JPS6230129A - Production of laminated board - Google Patents
Production of laminated boardInfo
- Publication number
- JPS6230129A JPS6230129A JP16932085A JP16932085A JPS6230129A JP S6230129 A JPS6230129 A JP S6230129A JP 16932085 A JP16932085 A JP 16932085A JP 16932085 A JP16932085 A JP 16932085A JP S6230129 A JPS6230129 A JP S6230129A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- thermosetting resin
- unsaturated polyester
- base material
- polyester resin
- 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.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は打抜加工性の良好な熱硬化性樹脂積層板の製造
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for manufacturing a thermosetting resin laminate having good punching workability.
（従来の技術）
最近、電子機器に使用される印刷配＃ｊ板は高密度化に
伴い、自動部品、実装技術も進歩し、より厳しい寸法精
度が要求さｎ、この要求を満たすため低温打抜加工が行
なわれる様になっている。従来、打抜加工性を向上させ
るためには、熱硬化性樹脂に外部可塑剤ｔ−添加したり
、内部可塑剤による樹脂の改質がなされている。(Prior art) Recently, printed circuit boards used in electronic devices have become denser, and automated parts and mounting technology have also advanced, requiring stricter dimensional accuracy.In order to meet this requirement, low-temperature stamping It looks like punching is going to be done. Conventionally, in order to improve punching workability, external plasticizers have been added to thermosetting resins, or resins have been modified with internal plasticizers.
外部可塑剤としては従来よりリン酸エステル類、ポリエ
ーテル類等が使用され、内部可塑剤としては、高級脂肪
酸エステル類、ポリブタジェン類等が使用されている。As external plasticizers, phosphoric acid esters, polyethers, etc. have been used, and as internal plasticizers, higher fatty acid esters, polybutadienes, etc. have been used.
（発明が解決しようとする問題点）
打抜加工性の低温化に伴い、更に可塑剤使用量の増加が
必要となっているが、外部可塑剤を多量に使用すると樹
脂架橋密度の低下に伴い打抜加工法の低下や耐溶剤性の
低下が著しい。また、高級脂肪酸エステル類、ポリブタ
ジェン類を多量に使用すると打抜加工性での打抜式周囲
での目印（バルジ）の発生が著しく、また、熱硬化性樹
脂との相溶性が者しく低下し、均一な含浸ワニスが得ら
れず、底形した積層板が不透明となり、品質のばらつき
が大きくなる。(Problem to be solved by the invention) As the temperature of punching processability decreases, it is necessary to further increase the amount of plasticizer used, but if a large amount of external plasticizer is used, the resin crosslink density decreases. The deterioration of the punching process and solvent resistance are significant. In addition, if a large amount of higher fatty acid esters or polybutadiene is used, marks (bulges) will be formed around the punching process, and the compatibility with thermosetting resins will be significantly reduced. , a uniform impregnated varnish cannot be obtained, the bottom-shaped laminate becomes opaque, and the quality varies widely.
本発明は低温打抜加工性に５ｔｚた熱硬化性樹脂積層板
の製造法を提供することである。The object of the present invention is to provide a method for producing a thermosetting resin laminate having 5 tz of low-temperature punching workability.
（問題点を解決するための手段）
本発明は１分子中に１個以上の二重結付を有する不飽和
ポリエステル樹脂全含有した熱硬化性樹脂を所定量含浸
付着させた基材を成形することを特徴とするものである
。(Means for Solving the Problems) The present invention involves molding a base material impregnated with a predetermined amount of a thermosetting resin completely containing an unsaturated polyester resin having one or more double bonds in one molecule. It is characterized by this.
不飽和ポリエステル樹脂としてはマレイン酸、無水マレ
イン酸、フマル酸、シトラコン酸、イタコン酸等の二重
結付を有するα、β−不飽和二塩基酸、グリコール類と
してはエチレングリコール、ジエチレングリコール、ト
リエチレンｆ ＩＪ コ−ル、プロピレングリコール、
ジエチレングリコール、ブタンジオール、ベンタンジオ
ール、ヘキサンジオール等によって反応温度１５０℃〜
２８０℃で通常に合成されるもので、可撓性を増すため
に、アジピン酸、アゼライン酸、セバシン酸やダイマー
酸等の高級脂肪酸を用いた方がよい。また、必要に応じ
、フタル酸、イソフタル酸、テレフタル酸、無水フタル
酸、ジメチルテレフタル酸、ヘキサハイドロ７タル酸、
ヘキナハイドロ無水７タル酸等の多塩基酸を用いてもよ
い。不飽和ポリエステル樹脂の平均分子量は１０００〜
８０００が好ましく、分子量が大きいほど可溶性は増す
が平均分子量１２０００以上だと熱硬化性樹脂との相溶
性が低下する。Unsaturated polyester resins include α,β-unsaturated dibasic acids with double bonds such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, and itaconic acid, and glycols include ethylene glycol, diethylene glycol, and triethylene. f IJ cole, propylene glycol,
Depending on diethylene glycol, butanediol, bentanediol, hexanediol, etc., the reaction temperature is 150℃~
It is usually synthesized at 280°C, and in order to increase flexibility, it is better to use higher fatty acids such as adipic acid, azelaic acid, sebacic acid, and dimer acid. In addition, if necessary, phthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride, dimethyl terephthalic acid, hexahydroheptalic acid,
Polybasic acids such as hequinahydroheptalic anhydride may also be used. The average molecular weight of unsaturated polyester resin is 1000~
8,000 is preferable, and the higher the molecular weight, the higher the solubility, but if the average molecular weight is 12,000 or more, the compatibility with the thermosetting resin will decrease.
本発明で用いる熱硬化性樹脂とはフェノール樹脂、エポ
キシ側腹、ポリエステル樹脂、メラミン樹脂、ベンゾグ
アナミン樹脂等である。Thermosetting resins used in the present invention include phenolic resins, epoxy resins, polyester resins, melamine resins, benzoguanamine resins, and the like.
特に熱硬化性樹脂が乾性油変性フェノール系レゾールａ
１脂であると低温打抜加工性が更に良好となる。乾性油
としては桐油、脱水ヒマシ油、オイチシカ油等の乾性油
が使用され、フエトル系のフェノール類としてはフェノ
ール、メタクレゾール、バラクレゾール、オルソクレゾ
ール、パライソプロピルフェノール、パラターシャリ−
ブチルフェノール、バライソグロペニルフェノールのオ
リゴマー、ノニルフェノール、ビスフェノールＡ等が使
用さｎる。In particular, the thermosetting resin is a drying oil-modified phenolic resol a.
1 fat, the low-temperature punching workability becomes even better. Drying oils used include tung oil, dehydrated castor oil, and oiticica oil; examples of fetolytic phenols include phenol, metacresol, baracresol, orthocresol, paraisopropylphenol, and paratertiary phenol.
Butylphenol, oligomers of barisoglopenylphenol, nonylphenol, bisphenol A, etc. are used.
本発明の１分子中に１個以上の二重結付含有する不飽和
ポリエステルミ４脂は熱硬化性樹脂１ＣＯ部（Ｎ置部、
以下同じ）に対して６〜１２０￥Ａ含有されるが好しく
は７〜５０部が良い。The unsaturated polyester resin containing one or more double bonds in one molecule of the present invention is a thermosetting resin of 1 CO part (N part,
(same below), the content is 6 to 120 yen, preferably 7 to 50 parts.
１２０部以上だと成型した積層板の層間接着性が低下し
、打抜加工ではぐりゃ月日を生じやすくなる。このポリ
エステル樹脂を含有した熱硬化性ｍ脂に、）ルエン、ア
ルコール、メチルエチルケトン、アセトン、スチレン等
の溶剤を用いて、ワニスとし、紙、ガラスクロス、ガラ
ス不織布、合成繊維布等熱硬化性樹脂積層板の通常の基
材に所定量含浸付着させ、成型して積層板とする。If it exceeds 120 parts, the interlayer adhesion of the molded laminate will decrease, and it will tend to become loose during punching. This thermosetting resin containing polyester resin is made into a varnish using a solvent such as luene, alcohol, methyl ethyl ketone, acetone, styrene, etc., and then laminated with thermosetting resin such as paper, glass cloth, glass nonwoven fabric, synthetic fiber cloth, etc. A predetermined amount of the material is impregnated onto a regular base material of a board, and then molded to form a laminate.
成型は、１個以上二重結合を有する不飽和ポリエステル
樹脂を配合した熱硬化性樹脂ワニスを含浸した基材の一
枚或は必要枚数重ね付せ、必要な温度（室温も含む）、
必要な圧力（無圧も含む）で行なわれる。Molding is carried out by applying one sheet or the necessary number of sheets of a base material impregnated with a thermosetting resin varnish containing an unsaturated polyester resin having one or more double bonds, at the required temperature (including room temperature),
It is carried out under the necessary pressure (including no pressure).
実施例１
無水マレイン酸４９０ ｇ、 アジピン酸７５０ｇ１
エチレングリコール６８２ ｇｉ２１反応容器に入れ
、触媒としてテトラブチルジルコネートを用い２２０℃
で１０時間反応を続け、不飽和ポリエステル樹脂を得た
。二重結合は平均で１分子量７個で、酸価２０であった
。Example 1 Maleic anhydride 490 g, adipic acid 750 g1
Ethylene glycol 682 was placed in a gi21 reaction vessel and heated to 220°C using tetrabutyl zirconate as a catalyst.
The reaction was continued for 10 hours to obtain an unsaturated polyester resin. The molecular weight of the double bonds was 7 on average, and the acid value was 20.
メタクレゾール１０８ｇと８０％バラホルムアルデヒド
５５ ｇ’ｉ配台し、アルカリ触媒下でレゾール化した
。このフェノール樹脂１００部（固型分、Ｍ置部、以下
同じ）に上記に示したポリエステル樹脂２０部’ｃｔ５
加して、含浸ワニスとし、あらかじめ水溶性フェノール
樹脂で処理（樹脂付着僧１１％）し之、クラフト基材に
上記含浸用ワニスを樹脂付Ｎ量５０％になる様に含浸乾
燥させ、このプリプレグ５枚と接着剤付銅はくと組み合
せて、加熱加圧積層して１．６ｍｍの片面鋼張積層板を
得た。銅＠槓層叛の特性を別表に示す。108 g of meta-cresol and 55 g'i of 80% paraformaldehyde were arranged, and resolization was carried out under an alkali catalyst. To 100 parts of this phenolic resin (solid content, M part, same below), 20 parts of the polyester resin shown above'ct5
In addition, an impregnating varnish was prepared and treated with a water-soluble phenol resin in advance (resin adhesion rate: 11%).The craft base material was impregnated with the above impregnating varnish to a resin-coated N content of 50% and dried. The five sheets were combined with adhesive-coated copper foil and laminated under heat and pressure to obtain a 1.6 mm single-sided steel-clad laminate. The characteristics of copper@kaku layer are shown in the attached table.
実施例２
桐油とメタクレゾールを酸性触媒下で反応させ、次にパ
ラホルムアルデヒドとアルカリ触媒下でレゾール化した
桐油変性量２５％のレゾール化樹脂１００部に実施例１
で合成したポリエステル樹脂２０部ヲ砲加して、含浸ワ
ニスとした。以下実施例１と同様な方法で銅張積層板を
得た。銅張積層板の特性全別表に示す。Example 2 Example 1 was added to 100 parts of a resol-formed resin with a modified amount of tung oil of 25%, which was obtained by reacting tung oil and metacresol under an acidic catalyst and then resol-forming it with paraformaldehyde and an alkaline catalyst.
20 parts of the polyester resin synthesized above was added to prepare an impregnated varnish. Thereafter, a copper-clad laminate was obtained in the same manner as in Example 1. All properties of copper-clad laminates are shown in the attached table.
比較例１
実施例１で示したフェノール含浸ワニスを用いて、実施
例１と同様な方法で銅張積層板を得た。銅張積層板の特
性を別表に示す。Comparative Example 1 A copper-clad laminate was obtained in the same manner as in Example 1 using the phenol-impregnated varnish shown in Example 1. The characteristics of copper-clad laminates are shown in the attached table.
比較例２
実施例２で示した桐油置注フェノール含浸ワニスを用い
て、実施例１と同様な方法で、銅張積層板全部次。銅張
積層板の特性を別表に示す。Comparative Example 2 Using the phenol-impregnated varnish shown in Example 2 and injected with tung oil, a copper-clad laminate was made in the same manner as in Example 1. The characteristics of copper-clad laminates are shown in the attached table.
比較例３
桐油とメタクレゾールを酸性触媒下で反応させ、次にバ
ラホルムアルデヒドとアルカリ触媒下でレゾール化した
桐油変性−１ｆ１５７．５％のレゾール化樹脂を得、こ
れを含浸ワニスとして、以下実施例１と同様な方法で銅
彊槓層鈑金得た。Comparative Example 3 Tung oil and meta-cresol were reacted under an acidic catalyst, and then resolized with rose formaldehyde and an alkali catalyst to obtain a resolized resin of tung oil modified-1f157.5%, which was used as an impregnated varnish and used in the following Examples. A copper layer sheet metal was obtained in the same manner as in 1.
銅張積層板の特性を別表に示す。The characteristics of copper-clad laminates are shown in the attached table.
（発明の効果ン
本発明は１分子中に１個以上の二１結甘全有する不飽和
ポリエステル樹脂を熱硬化性樹力旨に用いることで、打
抜加工性、耐溶剤Ｉ注に優ｎる積層板を製造することが
出来る。(Effects of the Invention) The present invention uses an unsaturated polyester resin having one or more 21-bonds in one molecule as a thermosetting resin, which has excellent punching workability and solvent resistance. It is possible to produce laminates that
Claims (1)
エステル樹脂を含有した熱硬化性樹脂を所定量含浸付着
させた基材を成形することを特徴とする積層板の製造法
。 ２、熱硬化性樹脂が乾性油変性フェノール系レゾール樹
脂であることを特徴とする特許請求範囲第１項記載の積
層板の製造法。[Claims] 1. A lamination characterized by molding a base material impregnated with a predetermined amount of a thermosetting resin containing an unsaturated polyester resin having one or more double bonds in each molecule. Method of manufacturing boards. 2. The method for manufacturing a laminate according to claim 1, wherein the thermosetting resin is a drying oil-modified phenolic resol resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60169320A JPH0717766B2 (en) | 1985-07-31 | 1985-07-31 | Laminated board manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60169320A JPH0717766B2 (en) | 1985-07-31 | 1985-07-31 | Laminated board manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6230129A true JPS6230129A (en) | 1987-02-09 |
| JPH0717766B2 JPH0717766B2 (en) | 1995-03-01 |
Family
ID=15884355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60169320A Expired - Lifetime JPH0717766B2 (en) | 1985-07-31 | 1985-07-31 | Laminated board manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0717766B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100420715C (en) * | 2006-05-12 | 2008-09-24 | 吴江市太湖绝缘材料厂 | Solventless immersion resin used for high voltage electric machine vacuum pressure immersion |
| CN100453578C (en) * | 2006-05-12 | 2009-01-21 | 吴江市太湖绝缘材料厂 | Bi-maleimide modified heat resistant unsaturated polyester resin |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4924272A (en) * | 1972-07-03 | 1974-03-04 | ||
| JPS5476671A (en) * | 1977-11-30 | 1979-06-19 | Matsushita Electric Works Ltd | Production of phenolic resin laminate |
| JPS54116050A (en) * | 1978-02-28 | 1979-09-10 | Matsushita Electric Works Ltd | Phenolic resol varnish for laminated material |
| JPS59182816A (en) * | 1983-04-01 | 1984-10-17 | Matsushita Electric Works Ltd | Oil-modified phenolic resin and electrical laminated board using the said resin |
-
1985
- 1985-07-31 JP JP60169320A patent/JPH0717766B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4924272A (en) * | 1972-07-03 | 1974-03-04 | ||
| JPS5476671A (en) * | 1977-11-30 | 1979-06-19 | Matsushita Electric Works Ltd | Production of phenolic resin laminate |
| JPS54116050A (en) * | 1978-02-28 | 1979-09-10 | Matsushita Electric Works Ltd | Phenolic resol varnish for laminated material |
| JPS59182816A (en) * | 1983-04-01 | 1984-10-17 | Matsushita Electric Works Ltd | Oil-modified phenolic resin and electrical laminated board using the said resin |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100420715C (en) * | 2006-05-12 | 2008-09-24 | 吴江市太湖绝缘材料厂 | Solventless immersion resin used for high voltage electric machine vacuum pressure immersion |
| CN100453578C (en) * | 2006-05-12 | 2009-01-21 | 吴江市太湖绝缘材料厂 | Bi-maleimide modified heat resistant unsaturated polyester resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0717766B2 (en) | 1995-03-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |