JPH02143857A - Continuous manufacture of laminated sheet - Google Patents

Continuous manufacture of laminated sheet

Info

Publication number
JPH02143857A
JPH02143857A JP63297404A JP29740488A JPH02143857A JP H02143857 A JPH02143857 A JP H02143857A JP 63297404 A JP63297404 A JP 63297404A JP 29740488 A JP29740488 A JP 29740488A JP H02143857 A JPH02143857 A JP H02143857A
Authority
JP
Japan
Prior art keywords
base material
heating
resin liquid
impregnation
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.)
Pending
Application number
JP63297404A
Other languages
Japanese (ja)
Inventor
Atsuhiko Matsuda
松田 淳彦
Norikazu Mimura
三村 範一
Takeshi Onoda
小野田 武士
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Holdings Corp
Original Assignee
Showa Denko KK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Showa Denko KK filed Critical Showa Denko KK
Priority to JP63297404A priority Critical patent/JPH02143857A/en
Priority to EP19890111478 priority patent/EP0347936A3/en
Priority to KR1019890008758A priority patent/KR910000355A/en
Publication of JPH02143857A publication Critical patent/JPH02143857A/en
Pending legal-status Critical Current

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Abstract

PURPOSE:To form a laminated sheet which is practically free from residual bubbles and has high base material content, by a method wherein the base material is heated and pressurized while contriving infiltration of an impregnating resin solution into the whole of the base material by making use of a double belt press constituted of an endless belt. CONSTITUTION:A thermosetting resin solution which does not generate a reactive by-product such as gas or a liquid is infiltrated into a long-sized base material 1. Then a plurality sheets of the base materials impregnated with the resin are piled upon each other, the resin solution is cured through heating and pressurization and unified. The above-mentioned impregnating process and heating and pressurization process are arranged almost vertically to each other and partial impregnation of the base material 1 with the resin solution 3 is performed in the impregnation process. Infiltration of partial impregnation of the resin solution 3 into the whole of the base material 1 is contrived by making use of a double belt press 11 possessing practically even pressure extending over the whole sphere of a pressurizing zone, in the heating and pressurizing process. Then since heating and pressurization, are performed, discharge of the impregnating resin solution other than small quantity of adhesion amount is streamed down with action of gravity and recovered at the time of the pressurization with the double belt press 11. Therefore, problem of contamination is not generated and a laminated sheet which is free from the bubbles and having high content of the base material can be formed continuously.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、特に各種電気絶縁用、プリント基板用等に好
適な積層板を連続的に製造する方法に関する。
DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for continuously producing a laminated board suitable for various electrical insulations, printed circuit boards, etc., in particular.

〔従来の技術〕[Conventional technology]

クラフト紙などの長尺の基材に空隙を残すことなく熱硬
化性樹脂液を充分含浸し、この含浸基材を複数枚重ね合
せ、加圧し、または加圧することなく加熱して樹脂液を
硬化させて連続的に積層板を製造することは従来より行
われている。
A long base material such as kraft paper is sufficiently impregnated with thermosetting resin liquid without leaving any voids, and multiple sheets of this impregnated base material are stacked together and the resin liquid is cured by applying pressure or heating without applying pressure. Conventionally, it has been conventional to continuously manufacture laminates.

しかし、これらの方法のうち、無加圧下での硬化は基材
間に熱硬化性樹脂層が形成されるほか、得られる積層板
中の基材の含量が相対的に低いものとなり、強度、剛性
等の機械的特性に不足を来す傾向にある。
However, among these methods, curing without pressure forms a thermosetting resin layer between the base materials, and the content of the base material in the resulting laminate is relatively low, resulting in poor strength and They tend to lack mechanical properties such as rigidity.

このような基材含量の不足を解決するための方策として
前記のごとく空隙を残すことなく充分含浸した含浸基材
を複数枚重ね合せ、ダブルベルトプレス等を用いて加圧
硬化させる方法によれば、基材含量を高め樹脂含量を減
らすことが可能となるが、加圧時に含浸樹脂の大部分が
基材から排出されて周りの機械を汚し易い他、この排出
量が膨大であることから排出樹脂の回収が必要であるに
もかかわらずその作業が非常に困難である不都合がある
In order to solve this problem of insufficient base material content, there is a method in which multiple sheets of impregnated base materials that are sufficiently impregnated without leaving any voids are stacked together and cured under pressure using a double belt press, etc., as described above. , it is possible to increase the base material content and reduce the resin content, but most of the impregnated resin is discharged from the base material when pressurized, which tends to contaminate surrounding machinery, and the amount of discharge is huge, so it is difficult to discharge. Although it is necessary to recover the resin, there is the disadvantage that the task is extremely difficult.

r発明が解決しようとする課題〕 よって、本発明にあっては、長尺の基材に熱硬化性樹脂
液を含浸し、この含浸基材の複数枚を重ね合せてエンド
レスベルトにより構成されるダブルベルトプレスにより
加熱加圧して、基材含量の大きな積層板を得るに際し、
加圧時に基材より排出された含浸樹脂液の機器加圧面か
らの除去が速やかに行われ、かつ実質的に残存気泡がな
く、しかも基材含量の高い積層板を製造する方法を提供
することを目的とするものである。
Problems to be Solved by the Invention] Therefore, in the present invention, an endless belt is constructed by impregnating a long base material with a thermosetting resin liquid and stacking a plurality of sheets of this impregnated base material. When heating and pressing with a double belt press to obtain a laminate with a large base material content,
To provide a method for manufacturing a laminate in which an impregnated resin liquid discharged from a base material during pressurization is quickly removed from a pressurizing surface of a device, has substantially no residual air bubbles, and has a high base material content. The purpose is to

〔課題を解決するための手段〕[Means to solve the problem]

本発明では、長尺の基材に、本質的に乾燥工程を必要と
せず、かつ硬化反応過程で気体や液体等の反応副生成物
を実質的に発生しない熱硬化性樹脂液を含浸させる含浸
工程と、含浸された基材の置数枚を重ね合わせて加熱加
圧して樹脂液を硬化させて一体化する加熱加圧工程を有
する積層板の連続製造方法において、前記含浸工程にお
いては、各基材を巾方向にほぼ均一に前記樹脂液を含浸
し、前記加熱加圧工程においては、前記含浸工程の略ね
垂直上方に設置された加圧帯全域にわたり実質的に均等
な圧力を有する、エンドレスベルトにより構成されるダ
ブルベルトプレスを用いて、前記含浸の樹脂液の基材全
体への浸透を計りつつ、加熱加圧することにより、上記
課劇を解決するようにした。
In the present invention, a long base material is impregnated with a thermosetting resin liquid that essentially does not require a drying process and does not substantially generate reaction by-products such as gas or liquid during the curing reaction process. In the continuous production method of a laminate, the method includes a heating and pressing step of superimposing a number of impregnated base materials and heating and pressing them to harden and integrate the resin liquid, in the impregnation step, each impregnating the base material with the resin liquid almost uniformly in the width direction, and in the heating and pressurizing step, having a substantially uniform pressure over the entire area of a pressure band installed approximately vertically above the impregnating step; The above problem was solved by heating and pressurizing the impregnated resin liquid while measuring the penetration of the impregnated resin liquid into the entire base material using a double belt press constituted by an endless belt.

以下、本発明の詳細な説明する。The present invention will be explained in detail below.

本発明でいう長尺の基材は、例えば長尺のガラス繊維布
、ガラス不織布等のガラス繊維系のもの、クラフト紙、
水酸化アルミニウム混抄紙、リンター紙等のセルロース
系繊維を主体とした紙、石綿布等の無機質繊維系のシー
ト状または帯状物を指す。シート状基材として紙を用い
る場合、含浸性や品質上の観点から、風乾時の密度(か
さ比重)がOt  3〜0.7g/ccであるようなセ
ルロース繊維を主体としだ紙例えばクラフト紙が好まし
い。
The elongated base material as used in the present invention is, for example, elongated glass fiber cloth, glass fiber-based material such as glass nonwoven fabric, kraft paper,
It refers to paper made mainly of cellulose fibers such as aluminum hydroxide mixed paper and linter paper, and sheets or strips made of inorganic fibers such as asbestos cloth. When using paper as a sheet-like base material, from the viewpoint of impregnability and quality, paper mainly composed of cellulose fibers with an air-dried density (bulk specific gravity) of Ot 3 to 0.7 g/cc, such as kraft paper, is recommended. is preferred.

これら基材は、熱硬化性樹脂液で含浸させる前にあらか
じめメチロールメラミン、メチロールフェノール、メチ
ロールグアナミン、N−メチロール化合物等の処理剤を
用い含浸乾燥処理を施すことにより耐水性が向上しまた
、吸湿性が少なくなることにより電気特性の向上が図れ
るので好ましい。
Before impregnating these base materials with thermosetting resin liquid, they can be impregnated and dried using a treatment agent such as methylol melamine, methylol phenol, methylol guanamine, or N-methylol compound to improve their water resistance and absorb moisture. This is preferable because electrical properties can be improved by reducing the electrical properties.

ここでの処理剤の付tfffiは基材(100重量部)
に対し通常5〜35重量部である。
Here, tfffi to which the treatment agent is applied is the base material (100 parts by weight)
The amount is usually 5 to 35 parts by weight.

また、本発明にいう本質的に乾燥工程を必要とせず、か
つ硬化反応過程で気体や液体等の反応副生物を実質的に
発生しない熱硬化性樹脂液とは、従来公知の不飽和ポリ
エステル系樹脂、ジアリルフタレート系樹脂、ビニルエ
ステル系樹脂、エポキシアクリレート系樹脂の他、以下
に説明する側鎖二重結合型樹脂等をいい、これらは分子
中に不飽トD基を育し、この不飽和基間においてまたは
架橋用ビニルモノマーを介して架橋される特徴を有する
樹脂であり、更にエポキシ樹脂も含まれる。
In addition, the thermosetting resin liquid referred to in the present invention that essentially does not require a drying process and does not substantially generate reaction by-products such as gas or liquid during the curing reaction process is a conventionally known unsaturated polyester resin liquid. In addition to resins, diallyl phthalate resins, vinyl ester resins, and epoxy acrylate resins, these resins include side chain double bond type resins described below. It is a resin that is characterized by being crosslinked between saturated groups or via a crosslinking vinyl monomer, and also includes epoxy resins.

これら熱硬化性樹脂は基材に含浸時には粘性が低い液状
であり、基材に含浸後硬化させると基材との結合性もよ
い特徴を有し、好適である。上記側鎖二重結合型樹脂は
架橋用ビニルモノマーと併用することにより特に含浸性
に秀れている。
These thermosetting resins are suitable because they are in a liquid state with low viscosity when impregnated into a substrate, and have good bonding properties with the substrate when cured after being impregnated into the substrate. The side chain double bond type resin has particularly excellent impregnating properties when used in combination with a crosslinking vinyl monomer.

上記側鎖二重結合型樹脂とは主鎖と側鎖とから構成され
る重合体であって、主鎖は官能基を有するビニルモノマ
ー単位を含む幹ポリマーであり、側鎖は該主鎖の官能基
を介して構成されてなるラジカル反応可能な炭素−炭素
二重結合を有する技である樹脂をいい、側鎖二重結合型
樹脂の主鎖を構成するビニルモノマー単位とは官能基を
有するビニルモノマー単位を必須単位とし、これに必要
に応じ官能基をもたないビニルモノマー単位を含ませた
ものであり、これらが重合して主鎖が構成される。上記
必須単位を構成するモノマーとしてはアクリル酸、メタ
クリル酸、無水マレイン酸、マレイン酸モノエステル等
の官能基としてカルボキシル基を有するビニル単量体、
グリシジルメタクリレート、グリシジルアクリレート等
の官能基としてグリシジル基を有するビニル単量体とそ
の他アリルアルコール、2−ヒドロキシエチルメタクリ
レート、2−ヒドロ牛ジエチルアクリレート、2−ヒド
ロキシプロピルアクリレート、N−メチロールアクリル
アミド等の官能基としてヒドロキシル基を有するビニル
単量体等が代表的であり、特にアクリル酸およびメタク
リル酸が最も好適である。
The above-mentioned side chain double bond type resin is a polymer composed of a main chain and a side chain, where the main chain is a backbone polymer containing vinyl monomer units having a functional group, and the side chains are It refers to a resin that has a radically reactive carbon-carbon double bond that is configured through a functional group, and the vinyl monomer unit that makes up the main chain of a side chain double bond type resin has a functional group. Vinyl monomer units are essential units, and if necessary, vinyl monomer units without functional groups are included, and these are polymerized to form the main chain. Monomers constituting the above essential units include vinyl monomers having a carboxyl group as a functional group such as acrylic acid, methacrylic acid, maleic anhydride, and maleic acid monoester;
Vinyl monomers having a glycidyl group as a functional group such as glycidyl methacrylate and glycidyl acrylate, and other functional groups such as allyl alcohol, 2-hydroxyethyl methacrylate, 2-hydro-cow diethyl acrylate, 2-hydroxypropyl acrylate, and N-methylol acrylamide. Typical examples include vinyl monomers having a hydroxyl group, with acrylic acid and methacrylic acid being particularly preferred.

またここで言うところの官能基を有するビニルモノマー
単位とは主鎖を重合により形成する場合に活性な官能基
として存在させる場合のほか、後述の側鎖を予め該モノ
マーの官能基と反応させておいて重合させて主鎖を形成
する場合の区別なく側鎖を主鎖に形成せしめる役目をし
た官能基かある形のビニルモノマー単位を指す。
Furthermore, the vinyl monomer unit having a functional group as used herein refers to the case in which it exists as an active functional group when the main chain is formed by polymerization, as well as the case in which the side chain described below is reacted with the functional group of the monomer in advance. Refers to a type of vinyl monomer unit with a functional group that serves to form a side chain into the main chain, regardless of whether it is polymerized to form the main chain.

官能基を有しないビニルモノマーとしては、スチレン、
α−メチルスチレン、クロロスチレン、ビニルトルエン
、塩化ビニル、塩化ビニリデン、臭化ビニル、アクリロ
ニトリル、エチレン、プロピレン、ブタジェン、アクリ
ル酸エステル、メタクリル酸エステル、酢酸ビニル、プ
ロピオン酸ビニル、マレイン酸ジエステル、エチルビニ
ルベンゼン等が挙げられる。これらビニルモノマー11
から構成される主鎖の重量平均分子量は5,000ない
し400,000であり、好適には10゜000ないし
200,000である。この値は、側鎖の種類に対応さ
せて適宜選択される。この分子量はプリント基板用の積
層板あるいは電気絶縁用積層板としての物性や含浸性に
影響し、5,000未満では硬化後の積層板の機械的物
性が不十分となり、逆に400,000を越えると基材
への樹脂含浸性が劣り、いずれも好ましくない。また主
鎖中の官能基を有するモノマー単位の量は側鎖の密度に
関係し、側鎖間の硬化反応性に影響するので適宜の比率
が選ばれるが、主鎖1000g中の側鎖密度は0.1〜
2モルが好ましく、より好適には0.4〜1.5モルで
ある。この側鎖二重結合型樹脂にいう側鎖とは、末端ま
たは中間に>C=Cくなる二重結合を有するもので、前
期主鎖にその官能基を介して枝を構成しているものを指
すが、側鎖間に架橋ビニルモノマーによりラジカル反応
により架橋を形成しうるちのであれば適用しうる。
Examples of vinyl monomers without functional groups include styrene,
α-methylstyrene, chlorostyrene, vinyltoluene, vinyl chloride, vinylidene chloride, vinyl bromide, acrylonitrile, ethylene, propylene, butadiene, acrylic ester, methacrylic ester, vinyl acetate, vinyl propionate, diester maleate, ethyl vinyl Examples include benzene. These vinyl monomers 11
The weight average molecular weight of the main chain composed of is from 5,000 to 400,000, preferably from 10°000 to 200,000. This value is appropriately selected depending on the type of side chain. This molecular weight affects the physical properties and impregnability of laminates for printed circuit boards or electrical insulation laminates; if it is less than 5,000, the mechanical properties of the laminate after curing will be insufficient; If it exceeds this, the impregnating property of the resin into the base material will be poor, which is not preferable. In addition, the amount of monomer units having functional groups in the main chain is related to the density of the side chains and affects the curing reactivity between side chains, so an appropriate ratio is selected, but the density of side chains in 1000 g of the main chain is 0.1~
The amount is preferably 2 mol, more preferably 0.4 to 1.5 mol. The side chain referred to in this side chain double bond type resin is one that has a double bond >C=C at the end or in the middle, and has branches in the main chain via the functional group. However, it can be applied as long as a crosslink can be formed between the side chains by a radical reaction using a crosslinking vinyl monomer.

この側鎖二重結合型樹脂において上記主鎖を[■成する
重合体に対して側鎖末端に二重結合を有する側鎖を導入
する方法としては多様な方法を採用しうる。幾つかの例
を挙げれば次のようである。
In this side chain double bond type resin, various methods can be employed to introduce a side chain having a double bond at the end of the side chain into the polymer forming the main chain. Some examples are as follows.

(ア)主鎖の官能基のカルボキシル基に対して、ビスフ
ェノールのジグリシジルエーテル型エポキシ基のような
ジェポキシ基を有する化合物の一方のエポキシ基を反応
させ、残るエポキシ基とアクリル酸もしくはメタクリル
酸を反応さける。
(a) One epoxy group of a compound having a jepoxy group, such as the diglycidyl ether type epoxy group of bisphenol, is reacted with the carboxyl group of the main chain functional group, and the remaining epoxy group is reacted with acrylic acid or methacrylic acid. Avoid reactions.

(イ)主鎖の官能基のカルボキシル基と、グリシジルア
クリレートもしくはグリシジルメタクリレートとをエス
テル反応させる。
(a) The carboxyl group of the main chain functional group and glycidyl acrylate or glycidyl methacrylate are subjected to an ester reaction.

(つ)主鎖の官能基のエポキシ基と、メタクリル酸もし
くはアクリル酸とをエステル反応させる。
(1) The epoxy group of the main chain functional group is subjected to an ester reaction with methacrylic acid or acrylic acid.

(1)ジイソシアネート化合物にヒドロキシエチル、(
メタ)アクリレートを反応させ、モノイソシアネートを
主成分としジイソシアネート化合物をほとんど含まない
反応物を作っておき、この反応物に含まれるインシアネ
ートを主鎖ポリマーの水酸基を反応させる。
(1) Hydroxyethyl, (
A reaction product containing monoisocyanate as a main component and almost no diisocyanate compound is prepared by reacting meth)acrylate, and the incyanate contained in this reaction product is reacted with the hydroxyl group of the main chain polymer.

例示した方法では主鎖の共重合を先に行ったが、当然な
がら予め側鎖を構成する反応を先に行い、かかる単量体
を最後に単独または共重合させることにより側鎖末端に
アクリロイル基もしくはメタアクリロイル基を含む側鎖
二重結合型樹脂を製造してもよい。
In the exemplified method, the main chain was copolymerized first, but it goes without saying that the reaction for forming the side chain was first carried out, and these monomers were finally monopolymerized or copolymerized to form an acryloyl group at the end of the side chain. Alternatively, a side chain double bond type resin containing a methacryloyl group may be produced.

また架m用ビニルモノマーには、スチレン、ビニルトル
エン、クロロスチレン、アクリル酸メチル、アクリル酸
エチル、アクリル酸ブチル、アクリル酸−2−エチルヘ
キシル、メタクリル酸メチル、メタクリル酸エチル、メ
タクリル酸ブチル、メタクリル酸ラウリル、メタクリル
酸ベンジル、マレイン酸ジブチル、マレイン酸ジオクチ
ル、酢酸ビニノ11プロピオン酸ビニル、ジビニルベン
ゼン等が包含される。これらの単量体は2種以上を混合
して用いてもよい。
Vinyl monomers for frame m include styrene, vinyltoluene, chlorostyrene, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and methacrylic acid. Examples include lauryl, benzyl methacrylate, dibutyl maleate, dioctyl maleate, vinyl acetate-11 propionate, divinylbenzene, and the like. These monomers may be used in combination of two or more.

なお基材への含浸に用いられる上記熱硬化性樹脂液には
必要によりハロゲン含有の難燃性付与成分並びにリン酸
エステル、二酸化アンチモンや水酸化アルミニウム等の
難燃化補助剤を加えて用いても良い。
Note that the thermosetting resin liquid used for impregnating the base material may contain a halogen-containing flame retardant component and a flame retardant aid such as phosphoric acid ester, antimony dioxide, or aluminum hydroxide, if necessary. Also good.

またいずれの熱硬化性樹脂液を用いる場合にも、その粘
度は製造する積層板の使用目的や加圧成形する際の圧力
等に応じ適宜選択することができるが、通常は25℃に
おいて0.05〜500ポワズ程度が好適であり、50
0ポワズを超えると基材の含浸性が悪く、得られる積層
板中に気泡が残り易い。また、0.05ボワズ未満であ
ると含tl性は良いが外部空気の侵入の影響を受は易い
間1Fがある。
In addition, when using any thermosetting resin liquid, its viscosity can be appropriately selected depending on the purpose of use of the laminate to be manufactured, the pressure during pressure molding, etc., but it is usually 0.0001 at 25°C. Approximately 0.05 to 500 poise is suitable;
If it exceeds 0 poise, the impregnating properties of the base material will be poor and air bubbles will tend to remain in the resulting laminate. Moreover, if it is less than 0.05 Boise, the TL content is good, but it is easily affected by the intrusion of outside air.

ついで、このような熱硬化性樹脂を用いて、前記長尺の
基材に対して含浸が行われる。この含浸方法としては部
分的含浸が望ましい。
Next, the elongated base material is impregnated with such a thermosetting resin. Partial impregnation is preferred as this impregnation method.

すなわち、前記部分的含浸は、各基材の空隙の全て満た
すことなく巾方向にほぼ均一に前記樹脂液を部分含浸す
るものである。基材としてグラフト紙を例示した場合、
クラフト紙の空隙等は通常60〜70体積%(風乾時)
であるが、この空隙率が例えば30〜45体積%程度と
、基材含浸部分のどの位置においてもなるように含浸す
るものである。空隙を埋める樹脂の必要量は加圧成形圧
力によって変わるが樹脂の過剰量か1%以下であると樹
脂液が部分的に不足し、白化の原因となる。
That is, the partial impregnation is to partially impregnate each base material with the resin liquid almost uniformly in the width direction without filling all the voids. When graft paper is used as an example of the base material,
Voids in kraft paper are usually 60 to 70% by volume (when air-dried)
However, the impregnation is performed so that the porosity is, for example, about 30 to 45% by volume at any position of the impregnated portion of the base material. The required amount of resin to fill the voids varies depending on the pressure of the molding, but if the amount of resin is excessive or less than 1%, the resin liquid will be partially insufficient, causing whitening.

一方、50%以上は樹脂液の含浸に不必要であるばかり
でなく、重力による流下が困難となり、機器側面へ流れ
る樹脂が増大して汚染し易くなる。
On the other hand, 50% or more is not only unnecessary for resin liquid impregnation, but also makes it difficult to flow down due to gravity, increasing the amount of resin flowing to the side of the device, making it easy to contaminate the device.

これらの長尺基材への硬化性樹脂液の含浸は、浸漬絞り
組合わせ法、塗布法等の公知の方法を適宜選択して行わ
れる。例えば、第1図に示すように、複数の基材l・・
・を送り出し、これに浸漬槽2・・・及び各基材間を開
いて樹脂を流入させるスペーサー5・・・を用いて、基
材lに上述のように樹脂液を浸漬して、更に樹脂M調整
ロール6・・・で不要の樹脂を排出することにより基材
l・・・への部分的含浸を行う。第1図に示すように各
々の基材lにおいて、浸漬による樹脂含浸基材3を樹脂
量調整ロール6・・・で積層一体化することにより含浸
積層基材4とする。
Impregnation of the curable resin liquid into these elongated substrates is carried out by appropriately selecting a known method such as a dipping and squeezing combination method or a coating method. For example, as shown in FIG.
Using the dipping tank 2... and the spacer 5 which opens between each base material and allows the resin to flow in, the base material l is immersed in the resin liquid as described above, and then the resin is further soaked. Partial impregnation of the base material l is performed by discharging unnecessary resin with the M adjusting roll 6. As shown in FIG. 1, in each base material 1, the resin-impregnated base material 3 by dipping is laminated and integrated with a resin amount adjusting roll 6 to form an impregnated laminated base material 4.

また、硬化性樹脂液′の含浸mは、次工程のタプルベル
トプレスでの加圧時の圧力に関係し、その圧力で所定の
厚みの積層板か得られかつ得られる積層板に気泡が実質
的に存在しないように調整され、タプルベルトプレスで
の加圧時に基材積層物から逆、XLにより上流へ排出さ
れる樹脂液量が製品−積層板中の硬化樹脂量の50%以
下、好ましくは10%以下となるようにすることが望ま
しい。加圧時の圧力に対して適正量以下の含浸量である
と得られる積層板中に気泡が残存し全体的な白化現象を
起こす。
In addition, the impregnation m of the curable resin liquid is related to the pressure during pressurization in the tuple belt press in the next step, and the pressure allows a laminate of a predetermined thickness to be obtained and substantially eliminates air bubbles in the resulting laminate. The amount of resin liquid discharged from the base laminate backwards and upstream by XL when pressurized with a tuple belt press is preferably 50% or less of the amount of cured resin in the product-laminate. It is desirable that it be 10% or less. If the amount of impregnation is less than the appropriate amount for the pressure during pressurization, air bubbles will remain in the resulting laminate, causing an overall whitening phenomenon.

このようにして硬化性樹脂液が含浸された長尺のノλ材
は、その複数枚が重ね合され、積層物とされたのち、浸
漬槽の上方に竪型に配置され、加叩帯全域にわたり実質
的に均等な圧力を有するタフルベルドブレスによって加
熱加圧され含浸樹脂は基材の空隙を可及的に広く埋めて
積層板とされる。
The long material impregnated with the curable resin liquid in this way is stacked together to form a laminate, and then placed in a vertical shape above the dipping tank, covering the entire area of the dipping zone. The impregnated resin is heated and pressurized by a tuffle belt press having a substantially uniform pressure over the entire length, filling the voids in the base material as widely as possible to form a laminate.

本発明にいう加圧帯全域にわたり実質的に均等な圧力を
有するエンドレスベルトにより構成されるダブルベルト
プレスとは、例えば厚さIRl、程度のステンレススチ
ール製のエンドレスベルト状のものを上下に設置し、上
下のベルト間に樹脂液含浸基材をはさみ加熱加圧可能と
するものであり、加圧帯の圧力が実質的に均等となるよ
うなta造を有するものである。具体的な例示をなすと
、(1)上下のベルトをはさみ込みベルトに圧力を付与
するためのロール対を複数列配置しり上、このロール径
が5’0xttt以下でかつロールピッチとロール径の
比が1.2以下となるようにして相隣るロール間の圧力
降下を小さくする方式のもので、ロールの位置は固定で
もよく、あるいはエンドレスベルトの上下に設けた加圧
板と該エンドレスベルトとの間に配置され、XX加圧坂
周囲を公転しても良い。ロールの径が大きくなり、ロー
ル間隔があきすぎると基材にかかる圧力に大きな彼を生
じ好ましくない。
The double belt press according to the present invention, which is composed of an endless belt that exerts substantially uniform pressure over the entire pressure zone, is a double belt press that is constructed by installing stainless steel endless belts with a thickness of about IRl above and below, for example. , a base material impregnated with a resin liquid is sandwiched between upper and lower belts so that it can be heated and pressurized, and has a structure that allows the pressure of the pressure band to be substantially equal. To give a specific example, (1) A plurality of rows of roll pairs are arranged to sandwich the upper and lower belts and apply pressure to the belts, and the roll diameter is 5'0xttt or less and the roll pitch and roll diameter are equal to each other. This method reduces the pressure drop between adjacent rolls so that the ratio is 1.2 or less, and the position of the rolls may be fixed, or the endless belt may be connected to pressurizing plates installed above and below the endless belt. It may be placed between the two and revolve around the XX pressurizing slope. If the diameter of the rolls becomes large and the distance between the rolls is too large, the pressure applied to the base material will be undesirably large.

(2)上下のエンドレスベルトをはさみ込み、ベルトに
圧力を付与するための加圧板を配置した上、潤滑を目的
として加圧板とエンドレスベルトの間に圧力媒体を圧入
循環させる方式のもの。
(2) A type in which the upper and lower endless belts are sandwiched, a pressure plate is placed to apply pressure to the belt, and a pressure medium is press-fitted and circulated between the pressure plate and the endless belt for the purpose of lubrication.

(3)上下のエンドレスベルトをはさみ込んで圧力媒体
収納用の容器をもうけ、この容器の開口部がエンドレス
ベルトと接し、圧力媒体が直接エンドレスベルトを押圧
する方式のものが挙げられ、圧力媒体収納式が加圧帯全
域にわたっての圧力差が小さく、特に好適である。
(3) A container for storing the pressure medium is created by sandwiching the upper and lower endless belts, and the opening of this container is in contact with the endless belt, and the pressure medium directly presses the endless belt. This formula is particularly suitable because the pressure difference across the entire pressure zone is small.

第1図に示すものは、この圧力媒体収納方式のダブル゛
ベルトプレスの例を示すものである。このダブルベルト
プレス11はドラム12.12aと、エンドレスベルト
13.13と、加圧室I4と、高温の流体からなる圧力
媒体15とから概略構成され、圧力媒体供給装置J6は
、ポンプ17きヒータ18とを配管パイプ19で接続し
てなるものである。ドラム12.12および12a、1
2aは含浸基材5・・・の進行方向に沿い、かつ互いに
逆方向に回転する上下一対のドラムからなり、含浸基材
5の片側に前後して並列された同方向に回転するドラム
12.12a間にはエンドレスベルト13.13かそれ
ぞれ緊張して掛けられている。
What is shown in FIG. 1 is an example of a double belt press of this pressure medium storage type. This double belt press 11 is roughly composed of a drum 12.12a, an endless belt 13.13, a pressurizing chamber I4, and a pressure medium 15 made of high-temperature fluid. 18 are connected by a plumbing pipe 19. Drum 12.12 and 12a, 1
2a consists of a pair of upper and lower drums that rotate in opposite directions to each other along the traveling direction of the impregnated base material 5, and drums 12. Endless belts 13 and 13 are tensioned between each of the belts 12a.

そしてこのエンドレスベルト13.13のNi&には、
含浸基材5・・・に含浸された樹脂の硬化と含浸基材5
・・の一体化に必要な熱と圧力をくわえるための圧力媒
体15が充填される加圧室14が設けられている。この
加圧室14は任意形状の容器であって、その−構成面が
上記エンド°レスベルI−13により構成されているも
ので、この加圧室14内にはエンドレスベルト13より
含浸状基材5・・・に熱と圧力を加えるための圧力媒体
I5が圧入されている。さらに加圧室14には圧力媒体
15を正大供給するポンプ17および圧力媒体15を加
熱する電気ヒータ等のヒータ18が配管パイプ19によ
り配管されることにより構成された圧力媒体供給装置1
6が配設されている。なおヒータ18はこの加圧室14
に組み込まれていても良い。
And for Ni& of this endless belt 13.13,
Curing of the resin impregnated into the impregnated base material 5... and the impregnated base material 5
A pressurizing chamber 14 is provided, which is filled with a pressure medium 15 for adding the heat and pressure necessary for the integration of.... This pressurizing chamber 14 is a container of any shape, and its structural surface is constituted by the above-mentioned endless belt I-13. A pressure medium I5 for applying heat and pressure to 5... is press-fitted. Further, the pressurizing chamber 14 is equipped with a pressure medium supply device 1 configured by a pump 17 for supplying a pressure medium 15 at a constant rate, and a heater 18 such as an electric heater for heating the pressure medium 15, which is connected through a piping 19.
6 are arranged. Note that the heater 18 is connected to this pressurizing chamber 14.
It may be incorporated into.

圧力媒体15はこの圧力媒体供給装置16と加圧室14
との間をポンプ17により循環していて、加圧室14の
外部より圧力媒体15の補給や加圧および加熱か行える
ようになっている。加圧室14内の加熱は、ヒータ18
で圧力媒体15を加熱することにより間接的に行うこと
ができる。さらにエンドレスベルト13.13の走行に
伴って加圧室14外へ流出する川と同量の圧力媒体15
がポンプ17によって加圧室14内へ順次圧入供給され
るようになっており、加圧室14内の圧力が一定に保た
れるようになっている。そしてエンドレスベルト13.
13間に挟まれた含浸基材5・・・は、加圧室14内に
圧入された圧力媒体I5によって加熱、加圧されて、含
浸された樹脂液が均一に拡がり空隙を埋めて硬化される
とともに一体化される。圧力媒体15としてはダブルベ
ルトプレス!■の運転条件下で流動性を示すものであれ
ばどのような流体であっても良いが、これらを例示すれ
ば、ガス体としては空気または窒素等、液体としてはl
11滑油、熱媒油やシリンターオイル等、ワックスや低
融点ポリマーとしてはポリエチレンワックスやパラフィ
ン等であり、低融点金属としては半田やウッドメタル等
である。
The pressure medium 15 is connected to this pressure medium supply device 16 and the pressurizing chamber 14.
The pressure medium 15 is circulated between the pressurizing chamber 14 by a pump 17, and the pressure medium 15 can be replenished, pressurized, and heated from the outside of the pressurizing chamber 14. The inside of the pressurizing chamber 14 is heated by a heater 18.
This can be done indirectly by heating the pressure medium 15 at . Furthermore, the same amount of pressure medium 15 as the river flows out of the pressurizing chamber 14 as the endless belt 13.13 runs.
is sequentially pressurized and supplied into the pressurizing chamber 14 by the pump 17, so that the pressure within the pressurizing chamber 14 is kept constant. And endless belt 13.
The impregnated base material 5 sandwiched between the impregnated base materials 5... is heated and pressurized by the pressure medium I5 press-fitted into the pressurizing chamber 14, and the impregnated resin liquid spreads uniformly, fills the voids, and hardens. and become integrated. Double belt press as pressure medium 15! Any fluid may be used as long as it exhibits fluidity under the operating conditions described in (2), but examples of these include air or nitrogen as a gas, and l as a liquid.
11 Lubricant oil, heat transfer oil, cylinder oil, etc. Waxes and low melting point polymers include polyethylene wax and paraffin, and low melting point metals include solder and wood metal.

このダブルベルトプレスにおいてはいずれの方式のもの
であっても、大きな圧力分布の存在、特に進行方向での
大きな脈動圧力の存在は、樹脂液含浸基材内の気泡の選
択的排出を困難とするだけでなく、圧力帯の中での空気
の再侵入が起こりやすくなり、さけるべきであり、例え
ば圧力の分布は150%以下で且つ±5 kg/ cm
″以下が好ましい。
Regardless of the type of double belt press, the existence of a large pressure distribution, especially the existence of large pulsating pressure in the direction of movement, makes it difficult to selectively discharge air bubbles in the resin liquid-impregnated base material. In addition, re-entry of air in the pressure zone is likely to occur and should be avoided, for example, if the pressure distribution is less than 150% and ±5 kg/cm
″ or less is preferable.

また、適用される圧力は、使用される硬化性樹脂液や基
材の種類によっても異なるが、得られる積層板中の基材
含量を制御するため適宜選択される。通常、l ky/
cm” Gから100 kg/ cm” Gであり、好
ましくは10kg/c11″Gから50 kg/cm”
 Gである。圧力がl kg/ cm” Gより低い場
合、基材含量が増大しにくいだけでなく、空気の排出効
果が小さく、気泡の混入した積層板となり易い。
Further, the applied pressure varies depending on the curable resin liquid used and the type of base material, but is appropriately selected in order to control the base material content in the resulting laminate. Usually l ky/
cm"G to 100 kg/cm"G, preferably 10kg/c11"G to 50 kg/cm"
It is G. When the pressure is lower than 1 kg/cm''G, not only is it difficult to increase the base material content, but the air evacuation effect is small, and the laminate is likely to have air bubbles mixed in.

一方圧力が100 kg7 cm″Gより大であるのは
、気泡の除去に不必要であるばかりでなく、得られる積
層板中の基材含量が大きくなりすぎ、層間剥離等、強度
低下を引起し易い。
On the other hand, a pressure higher than 100 kg7 cm''G is not only unnecessary for removing air bubbles, but also causes the base material content in the resulting laminate to become too large, causing delamination and other deterioration in strength. easy.

また、加熱加圧成形に用いられる温度は使用される熱硬
化性樹脂液の種類や硬化触媒の種類等により変化するが
通例50℃から200℃の範囲である。50℃を下回る
温度では硬化に要する時間か長すぎて不経済であり、2
00℃を越えると急激な硬化の進行により内部ヒズミの
発生や、発泡等の問題が生ずる。
Further, the temperature used for hot-press molding varies depending on the type of thermosetting resin liquid used, the type of curing catalyst, etc., but is generally in the range of 50°C to 200°C. At temperatures below 50°C, the time required for curing is too long, making it uneconomical;
When the temperature exceeds 00°C, problems such as internal distortion and foaming occur due to the rapid progress of curing.

このようなダブルベルトプレスによる加圧にあっては、
熱硬化性樹脂液で部分的含浸がなされた1夏数枚の基材
の積層物中の樹脂液がその加圧によって基材の未含浸部
分に浸透してゆき、積層物厚み方向に均一に含浸された
状態となる。これは、ダブルベルトプレス人口部におい
て上記積層物中で積層物の進行方向とは逆方向の大きな
圧力勾配が生じ、この圧力勾配が樹脂液の基材未含浸部
分への浸透、含浸を促進するとともに基材に残存する気
泡と樹脂液との間での置換が促進されるためと推定され
る。そして、置換された気泡の一部は連続的に基材積層
物中を進行方向とは逆方向に追いやられ、加圧下にある
積層物から排除されつづける。また、気泡の一部は、積
層物の巾方向にも生ずる圧力勾配によって積層物の両側
縁部に追いやられ、両端部からの若干量の樹脂液の排出
とともに気泡が排除され、これによって実質的に気泡の
存在しない積層板が得られる。そして、基材への熱硬化
性樹脂液の含浸が部分的含浸であることから、ダブルベ
ルトプレスによる加圧によっても、基材積層物からの樹
脂液の排出量は少なくすることができる。すなわち、得
られる積層板中の樹脂に相当する量の樹脂液だけを基材
に部分的に含浸せしめうるため、余分の樹脂液量は少な
く、ダブルベルトプレスは竪に配置されている為、排出
される樹脂液は容易に下方に流下し、幅方向への広がり
は極めて小さい。樹脂液の排出が小さければ、ダブルベ
ルトプレスにおいてこれを回収する必要はなく、またダ
ブルベルトプレスを汚すこともなくなり、ダブルベルト
プレスの構造を単純化することも可能である。したがっ
て、加圧室14を通過した後の積層板では、含浸基材部
の幅よりも僅かに両側方向に拡がった樹脂排出部が形成
されるか比率としては1%程度と小さい。
When pressurizing with such a double belt press,
The resin liquid in the laminate of several base materials partially impregnated with thermosetting resin liquid per summer penetrates into the unimpregnated parts of the base materials due to the pressure applied, and the laminate is uniformly distributed in the thickness direction. It becomes impregnated. This is because a large pressure gradient occurs in the laminate in the double belt press section in the opposite direction to the direction in which the laminate travels, and this pressure gradient promotes the penetration and impregnation of the resin liquid into the unimpregnated parts of the base material. This is presumed to be because the replacement between the bubbles remaining in the base material and the resin liquid is promoted. A portion of the displaced air bubbles are then continuously driven through the base material laminate in a direction opposite to the traveling direction, and continue to be removed from the laminate under pressure. In addition, some of the air bubbles are driven to both side edges of the laminate due to the pressure gradient that also occurs in the width direction of the laminate, and as a small amount of resin liquid is discharged from both ends, the air bubbles are eliminated. A laminate with no air bubbles is obtained. Since the base material is partially impregnated with the thermosetting resin liquid, the amount of resin liquid discharged from the base material laminate can be reduced even by applying pressure using a double belt press. In other words, since the base material can be partially impregnated with only the amount of resin liquid equivalent to the resin in the resulting laminate, the amount of excess resin liquid is small, and since the double belt press is vertically arranged, it can be discharged easily. The resin liquid easily flows downward, and its spread in the width direction is extremely small. If the discharge of the resin liquid is small, there is no need to collect it in the double belt press, and the double belt press will not be contaminated, and the structure of the double belt press can be simplified. Therefore, in the laminate after passing through the pressurizing chamber 14, resin discharge portions are formed that are slightly wider in both directions than the width of the impregnated base material portion, or the ratio is as small as about 1%.

このようにして得られた積層板中の基材arJtは、用
いられる基材、熱硬化性樹脂液などの種類、加圧条件等
によって異なるが、通常30重M%から80重量%の範
囲であり、例えば基材としてクラフト紙を用い、熱硬化
性樹脂液として前述の側鎖二重結合型樹脂を用いた場合
では35〜65重世%か好ましく、35重量%未満では
積層板の機械的強度、曲げ剛性が不足して好ましくなく
、65重量%を越えると層間剥離が生じ易くなるだけで
なく、打抜性、l1ff、l湿性の低下か生しるように
なって不都合である。
The base material arJt in the laminate thus obtained varies depending on the base material used, the type of thermosetting resin liquid, pressurizing conditions, etc., but is usually in the range of 30% by weight to 80% by weight. For example, if kraft paper is used as the base material and the side chain double bond type resin mentioned above is used as the thermosetting resin liquid, it is preferably 35 to 65 weight%, and if it is less than 35 weight%, the mechanical strength of the laminate It is undesirable because it lacks strength and bending rigidity, and when it exceeds 65% by weight, it not only tends to cause delamination, but also causes a decrease in punchability, l1ff, and l wetness, which is disadvantageous.

一方、金属箔張積層板を’!i2造するには含浸基材の
積層物の片面もしくは両面に基材の重ね合わせと同時ま
たは少しお(れて金属箔を重ね合せ、これをダブルベル
トプレスに供給することによって行われる。ここで用い
られる金属箔としては印刷回路板の用途を目的とした電
解銅箔かあり、これを用いることが耐蝕性、エツチング
性、接青性の観点より好ましいが、池に電解鉄箔、アル
ミニウム箔も用いられる。
On the other hand, metal foil clad laminates'! i2 fabrication is carried out by overlapping a metal foil on one or both sides of the laminate of impregnated base materials at the same time as or slightly after the overlapping of the base materials, and feeding this into a double belt press. The metal foil that can be used is electrolytic copper foil intended for use in printed circuit boards, and it is preferable to use this from the viewpoints of corrosion resistance, etching properties, and blue-tatchability, but electrolytic iron foil and aluminum foil may also be used. used.

金属箔は厚み10=100pmのものが通例使用される
A metal foil having a thickness of 10=100 pm is usually used.

また、金属箔の接a面は接着性を向上する目的で粗面化
処理されていることがより好ましい。
Moreover, it is more preferable that the contact surface of the metal foil is roughened for the purpose of improving adhesiveness.

金属箔と樹脂含浸基材との接着を効果的に達成するため
には、接着剤を用いることが好ましく、接着剤としては
、硬化過程で、不必要な反応副生成物を発生しない、液
状もしくは半流動体、すなわち粘度にして好ましくは5
000ボイズ以下であるような接着剤か好適である。か
かる観点から、例えばエポキシ−アクリレート系接着剤
、エポキシ樹脂系接着剤、ポリイソシアネート系接着剤
、もしくはこれらの各種変性接着剤が好適である。
In order to effectively achieve adhesion between the metal foil and the resin-impregnated substrate, it is preferable to use an adhesive. Semi-fluid, i.e. viscosity preferably 5
Adhesives having 0.000 voids or less are suitable. From this viewpoint, for example, epoxy-acrylate adhesives, epoxy resin adhesives, polyisocyanate adhesives, or various modified adhesives thereof are suitable.

エポキシ系接着剤としては、ビスフェノールA型エポキ
シ樹脂とポリアミド樹脂やアミン煩の如き硬化剤からな
る混合物等が好適である。かかる接着剤の導入により金
属箔の接着強度に優れ、かつハンダ耐熱性や電気絶縁性
に優れた金属箔張積層板を製造できる。
As the epoxy adhesive, a mixture of a bisphenol A type epoxy resin and a curing agent such as a polyamide resin or an amine adhesive is suitable. By introducing such an adhesive, it is possible to produce a metal foil-clad laminate that has excellent adhesion strength of metal foil, as well as excellent solder heat resistance and electrical insulation properties.

接着剤は金属箔に塗布した状態で使用する場合、塗布後
、60〜150℃で2〜7分間熱処理し、半硬化状態ま
で予備硬化させても良い。接着剤は績層仮に同時に塗布
して用いることもできる。接着剤の塗膜の厚みはIO〜
100μM程度でよく、特に20〜50μ肩が好適であ
る。
When the adhesive is used in a state where it is applied to metal foil, it may be precured to a semi-cured state by heat treatment at 60 to 150° C. for 2 to 7 minutes after application. The adhesive can also be applied to both layers at the same time. The thickness of the adhesive coating is IO ~
It may be about 100 μM, and 20 to 50 μM is particularly suitable.

本発明で得られる積層板の厚みは基材の種類、熱硬化性
樹脂液の組成、積層板の用途等により異なるか通常0.
5〜3.Ouが好適である。
The thickness of the laminate obtained by the present invention varies depending on the type of substrate, the composition of the thermosetting resin liquid, the use of the laminate, etc., or is usually 0.
5-3. Ou is preferred.

〔実施例〕〔Example〕

以下、本発明を実施例によって詳しく述べるが、本発明
の要旨を逸脱しない限り、これらの実施例のみに限定さ
れるものではない。
Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples unless it departs from the gist of the present invention.

なお、この明細書を通して、温度は全て00であり、部
および%は特記しない限り重量基準である。
Throughout this specification, all temperatures are 00, and parts and percentages are by weight unless otherwise specified.

(側鎖二重結合型樹脂の調製) 撹拌機、ガス導入管付き温度計、還流コンデンサー、滴
下ロートを具備したセパラブルフラスコ(30003!
12)にメタクリル酸(35g、0.41モル)、メチ
ルエチルケトン(400g)、スチレンモノマー(80
0g、7.7モル)、アゾビスイソブチロニトリル(5
,0g)  ドデシルメルガブタン(12g)を仕込み
、窒素雰囲気下75〜80°Cで10時間重合を行った
。ハイドロキノン(0,5g)を添加して重合を禁止し
た。スチレンモノマーの重合率は76%、メタクリル酸
の重合率は93%であり、重量平均分子量約5万のスチ
レン−メタクリル酸共重合体を含有するポリマー含有液
が得られた。
(Preparation of side chain double bond type resin) A separable flask (30003!) equipped with a stirrer, a thermometer with a gas introduction tube, a reflux condenser, and a dropping funnel.
12), methacrylic acid (35 g, 0.41 mol), methyl ethyl ketone (400 g), styrene monomer (80
0 g, 7.7 mol), azobisisobutyronitrile (5
, 0g) dodecyl mergabutane (12g) was charged, and polymerization was carried out at 75 to 80°C for 10 hours under a nitrogen atmosphere. Hydroquinone (0.5 g) was added to inhibit polymerization. The polymerization rate of styrene monomer was 76%, and the polymerization rate of methacrylic acid was 93%, and a polymer-containing liquid containing a styrene-methacrylic acid copolymer having a weight average molecular weight of about 50,000 was obtained.

また上記と同じ構成の別の反応装置に「エピコート82
7J  (エポキシ樹脂の商品名、油化シェルエポキシ
社製)(360g、1モル)、メタクリル酸(138g
、1.6モル)、ベンジルジメチルアミン(1,2g)
、バラベンゾキノン(0゜12g)を仕込み、l 20
 ’Cで窒素雰囲気下3時間反応させた。反応後の酸価
は殆どゼロとなり、不飽和基含有エポキシ樹脂を含むビ
ニル化試剤が得られた。先に調製したポリマー含有液を
全量ビニル化試剤に加えて、トリフェニルホスフィン(
5g)、バラベンゾキノン(0,lOg)をrB 加し
て加熱し、沸点110°Cにおいてメチルエチルケトン
溶媒を留出させ、同温度で5時間反応させた。
In addition, another reactor with the same configuration as above was installed with "Epicoat 82".
7J (trade name of epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd.) (360 g, 1 mol), methacrylic acid (138 g
, 1.6 mol), benzyldimethylamine (1.2 g)
, prepared rosebenzoquinone (0°12g), l 20
The mixture was reacted for 3 hours at C'C under a nitrogen atmosphere. After the reaction, the acid value became almost zero, and a vinylation reagent containing an epoxy resin containing an unsaturated group was obtained. Add the entire amount of the previously prepared polymer-containing solution to the vinylation reagent and add triphenylphosphine (
5g) and rosebenzoquinone (0.1Og) were added to rB and heated, the methyl ethyl ketone solvent was distilled off at a boiling point of 110°C, and the mixture was reacted at the same temperature for 5 hours.

反応後には、不飽和基含有エポキシ樹脂は反応前の約1
5%になった。スチレンモノマー(1000g)を間欠
的に添加しながら、30〜50々1119で加熱蒸発を
続けた。留出液から検出されるメチルエチルケトンか0
.1%以下となったとき1M作を終了した。かくして得
られた硬化性プレポリマーを含む樹脂液は不揮発分52
重量%より成る粘度6.12ポイズ(25°C)の黄褐
色液であった。
After the reaction, the unsaturated group-containing epoxy resin is about 1
It became 5%. Heat evaporation was continued at 30-50 ml while adding styrene monomer (1000 g) intermittently. Methyl ethyl ketone detected in distillate
.. When it became less than 1%, I finished the 1M production. The thus obtained resin liquid containing the curable prepolymer has a non-volatile content of 52
It was a yellow-brown liquid with a viscosity of 6.12 poise (25°C) consisting of % by weight.

(実施例および比較例) 市販の長尺クラフト紙(秤m135g/m’密度0.4
9g/cR” )100重量部1: N −メfロール
メラミン(日本カーバイド(株)!2ニカレジンS−3
05)が付着量20重量部となるよう含浸、乾燥させた
処理基材8枚を用い、硬化触媒を加えた上記側鎖二重結
合型樹脂液、不飽和ポリエステル樹脂液、エポキシ樹脂
液を所定の方法及び量で連続的に含浸したのち、必要に
よりその最外層にエポキシ樹脂系接着剤骨の厚さ35μ
屑の電解銅箔を積層し、第1図に示すような圧力媒体収
納式ダブルベルトプレスを用いて連続的に100℃で5
分間加圧、加熱成形し更に120℃で1時間後硬化して
積層板並びに片面銅張積層板を得た結果を第1表に示す
。なお、第1表中の「含浸法」の内、“部分的含浸(A
)”とは、含浸時に浸漬法を採用、絞りロール対により
含浸樹脂量を調整したものを積層するもの。゛部分的含
浸(B)”とは、8枚の基材の各々について全体に同程
度に熱硬化性樹脂を含浸するが、基材の巾方向に亘って
すべてを樹脂液で含浸するもので、塗布装置(スリット
ノズル)を用いたもの。“完全含浸”とは8枚の基材全
部を浸漬法によって完全に含浸したもの。なお、いずれ
の含浸においても紙幅は10701πである。
(Example and Comparative Example) Commercially available long kraft paper (weighing m 135 g/m' density 0.4
9g/cR") 100 parts by weight 1: N-Mefol melamine (Nippon Carbide Co., Ltd.!2 NiResin S-3
05) was impregnated and dried to a coating amount of 20 parts by weight, and using 8 treated substrates, the above-mentioned side chain double bond type resin liquid, unsaturated polyester resin liquid, and epoxy resin liquid to which a curing catalyst was added were predetermined. After continuous impregnation in the method and amount of
Scrap electrolytic copper foils were laminated and continuously heated at 100°C for 55 minutes using a double belt press with pressure medium storage as shown in Figure 1.
Table 1 shows the results of pressurizing and heat molding for a minute and post-curing at 120° C. for 1 hour to obtain a laminate and a single-sided copper-clad laminate. In addition, among the "impregnation methods" in Table 1, "partial impregnation (A
)" refers to the method in which the dipping method is used during impregnation, and the amount of impregnated resin is adjusted using a pair of squeezing rolls. "Partial impregnation (B)" refers to the method in which each of the eight base materials is laminated in the same manner throughout. This method uses a coating device (slit nozzle) to impregnate the entire width of the substrate with a thermosetting resin. "Complete impregnation" means that all eight substrates are completely impregnated by the dipping method. In addition, the paper width in any impregnation is 10701π.

第1表の結果から明らかなように、竪方向に配置された
ダブルベルトプレスによって、樹脂液の加圧時の排出m
を極めて少毒に抑えることができるにもかかわらず、基
材含量の高い積層板を得ることがわかる。なお、比較例
1は排出樹脂量が過大で機外へ樹脂がはみ出したもので
あるが、良品は得られている。比較例2は、部分的含浸
を行うものであるが、基材全体としての樹脂含浸1が不
足し、比較例3は加圧力不足により含浸が不充分なもの
、比較例4は過剰な圧力により樹脂が不足して剥離を起
こし、良品が得られないものである。
As is clear from the results in Table 1, when the resin liquid is pressurized, the discharge m
It can be seen that a laminate with a high base material content can be obtained even though the toxicity can be suppressed to an extremely low level. In Comparative Example 1, the amount of discharged resin was excessive and the resin protruded outside the machine, but a good product was obtained. In Comparative Example 2, partial impregnation was performed, but resin impregnation 1 was insufficient for the entire base material, in Comparative Example 3, impregnation was insufficient due to insufficient pressure, and in Comparative Example 4, impregnation was insufficient due to excessive pressure. Due to lack of resin, peeling occurs and good products cannot be obtained.

〔発明の効果〕〔Effect of the invention〕

以上説明したように、この発明の積層板の連続製造方法
は、長尺の基材に、本質的に乾燥工程を必要とせず、か
つ硬化反応過程で気体や液体等の反応副生成物を実質的
に発生しない熱硬化性樹脂液を含浸させる含浸工程と、
含浸された基材の複数枚を重ね合わせて加熱加圧して樹
脂液を硬化させて一体化する加熱加圧工程を有する積層
板の連続製造方法において、含浸工程と加熱加圧工程を
略ね垂直に配置し、前記含浸工程においては、前記樹脂
液の基材への部分的含浸を行い、前記加熱加圧工程にお
いては、加圧帯全域にわたり実質的に均等な圧力を有す
るダブルベルトプレスを用いて、前記部分的含浸の樹脂
液の基材全体への浸透を計りつつ、加熱加圧するもので
あるので、ダブルベルトプレスによる加圧時に含浸樹脂
液の排出が小量の付着分を除いて重力の作用により、流
下、回収されるため汚染の問題が発生せず、かつ実質的
に気泡が存在せぬ基材含量の高い積層板を連続的に製造
することができる。
As explained above, the method for continuously manufacturing a laminate of the present invention essentially does not require a drying process and substantially eliminates reaction by-products such as gas and liquid during the curing reaction process. an impregnation step of impregnating with a thermosetting resin liquid that does not generate
In a continuous manufacturing method for laminates that includes a heating and pressing step in which multiple sheets of impregnated base materials are piled up and heated and pressed to harden and integrate the resin liquid, the impregnation step and heating and pressing step are performed approximately vertically. In the impregnation step, the base material is partially impregnated with the resin liquid, and in the heating and pressing step, a double belt press having substantially uniform pressure over the entire area of the pressure zone is used. Since the partially impregnated resin liquid is heated and pressurized while measuring its penetration into the entire base material, the impregnated resin liquid is discharged by gravity except for a small amount of adhered material when pressurized by a double belt press. Due to this action, the laminate is flowed down and collected, so there is no problem of contamination, and it is possible to continuously produce a laminate with a high base material content and substantially no air bubbles.

【図面の簡単な説明】[Brief explanation of the drawing]

第1図はこの発明で用いられる製造装置の例を示す概略
構成図である。 1・・・・・・基材、 2・・・・・・浸漬槽、3・・
・・・・樹脂含浸基材、4・・・・・・含浸積属基材、
5・・・・・スペーサー 6・・・・・・[7脂m F
l 整ロール、11・・・・・・ダブルベルトプレス。
FIG. 1 is a schematic configuration diagram showing an example of a manufacturing apparatus used in the present invention. 1...Base material, 2...Immersion tank, 3...
... Resin-impregnated base material, 4... Impregnated metal base material,
5...Spacer 6...[7 fat m F
l Adjusting roll, 11...Double belt press.

Claims (5)

【特許請求の範囲】[Claims] (1)長尺の基材に、本質的に乾燥工程を必要とせず、
かつ硬化反応過程で気体や液体等の反応副生成物を実質
的に発生しない熱硬化性樹脂液を含浸させる含浸工程と
、含浸された基材の複数枚を重ね合わせて加熱加圧して
樹脂液を硬化させて一体化する加熱加圧工程を有する積
層板の連続製造方法において、 前記含浸工程と前記加熱加圧工程を略ね垂直に配置し、 前記含浸工程においては、各基材の空隙を巾方向にほぼ
均一に前記樹脂液を含浸し、 前記加熱加圧工程においては、加圧帯全域にわたり実質
的に均等な圧力を有する、エンドレスベルトにより構成
されるダブルベルトプレスを用いて、前記含浸の樹脂液
の基材全体への浸透を計りつつ、加熱加圧することによ
り過剰の樹脂液を基材外へ排出し重力を利用して流下せ
しめ前記含浸工程へ戻すことを特徴とする積層板の連続
製造方法。
(1) Essentially no drying process is required for long base materials;
In addition, there is an impregnation step in which a thermosetting resin liquid that does not substantially generate reaction by-products such as gas or liquid during the curing reaction process is applied, and a plurality of impregnated substrates are stacked and heated and pressurized to form a resin liquid. In the continuous manufacturing method of a laminate including a heating and pressing step of curing and integrating the substrates, the impregnation step and the heating and pressing step are arranged approximately perpendicularly, and in the impregnation step, the voids in each base material are The resin liquid is impregnated almost uniformly in the width direction, and in the heating and pressurizing step, the impregnation is carried out using a double belt press constituted by an endless belt that applies substantially uniform pressure over the entire pressure zone. While measuring the permeation of the resin liquid into the entire base material, the excess resin liquid is discharged out of the base material by heating and pressurizing, and is made to flow down using gravity and returned to the impregnation process. Continuous manufacturing method.
(2)積層板が金属箔を含浸された基材の複数枚と同時
に又は別工程にて重ね合わされてなる金属箔張積層板で
ある請求項1記載の積層板の連続製造方法。
(2) The continuous production method of a laminate according to claim 1, wherein the laminate is a metal foil-clad laminate formed by laminating a plurality of base materials impregnated with metal foil simultaneously or in a separate process.
(3)加圧帯全域にわたり実質的に均等な圧力を有する
、エンドレスベルトにより構成されるダブルベルトプレ
スが、該エンドレスベルトを一構成面とする加圧室を有
し、圧力媒体として流体を用いるダブルベルトプレスで
ある請求項1記載の積層板の連続製造方法。
(3) A double belt press consisting of an endless belt that has a substantially uniform pressure over the entire pressure zone, has a pressurizing chamber with the endless belt as one constituent surface, and uses a fluid as a pressure medium. The method for continuously manufacturing a laminate according to claim 1, which is a double belt press.
(4)加熱加圧工程での圧力が1〜100kg/cm^
2の範囲である請求項1記載の積層板の連続製造方法。
(4) Pressure in heating and pressurizing process is 1 to 100 kg/cm^
2. The method for continuously manufacturing a laminate according to claim 1.
(5)基材が紙である請求項1記載の積層板の連続製造
方法。
(5) The method for continuously manufacturing a laminate according to claim 1, wherein the base material is paper.
JP63297404A 1988-06-24 1988-11-25 Continuous manufacture of laminated sheet Pending JPH02143857A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP63297404A JPH02143857A (en) 1988-11-25 1988-11-25 Continuous manufacture of laminated sheet
EP19890111478 EP0347936A3 (en) 1988-06-24 1989-06-23 Continuous production of laminated sheet
KR1019890008758A KR910000355A (en) 1988-06-24 1989-06-24 Continuous manufacturing method of laminated sheet

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP63297404A JPH02143857A (en) 1988-11-25 1988-11-25 Continuous manufacture of laminated sheet

Publications (1)

Publication Number Publication Date
JPH02143857A true JPH02143857A (en) 1990-06-01

Family

ID=17846064

Family Applications (1)

Application Number Title Priority Date Filing Date
JP63297404A Pending JPH02143857A (en) 1988-06-24 1988-11-25 Continuous manufacture of laminated sheet

Country Status (1)

Country Link
JP (1) JPH02143857A (en)

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