で160℃、80〜90kg／cm2で60分間加
熱加圧し、厚さ1.6mmの銅張りフェノール樹脂積層板を
得た。Further, 1000 g of phenol, 37% formalin
9800 g and triethylamine 20 g were mixed and reacted at 60 ° C. for 2 hours, and then concentrated under reduced pressure.
It was diluted with a mixed solvent of water = 80/20 to obtain a water-soluble low-molecular phenol resin solution (resin 2) having a resin content of 50% by weight. Then, kraft paper is impregnated with resin 2 and dried to give a resin content of 10.5
% Of treated substrate was obtained. The treated base material was impregnated with resin 2 and dried to obtain a prepreg having a total resin content of 56%. Eight pieces of this are laminated, and a copper foil of 35 μm is laminated on one side, and heated and pressed at 160 ° C. and 80 to 90 kg / cm 2 for 60 minutes between two hot plates of a laminated plate press, and a thickness of 1.6 mm. A copper-clad phenolic resin laminate was obtained.
【００２４】（実施例２）フェノール類として、m-クレ
ゾール60％、p-クレゾール40％からなる混合クレゾール
（III）を準備した。混合クレゾールの数平均官能数は
2.600、量平均官能数は2.692、数平均分子量は108であ
る。Ｘは1.687である。５リットルの撹拌機付きフラス
コに混合クレゾール（III）を2500ｇ、桐油（II）を500
ｇ仕込み｛重量比（III）／（II）＝５｝、適量のパラ
トルエンスルホン酸を触媒として、100℃で桐油の官能
基の反応が完結するまで反応させた。反応に要した時間
は4.5時間であった。桐油の官能基の反応状態は核磁気
共鳴スペクトルで追跡した。得られた反応組成物は、ク
レゾールが十分付加した桐油が26重量％、未反応クレゾ
ールが74重量％であった。この反応組成物をトリエタノ
ールアミンで中和し、反応組成物中の未反応クレゾール
が22重量％になるまで、真空下で未反応クレゾールを蒸
発除去し、仕込み桐油に対し、結合クレゾールも含めた
全クレゾール成分の重量比が1.0の混合物を得た。この
混合物の蒸気圧平衡法で測定した平均分子量は390であ
った。次いで、これに触媒としてトリエチルアミンを適
量、パラホルムアルデヒドを400ｇ、トルエンを500ｇ添
加し、樹脂の150℃の熱板上でのゲル化時間が６分にな
るまで80℃で反応させた後、真空下で脱水、脱溶媒を行
いトルエンとメタノールの１／１の混合溶剤を添加して
冷却し、樹脂分50重量％のレゾール型変性フェノール樹
脂組成物（樹脂３）を得た。次いで、実施例１で得た処
理基材に実施例１と同様にして樹脂３を含浸して乾燥
し、以下同様にして厚さ1.6mmの銅張りフェノール樹脂
積層板を得た。Example 2 As a phenol, mixed cresol (III) consisting of 60% m-cresol and 40% p-cresol was prepared. The number average functionality of mixed cresol is
2.600, the number average functional number is 2.692, and the number average molecular weight is 108. X is 1.687. In a 5 liter flask equipped with a stirrer, 2500 g of mixed cresol (III) and 500 g of tung oil (II) were mixed.
g Charged (weight ratio (III) / (II) = 5), using a proper amount of paratoluenesulfonic acid as a catalyst, the reaction was carried out at 100 ° C. until the reaction of the functional group of tung oil was completed. The time required for the reaction was 4.5 hours. The reaction state of functional groups of tung oil was traced by nuclear magnetic resonance spectroscopy. The reaction composition thus obtained contained 26% by weight of tung oil with sufficient addition of cresol and 74% by weight of unreacted cresol. This reaction composition was neutralized with triethanolamine, the unreacted cresol in the reaction composition was removed by evaporation under vacuum until the unreacted cresol in the reaction composition became 22% by weight, and the added cresol was also included in the tung oil charged. A mixture with a weight ratio of all cresol components of 1.0 was obtained. The average molecular weight of this mixture measured by the vapor pressure equilibrium method was 390. Then, triethylamine as a catalyst, 400 g of paraformaldehyde and 500 g of toluene were added thereto, and the mixture was reacted at 80 ° C. until the gelation time of the resin on a hot plate at 150 ° C. reached 6 minutes, and then under vacuum. Then, the mixture was dehydrated and desolvated, and a 1/1 mixed solvent of toluene and methanol was added and cooled to obtain a resol-type modified phenol resin composition (resin 3) having a resin content of 50% by weight. Then, the treated substrate obtained in Example 1 was impregnated with resin 3 in the same manner as in Example 1 and dried, and a copper-clad phenolic resin laminate having a thickness of 1.6 mm was obtained in the same manner.
【００２５】（比較例１）５リットルの撹拌機付きフラ
スコにフェノール（Ｉ）を1000ｇ、桐油（II）を800ｇ
仕込み｛重量比（Ｉ）／（II）＝1.25｝、適量のパラト
ルエンスルホン酸を触媒として、100℃で反応させた。
反応開始後1.5時間経過すると、急に粘度が上昇し、攪
拌困難となって、ゲル化した。そこで、反応開始後１時
間で、まだゲル化が起こる前に反応を停止し、トリエタ
ノールアミンを添加して中和し、冷却した。この反応混
合物の桐油の官能基の反応率は核磁気共鳴スペクトルで
測定したところ、55％であった。得られた反応組成物
は、フェノールが不十分に付加した桐油57重量％、未反
応フェノールが43重量％であった。またこの反応組成物
の蒸気圧平衡法で測定した平均分子量は198であった。
次いで、これに触媒としてアンモニアを適量、パラホル
ムアルデヒドを430ｇ、トルエンを500ｇ添加し、樹脂の
150℃の熱板上でのゲル化時間が６分になるまで80℃で
反応させた後、真空下で脱水、脱溶媒を行い、トルエン
とメタノールの１／１の混合溶剤を添加して冷却し、樹
脂分52重量％のレゾール型変性フェノール樹脂組成物
（樹脂４）を得た。次いで、実施例１で得た処理基材に
実施例１と同様にして樹脂４を含浸して乾燥し、以下同
様にして厚さ1.6mmの銅張りフェノール樹脂積層板を得
た。(Comparative Example 1) 1000 g of phenol (I) and 800 g of tung oil (II) were placed in a 5-liter flask equipped with a stirrer.
Charged (weight ratio (I) / (II) = 1.25}, and reacted at 100 ° C. using an appropriate amount of paratoluenesulfonic acid as a catalyst.
After 1.5 hours from the start of the reaction, the viscosity suddenly increased, making it difficult to stir and gel. Therefore, one hour after the start of the reaction, the reaction was stopped before gelation still occurred, triethanolamine was added to neutralize, and the mixture was cooled. The reaction rate of functional groups of tung oil in this reaction mixture was 55% as measured by nuclear magnetic resonance spectrum. The reaction composition obtained was 57% by weight of tung oil with insufficient addition of phenol and 43% by weight of unreacted phenol. The average molecular weight of this reaction composition measured by the vapor pressure equilibrium method was 198.
Then, to this was added an appropriate amount of ammonia as a catalyst, 430 g of paraformaldehyde and 500 g of toluene, and
After reacting at 80 ° C until gelling time on a hot plate at 150 ° C reaches 6 minutes, dehydration and desolvation are performed under vacuum, and a 1/1 mixed solvent of toluene and methanol is added to cool. Then, a resole-type modified phenolic resin composition (resin 4) having a resin content of 52% by weight was obtained. Then, the treated base material obtained in Example 1 was impregnated with the resin 4 and dried in the same manner as in Example 1 to obtain a copper-clad phenol resin laminate having a thickness of 1.6 mm.
【００２６】実施例１、２および比較例１で得た、フェ
ノール樹脂積層板の特性を表１に示した。実施例１およ
び２の本発明のフェノール樹脂積層板は、比較例１の積
層板に比べて、絶縁抵抗、曲げ強度、曲げ弾性率、引張
り強度および打抜き加工性が優れている。とりわけ、従
来は、機械的特性を向上させると、打抜き加工性が低下
する問題があったが、本発明のフェノール樹脂積層板は
機械的強度と打抜き加工性との両方が向上していること
がわかる。The characteristics of the phenolic resin laminates obtained in Examples 1 and 2 and Comparative Example 1 are shown in Table 1. The phenolic resin laminates of Examples 1 and 2 of the present invention are superior to the laminate of Comparative Example 1 in insulation resistance, flexural strength, flexural modulus, tensile strength and punching workability. In particular, conventionally, when the mechanical properties were improved, there was a problem that the punching workability was deteriorated, but the phenolic resin laminate of the present invention has improved mechanical strength and punching workability. Recognize.
【００２７】[0027]
【表１】 [Table 1]
【００２８】このように、本発明の変性フェノール樹脂
積層板は、従来の同様の変性率の樹脂に比べて、可撓性
と強靭性に優れている。また、本発明のフェノール樹脂
積層板の製造方法により、はじめて優れたフェノール樹
脂積層板を得ることが可能になった。As described above, the modified phenolic resin laminate of the present invention is superior in flexibility and toughness as compared with the conventional resin having the same modification rate. Further, the method for producing a phenol resin laminated plate of the present invention makes it possible to obtain an excellent phenol resin laminated plate for the first time.
【００２９】[0029]
【発明の効果】本発明のフェノール樹脂積層板は、打抜
き加工性、耐水性、電気的特性、機械的特性が極めて優
れ、特に優れた打抜き加工性と高い強靭性とを兼ね備え
た性質を有しており、印刷配線板に好適に用いることが
できる。このように本発明のフェノール樹脂積層板が従
来の方法では得られなかった優れた打抜き加工性、強靭
性、電気的特性および機械的特性を有する理由は充分に
は明らかではないが、本発明で用いている変性フェノー
ル樹脂組成物の中の桐油の官能基に十分ないし完全にフ
ェノール類が付加しているため、硬化物の架橋がより十
分にでき、さらに未反応の桐油、結合不十分な桐油が殆
どないためと考えられる。また、このような桐油とフェ
ノール類とが十分に結合した高い変性率の樹脂によるフ
ェノール樹脂積層板は従来、得ることが困難であった
が、本発明によりはじめて可能になった。EFFECT OF THE INVENTION The phenolic resin laminate of the present invention has extremely excellent punching workability, water resistance, electrical properties and mechanical properties, and has a property of particularly excellent punching workability and high toughness. Therefore, it can be suitably used for a printed wiring board. Thus, the reason why the phenolic resin laminate of the present invention has excellent punching workability, toughness, electrical properties and mechanical properties which cannot be obtained by the conventional method is not fully clear, but in the present invention, Since the functional groups of tung oil in the modified phenolic resin composition used are sufficiently or completely added with phenols, the cured product can be more fully crosslinked, and unreacted tung oil and tung oil with insufficient bonding It is considered that there is almost no. Further, it has been difficult to obtain a phenol resin laminated plate of such a resin having a high modification rate in which tung oil and phenols are sufficiently bound, but the present invention made it possible for the first time.
Claims (3)
量積層し、加熱加圧してなる積層板において、樹脂成分
が、反応可能な二重結合にフェノール類が十分に付加し
た桐油とフェノール類とホルムアルデヒド類とが塩基性
触媒存在下で反応せしめられた変性フェノール樹脂組成
物であることを特徴とするフェノール樹脂積層板。1. A laminated board obtained by impregnating and drying a resin component on a substrate, laminating a predetermined amount thereof, and heating and pressurizing the resin component, and tung oil in which phenols are sufficiently added to a reactive double bond. A phenol resin laminate, which is a modified phenol resin composition obtained by reacting phenols and formaldehyde in the presence of a basic catalyst.
ル類（Ａ）と桐油（Ｂ）とを重量比 Ｘ ＜ Ａ／Ｂ ＜ 10 Ｘ＝0.024×（ｆｗ−１）× Ｍ／ｆｎ （ｆｎはフェノール類の数平均官能数、ｆｗはフェノー
ル類の量平均官能数、Ｍはフェノール類の数平均分子量
である）で酸性触媒存在下で反応させ、フェノール類が
十分に付加した桐油とフェノール類とからなる反応組成
物を得、該反応組成物より未反応フェノール類の所定量
（Ｃ）を重量比 （Ａ−Ｃ）／Ｂ＝0.4〜1.3 となるように除去し、次いで塩基性触媒存在下でホルム
アルデヒド類と反応させて得られる変性フェノール樹脂
である請求項１記載のフェノール樹脂積層板。2. The modified phenolic resin composition comprises a phenol (A) and tung oil (B) in a weight ratio of X <A / B <10 X = 0.024 × (fw-1) × M / fn (fn is phenol). From the tung oil and phenols with sufficient addition of phenols by reacting them in the presence of an acidic catalyst with the number average functionality of benzene, fw is the weight average functionality of phenols, and M is the number average molecular weight of phenols). To obtain a predetermined amount (C) of unreacted phenols from the reaction composition so that the weight ratio (AC) /B=0.4 to 1.3, and then in the presence of a basic catalyst. The phenol resin laminate according to claim 1, which is a modified phenol resin obtained by reacting with formaldehydes.
れている請求項１又は２記載のフェノール樹脂積層板。3. The phenol resin laminate according to claim 1, wherein a copper foil is laminated on at least one outermost layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4133897A JPH05318688A (en) | 1992-05-26 | 1992-05-26 | Phenolic resin laminated plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4133897A JPH05318688A (en) | 1992-05-26 | 1992-05-26 | Phenolic resin laminated plate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05318688A true JPH05318688A (en) | 1993-12-03 |
Family
ID=15115665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4133897A Pending JPH05318688A (en) | 1992-05-26 | 1992-05-26 | Phenolic resin laminated plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05318688A (en) |
-
1992
- 1992-05-26 JP JP4133897A patent/JPH05318688A/en active Pending
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