JPH05138792A - Manufacture of phenol ic resin laminate - Google Patents

Abstract

PURPOSE:To improve punchability, water resistance and curing property, etc., by a method in which base material is impregnated with the resin component in which specified xylene-modified bisphenol aldehyde resin is added to drying oil-modified phenol.formaldehyde resin, and after said materials have been dried, they are laminated. CONSTITUTION:The base materials for a laminate are impregnated with the resin component obtained by adding following component A to following component B and are dried, and then, they are laminated, whereby a phenol resin laminate is produced. That is to say, the component A is the xylene-modified bisphenol.aldehyde resin obtained by reacting xylene resin with bisphenol compound under the existence of acid catalyst, and the component B is drying oil-modified phenol.formaldehyde resin. The adding amount of the component A to the component B is set in 3-50wt.% to 100wt.% of the component B. By such method, since punchability and water resistance are excellent and moreover, electric properties, mechanical properties and curing properties are good, the laminate is used for the base plate of printed wiring board or the base plate of electric insulation, etc.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は印刷配線基板、電気絶縁
基板等に用いられるフェノール樹脂積層板の製造法に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a phenol resin laminate used for printed wiring boards, electrically insulating boards and the like.

【０００２】[0002]

【従来の技術】最近、絶縁材料特に通信機および電子機
器に使用される積層板および銅張積層板は、加工設備の
自動化、省エネルギー等の観点から常温又は常温付近の
比較的低温での打抜き加工性の優れたものが要求されて
いる。このため、通常、積層板用樹脂としては各種のア
ルキルフェノールをフェノールと併用し、乾性油等で変
性したフェノール・ホルムアルデヒド樹脂が使用されて
いる。2. Description of the Related Art Recently, a laminated plate and a copper clad laminated plate used for an insulating material, particularly a communication device and an electronic device, are punched at room temperature or a relatively low temperature around room temperature from the viewpoint of automation of processing equipment and energy saving. Those with excellent properties are required. For this reason, a phenol / formaldehyde resin obtained by modifying various alkylphenols with phenol and modifying them with a drying oil is usually used as the resin for the laminate.

【０００３】しかし、乾性油で変性したフェノール・ホ
ルムアルデヒド樹脂は乾性油による変性のため硬化速度
が遅く、架橋密度も低下するため、積層板中の樹脂は硬
化不足になりやすく、耐熱性、機械強度、耐水性、等の
特性が低下する。また打抜き加工の際には、架橋密度が
低いため層間剥離等が発生しやすい。即ち、従来の乾性
油−フェノール類の反応物は乾性油に対するフェノール
の付加モル数が低く、また乾性油の重合物を生成するた
め、ホルムアルデヒドとの反応、即ち樹脂化反応および
硬化反応において反応速度および硬化速度が低下し、諸
特性低下の原因になっていた。However, the phenol-formaldehyde resin modified with a drying oil has a slow curing rate due to the modification with a drying oil and the crosslink density is lowered, so that the resin in the laminated plate is apt to be insufficiently cured, and the heat resistance and the mechanical strength thereof are high. , Water resistance, etc. are deteriorated. Further, during punching, delamination and the like are likely to occur due to the low crosslink density. That is, since the conventional drying oil-phenols reaction product has a low number of moles of phenol added to the drying oil and produces a polymer of the drying oil, the reaction rate in the reaction with formaldehyde, that is, the resinification reaction and the curing reaction. In addition, the curing speed was lowered, which was a cause of deterioration of various properties.

【０００４】この硬化性改良法としてフェノールとホル
ムアルデヒドとを酸触媒の存在下で反応させた反応生成
物を乾性油変性フェノール・ホルムアルデヒド樹脂に添
加する方法（特開昭６１−１２１９３２号公報）が提案
されている。この方法により若干の硬化性向上はみられ
るが、打抜き加工性、強靱性等の点において最近積層板
に要求されているレベルに対し未だ不十分なものであ
る。As a method for improving the curability, a method of adding a reaction product obtained by reacting phenol and formaldehyde in the presence of an acid catalyst to a drying oil-modified phenol-formaldehyde resin (Japanese Patent Laid-Open No. 61-121932) is proposed. Has been done. Although a slight improvement in curability can be observed by this method, it is still insufficient in terms of punching workability, toughness, etc. with respect to the level recently demanded for laminated sheets.

【０００５】[0005]

【発明が解決しようとする課題】本発明は、打抜き加工
性、耐水性に優れ、電気的特性、機械的特性、硬化性の
良好なフェノール樹脂積層板の製造法を提供するもので
ある。DISCLOSURE OF THE INVENTION The present invention provides a method for producing a phenolic resin laminate excellent in punching workability and water resistance, and having good electrical properties, mechanical properties and curability.

【０００６】[0006]

【課題を解決するための手段】本発明は、積層板用基材
に含浸する樹脂として下記（Ａ）成分を下記（Ｂ）成分
に添加した樹脂成分を使用するものである。 （Ａ）成分：キシレン樹脂とビスフェノール化合物とを
酸触媒存在下で反応させて得られるキシレン変性ビスフ
ェノール・アルデヒド樹脂。 （Ｂ）成分：乾性油変性フェノール・ホルムアルデヒド
樹脂。The present invention uses a resin component obtained by adding the following component (A) to the following component (B) as the resin with which the base material for a laminated plate is impregnated. Component (A): A xylene-modified bisphenol / aldehyde resin obtained by reacting a xylene resin and a bisphenol compound in the presence of an acid catalyst. (B) component: Dry oil-modified phenol-formaldehyde resin.

【０００７】本発明において、（Ａ）成分はフェノール
源としてビスフェノールＡやビスフェノールＦなどのビ
スフェノール化合物を用い、キシレン樹脂と酸触媒下で
反応させてキシレン変性ビスフェノール化合物を得る。
ビスフェノール化合物としては、ビスフェノールＡやビ
スフェノールＦの外に、ビスフェノールＡＤ、ビスフェ
ノールＡＦ等がある。酸触媒としては、三弗化硼素、塩
酸、硫酸等の無機酸や、蓚酸、酢酸、パラトルエンスル
ホン酸等の有機酸が用いられる。ビスフェノール化合物
とキシレン樹脂との配合割合は、使用するビスフェノー
ル化合物とキシレン樹脂の種類により異なるが、ビスフ
ェノール化合物１００重量部に対してキシレン樹脂４０
〜１００重量部が好ましい。両者の反応は、通常酸性下
で１００〜１５０℃で１〜５時間程度行い、その後、生
成した縮合水を蒸留により除去する。In the present invention, the component (A) uses a bisphenol compound such as bisphenol A or bisphenol F as a phenol source and is reacted with a xylene resin under an acid catalyst to obtain a xylene-modified bisphenol compound.
Examples of the bisphenol compound include bisphenol A and bisphenol F, as well as bisphenol AD and bisphenol AF. As the acid catalyst, inorganic acids such as boron trifluoride, hydrochloric acid and sulfuric acid, and organic acids such as oxalic acid, acetic acid and paratoluenesulfonic acid are used. The mixing ratio of the bisphenol compound and the xylene resin varies depending on the types of the bisphenol compound and the xylene resin used, but the xylene resin is 40 parts by weight with respect to 100 parts by weight of the bisphenol compound.
-100 parts by weight is preferred. The reaction between the two is usually carried out under acidic conditions at 100 to 150 ° C. for about 1 to 5 hours, and then the produced condensed water is removed by distillation.

【０００８】なお、フェノール源としてビスフェノール
化合物の外に、フェノール、クレゾール等とを併用する
こともできる。得られたキシレン変性ビスフェノール・
アルデヒド樹脂は単独では硬化しないが、レゾール型フ
ェノール樹脂と反応しそれに対して架橋剤的な作用をす
る。従って、（Ｂ）成分である乾性油変性フェノール・
ホルムアルデヒド樹脂と架橋反応して硬化し、可撓性の
みでなく耐水性等をも向上させる。乾性油変性フェノー
ル・ホルムアルデヒド樹脂は、例えば桐油等の乾性油と
フェノール類とを酸触媒で反応させ、さらにホルムアル
デヒドと塩基性触媒存在下で反応させてレゾール化する
ことにより合成できる。In addition to the bisphenol compound as the phenol source, phenol, cresol or the like may be used in combination. Obtained xylene-modified bisphenol
Although the aldehyde resin does not cure by itself, it reacts with the resol-type phenol resin and acts as a crosslinking agent for it. Therefore, the dry oil-modified phenol, which is the component (B),
Crosslinking reaction with formaldehyde resin cures and improves not only flexibility but also water resistance. The dry oil-modified phenol-formaldehyde resin can be synthesized, for example, by reacting a dry oil such as tung oil with phenols with an acid catalyst, and further reacting formaldehyde with a basic catalyst in the presence of a resol to form a resole.

【０００９】本発明の積層板は以上のようにして得られ
るキシレン変性ビスフェノール・アルデヒド樹脂を有機
溶剤に溶解した後あるいはそのまま乾性油変性フェノー
ル・ホルムアルデヒド樹脂に添加溶解してワニスとし、
クラフト紙、リンター紙、ガラス布、ガラス不織布、ポ
リエステル布、アラミド繊維布、帆布等の基材に含浸乾
燥し、通常３〜１０枚積層して加熱加圧成形することに
より得ることができる。The laminated sheet of the present invention is a varnish obtained by dissolving the xylene-modified bisphenol / aldehyde resin obtained as described above in an organic solvent or by directly adding and dissolving it in a dry oil-modified phenol / formaldehyde resin.
It can be obtained by impregnating and drying a base material such as kraft paper, linter paper, glass cloth, glass non-woven cloth, polyester cloth, aramid fiber cloth, and sail cloth, and usually laminating 3 to 10 sheets and heating and pressing.

【００１０】乾性油変性フェノール・ホルムアルデヒド
樹脂に対するキシレン変性ビスフェノール・アルデヒド
樹脂の添加量は、乾性油変性フェノール・ホルムアルデ
ヒド樹脂１００重量部に対して３から５０重量部が好ま
しく、さらに好ましくは１０〜３５重量％である。３重
量部より少ないと耐水性や打ち抜き加工性の向上効果が
殆どなく、５０重量部を越えると打抜き加工性が低下す
る。The addition amount of the xylene-modified bisphenol / aldehyde resin to the dry oil-modified phenol / formaldehyde resin is preferably 3 to 50 parts by weight, more preferably 10 to 35 parts by weight, relative to 100 parts by weight of the dry oil-modified phenol / formaldehyde resin. %. If it is less than 3 parts by weight, there is almost no effect of improving water resistance and punching workability, and if it exceeds 50 parts by weight, punching workability is deteriorated.

【００１１】なお、本発明において、（Ａ）成分及び
（Ｂ）成分以外の樹脂を全樹脂成分中５０％以内で配合
してもよい。このような樹脂としては未変性のレゾール
樹脂、アルキルフェノールのレゾール樹脂などである。In the present invention, resins other than the components (A) and (B) may be blended within 50% of all resin components. Such resins include unmodified resole resins and alkylphenol resole resins.

【００１２】[0012]

【作用】本発明で得られるフェノール樹脂積層板は、そ
のワニス用樹脂成分中に乾性油と結合しておらず、可撓
性及び耐水性を付与するキシレン変性ビスフェノール・
アルデヒド樹脂を含有しているので、打抜き加工性、耐
水性、電気的特性および機械的特性が良好となっている
と考えられる。この樹脂は乾性油変性フェノール・ホル
ムアルデヒド樹脂に対して、架橋剤的に働いて硬化し、
その硬化速度は乾性油変性フェノール・ホルムアルデヒ
ド樹脂のみの場合と同等以上である。The phenol resin laminate obtained by the present invention has a xylene-modified bisphenol-containing resin component for varnish which is not combined with a drying oil and imparts flexibility and water resistance.
Since it contains an aldehyde resin, it is considered that punching workability, water resistance, electrical characteristics and mechanical characteristics are good. This resin acts as a cross-linking agent and hardens against the drying oil modified phenol-formaldehyde resin,
The curing rate is equal to or higher than that of the case of only the dry oil-modified phenol / formaldehyde resin.

【００１３】[0013]

【実施例】以下、実施例をあげて本発明を説明する。 （合成例１）ビスフェノールＡ１５００ｇ、キシレン樹
脂（三菱瓦斯化学製「ニカノールＨ」）９００ｇ及び蓚
酸４５ｇを混合し、１３０℃で３時間反応した後、減圧
下で内温が１５０℃になるまで脱水し、メタノールで溶
解して樹脂分５０重量％のキシレン変性ビスフェノール
・ホルムアルデヒド樹脂（樹脂１）を得た。EXAMPLES The present invention will be described below with reference to examples. (Synthesis Example 1) 1500 g of bisphenol A, 900 g of xylene resin (“Nicanol H” manufactured by Mitsubishi Gas Chemical Co., Inc.) and 45 g of oxalic acid were mixed, reacted at 130 ° C. for 3 hours, and then dehydrated under reduced pressure until the internal temperature reached 150 ° C. Then, it was dissolved in methanol to obtain a xylene-modified bisphenol-formaldehyde resin (resin 1) having a resin content of 50% by weight.

【００１４】（合成例２）ビスフェノールＦ１３００
ｇ、キシレン樹脂（三菱瓦斯化学製「ニカノールＨ」）
９００ｇ及び蓚酸４５ｇを混合し、１３０℃で３時間反
応した後、減圧下で内温が１５０℃になるまで脱水し、
メタノールで溶解して樹脂分５０重量％のキシレン変性
ビスフェノール・ホルムアルデヒド樹脂（樹脂２）を得
た。(Synthesis Example 2) Bisphenol F1300
g, xylene resin ("Nicanol H" manufactured by Mitsubishi Gas Chemical Co., Ltd.)
After mixing 900 g and 45 g of oxalic acid and reacting at 130 ° C. for 3 hours, dehydration was performed under reduced pressure until the internal temperature reached 150 ° C.,
It was dissolved in methanol to obtain a xylene-modified bisphenol-formaldehyde resin (resin 2) having a resin content of 50% by weight.

【００１５】（合成例３）フェノール９４０ｇ、３７％
ホルマリン６４９ｇ、３５％塩酸２ｇの混合物を４時間
還流温度で反応後、減圧下で内温が１６０℃になるまで
脱水し、これをメタノールで溶解して樹脂分５０重量％
のフェノール・ホルムアルデヒド樹脂（樹脂３）を得
た。(Synthesis Example 3) 940 g of phenol, 37%
A mixture of 649 g of formalin and 2 g of 35% hydrochloric acid was reacted at reflux temperature for 4 hours, dehydrated under reduced pressure until the internal temperature reached 160 ° C, and dissolved in methanol to obtain a resin content of 50% by weight.
To obtain a phenol-formaldehyde resin (resin 3).

【００１６】（合成例４）フェノール１２００ｇ、桐油
８００ｇ、パラトルエンスルホン酸５ｇの混合物を８０
℃で３時間反応させた。次いでこれにトルエン８００ｇ
とトリエタノールアミン２０ｇを添加して希釈、中和
後、パラホルムアルデヒド５００ｇ、２５％アンモニア
水３０ｇを添加し、９０から１００℃で４時間反応さ
せ、次いで減圧下、脱水、脱トルエンを行ない、トルエ
ン１０００ｇとメタノール１０００ｇを添加して希釈
し、樹脂分５０重量％の桐油変性フェノール・ホルムア
ルデヒド樹脂（樹脂４）を得た。(Synthesis Example 4) 80 g of a mixture of 1200 g of phenol, 800 g of tung oil, and 5 g of paratoluenesulfonic acid was used.
The reaction was carried out at ℃ for 3 hours. Then 800 g of toluene
After diluting and neutralizing by adding 20 g of triethanolamine, 500 g of paraformaldehyde and 30 g of 25% ammonia water are added, and the mixture is reacted at 90 to 100 ° C. for 4 hours, then dehydrated and detoluene under reduced pressure. 1000 g and 1000 g of methanol were added and diluted to obtain a tung oil-modified phenol-formaldehyde resin (resin 4) having a resin content of 50% by weight.

【００１７】（合成例５）フェノール１０００ｇ、３７
％ホルマリン９８０ｇ、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・ホルム
アルデヒド樹脂（樹脂５）を得た。(Synthesis Example 5) Phenol 1000 g, 37
% Formalin 980 g and triethylamine 20 g are mixed and reacted at 60 ° C. for 2 hours, then concentrated under reduced pressure,
This was diluted with a mixed solvent of methanol / water = 80/20 to obtain a water-soluble low molecular weight phenol-formaldehyde resin (resin 5) having a resin content of 50% by weight.

【００１８】［実施例１，２および比較例１，２］合成
例５で得られた樹脂５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。次いでこの処理基
材に表１の配合で、それぞれ別々に調製した上塗りワニ
ス（樹脂１〜樹脂４）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３５
μｍの銅箔を重ね合わせ、１６０℃、８０ｋｇ／ｃｍ²
で６０分間加熱加圧し、厚さ１．６ｍｍのフェノール樹
脂積層板を得た。[Examples 1 and 2 and Comparative Examples 1 and 2] Kraft paper was impregnated with the resin 5 obtained in Synthesis Example 5 and dried,
A treated substrate having a resin content of 10.5% was obtained. Then, the treated base material was impregnated with the top coating varnishes (Resin 1 to Resin 4) separately prepared according to the composition shown in Table 1 and dried to obtain a total resin content 56
% Prepreg was obtained. Stack 8 of these, 35 on one side
Layered with copper foil of μm, 160 ℃, 80kg / cm ²
Was heated and pressed for 60 minutes to obtain a phenol resin laminate having a thickness of 1.6 mm.

【００１９】表１に各上塗りワニスの１５０℃熱盤上で
のゲル化時間と実施例１，２および比較例１，２で得た
積層板の特性を示す。Table 1 shows the gelling time of each topcoat varnish on a hot plate at 150 ° C. and the characteristics of the laminates obtained in Examples 1 and 2 and Comparative Examples 1 and 2.

【００２０】[0020]

【表１】 [Table 1]

【００２１】[0021]

【発明の効果】本発明の製造法によるフェノール樹脂積
層板は、表１の結果から明らかのように、打抜き加工
性、耐水性に優れ、電気的特性、機械的特性、硬化性が
良好であるので、印刷配線基板、電気絶縁基板等に好適
に用いることができる。As is clear from the results shown in Table 1, the phenol resin laminate obtained by the production method of the present invention is excellent in punching workability and water resistance, and is excellent in electrical properties, mechanical properties and curability. Therefore, it can be suitably used for a printed wiring board, an electrically insulating board, and the like.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.⁵ 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０５Ｋ 1/03 Ｊ 7011−4Ｅ // Ｂ２９Ｋ 61:04 (72)発明者 伊藤 幹雄 東京都千代田区内幸町１丁目２番２号 住 友ベークライト株式会社内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number in the agency FI Technical display location H05K 1/03 J 7011-4E // B29K 61:04 (72) Inventor Mikio Ito Chiyoda-ku, Tokyo Uchisaiwaicho 1-2-2 Sumitomo Bakelite Co., Ltd.

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】 下記（Ａ）成分を下記（Ｂ）成分に添加
した樹脂成分を積層板用基材に含浸乾燥し、積層成形す
ることを特徴とするフェノール樹脂積層板の製造法。 （Ａ）成分：キシレン樹脂とビスフェノール化合物とを
酸触媒存在下で反応させて得られるキシレン変性ビスフ
ェノール・アルデヒド樹脂。 （Ｂ）成分：乾性油変性フェノール・ホルムアルデヒド
樹脂。1. A method for producing a phenolic resin laminate, which comprises impregnating and drying a resin component obtained by adding the following component (A) to the following component (B) into a laminate substrate, and laminating and molding the resin component. Component (A): A xylene-modified bisphenol / aldehyde resin obtained by reacting a xylene resin and a bisphenol compound in the presence of an acid catalyst. (B) component: Dry oil-modified phenol-formaldehyde resin. 【請求項２】 （Ｂ）成分に対する（Ａ）成分の添加量
が（Ｂ）成分１００重量部に対して３から５０重量部で
あることを特徴とする請求項１記載のフェノール樹脂積
層板の製造法。2. The phenol resin laminate according to claim 1, wherein the amount of the component (A) added to the component (B) is 3 to 50 parts by weight per 100 parts by weight of the component (B). Manufacturing method.