JPH03218826A - Manufacture of laminated sheet - Google Patents
Manufacture of laminated sheetInfo
- Publication number
- JPH03218826A JPH03218826A JP1251590A JP1251590A JPH03218826A JP H03218826 A JPH03218826 A JP H03218826A JP 1251590 A JP1251590 A JP 1251590A JP 1251590 A JP1251590 A JP 1251590A JP H03218826 A JPH03218826 A JP H03218826A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- epoxy resin
- novolac
- copper foil
- type epoxy
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 17
- 239000003822 epoxy resin Substances 0.000 claims abstract description 16
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011889 copper foil Substances 0.000 claims abstract description 15
- 229920003986 novolac Polymers 0.000 claims abstract description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000002966 varnish Substances 0.000 claims abstract description 9
- 229910001369 Brass Inorganic materials 0.000 claims abstract description 8
- 239000010951 brass Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 239000011888 foil Substances 0.000 abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000853 adhesive Substances 0.000 abstract description 5
- 239000007822 coupling agent Substances 0.000 abstract description 3
- 238000004381 surface treatment Methods 0.000 abstract description 3
- 238000010306 acid treatment Methods 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 5
- 238000003860 storage Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
Landscapes
- 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、ノボラック樹脂硬化処方の耐熱性エポキシ樹
脂積層板の接着性改良に関するものであり、通常硬化剤
としてよく使われているジシアンジアミドを使用した積
層板と同等の接着性を有する積層板を得る方法に関する
ものである．〔従来の技術〕
従来、ノボラック樹脂硬化処方のエポキシ樹脂積層板は
耐熱性が優れているものの、銅箔引き剥がし強さ等の接
着力が弱い欠点がある．これを改良するためには、エポ
キシ樹脂中のビスフェノールＡ型エポキシ樹脂やビスフ
ェノールＦ型エポキシ樹脂などの割合を大きくするか、
接着面粗化の程度の大きい銅箔を使用する方法があるが
、積層板の耐熱温度が下がったり、ファインパターンが
作りにくくなるなどの欠点があった。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to improving the adhesion of heat-resistant epoxy resin laminates with novolac resin curing formulation, and uses dicyandiamide, which is commonly used as a curing agent. This article concerns a method for obtaining a laminate with adhesive properties equivalent to that of a laminate that has been manufactured. [Prior Art] Conventionally, epoxy resin laminates with a novolac resin curing formula have excellent heat resistance, but have the disadvantage of poor adhesive strength such as copper foil peel strength. In order to improve this, either increase the proportion of bisphenol A type epoxy resin or bisphenol F type epoxy resin in the epoxy resin, or
There is a method of using copper foil, which has a highly roughened adhesive surface, but this method has drawbacks such as lowering the heat resistance of the laminate and making it difficult to create fine patterns.
本発明者は、積層板の耐熱性を低下させることなく、接
着性即ち、銅箔引き剥がし強さや層間接着力を向上させ
るべく検討した結果、シランカノブリング剤が前記目的
のために優れた効果があり、また銅箔粗化面の表面処理
が影響することを見出し、本発明を完成するに至った。The inventor of the present invention conducted studies to improve the adhesion, that is, the copper foil peeling strength and the interlayer adhesion strength, without reducing the heat resistance of the laminate, and found that the silane canobling agent has an excellent effect for the above purpose. The inventors have also discovered that the surface treatment of the roughened surface of the copper foil has an effect, leading to the completion of the present invention.
本発明は、樹脂フェスを含浸して得たプリプレグを１枚
もしくは複数枚重ね合わせ、これを金属鏡面板の間に挟
み加熱加圧する積層板の製造方法において、樹脂フェス
としてノポラック型エポキシｔａｌｌ Ｎ １０ ０〜
５０部及びビスフェノールＡ型エポキシ樹脂Ｏ〜５０部
からなる樹脂と硬化剤としてのノボラック樹脂及びエポ
キシ シラン系カップリング剤をエポキシ樹脂とノボラ
ック樹脂の固型分に対し０．０１−０．２％配合し、か
つ片面又は両面に張り合わせる銅箔として粗化面側に黄
銅による表面処理を行ったものを使うことを特徴とする
積層板の製造方法である．
通常、ノボラック型エポキシ樹脂とノボラック樹脂での
組合せで積層板を製造すると、耐熱性、耐湿性は優れて
いるが、層間接着力や銅箔接着力はジシアンシアミドを
硬化剖とする積層板と比較して劣っている。しかし、本
発明のように、エポキシシラン系カップリング剤を配合
すると、ワニスの保存性に悪影響を与えることなく銅箔
接着力等の接着性の改良が出来、耐熱性や耐湿性を低下
させることはない。更に、銅箔として、黄銅処理をした
ｗ４箔を使用しているので、ファインパターン用のロー
プロファイルのｗ４箔を使用しても、パターン加工時の
塩酸処理工程においても問題なくファインパターン加工
が実施できる積層板を得ることが出来る．
本発明に使用する黄銅処理した銅箔は、通常の方法で製
造した粗化ｗ４Ｗｉの粗化面に黄銅めっきを行うことに
より得られる。The present invention relates to a method for manufacturing a laminate in which one or more prepregs obtained by impregnating a resin face are stacked, sandwiched between metal mirror plates, and heated and pressed.
A resin consisting of 50 parts and 0 to 50 parts of bisphenol A type epoxy resin, a novolac resin as a hardening agent, and an epoxy silane coupling agent are blended in an amount of 0.01-0.2% based on the solid content of the epoxy resin and novolak resin. This method of manufacturing a laminate is characterized in that the copper foil that is laminated on one or both sides is surface-treated with brass on the roughened side. Normally, when a laminate is manufactured using a combination of novolac type epoxy resin and novolac resin, it has excellent heat resistance and moisture resistance, but the interlayer adhesion strength and copper foil adhesion strength are lower than that of a laminate that is cured with dicyancyamide. It's inferior. However, when an epoxy silane coupling agent is blended as in the present invention, adhesive properties such as copper foil adhesion can be improved without adversely affecting the storage stability of the varnish, and it does not reduce heat resistance or moisture resistance. There isn't. Furthermore, since we use brass-treated W4 foil as the copper foil, fine pattern processing can be carried out without any problems even in the hydrochloric acid treatment process during pattern processing, even when using low-profile W4 foil for fine patterns. It is possible to obtain a laminate that can be used. The brass-treated copper foil used in the present invention is obtained by performing brass plating on the roughened surface of roughened w4Wi manufactured by a conventional method.
エポキシシラン系カップリング剤は樹脂フェスに配合し
た段階では、フェスと反応しないが、積層形成時、樹脂
分やガラス布等の基材、銅箔と反応して、接着力の向上
をもたらす。The epoxy silane coupling agent does not react with the resin face when it is blended with the face, but during lamination formation, it reacts with the resin, base materials such as glass cloth, and copper foil, improving adhesive strength.
エポキシシラン系カップリング荊としては、具体的には
、γ−グリシドキシプロピルトリノトキシシラン（Ａ−
１８７）などがある。Specifically, the epoxysilane coupling agent is γ-glycidoxypropyltrinotoxysilane (A-glycidoxypropyltrinotoxysilane).
187) etc.
このシランカップリング刑の配合量はエポキシ樹脂とノ
ボラック樹脂の合計量に対し０．０１〜０．２重量％で
ある． ０．０１％以下では配合する効果が小さく、０
．２％以上配合しても効果がそれ以上向上せず、コスト
高となるので好ましくない。The amount of this silane coupling compound is 0.01 to 0.2% by weight based on the total amount of epoxy resin and novolak resin. If it is less than 0.01%, the effect of blending is small, and 0.
．． Even if it is blended in an amount of 2% or more, the effect will not be further improved and the cost will increase, which is not preferable.
なお、アミノ系シランカップリング剤やイソシアネート
系シランカップリング剤は常温でフェスと徐々に反応が
進行するので保存性に問題があり、好ましくない。It should be noted that amino-based silane coupling agents and isocyanate-based silane coupling agents are undesirable because they react slowly with festivals at room temperature, causing problems in storage stability.
第１表に示す配合で樹脂分約４５重量％のワニスを調製
し、ガラスクロスに含浸してプリプレグ（樹脂分約４０
％）を得た。このプリブレグと１８μ銅箔とを重ね合わ
せ常温により積層成形した。得られた銅張積層板につい
て特性を測定し、第１表に示した．
なお、ｗ４箔は黄銅処理したもの、及び酸化銅処理した
ものを使用した．
（測定方法）
ｌ．ワニス保存性：ワニスを常温で３０日間保存し、保
存前後のゲルタイム（１７０゜Ｃ）を測定し、３０％以
上短くなったものを×とし、それ以外を○とした。A varnish with a resin content of approximately 45% by weight was prepared according to the formulation shown in Table 1, and a glass cloth was impregnated with the varnish (resin content of approximately 40% by weight).
%) was obtained. This pre-reg and 18μ copper foil were laminated and molded at room temperature. The properties of the obtained copper-clad laminate were measured and are shown in Table 1. The W4 foil used was one treated with brass and one treated with copper oxide. (Measurement method) l. Varnish storage stability: The varnish was stored at room temperature for 30 days, and the gel time (170°C) before and after storage was measured. Those that were shortened by 30% or more were marked x, and the others were marked ○.
２．ガラス転移点：粘弾性スペクトルより求めた．３．
吸水率：予傭処理としてプレノシ中クッカー（１２５゜
Ｃ、２．３気圧、２４時間）し、吸水率をＪ Ｉ Ｓ
Ｃ６４８１により測定した．４．ｗ４箔引８剥カＬ強サ
： Ｊ ＩＳ Ｃ６４ｅｌニヨル，なお、ＨＣＩ．処理
は、１８％ＨＣｌに６０分浸漬して行った．
〔発明の効果〕2. Glass transition point: Determined from viscoelastic spectrum. 3.
Water absorption rate: As a preliminary treatment, the water absorption rate was determined using a preheating medium cooker (125°C, 2.3 atm, 24 hours).
Measured using C6481. 4. w4 foil 8 peeling L strength: JIS C64el, HCI. The treatment was performed by immersion in 18% HCl for 60 minutes. 〔Effect of the invention〕
Claims (1)
くは複数枚重ね合わせ、これを金属鏡面板の間に挟み加
熱加圧する積層板の製造方法において、樹脂ワニスとし
てノボラック型エポキシ樹脂１００〜５０部及びビスフ
ェノールＡ型エポキシ樹脂０〜５０部からなる樹脂と硬
化剤としてのノボラック樹脂及びエポキシシラン系カッ
プリング剤をエポキシ樹脂とノボラック樹脂の固型分に
対し０．０１〜０．２％配合し、かつ片面又は両面に張
り合せる銅箔として粗化面側に黄銅による表面処理を行
ったものを使うことを特徴とする積層板の製造方法。(1) A method for manufacturing a laminate in which one or more prepregs impregnated with a resin varnish are stacked together, sandwiched between metal mirror plates, and heated and pressed. A resin consisting of 0 to 50 parts of bisphenol A type epoxy resin, a novolak resin as a hardening agent, and an epoxy silane coupling agent are blended in an amount of 0.01 to 0.2% based on the solid content of the epoxy resin and novolak resin, and A method for manufacturing a laminate, characterized in that the copper foil that is laminated on one or both sides is surface-treated with brass on the roughened side.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1251590A JPH03218826A (en) | 1990-01-24 | 1990-01-24 | Manufacture of laminated sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1251590A JPH03218826A (en) | 1990-01-24 | 1990-01-24 | Manufacture of laminated sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03218826A true JPH03218826A (en) | 1991-09-26 |
Family
ID=11807487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1251590A Pending JPH03218826A (en) | 1990-01-24 | 1990-01-24 | Manufacture of laminated sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03218826A (en) |
-
1990
- 1990-01-24 JP JP1251590A patent/JPH03218826A/en active Pending
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