JP2502611B2 - Laminated board manufacturing method - Google Patents
Laminated board manufacturing methodInfo
- Publication number
- JP2502611B2 JP2502611B2 JP62188093A JP18809387A JP2502611B2 JP 2502611 B2 JP2502611 B2 JP 2502611B2 JP 62188093 A JP62188093 A JP 62188093A JP 18809387 A JP18809387 A JP 18809387A JP 2502611 B2 JP2502611 B2 JP 2502611B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- glass cloth
- treatment liquid
- producing
- laminated board
- 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.)
- Expired - Fee Related
Links
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Description
本発明はガラスクロスの樹脂ワニスとの密着性を向上
させると共に樹脂ワニスのライフを延長させる技術に関
する。The present invention relates to a technique for improving the adhesion of a glass cloth to a resin varnish and extending the life of the resin varnish.
ガラスクロスは溶融原料を押し出し、次いで集束機で
束ねた後紡糸され織られて製造されているが、集束する
際に澱粉、油脂などが配合された有機組成物であるバイ
ンダーを使用しており、このバインダーはガラスクロス
と樹脂ワニスとの密着性を損なわせるので、従来にあっ
ては、約300〜450℃に昇温された電気炉内を通してバイ
ンダーが焼去され、次いでカップリング剤を含有する処
理液に浸漬され、乾燥されて積層板用基材としてのガラ
スクロスが製造されているが、ガラスクロスへの処理液
の含浸が不均一で未含浸部が形成されてしまいこの部分
での樹脂ワニスとの密着性が損なわれてしまっていた。
一方、ガラスクロスに処理液を過剰に含浸させると、フ
ィラメント間のブロッキングによって樹脂ワニスに含浸
不良が生じてしまっていた。いずれにしてもガラスクロ
スと樹脂ワニスとの密着性が不十分で得られた積層板は
耐熱性及び成形性が要望するレベルにまで到達しないも
のであった。 又、エポキシ樹脂ワニスには通常、硬化促進剤が配合
されているが、この硬化促進剤によりエポキシ樹脂ワニ
スのライフが短くなってしまっていた。The glass cloth is manufactured by extruding the molten raw material, then bundling it with a bundling machine, and then spinning it and weaving it.However, when bundling it, it uses a binder that is an organic composition in which starch, fats and oils are blended, Since this binder impairs the adhesion between the glass cloth and the resin varnish, in the conventional case, the binder is burned off through an electric furnace heated to about 300 to 450 ° C, and then a coupling agent is contained. A glass cloth as a substrate for laminated plates is manufactured by being dipped in the treatment liquid and dried, but the impregnation of the glass cloth with the treatment liquid is uneven and an unimpregnated part is formed, resulting in resin in this part. The adhesion to the varnish was lost.
On the other hand, when the glass cloth is excessively impregnated with the treatment liquid, impregnation failure occurs in the resin varnish due to blocking between filaments. In any case, the adhesion between the glass cloth and the resin varnish was insufficient, and thus the obtained laminate did not reach the desired level of heat resistance and moldability. Further, a curing accelerator is usually blended in the epoxy resin varnish, but this curing accelerator shortens the life of the epoxy resin varnish.
本発明は上記事情に鑑みて為されたものであり、その
目的とするところは、ガラスクロスと樹脂ワニスとの密
着性を向上せしめると共にエポキシ樹脂ワニスのライフ
を延長させることにある。The present invention has been made in view of the above circumstances, and an object thereof is to improve the adhesion between the glass cloth and the resin varnish and extend the life of the epoxy resin varnish.
本発明は、バインダーが除去されたガラスクロスにカ
ップリング剤を含有する処理液を含浸させ、乾燥させて
ガラスクロスに表面処理を施し、このガラスクロスにエ
ポキシ樹脂ワニスを含浸させ乾燥させてプリプレグを形
成し、複数枚のプリプレグを積層成形する積層板の製造
方法において、処理液にエポキシ樹脂硬化促進剤を加え
て予め減圧脱気させておくことを特徴とするものであ
り、この構成により上記目的が達成されたものである。 本発明において使用するガラスクロスは従来と同じも
のであり、溶融原料を押し出し、澱粉、油脂などが配合
された有機組成物であるバインダーを使用して集束機で
束ねた後、紡糸され、織られて製造されたものである。 まず、このガラスクロスは、例えばロール状に巻取ら
れ、巻戻されながら横型の処理室炉内に通されバインダ
ーが約300〜450℃で焼却除去されたり、プラズマ処理に
より除去される。 このようにしてバインダーが除去されたガラスクロス
にカップリング剤を含有する処理液が含浸される。処理
液にはエポキシ樹脂硬化促進剤が配合されている。エポ
キシ樹脂硬化促進剤としては、第３アミン、イミダゾー
ル類などが使用される。このエポキシ樹脂硬化促進剤は
MEKのような有機溶剤に溶解した後投入するのが好まし
い。処理液は90重量％以上の水と1.0重量％未満のカッ
プリング剤とを含有したものが好ましい。他に酢酸とか
有機溶剤が配合されていてもよい。カップリング剤とし
ては、γ−アミノプロピルトリエトキシシラン、Ｎ−
（β−アミノエチル）−γ−アミノプロピルトリメトキ
シシラン、Ｎ−（β−アミノエチル）−γ−アミノプロ
ピルメチルジメトキシシランなどのアミノシラン系、γ
−グリシドキシプロピルトリメトキシシラン、γ−メタ
クリロキシプロピルトリメトキシシランなどのエポキシ
シラン系、その他カチオニックシラン系、フェニルシラ
ン系などが採用できる。浸漬されたり、スプレーにより
塗布されてガラスクロスにエポキシ樹脂硬化促進剤が配
合された処理液が含浸される。処理液とエポキシ樹脂硬
化促進剤の混合溶液は減圧脱気されている。減圧度は50
Torr以上が好ましく、30分以上かけて脱気する。 処理液が含浸された後乾燥されて処理液の溶剤が蒸発
される。 このようにしてエポキシ樹脂硬化促進剤が配合された
処理液がガラスクロス内部にまで均一に含浸される。 このガラスクロスはエポキシ樹脂ワニス槽に浸漬され
樹脂が含浸され乾燥させてプリプレグが形成される。エ
ポキシ樹脂としては難燃性を確保するためにブロム化ノ
ボラックエポキシ樹脂、テトラブロムビスフェノールＡ
のジアリルエーテル化物、テトラブロムビスフェノール
Ａのジグリシジルエーテル化物などの臭素化エポキシ樹
脂が好適に使用される。加水分解性塩素の含有率の低い
エポキシ樹脂を使用することが好ましい。この場合、好
ましくは加水分解性塩素の含有率が500ppm以下である。
低加水分解性塩素エポキシ樹脂により硬化促進剤が少量
でよく、これによりガラスクロスへ塗布する量を少なく
できる。 このようにして形成したプリプレグを複数枚積み重ね
てその片面又は両面に金属箔を重ねて、このものを一組
として、熱盤間に複数組み配置し、加熱加圧成形により
一体化させて積層板が製造される。 この積層板からは常法によりプリント配線板が製造さ
れる。例えば、サブトラクティブ法であれば、孔明け、
活性化処理、無電解銅めっき、スクリーン印刷、電解銅
めっき、電解半田めっき（エッチングレジスト）、めっ
きレジスト剥離、エッチング、ヒュージング、ソルダー
レジスト印刷といった工程を経てプリント配線板が製造
される。 次に本発明の実施例を説明する。以下において％とあ
るのは重量％を示し、部とあるのは重量部を示す。 （実施例） ガラスクロス（7628）からバインダーを焼却除去し
た。次いで、水93.8％、エポキシシラン（＃303）0.5
％、酢酸0.5％、MEK5％に２−エチル−４−メチルイミ
ダゾール0.2％を加えて減圧度50Torrで30分減圧脱気し
た後、ガラスクロスに塗布して含浸させ、乾燥させた。 一方、Br化エポキシ樹脂（加水分解性塩素40ppm）100
部、ジシアンジアミド３部を配合させてエポキシ樹脂ワ
ニスを調製した。このエポキシ樹脂ワニスの硬化時間及
び１月後の劣化の程度を測定した。結果を第１表に示
す。 次いで、ガラスクロスをエポキシ樹脂ワニスに浸漬
し、170℃で100秒間かけて硬化させて樹脂含有量が45％
のプリプレグを調製した。プリプレグの硬化時間を測定
した。結果を第１に示す。 このプリプレグを複数枚積層成形して積層板を製造し
た。この積層板の成形性及び耐熱性を観察した。結果を
第２表に示す。 （比較例１） Br化エポキシ樹脂として加水分解性塩素の含有率が高
い（800ppm）ものを使用した以外は実施例と同様にして
積層板を製造し、実施例と同様の測定及び観察を行っ
た。結果を第１表及び第２表に示す。 （比較例２） 処理液の水の量を99％として、処理液に有機溶剤とエ
ポキシ樹脂硬化促進剤を配合しないで、エポキシ樹脂ワ
ニスに２−エチル−４−メチルイミダゾール0.05部配合
した以外は実施例と同様にして積層板を製造し、実施例
と同様の測定及び観察を行った。結果を第１表及び第２
表に示す。 （比較例３） 処理液に減圧脱気処理を施さなかった以外は比較例２
と同様にして積層板を製造し、比較例２と同様の測定及
び観察を行った。結果を第１表及び第２表に示す。 （比較例４） 水98.5％、エポキシシラン1.0％、酢酸0.5％とで処理
液を調製した以外は比較例３と同様にして積層板を製造
し、比較例３と同様の測定及び観察を行った。結果を第
１表及び第２表に示す。 比較例のものに対して本発明の実施例にものは、ワニ
スのライフが長く、しかも積層板特性においても成形性
及び耐熱性に優れていることが理解できる。The present invention, impregnated with a treatment liquid containing a coupling agent to the glass cloth from which the binder is removed, is subjected to a surface treatment on the glass cloth, and the glass cloth is impregnated with an epoxy resin varnish and dried to form a prepreg. In the method for producing a laminated plate by forming and laminating a plurality of prepregs, an epoxy resin curing accelerator is added to the treatment liquid and degassing is performed in advance under reduced pressure. Has been achieved. The glass cloth used in the present invention is the same as the conventional one, extruding a molten raw material, bundling it with a bundling machine using a binder which is an organic composition containing starch, fats and oils, and then spinning and weaving. It is manufactured by First, the glass cloth is wound into, for example, a roll and passed through a horizontal processing chamber furnace while being unwound to remove the binder by incineration at about 300 to 450 ° C. or by plasma processing. The glass cloth from which the binder has been removed in this manner is impregnated with the treatment liquid containing the coupling agent. An epoxy resin curing accelerator is added to the treatment liquid. As the epoxy resin curing accelerator, tertiary amine, imidazoles, etc. are used. This epoxy resin curing accelerator
It is preferable to add after dissolving in an organic solvent such as MEK. The treatment liquid preferably contains 90% by weight or more of water and less than 1.0% by weight of a coupling agent. In addition, acetic acid or an organic solvent may be blended. As the coupling agent, γ-aminopropyltriethoxysilane, N-
Aminosilane-based compounds such as (β-aminoethyl) -γ-aminopropyltrimethoxysilane and N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ
-Epoxysilanes such as glycidoxypropyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane, as well as cationic silanes and phenylsilanes can be adopted. The glass cloth is dipped or sprayed and impregnated with a treatment liquid containing an epoxy resin curing accelerator. The mixed solution of the treatment liquid and the epoxy resin curing accelerator is degassed under reduced pressure. Decompression degree is 50
Torr or higher is preferable, and degassing is performed for 30 minutes or longer. The treatment liquid is impregnated and then dried to evaporate the solvent of the treatment liquid. In this way, the treatment liquid containing the epoxy resin curing accelerator is uniformly impregnated into the inside of the glass cloth. This glass cloth is dipped in an epoxy resin varnish bath, impregnated with a resin, and dried to form a prepreg. As an epoxy resin, brominated novolac epoxy resin and tetrabromobisphenol A are used to ensure flame retardancy.
A brominated epoxy resin such as a diallyl etherified product of the above or a diglycidyl etherified product of tetrabromobisphenol A is preferably used. It is preferable to use an epoxy resin having a low content of hydrolyzable chlorine. In this case, the content of hydrolyzable chlorine is preferably 500 ppm or less.
The low-hydrolyzable chlorine epoxy resin requires a small amount of a curing accelerator, which reduces the amount applied to the glass cloth. A plurality of prepregs formed in this way are stacked and metal foils are stacked on one or both sides of the prepreg, and a plurality of these prepregs are placed between hot plates and integrated by heat and pressure molding to form a laminated plate. Is manufactured. A printed wiring board is manufactured from this laminated board by a conventional method. For example, if the subtractive method is used,
A printed wiring board is manufactured through steps such as activation treatment, electroless copper plating, screen printing, electrolytic copper plating, electrolytic solder plating (etching resist), plating resist peeling, etching, fusing, and solder resist printing. Next, examples of the present invention will be described. In the following,% means% by weight, and part means part by weight. (Example) The binder was incinerated and removed from the glass cloth (7628). Next, water 93.8%, epoxy silane (# 303) 0.5
%, Acetic acid 0.5%, MEK 5%, and 2-ethyl-4-methylimidazole 0.2% were added, and the mixture was degassed under reduced pressure at a reduced pressure of 50 Torr for 30 minutes, then coated on a glass cloth, impregnated and dried. On the other hand, Br epoxy resin (hydrolyzable chlorine 40ppm) 100
Parts and 3 parts of dicyandiamide were mixed to prepare an epoxy resin varnish. The curing time of this epoxy resin varnish and the degree of deterioration after one month were measured. The results are shown in Table 1. Then, the glass cloth is dipped in epoxy resin varnish and cured at 170 ° C for 100 seconds so that the resin content is 45%.
The prepreg of was prepared. The curing time of the prepreg was measured. The results are shown first. A plurality of these prepregs were laminated and molded to produce a laminated plate. The formability and heat resistance of this laminate were observed. The results are shown in Table 2. (Comparative Example 1) A laminated board was produced in the same manner as in Example except that a Br-epoxy resin having a high content rate of hydrolyzable chlorine (800 ppm) was used, and the same measurement and observation as in Example were carried out. It was The results are shown in Tables 1 and 2. (Comparative Example 2) Except that the amount of water in the treatment liquid was 99%, the organic solvent and the epoxy resin curing accelerator were not blended in the treatment liquid, and 0.05 part of 2-ethyl-4-methylimidazole was blended in the epoxy resin varnish. A laminated board was manufactured in the same manner as in the example, and the same measurements and observations as in the example were performed. The results are shown in Tables 1 and 2.
Shown in the table. Comparative Example 3 Comparative Example 2 except that the treatment liquid was not subjected to vacuum degassing treatment.
A laminated plate was manufactured in the same manner as in, and the same measurement and observation as in Comparative Example 2 were performed. The results are shown in Tables 1 and 2. (Comparative Example 4) A laminated plate was produced in the same manner as in Comparative Example 3 except that the treatment liquid was prepared with 98.5% water, 1.0% epoxysilane and 0.5% acetic acid, and the same measurements and observations as in Comparative Example 3 were performed. It was The results are shown in Tables 1 and 2. It can be understood that the examples of the present invention have a long life of the varnish as compared with the comparative examples and are excellent in moldability and heat resistance in terms of laminated plate properties.
本発明にあっては、バインダーが除去されたガラスク
ロスにカップリング剤を含有する処理液を含浸させ、乾
燥させてガラスクロスに表面処理を施し、このガラスク
ロスにエポキシ樹脂ワニスを含浸させ乾燥させてプリプ
レグを形成し、複数枚のプリプレグを積層成形する積層
板の製造方法において、処理液にエポキシ樹脂硬化促進
剤を加えて予め減圧脱気させておくので、エポキシ樹脂
硬化促進剤を含有する処理液をガラスクロスに均一に含
浸させることができ、処理液の未含浸部が形成されるこ
とがなく、従って、ガラスクロスと樹脂ワニスとの密着
性が良好となって、このガラスクロスを使用して製造さ
れた積層板の成形性及び耐熱性は優れたものとなり、し
かもエポキシ樹脂硬化促進剤を処理液に配合させている
ので、エポキシ樹脂ワニスのライフを延長させることが
できるものである。In the present invention, the glass cloth from which the binder has been removed is impregnated with a treatment liquid containing a coupling agent, dried to perform a surface treatment on the glass cloth, and the glass cloth is impregnated with an epoxy resin varnish and dried. In the method for producing a laminated plate in which a prepreg is formed by laminating and molding a plurality of prepregs, the epoxy resin curing accelerator is added to the treatment liquid and degassed in advance so that the treatment containing the epoxy resin curing accelerator is performed. The liquid can be uniformly impregnated into the glass cloth, and the non-impregnated portion of the treatment liquid is not formed. Therefore, the adhesion between the glass cloth and the resin varnish becomes good, and this glass cloth is used. The laminate produced by the above process has excellent moldability and heat resistance, and the epoxy resin curing accelerator is mixed in the treatment liquid. One in which it is possible to extend the life of the varnish.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭61−118430（ＪＰ，Ａ) 特開 昭60−177032（ＪＰ，Ａ) 特開 昭62−144934（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP 61-118430 (JP, A) JP 60-177032 (JP, A) JP 62-144934 (JP, A)
Claims (6)
ップリング剤を含有する処理液を含浸させ、乾燥させて
ガラスクロスに表面処理を施し、このガラスクロスにエ
ポキシ樹脂ワニスを含浸させ乾燥させてプリプレグを形
成し、複数枚のプリプレグを積層成形する積層板の製造
方法において、処理液にエポキシ樹脂硬化促進剤を加え
て予め減圧脱気させておくことを特徴とする積層板の製
造方法。1. A glass cloth from which a binder has been removed is impregnated with a treatment liquid containing a coupling agent and dried to surface-treat the glass cloth, and this glass cloth is impregnated with an epoxy resin varnish and dried to obtain a prepreg. In the method for producing a laminated plate in which a plurality of prepregs are formed by laminating, an epoxy resin curing accelerator is added to the treatment liquid and deaeration is performed in advance under reduced pressure.
脂を使用することを特徴とする特許請求の範囲第１項記
載の積層板の製造方法。2. The method for producing a laminated board according to claim 1, wherein an epoxy resin having a low content of hydrolyzable chlorine is used.
500ppm以下であることを特徴とする特許請求の範囲第１
項記載の積層板の製造方法。3. The content of hydrolyzable chlorine in the epoxy resin is
Claim 1 which is 500 ppm or less
A method for producing a laminated board according to item.
する特許請求の範囲第１項記載の積層板の製造方法。4. The method for producing a laminated board according to claim 1, wherein degassing under reduced pressure is 50 Torr or less.
満のカップリング剤とを含有することを特徴とする特許
請求の範囲第１項記載の積層板の製造方法。5. The method for producing a laminated board according to claim 1, wherein the treatment liquid contains 90% by weight or more of water and less than 1.0% by weight of a coupling agent.
理液に投入することを特徴とする特許請求の範囲第１項
記載の積層板の製造方法。6. The method for producing a laminated plate according to claim 1, wherein the curing accelerator is dissolved in an organic solvent in advance and then added to the post-treatment liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62188093A JP2502611B2 (en) | 1987-07-28 | 1987-07-28 | Laminated board manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62188093A JP2502611B2 (en) | 1987-07-28 | 1987-07-28 | Laminated board manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6431638A JPS6431638A (en) | 1989-02-01 |
| JP2502611B2 true JP2502611B2 (en) | 1996-05-29 |
Family
ID=16217579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62188093A Expired - Fee Related JP2502611B2 (en) | 1987-07-28 | 1987-07-28 | Laminated board manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2502611B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04350698A (en) * | 1991-05-28 | 1992-12-04 | Kawai Musical Instr Mfg Co Ltd | Electronic musical instrument |
| CN111746069B (en) * | 2020-05-14 | 2022-04-12 | 江阴市沪澄绝缘材料有限公司 | Low-smoke environment-friendly glass cloth laminated board and production method thereof |
-
1987
- 1987-07-28 JP JP62188093A patent/JP2502611B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6431638A (en) | 1989-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4882216A (en) | Epoxy resin film covered with metal foil and flexible printed wiring board | |
| US7390571B2 (en) | Varnish for laminate or prepreg, laminate or prepreg prepared using this varnish, and printed wiring board prepared using this laminate or prepreg | |
| JP2502611B2 (en) | Laminated board manufacturing method | |
| JP4797248B2 (en) | Pre-preg for printed wiring board and laminated board using the same | |
| JPH0722718A (en) | Epoxy resin composition for printed wiring board, manufacture of prepreg for printed wiring board, and manufacture of composite laminated sheet | |
| JP2008050566A (en) | Resin composition, prepreg, and laminate sheet clad with metal using the prereg | |
| JP4229509B2 (en) | Surface treatment agent for glass fiber | |
| JPH10180932A (en) | Manufacture of metal-clad laminate | |
| JP3906547B2 (en) | Copper-clad laminate, multilayer laminate | |
| JPH05154960A (en) | Production of laminated sheet for printed circuit board | |
| JP3027385B2 (en) | Prepreg for laminated board | |
| JPS62169828A (en) | Production of substrate for printed circuit | |
| JP3159390B2 (en) | Manufacturing method of laminated board | |
| JP2000239419A (en) | Printed-wiring board prepreg and printed-wiring board using same | |
| JP2800420B2 (en) | Glass fiber substrate and glass fiber reinforced resin laminate using the same | |
| JP3596819B2 (en) | Printed circuit laminate | |
| JPH04348938A (en) | Manufacture of laminated sheet | |
| JPS6341937B2 (en) | ||
| JP3088817B2 (en) | Flame resistant copper clad laminate | |
| JP2002294034A (en) | Resin composition, prepreg for printed circuit board using the same and metal-clad laminated plate | |
| JPH0145418B2 (en) | ||
| JPH0489843A (en) | Production of laminate | |
| JPH06134926A (en) | Laminated sheet | |
| JP2008010517A (en) | Method of manufacturing prepreg and flexible rigid wiring board | |
| JP2000068617A (en) | Board for printed wiring |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |