JPS5924661A - Metallic foil 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】 この発明は金属箔張り積層板に関するものである。[Detailed description of the invention] This invention relates to a metal foil-clad laminate.

金属箔張り積層板には、打抜き加工性、耐衝撃性に優れ
、しかも當温下でも高温下でも優れたビーリング強度を
有することが望まれている。発明者らは、このような要
望に応えるために一連の研究を重ねた結果、硬化物の熱
変形温度が７５℃以上の熱硬化性樹脂を基材含浸用樹脂
として用いると、常温および高温下において優れたビー
リング強度を伺与できるようになることを見いだした。Metal foil-clad laminates are desired to have excellent punching workability and impact resistance, as well as excellent beering strength at both low and high temperatures. As a result of a series of studies to meet these demands, the inventors found that when a thermosetting resin with a heat deformation temperature of the cured product of 75°C or higher is used as a base material impregnation resin, it can be used at room temperature and high temperature. It was discovered that excellent beer strength can be obtained in the following manner.

しかし、この場合には、打抜き加工性および耐衝９性は
低下する。これに対して、硬化物の熱変形温度が７５℃
未満の熱硬化性樹脂を基材含浸用樹脂として用いると、
打抜き加工性、耐衝撃性お□よび常温でのビーリング強
度の優れたものは得られるが、高温下でのビーリング強
度が著しく低下する。そこで、さらに研究を重ねた結果
、硬化物の熱変形温度が７５℃以上の熱硬化性樹脂組成
物自身もしくはこれを基材に含浸させたものからなる層
を、金−箔の接着剤層に続いて形成し、さらにその層に
続いて硬化物の熱変形温度が７５℃未満の熱硬化性樹脂
組成物を基材に含浸させたものを形成し、その状態で硬
化処理すると、高温下でのピーリング強度が向上し、打
抜き加工性、面’ｒｔｆａｉ撃性、常温および高温下で
のビー１ノング強度の優りた金属箔張り積層板が得られ
るよ月こなることを見いだし、この発明を完成した。However, in this case, punching workability and impact resistance9 are reduced. On the other hand, the heat distortion temperature of the cured product is 75℃
When a thermosetting resin of less than
Although excellent punching workability, impact resistance, and bealling strength at room temperature can be obtained, the bealling strength at high temperatures is significantly reduced. Therefore, as a result of further research, a layer consisting of a thermosetting resin composition itself or a base material impregnated with the thermosetting resin composition with a heat distortion temperature of 75°C or higher was added to the gold-foil adhesive layer. Subsequently, a layer is formed in which the base material is impregnated with a thermosetting resin composition whose heat distortion temperature of the cured product is less than 75°C, and when cured in this state, discovered that it would be possible to obtain a metal foil-clad laminate with improved peeling strength, punching workability, surface resistance, and B1N strength at room and high temperatures, and completed this invention. did.

すなわち、この発明は、金属箔と、接着Ｔｄｌ　Ｉ＠と
、硬化物の熱変形温度が７５℃以上の第１の熱硬イヒ性
樹脂組成物自身の硬化層もしくＣまその熱硬イヒ性樹脂
組成物を基材に含浸させて硬化させた硬イし層と、硬化
物の熱変形温度が７５℃未満の第２の熱硬化性樹脂組成
物を基材に含浸させて硬イヒさせた硬化層をこの順で連
続的に備えてし）ることを特徴とする金属箔張り積層板
をその要旨とするものである。In other words, the present invention provides a metal foil, an adhesive Tdl I@, and a cured layer or C itself of a first thermosetting resin composition having a heat deformation temperature of 75° C. or higher. A hardening layer was obtained by impregnating a base material with a resin composition and hardening it, and a second thermosetting resin composition having a heat deformation temperature of the cured product of less than 75°C was impregnated into a base material and hardening it. The gist of the invention is a metal foil-clad laminate characterized in that the hardened layers are continuously provided in this order.

つぎに、この発明の詳細な説明するつ この発明で用いる金属箔としてｌま、通常のものが用り
、、１られる。また、金属箔と第１の熱硬（Ｉｓ性樹脂
組成物自身の硬化層もしくζよその熱硬イヒ性樹ｎ旨組
成物を基材に含浸させて硬化させた硬イし層とを接着す
る接着剤層も通常用いられる接着剤４こよりμに設定す
ることが効果の点で好ましい。Next, a detailed explanation of the present invention will be given.General metal foils are used in the present invention. In addition, the metal foil and the first thermosetting resin composition (either a hardening layer of the IS resin composition itself or a hardening layer obtained by impregnating the base material with another thermosetting resin composition and curing the resin composition) can be used. From the viewpoint of effectiveness, it is preferable that the adhesive layer to be bonded is set to a μ smaller than 4, which is a commonly used adhesive.

上記第１の熱硬化性樹脂組成物自身の硬化層もしくはそ
の熱硬化性樹脂組成物を基材に含浸させた硬化層は、硬
化物の熱変形温度が７５℃以上の熱硬化性樹脂組成物（
ラジカル重合性樹脂組成物）をそのままもしくは：ｉ１
０常用いられる糸目（紙、布等）に含浸させて硬化させ
ることにより構成される。上記熱硬化性樹脂組成物は特
に限定するものではなく、硬化物の熱変形温度が７５℃
以上のものであればよい。また、第１の熱硬化性樹脂組
成物をそのままもしくはそれを基材に含浸させて硬化さ
せた硬化層の厚みは、３０〜３００μに設定することが
効果の点で好ましい。The cured layer of the first thermosetting resin composition itself or the cured layer obtained by impregnating the substrate with the thermosetting resin composition is a thermosetting resin composition whose heat distortion temperature of the cured product is 75°C or higher. (
Radical polymerizable resin composition) as it is or: i1
It is constructed by impregnating and curing commonly used threads (paper, cloth, etc.). The above thermosetting resin composition is not particularly limited, and the heat deformation temperature of the cured product is 75°C.
Any of the above is sufficient. Further, from the viewpoint of effectiveness, it is preferable that the thickness of the cured layer obtained by curing the first thermosetting resin composition as it is or by impregnating the base material with it is set to 30 to 300 μm.

上記の硬化層に続いて形成される、第２の熱硬化性樹脂
組成物を基月に含浸させて硬化させた硬、化層は、硬化
物の熱変形温度が７５℃未満の熱硬化性樹脂組成物（ラ
ジカル重合性樹脂組成物）を通常の基材に含浸させて硬
化させることにより構成される。このＩｓ　２の熱硬化
性樹脂組成物も特に限定するものではなく、硬化物の熱
変形温度が７５℃未満のものであればよい。The hardening layer, which is formed subsequent to the above-mentioned hardening layer and is made by impregnating and hardening the second thermosetting resin composition, is a thermosetting layer whose heat distortion temperature of the cured product is less than 75°C. It is constructed by impregnating a normal base material with a resin composition (radically polymerizable resin composition) and curing it. The thermosetting resin composition of Is 2 is not particularly limited as long as it has a heat deformation temperature of less than 75° C. as a cured product.

この発明の金属箔張り積層板は、以とのような層構造に
なっているため、打抜き加工性、耐衝撃性に富み、常温
のみならず高温下でのピーリング強度も優れているので
ある。Since the metal foil-clad laminate of the present invention has the layered structure as described below, it has excellent punching workability and impact resistance, and has excellent peeling strength not only at room temperature but also at high temperatures.

つぎに、実施例について説明する。Next, examples will be described.

（実施例１） 市販のＩＩ、解銅箔に接着剤としてビスフェノールＡ型
エポキシ樹脂（チバーガイギー社製、アラルダイトＧ　
Ｙ　２５０　）　１００重量部（以下「部」と略す）と
ポリアミド（チバーガイギー社製、）１−ドナー１１Ｙ
８４０）６０部を混合したものをロールコーターで厚み
３０μに塗布し、１２０℃で５分間予備硬化させた。つ
ぎに、これに、硬化物の熱変形温度が９０℃である不飽
和ポリエステル樹脂１００部にも一ブチルパーオキシベ
ンゾエート１部を添加した樹脂組成物（樹脂組成物Ａ）
をロールコーターで厚み８０μに塗布し、さらに硬化物
の熱変形温度が５５℃である不飽和ポリエステル樹脂１
００部にｔ−ブチルパーオキシベンゾエート１部を添加
した樹脂組成物（樹脂組成物Ｂ）を含浸させたクラフト
紙５枚を２ミネートし、・続いてポリエステルフィルム
により被徨し、その状態で１１０℃で１０分間、さらに
１５０℃で１０分間硬化させることにより厚み約１．６
門の片面銅張り積層板を得た。(Example 1) Bisphenol A type epoxy resin (manufactured by Civer Geigy, Araldite G
Y250) 100 parts by weight (hereinafter abbreviated as "parts") and polyamide (manufactured by Civer Geigy) 1-Donor 11Y
A mixture of 60 parts of 840) was applied to a thickness of 30 μm using a roll coater, and precured at 120° C. for 5 minutes. Next, a resin composition (resin composition A) was prepared by adding 1 part of monobutyl peroxybenzoate to 100 parts of an unsaturated polyester resin whose cured product has a heat distortion temperature of 90°C.
Unsaturated polyester resin 1 was coated with a roll coater to a thickness of 80μ, and the cured product had a heat deformation temperature of 55°C.
Five sheets of kraft paper impregnated with a resin composition (resin composition B) containing 1 part of t-butyl peroxybenzoate and 1 part of t-butyl peroxybenzoate were laminated, and then covered with a polyester film, and in that state was heated to 110 By curing at ℃ for 10 minutes and then at 150℃ for 10 minutes, the thickness is approximately 1.6
I got a single-sided copper-clad laminate for the gate.

（実施例２） 実施例１と同様にして市販の電解銅箔に対して接着剤の
塗布および予備硬化を施したのち、硬化時の熱変形温度
が８５℃である不飽和ポリエステル樹脂１００部に（−
ブチルパーオキシベンゾエート１部を添加した樹脂組成
物をロールコータ−で厚み１００μに塗布し、１００℃
で３分間予備硬化させた。これ以降は実施例１と同様に
して厚み約１．６馴の片面銅張り積層板を得た。(Example 2) A commercially available electrolytic copper foil was coated with an adhesive and precured in the same manner as in Example 1, and then 100 parts of an unsaturated polyester resin having a heat distortion temperature of 85°C during curing was applied. (−
A resin composition containing 1 part of butyl peroxybenzoate was applied to a thickness of 100 μm using a roll coater, and heated to 100°C.
It was precured for 3 minutes. Thereafter, the same procedure as in Example 1 was carried out to obtain a single-sided copper-clad laminate having a thickness of about 1.6 mm.

（比較例１） 樹脂組成物Ａの塗布をとりやめ、接着剤層に直接樹脂組
成物Ｂを含浸させたクラフト紙をラミネートした。得ら
れた゛片面銅張り積層板は厚み約１．６門のものであっ
た。(Comparative Example 1) Application of resin composition A was stopped, and kraft paper impregnated with resin composition B was directly laminated onto the adhesive layer. The obtained single-sided copper-clad laminate had a thickness of about 1.6 mm.

（比１１佼（列　２　） 実施例１と同Ｊ＋Ａ＞にして市販のｔｌｌ、　ｆ’ｌ”
（銅箔に対して接ン１゛１剤の塗布および予信Ｉ硬化を
施したのち、樹脂、ｔｌｔ成物Ａを含浸さぜたクラフト
紙５枚をラミホー１’シ、ａらにポリニスデルフィルム
で被覆し、１１０℃で１．　（１３，）間、続いて１．
５０　’Ｃで１０分間硬化させ、ｊｌｙみ約１．、６　
ｍｍの片面銅張り積層板を得た。(Ratio 11 (column 2) Same as Example 1 J+A> and commercially available tll, f'l"
(After applying adhesive 1 to the copper foil and pre-curing it, apply 5 sheets of kraft paper impregnated with resin and TLT product A to lamiho 1' and polyurethane to a. coated with Delfilm and heated at 110° C. for 1. (13,) minutes, followed by 1.
Cure for 10 minutes at 50'C, approximately 1. ,6
A single-sided copper-clad laminate of mm was obtained.

す、−１−の実施例、比較例で得られた片面銅張り積層
ＩＪｑについて、打抜き加工性、耐％ｉ撃性、常温およ
び１１１℃におけるビーリング強バ（の試験結果を下１
尼の表に示した。Regarding the single-sided copper-clad laminated IJq obtained in Examples and Comparative Examples of -1-, the test results for punching workability, %I impact resistance, and beer strength at room temperature and 111°C are shown below.
It is shown in the table below.

す：優れている　　　　×：劣っている一Ｊジ続１ｉ１
ｆ正居：（自発） 昭ｆ１．Ｉ５Ｂ年１０月１８１１ 特許庁長官　殿 １、串（／ｌの表示 昭ｔｌ１５７（Ｔ’閘猜萌０３４００７号２、発明の名
称 金属箔張り積層板 ３、　　？ｉｉ正をする考 事件との関係　　　　　２１１１出１９１友住　　　所
　　　　人１切ｒＪ門真市大字門真１０４１１１？Ｉｔ
地名　称（５１１３）松下電工株式会社 代表者　　代表１叫帝没　小　林　郁（はが１名）４、
代理人 な　　　　し 〔特願昭５７−１３４００７号に関する補正の内容〕７
、補正の内容 （１）明８１１１１の特許請求の範囲ＩＷの全文を別紙
のとおりにＩＩＩ正する。S: Excellent ×: Inferior
f Masai: (spontaneous) Showa f1. I5B October 1811 Commissioner of the Japan Patent Office 1, Kushi (/l indication Showa tl 157 (T' 閘猜え034007No. 2, title of the invention Metal foil clad laminate 3, ?ii Correlation with the case to be corrected 2111 Out 191 Tomozumi Address 1 person rJ Kadoma City Oaza Kadoma 104111?It
Place name Name (5113) Matsushita Electric Works Co., Ltd. Representative Representative 1 Shou Tei passed away Iku Kobayashi (1 person) 4.
No agent [Contents of amendment regarding patent application No. 57-134007] 7
, Contents of amendment (1) The entire text of claim IW of Mei 81111 is revised as shown in the attached sheet.

（２）明９■１吉第４頁第１行に「５〜１０」とあるを
、１−５〜３０」と訂正する。(2) In the first line of page 4 of page 4 of 9.1.1, correct the text ``5 to 10'' to ``1-5 to 30''.

〔補正後の特許請求の範囲〕[Claims after amendment]

２、特許請求の範囲 １１１　　金属箔と、接着剤層と、硬化物の熱変形温度
が７５℃以上の第１の熱硬化性４＾１脂組成物自月の硬
化層もしくはその熱硬化性樹脂組成物を基４Ａに含浸さ
せ゛ζ硬化させた硬化層と、硬化物の熱変形温度が７５
℃未満の第２の熱硬化性樹脂組成物を基材に含浸させて
硬化さ（た硬化層をこの順で連続的に備えていることを
特徴とする金属箔張り積層板。2. Claim 111 A metal foil, an adhesive layer, a first thermosetting 4^1 resin composition having a heat deformation temperature of 75° C. or higher, or a thermosetting resin thereof. The cured layer obtained by impregnating the base 4A with the composition and curing it, and the heat distortion temperature of the cured product are 75
A metal foil clad laminate, characterized in that it comprises a cured layer which is formed by impregnating a base material with a second thermosetting resin composition having a temperature of less than 0.degree. C. and curing the layer in this order.

（２）接着剤層の厚めが５〜■〆１であり、第１の熱硬
化性樹脂組成物自書の硬化層もしくはその熱硬化性樹脂
組成物を基材に含浸さ−１゛ζ硬化さ・Ｕノζ硬化層の
厚みが３０〜３００　ｐである特許ｉｆｆ求の範囲第１
項記載の金属箔張り積層板。(2) The thickness of the adhesive layer is 5~1゛1, and the first thermosetting resin composition is a hardened layer or the thermosetting resin composition is impregnated into the base material and cured by -1゛ζ The first range of the patent if the thickness of the S/U-ζ hardened layer is 30 to 300p
The metal foil-clad laminate described in Section 1.

Claims (2)

【特許請求の範囲】[Claims] （１）金や４１箔と、接着剤層と、硬化物の熱変形温度
が７５℃以上の第１の熱硬化性樹脂組成物自身の硬化層
もしくはその熱硬化性樹脂組成物を基材に含浸させて硬
化させた硬化層と、硬化物の熱変形温度が７５℃未満の
第２の熱硬化性樹脂組成物を基材に含浸させて硬化させ
た硬化層をこの順で連続的に備えていることを特徴とす
る金属箔張り積層板。(1) Gold or 41 foil, an adhesive layer, and a cured layer of the first thermosetting resin composition whose heat distortion temperature of the cured product is 75°C or higher or the thermosetting resin composition as a base material. A cured layer that has been impregnated and cured, and a cured layer that has been cured by impregnating a base material with a second thermosetting resin composition whose heat distortion temperature of the cured product is less than 75 ° C. are successively provided in this order. A metal foil-clad laminate characterized by: （２）接着剤層の厚みが５〜１０μであり、第１の熱硬
化性樹脂組成物自身の硬化層もしくはその熱硬化性樹脂
ｌｌｌ１１．　ＩＢＭ物を基材に含浸させて硬化させた
硬化層の厚みが３０〜３００μである特許請求の範囲第
１項記載の金属箔張シ積層板。(2) The thickness of the adhesive layer is 5 to 10 μm, and the cured layer of the first thermosetting resin composition itself or its thermosetting resin lll11. The metal foil-clad laminate according to claim 1, wherein the thickness of the cured layer obtained by impregnating and curing the IBM material into the base material is 30 to 300 microns.