JPS58112733A - Manufacture of copper lined laminated board - Google Patents

Abstract

(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

【発明の詳細な説明】 不発ｄＡは紙ｔｆｌ材とし熱硬化性樹脂を結合剤とする
銅張横層板の製造法、評しくｒｔ町朧化さｎた水溶性ま
たは手本溶性）瓢ノール樹脂ＩＩ−祇基材用前処塩液と
する銅張横層板の製造法に関丁；ｂものでその目的は安
定したそつ、ねじ３％性を付与するとと％に打抜加工性
ｒより低椙化すゐ銅張横層板を提供丁４にある。DETAILED DESCRIPTION OF THE INVENTION The unexploded dA is a method for manufacturing copper-clad horizontal laminates using paper TFL material and thermosetting resin as a binder, and is a method for producing copper-clad horizontal laminates using paper TFL material and thermosetting resin as a binder. Resin II - A method for manufacturing copper-clad horizontal laminates using a pre-treatment salt solution for base materials; The lower thickness of the copper clad horizontal laminate is provided in Table 4.

従来紙基材に一硬化性樹脂を含浸丁ゐ前Ｖも埋板として
用いらｎていゐ水浴性またに生水ｍ性ア２ノール情脂に
２２ノール鵡としてア瓢ノール、ｔたにクレゾール等側
鎖炭単数（Ｄ少ない２エノール類を用いた）凰ノールレ
ゾール１Ｉｆｆ！Ｉか用いらｎてい々０ ｃＱＪ方６＆は電気的耐湿轡性等に有効な方法として知
られているか１反向可佛性に乏しいため処堆液匠よゐ処
ｍ恢塗布１れる上塗ｇ衝詣との加熱加圧積層成形時の！
ｉＬル収縮に差を生じよ―す＠脂の％敏を生かせすまた
受塩状聰のそりｒ感化させる資因となって−る０ ”１７？、、水浴性またに生水溶性ｌＩｌ脂は加熱硬化
の際の硬化ＩｆＬ細か大き−ため銅張積層板として加熱
加圧成形さｒｔｂ際の肉方向の収細か表向に１ねらｎた
鋼σ（のＩＩＩ量形よりはるかにλきいため鋼はく幽か
凸状にそ、０か発生するため実際にプリント配−板とし
て加工丁４際にトラブルｒ生じ易い。Conventionally, a paper base material impregnated with a monocuring resin has not been used as a filling plate. Isoside chain carbon single (using 2 enols with less D) 凰norresol 1Iff! QJ method 6 & is known as an effective method for electrical moisture resistance, etc. However, due to its poor reversibility, it is recommended to use a topcoat which is often applied by a liquid manufacturer. During heating and pressure lamination molding with pressure!
It makes a difference in the contraction of lIl and takes advantage of the sensitivity of fat, and also causes the sensitization of warping in the salt-receiving body. Because the hardening IfL during heat hardening is large, the shrinkage in the thickness direction when heated and press-formed as a copper clad laminate is much λ larger than the steel σ (III), which has a surface direction of 1 Since the steel flakes may be warped or warped in a convex shape, troubles are likely to occur when it is actually processed as a printed circuit board.

筐霞、近年着しい畳及を示している電子５Ｉｊｂその他
の部品を自動的に挿入子ゐ効皐を低下させる大きな要因
となり−てい；ｂ。The electronic 5IJB and other parts, which have been showing increasing decline in recent years, have become a major factor in reducing the effectiveness of the automatic inserter; b.

不発明にＣｔ）ような点に鑑みてなさｎたもので紙ｒ基
材、熱硬化性樹脂ｒＭ合剤とし、表面ＫｇＡｒＸ＜を重
ね合せて加熱加圧して銅侵横層数ン製造丁４に際し、紙
基材に勢硬化性樹脂ｒ宮浸す、ｅ１削或いは含浸する時
に紙題材に２Ｓノ一ル１モルニ対してオルソクレゾール
０．０５％ル以上さらＫ　７　ｓノールｗ４１モルに対
し１．０モル以止のホルムアルデヒドｒ反応させて１６
町像化さｎた水溶性ｆたに半水溶性のレゾール型フェノ
ール樹脂ｒ含浸させること１上％黴と丁ゐものでろゐ。In view of the above-mentioned points (Ct), the paper base material and thermosetting resin mixture were used, and the surfaces KgAr When immersing, removing or impregnating the paper substrate with a hardening resin, 0.05% or more of orthocresol per 1 mole of 2S alcohol is added to the paper material, and 1. 16 by reacting with formaldehyde r of 0 mol or more
If the water-soluble material that has been developed is impregnated with a semi-water-soluble resol type phenolic resin, it will contain 1% mold and mildew.

不発明の紙基材処理用の水浴性または半水溶性フェノー
ル樹脂にフェノール１モルに対しオルソクレゾール０．
０５モル〜１．０モル、望ましくは０．０５モル−０，
５モル、敵も望ｌしくに０゜１〜０．２モル【・用−ア
ルデヒドとしてにホルムアルデヒドｒ全２瓢ノール類ｆ
対して１．０〜６゜０モル］１ｌｌＬ（に２．０〜５．
０モル【、またレゾール化触媒としてアミン類、アルカ
リ金属水酸化物、アルカリ金属酸化物のうちｍ″ｔしく
に５級ア建ン【ア誂ノール１１１１モルに対してｏ、ｏ
　ｏ　ｓ〜０．５モル望１しくは０．４モルｒ用い低温
で長時間緩やかＫｒ５Ｌ応名せることれより低分子量（
７Ｊメチロール化物ｒ多く富む可塑化さｎた樹脂液で７
ｈる。A water-bathable or semi-water-soluble phenolic resin for treating paper substrates containing 0.0% orthocresol per mole of phenol.
05 mol to 1.0 mol, preferably 0.05 mol-0,
5 mol, the enemy preferably 0゜1~0.2 mol [・Formaldehyde as aldehyde r all 2 gourd nols f
1.0-6゜0mol] 1llL (2.0-5゜mol)
0 mol [, and m''t of amines, alkali metal hydroxides, and alkali metal oxides as resolization catalysts]
0.5 mol preferably 1 or 0.4 mol.
7J with a plasticized resin liquid rich in methylol compounds.
hru.

かくして得られた樹脂液は電気Ｐ３＃用リンター＃’！
またにり９？ト紙もしくに罰・・記り／ター紙、り２フ
ト紙の混抄紙等に対し極めて艮好な浸透性ｒ有するもの
であって可塑化さｒしたことによる第２含浸上ｍｐ樹脂
との硬化性、架檎度等か近似することから層形収縮か均
一化かつ緩和され積層品としてのそｖｍ象ｒより少ｌ〈
なゐ０また。　ｏＪｍ化により打抜加工時の瞬間的な伽
撃およびゼん断破壊の伝播【轍やかにすることから、よ
り低い温度での打抜加工ｒ可能れ丁ゐ。The resin liquid thus obtained is used as a linter for electric P3#!
Mata Niri 9? It has an extremely good permeability to mixed paper such as 2-ft paper, 2-ft paper, etc., and the second impregnation layer is made of MP resin by being plasticized. Since the curing properties, curvature, etc. of
Nai 0 again. OJm reduces the propagation of instantaneous shock and shear fracture during punching, making it possible to punch at lower temperatures.

尚ここで用いる紙基材としてにリンター紙、クラット紙
＊２者の混抄紙、レーヨン紙など電気絶縁用原紙として
用−らｒする全てＫｊｌ用嘔れるＯ窒累化合物等鵞當む
他ｅ＞水溶性、半水溶性樹脂に対しても有効である０ レゾール化用触媒として框通常３級アミンか用いらｎト
リメチルアミン、トリエチルアミントリエタノールアミ
ン等かＴｏケらｎ、こ〕他Ｃアルカリ金属水酸化物の水
酸化リチウム゛、水酸化パリクムや水酸化マグネシウム
、水酸化カリウム、水酸化ナトリウム、等のほか、多く
のものか使用さ′ｎるかこの場合Ｋに反応のｊｌｉ終工
程で炭酸ガスによる結晶化やＩＩｌ！による中和等によ
りて系外に除去さｎ　；ｂ　。The paper base materials used here include linter paper, Krat paper*2 mixed paper, and rayon paper, all of which are used as base papers for electrical insulation, including O-nitrogen compounds, etc. It is also effective for water-soluble and semi-water-soluble resins. As a catalyst for resolization, tertiary amines are usually used, such as trimethylamine, triethylamine, triethanolamine, etc., and other alkali metal hydroxides. In addition to lithium hydroxide, paricum hydroxide, magnesium hydroxide, potassium hydroxide, sodium hydroxide, etc., many other substances are used. Crystallization and IIl! It is removed from the system by neutralization with n;b.

アルデヒド源としては、３７％以上ホルマリン、８０％
バラホルムアルデヒド等か単独またに併用さｒするか限
定さｎるもの′Ｃにない０このようドして得られた几埴
液は前述Ｑ）紙基材に＆漬また框吹き付け１％により含
浸さ２ｔ；ｂＱさらに一’ｔ（０上に目的とする棟々Ｑ
）時性に得るための上塗り用樹脂【含浸塗布して検層用
プリプレグに侍、こ１ｒＬ２Ｆ９ｒ定枚数重ねその最外
側Ｃ銅に＜１を重ね付せ常法によｏ７！１ｌｌｌｌｌｌ
Ｉ％加圧敢形して銅張積層板に得ゐ０又、処理液は５紙
基材に。As an aldehyde source, 37% or more formalin, 80%
There are no limitations on whether rose formaldehyde or the like can be used alone or in combination.The clay solution obtained in this way is impregnated with the paper base material mentioned above in Q) by dipping or by spraying 1% on the frame. 2t; bQ further 1't (target ridge Q on 0
) Resin for topcoating to obtain the desired temperature [Apply impregnation and apply a certain number of sheets of this 1rL2F9r to the prepreg for logging, and apply <1 to the outermost C copper using the usual method o7!1llllllll
I% pressure was applied to the copper-clad laminate, and the treatment solution was applied to the paper base material.

上塗り用樹脂と混付して含浸することも出来ゐ０実施例 フェノール１８８ｇ、オルンクレゾール６６ｇ、３７％
ホルマリン１８０ｇｋＲ＆コンデンサｒセットした２２
スコに取り攪拌しながら水散化バリウム７ｇ１ｒ加χて
から７０℃ｌで加勢して反応させ１６０℃でのゲル化か
５分にな心まで反応さゼたのち冷却子ゐ。次に＆応系内
Ｃ炭酸ガスｒ吹き込んで攪拌に絖は霞のち沈際物１を系
外に除いた但・Ｊ脂ａｖ＊ｐよひメチルアルコールによ
り固形分１０％代稀釈してリンター紙に含浸嘔せ、１５
０℃で５分間乾燥石ぜ７？、（１）ち。It can also be impregnated by mixing it with the top coating resin.Example: 188g of phenol, 66g of orincresol, 37%
22 with formalin 180gkR & capacitor r set
Add 7g 1r of aqueous barium to the solution while stirring, then react at 70°C to gelatinize at 160°C.After reacting to the core in 5 minutes, cool the mixture. Next, carbon dioxide gas was blown into the reaction system and stirred until it became hazy, and then the sediment 1 was removed from the system. Impregnated with vomiting, 15
Dry stones for 5 minutes at 0℃7? , (1) Chi.

上塗、０用植物油瀝こ性フェノール樹脂ｒ官浸乾旅（１
４０℃５分）させ全付層樹脂分５０％の含浸紙を得る。Topcoat, 0 vegetable oil, succulent phenolic resin, 1
40° C. for 5 minutes) to obtain impregnated paper with a total resin content of 50%.

Ｃの宮浸紙８枚と最外側に飯層剤付５５ミクロン銅ｔ’
ｘ＜’ｒａｇし両１１１にステンレス似およびクツシラ
ン材でサンドウィッチ状にしてから１７０℃１００ｋｇ
／ａｔの温度および圧力ｆより６０分閣加熱硬化させて
冷却し片面に銅に〈層ｒ有する蛸張積層叡ｒ得る。8 pieces of paper C and 55 micron copper t' with rice layer on the outermost layer
x<'rag, make both 111 into a sandwich shape with stainless steel-like material and Kutsushiran material, then 100kg at 170℃
The material is heated and cured at a temperature and pressure of /at for 60 minutes and then cooled to obtain a laminate having a layer of copper on one side.

比較例１ フェノール１８８ｇ、インプロビルフェノール４０ｇ。Comparative example 1 188g of phenol, 40g of Improvirphenol.

５７％ホルマリン５３５　ｇｋ還還流コンデンサー上セ
ツトたフラスコに取り攪拌しながらトリメチルアミツ１
０ｇｋ加えてから、加熱ｒ開始して６０℃で＆応させ１
６０℃でのゲル化か３分〜４分になる１で反応さぜたの
ち冷却する０この樹脂液を水とメチルアルコールにより
固形分１０％に稀釈してリンター紙匠せ浸させ実施例１
と同様にして含浸紙を作既しざらＶ（実施例１と同様に
して片Ｉｌ！１ｌｌＫ＃ｉｌはく層ｒ有する銅＊Ｓｔ層
板χ得ゐ。57% formalin 535gk reflux In a flask set on a reflux condenser, add trimethylamic acid 1 while stirring.
After adding 0 gk, start heating at 60℃ & let it react 1
The resin liquid was diluted with water and methyl alcohol to a solid content of 10% and soaked in linter paper.Example 1
Impregnated paper was prepared in the same manner as in Example 1. A copper*St layered plate having a foil layer r was prepared in the same manner as in Example 1.

比較例２ ）２ノ一ル１８８ｇ、５７゛％ホルマリン４８５ｇ、ト
リメチルアミツ１０ｇｋ還流コンデンサｔセットしたフ
ラスコにと９７０℃で反工６させ１６０℃にンけるグル
化か５分に７）ったと（ろで反応？終了し米施例１と同
様にして片面Ｃ銅はく層に有丁ゐ鋼張積層板ｒ得ゐ。Comparative Example 2) 188 g of 2-lol, 485 g of 57% formalin, and 10 g of trimethylammonium were placed in a flask set with a reflux condenser, heated at 970°C, and heated to 160°C for 5 minutes. (After the reaction was completed, a steel clad laminate with a copper foil layer on one side was obtained in the same manner as in Example 1.

前述の実施例及び比較例のｆＡｓ張積層板ｔ５００ｍｍ
角に切断して受堆状態訃よび１３５℃１５分乾燥後のそ
９ｒ副定したところ次表の給米に侍た０ （単位：難） 注）測足万汰ａ、試桝を定盤上に２き４隅の１点′ｆｙ
さえ７′？時に最大Ｋにねよゐ倉１１−測定する。fAs clad laminates of the above-mentioned Examples and Comparative Examples T500mm
After cutting into corners and determining the condition of the pile and drying at 135℃ for 15 minutes, it was determined that the rice satisfies the rice feeding shown in the following table. 2 points on the top and 1 point in the 4 corners'fy
Sae 7'? At the same time, the maximum K is measured.

表に示すよりに本発明（／Ｊものに比較例Ｖ（対してい
ｆｎの場付もえ−９の埴に小さぐ加熱後の厘も大幅に数
置さγし心ことがわかゐ０ また不発明の紙基材処理液ｒ町豫化することによって打
抜加工時の予備加熱Ｉｉ度に１０〜２０℃低温化で＊＊
際にプリント配線板加工の際の那工効率向上か可能と７
１ｖた０ １１As shown in the table, it can be seen that compared to Comparative Example V (fn) of the present invention (/J), the amount of heat after heating was significantly lower than that of fn. The paper base treatment liquid of the invention can be heated at a temperature of 10 to 20 degrees Celsius to preheat during punching.
It is possible to improve efficiency when processing printed wiring boards.7
1vta0 11

Claims (1)

【特許請求の範囲】[Claims] １゜紙ｔｊｌｔ材、熱硬化性樹脂を結合剤とし、表向に
＠框（會１ね曾せて加部加圧する銅張横層板の製造法に
於て、舐基材に熱硬化性樹脂を含浸する前或いは含浸す
る時に１紙基材パフエノール１モルに対して、オルソク
レゾール０．０５モル以上、さらにフェノール類１モに
＃を対し１．０モル以上のホルムアルデヒドｒ反応させ
てなる可塑化石Ｒた水溶性またに牛水杉性のレゾールＪ
ｉ１７ｓノール樹脂を含浸させることに特徴とする銅張
積層板の製造法。1゜In the manufacturing method of copper-clad horizontal laminate board, which uses paper tjlt material and thermosetting resin as a binder, and pressurizes the surface by applying pressure, thermosetting resin is used as the base material. A plasticizer made by reacting 0.05 mol or more of orthocresol with 1 mol of parphenol per paper base material and 1.0 mol or more of formaldehyde with 1 mol of phenol and #1 before or during impregnation with resin. Fossil R, water soluble and bovine water cedar resol J
A method for producing a copper-clad laminate, characterized by impregnating it with i17s nord resin.