JPH07266499A - Manufacture of copper-clad laminated plate - Google Patents
Manufacture of copper-clad laminated plateInfo
- Publication number
- JPH07266499A JPH07266499A JP6058694A JP6058694A JPH07266499A JP H07266499 A JPH07266499 A JP H07266499A JP 6058694 A JP6058694 A JP 6058694A JP 6058694 A JP6058694 A JP 6058694A JP H07266499 A JPH07266499 A JP H07266499A
- Authority
- JP
- Japan
- Prior art keywords
- copper
- clad laminate
- resin varnish
- inorganic filler
- 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.)
- Withdrawn
Links
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電気・電子機器等に使
用される銅張積層板の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a copper clad laminate used for electric / electronic equipment and the like.
【０００２】[0002]
【従来の技術】ラジカル重合型熱硬化性樹脂及び無機充
填材を含有する樹脂ワニスをガラス基材に含浸した含浸
品を用いて銅張積層板を製造することが知られている。
この場合、樹脂ワニスをガラス基材に含浸した含浸品を
複数枚重ね、その上下に銅箔を配し、次いで上記ラジカ
ル重合型熱硬化性樹脂を架橋硬化させて銅張積層板を製
造するのが一般的である。そして、このラジカル重合型
熱硬化性樹脂を使用する製造方法によれば、樹脂ワニス
をガラス基材に含浸させる工程から、含浸品と銅箔とを
一体化する工程までを連続的に行うことが可能であり、
従って長尺のガラス基材と長尺の銅箔とを切断すること
なく一体化でき、ロスが少ない等の多くの利点がある。
さらに、上記ラジカル重合型熱硬化性樹脂として例えば
特公平５−２９５４８号に示されているようなビニルエ
ステルを含有する熱硬化性樹脂を使用した場合、耐熱
性、耐水性、電気特性、パンチング加工性及び板厚精度
が優れていることから、その用途を拡大している。2. Description of the Related Art It is known to manufacture a copper clad laminate using an impregnated product obtained by impregnating a glass substrate with a resin varnish containing a radical polymerization type thermosetting resin and an inorganic filler.
In this case, a plurality of impregnated products obtained by impregnating a glass substrate with a resin varnish are stacked, copper foils are arranged on the upper and lower sides thereof, and then the radical polymerization type thermosetting resin is crosslinked and cured to produce a copper clad laminate. Is common. Then, according to the manufacturing method using this radical polymerization type thermosetting resin, it is possible to continuously perform from the step of impregnating the glass substrate with the resin varnish to the step of integrating the impregnated product and the copper foil. Is possible,
Therefore, there are many advantages such that the long glass base material and the long copper foil can be integrated without cutting and the loss is small.
Further, when a thermosetting resin containing a vinyl ester as shown in Japanese Patent Publication No. 5-29548 is used as the radical polymerization type thermosetting resin, heat resistance, water resistance, electrical characteristics, punching Its excellent properties and plate thickness accuracy have expanded its applications.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、上記の
ラジカル重合型熱硬化性樹脂及び無機充填材を含有する
樹脂ワニスを１枚もしくは複数枚重ね、その少なくとも
一方の表面に銅箔を配し、次いで加熱硬化させる銅張積
層板の製造方法により得られた銅張積層板をプリント回
路板に加工した場合、そりが発生する問題があり、そり
の少ない銅張積層板が求められている。However, one or a plurality of resin varnishes containing the radical polymerization type thermosetting resin and the inorganic filler are superposed, a copper foil is arranged on at least one surface of the resin varnish, and When a copper-clad laminate obtained by the method for producing a copper-clad laminate that is heat-cured is processed into a printed circuit board, there is a problem that warpage occurs, and a copper-clad laminate with less warpage is desired.
【０００４】そこで、本発明はラジカル重合型熱硬化性
樹脂及び無機充填材を含有する樹脂ワニスを使用する銅
張積層板の製造方法であって、かつ、そりの少ない銅張
積層板が得られる製造方法を提供することを目的として
いる。Therefore, the present invention is a method for producing a copper-clad laminate using a resin varnish containing a radical polymerization type thermosetting resin and an inorganic filler, and a copper-clad laminate with less warpage can be obtained. It is intended to provide a manufacturing method.
【０００５】[0005]
【課題を解決するための手段】本発明に係る銅張積層板
の製造方法は、ラジカル重合型熱硬化性樹脂及び無機充
填材を含有する樹脂ワニスをガラス基材に含浸した含浸
品を１枚もしくは複数枚重ね、その少なくとも一方の表
面に銅箔を配し、次いで加熱硬化させる銅張積層板の製
造方法において、上記無機充填材の平均粒径が５μｍ以
下であって、上記樹脂ワニスに比表面積が１００ｍ2 ／
ｇ以上の微粉末である沈降防止剤が、樹脂ワニス合計量
の０．１〜５重量％添加されていることを特徴としてい
る。The method for producing a copper clad laminate according to the present invention comprises one impregnated product obtained by impregnating a glass substrate with a resin varnish containing a radical polymerization type thermosetting resin and an inorganic filler. Alternatively, in a method for producing a copper-clad laminate, in which a plurality of sheets are stacked, a copper foil is arranged on at least one surface of the sheets, and then heat curing is performed, the inorganic filler has an average particle size of 5 μm or less, Surface area is 100m 2 /
The anti-settling agent, which is a fine powder of g or more, is added in an amount of 0.1 to 5% by weight based on the total amount of the resin varnish.
【０００６】また、上記沈降防止剤がヒュームドシリカ
であることが好ましい。また、ヒュームドシリカが疎水
化処理されているヒュームドシリカであることが好まし
い。Further, it is preferable that the anti-settling agent is fumed silica. Moreover, it is preferable that the fumed silica is a fumed silica that has been subjected to a hydrophobic treatment.
【０００７】ここで本発明に到った経緯を説明する。本
発明者等は、そりが発生する原因について検討した結
果、樹脂ワニス中に含まれる無機充填材が、一体化され
た銅張積層板の厚さ方向に不均一な分布で存在している
ことが原因のひとつであることを見出した。そして、こ
の不均一な分布の原因は無機充填材の沈降のためであろ
うと考え、無機充填材の沈降を防止する手段について各
種の検討を行い、本発明に到ったものである。以下本発
明を詳細に説明する。The background of the invention will be described below. The present inventors, as a result of examining the cause of the warpage, that the inorganic filler contained in the resin varnish exists in a non-uniform distribution in the thickness direction of the integrated copper-clad laminate Was found to be one of the causes. Then, it is thought that the cause of this non-uniform distribution is due to the sedimentation of the inorganic filler, and various studies have been made on the means for preventing the sedimentation of the inorganic filler, which has led to the present invention. The present invention will be described in detail below.
【０００８】本発明で使用する無機充填材は平均粒径が
５μｍ以下のものに制限される。なぜなら、平均粒径が
５μｍを越える場合には、樹脂ワニスに沈降防止剤を添
加しても無機充填材の沈降を防止することが困難なため
である。The inorganic filler used in the present invention is limited to those having an average particle size of 5 μm or less. This is because when the average particle size exceeds 5 μm, it is difficult to prevent the inorganic filler from settling even if the settling agent is added to the resin varnish.
【０００９】本発明では樹脂ワニスに沈降防止剤を添加
することにより、無機充填材の沈降を防止するものであ
るが、使用する沈降防止剤は比表面積が１００ｍ2 ／ｇ
以上の微粉末であることが重要であり、１００ｍ2 ／ｇ
未満の粉末では無機充填材の沈降防止効果が乏しい。こ
の比表面積が１００ｍ2 ／ｇ以上の微粉末の材質につい
ては特に限定はないが、超微粉のアルミナ、ヒュームド
シリカ等が例示できる。また、銅張積層板をプリント回
路板に加工する際のドリル穴明け工程でのドリル磨耗の
点で超微粉のアルミナはドリルを著しく磨耗させる問題
があるが、ヒュームドシリカにはそのような問題がない
ので、本発明に使用する沈降防止剤として好適である。
また、ヒュームドシリカの種類としては、親水性タイプ
と疎水性タイプに大別されるが、親水性タイプを用いた
場合には銅張積層板の吸水率を増大させるため好ましく
なく、疎水性タイプが好ましい。なお、疎水性タイプの
ヒュームドシリカは、親水性タイプのヒュームドシリカ
の表面の水酸基がアルキル基等の有機官能基で置換され
た構造を有するものである。In the present invention, an anti-settling agent is added to the resin varnish to prevent the inorganic filler from settling. The anti-settling agent used has a specific surface area of 100 m 2 / g.
It is important that the above fine powder is 100 m 2 / g
If the amount is less than 5, the effect of preventing the inorganic filler from settling is poor. The material of the fine powder having a specific surface area of 100 m 2 / g or more is not particularly limited, but ultrafine powder of alumina, fumed silica and the like can be exemplified. Also, from the viewpoint of drill wear in the drilling process when processing a copper clad laminate into a printed circuit board, ultrafine alumina has a problem of significantly abrading the drill, but fumed silica has such a problem. Therefore, it is suitable as an anti-settling agent used in the present invention.
Further, the types of fumed silica are roughly classified into hydrophilic type and hydrophobic type, but when the hydrophilic type is used, it is not preferable because it increases the water absorption of the copper clad laminate, and the hydrophobic type Is preferred. The hydrophobic type fumed silica has a structure in which the hydroxyl groups on the surface of the hydrophilic type fumed silica are substituted with an organic functional group such as an alkyl group.
【００１０】本発明における沈降防止剤の添加量は、樹
脂ワニス合計量の０．１〜５重量％であることが重要で
ある。０．１重量％未満では、顕著な沈降防止効果がえ
られず、従って銅張積層板としたときのそりの低減効果
が乏しい。また、５重量％を越えて添加した場合には樹
脂ワニスの粘度が著しく増加し、ガラス基材への含浸が
困難になるので好ましくない。It is important that the amount of the anti-settling agent used in the present invention is 0.1 to 5% by weight based on the total amount of the resin varnish. If it is less than 0.1% by weight, a remarkable effect of preventing sedimentation cannot be obtained, and therefore, the effect of reducing warpage when a copper clad laminate is formed is poor. If it is added in excess of 5% by weight, the viscosity of the resin varnish increases remarkably, and impregnation into the glass substrate becomes difficult, which is not preferable.
【００１１】本発明で使用するラジカル重合型熱硬化性
樹脂については、特に限定するものではないが、例えば
ビニルエステル樹脂、不飽和ポリエステル樹脂等が使用
できる。そして、本発明の樹脂ワニスには、ラジカル重
合型熱硬化性樹脂と共にスチレン、ジアリルフタレー
ト、メタクリル酸等のラジカル重合性単量体を含有させ
ることも可能である。The radical polymerization type thermosetting resin used in the present invention is not particularly limited, but for example, vinyl ester resin, unsaturated polyester resin and the like can be used. The resin varnish of the present invention can also contain a radical-polymerizable monomer such as styrene, diallyl phthalate and methacrylic acid together with the radical-polymerizable thermosetting resin.
【００１２】[0012]
【作用】本発明では、樹脂ワニスに比表面積が１００ｍ
2 ／ｇ以上の微粉末である沈降防止剤を添加することに
より、平均粒径が５μｍ以下の無機充填材の沈降を防止
する。そして、この沈降防止により、一体化された銅張
積層板の厚さ方向の無機充填材の分布が均一化される。In the present invention, the resin varnish has a specific surface area of 100 m.
The addition of an anti-sedimentation agent, which is a fine powder of 2 / g or more, prevents sedimentation of the inorganic filler having an average particle size of 5 μm or less. By preventing this sedimentation, the distribution of the inorganic filler in the thickness direction of the integrated copper-clad laminate is made uniform.
【００１３】[0013]
【実施例】以下、本発明を実施例及び比較例に基づいて
説明する。EXAMPLES The present invention will be described below based on Examples and Comparative Examples.
【００１４】（実施例１〜実施例６及び比較例１〜比較
例３）表１及び表２に示すように配合し、ディスパーで
十分攪拌して樹脂ワニスを作製した。なお、表１及び表
２に示した原材料の詳細を下記に示す。ビニルエステル
樹脂としては昭和高分子（株）製のＳ−５１０を使用
し、無機充填材としては住友化学工業（株）製の水酸化
アルミニウムであるＣ−３０３（平均粒径２．５μ
ｍ）、Ｃ−３０１（平均粒径１μｍ）もしくはＣ−３０
８（平均粒径８μｍ）または竹原化学工業（株）製のカ
オリンクレーである商品名「グロマックスＬＬ」（平均
粒径１．８μｍ）を使用し、ラジカル開始剤としてはク
メンハイドロパーオキサイドを使用し、沈降防止剤とし
ては徳山曹達（株）製の疎水性ヒュームドシリカである
ＨＭ−３０（比表面積３００ｍ2 ／ｇ）もしくは同社製
の親水性ヒュームドシリカであるＱＳ−３０（比表面積
３００ｍ2 ／ｇ）を使用した。(Examples 1 to 6 and Comparative Examples 1 to 3) Resin varnishes were prepared by mixing as shown in Tables 1 and 2 and thoroughly stirring with a disper. The details of the raw materials shown in Tables 1 and 2 are shown below. Showa High Polymer Co., Ltd. S-510 was used as the vinyl ester resin, and Sumitomo Chemical Co., Ltd. aluminum hydroxide C-303 (average particle size 2.5 μm) was used as the inorganic filler.
m), C-301 (average particle size 1 μm) or C-30
8 (average particle size 8 μm) or Kaolin clay trade name “Glomax LL” (average particle size 1.8 μm) manufactured by Takehara Chemical Industry Co., Ltd., and cumene hydroperoxide is used as a radical initiator. As an anti-settling agent, HM-30 (specific surface area 300 m 2 / g), which is hydrophobic fumed silica manufactured by Tokuyama Soda Co., Ltd., or QS-30 (specific surface area 300 m, which is hydrophilic fumed silica manufactured by the same company). 2 / g) was used.
【００１５】上記の樹脂ワニスを厚さ２００μｍの平織
ガラス布（大きさ３００ｍｍ×３００ｍｍ）に含浸し、
得られた含浸品を８枚重ね、その両側の表面に厚さ１８
μｍの銅箔を配し、次いでこの積層物を金属プレートの
間にはさみ、平置きの状態で１１０℃で６０分加熱硬化
させて厚さ１．６ｍｍの銅張積層板（大きさ３００ｍｍ
×３００ｍｍ）を得た。A 200 μm thick plain woven glass cloth (size 300 mm × 300 mm) was impregnated with the above resin varnish,
8 pieces of the obtained impregnated products are piled up, and the thickness of 18
A copper foil having a thickness of μm is arranged, and then the laminate is sandwiched between metal plates and heat-cured at 110 ° C. for 60 minutes in a flat state to give a copper-clad laminate having a thickness of 1.6 mm (size: 300 mm).
× 300 mm) was obtained.
【００１６】得られた銅張積層板について、そり量及び
吸水率を測定し、得られた結果を表１及び表２に示す。
なお、そり量の測定は銅張積層板を大きさ２５０ｍｍ×
２５０ｍｍに切断し、これを１７０℃に加熱したオーブ
ン中に吊り下げた状態で入れ、３０分間の熱処理をし、
取り出して室温まで冷却し、そり量を測定する。そり量
は大きさ２５０ｍｍ×２５０ｍｍの前記サンプルをガラ
ス平板上に平置きし、最大持ち上がり量をそり量として
測定した。また、銅張積層板の吸水率は銅箔をエッチン
グで除去し、ＪＩＳ規格Ｃ６４８１に準拠して測定し
た。The amount of warpage and water absorption of the obtained copper clad laminate were measured, and the obtained results are shown in Tables 1 and 2.
The amount of warpage was measured using a copper clad laminate with a size of 250 mm ×
Cut it to 250 mm, put it in a state of hanging it in an oven heated to 170 ° C., heat it for 30 minutes,
Take out, cool to room temperature, and measure the amount of warpage. The amount of warpage was measured by placing the above sample having a size of 250 mm × 250 mm flat on a glass flat plate, and taking the maximum amount of lifting as the amount of warpage. The water absorption of the copper-clad laminate was measured in accordance with JIS C6481 after removing the copper foil by etching.
【００１７】[0017]
【表１】 [Table 1]
【００１８】[0018]
【表２】 [Table 2]
【００１９】表１、表２に見るように、本発明の実施例
はすべて、比較例１及び比較例３よりもそり量が小さ
く、また実施例１、２と実施例６との比較から疎水性ヒ
ュームドシリカを使用したものの方が（実施例１、２）
親水性ヒュームドシリカを使用したもの（実施例６）よ
りも吸水率が低いことが確認された。As can be seen from Tables 1 and 2, all of the examples of the present invention have a smaller amount of warpage than Comparative Examples 1 and 3, and comparison of Examples 1 and 2 with Example 6 shows that they are hydrophobic. Using fusible fumed silica (Examples 1 and 2)
It was confirmed that the water absorption rate was lower than that using hydrophilic fumed silica (Example 6).
【００２０】[0020]
【発明の効果】本発明の銅張積層板の製造方法は、上記
のように構成されているので、次の効果を奏する。請求
項１及び請求項２の銅張積層板の製造方法によれば、そ
りの少ない銅張積層板が得られ、また、請求項３の銅張
積層板の製造方法によれば、そりが少なく、かつ、吸水
率が低い銅張積層板が得られるので、電気・電子機器等
に使用される銅張積層板の製造方法として好適である。Since the method for manufacturing a copper clad laminate of the present invention is constructed as described above, it has the following effects. According to the method for producing a copper-clad laminate of claims 1 and 2, a copper-clad laminate with less warpage can be obtained, and with the method for producing a copper-clad laminate of claim 3, less warpage occurs. Moreover, since a copper-clad laminate having a low water absorption rate can be obtained, it is suitable as a method for producing a copper-clad laminate used in electric / electronic devices and the like.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｈ０５Ｋ 1/03 Ｇ 7011−4Ｅ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display location H05K 1/03 G 7011-4E
Claims (3)
填材を含有する樹脂ワニスをガラス基材に含浸した含浸
品を１枚もしくは複数枚重ね、その少なくとも一方の表
面に銅箔を配し、次いで加熱硬化させる銅張積層板の製
造方法において、上記無機充填材の平均粒径が５μｍ以
下であって、上記樹脂ワニスに比表面積が１００ｍ2 ／
ｇ以上の微粉末である沈降防止剤が、樹脂ワニス合計量
の０．１〜５重量％添加されていることを特徴とする銅
張積層板の製造方法。1. One or a plurality of impregnated products obtained by impregnating a glass substrate with a resin varnish containing a radical-polymerization type thermosetting resin and an inorganic filler, and laying a copper foil on at least one surface of the impregnated product. Then, in the method for producing a copper clad laminate which is heat-cured, the inorganic filler has an average particle size of 5 μm or less, and the resin varnish has a specific surface area of 100 m 2 /
A method for producing a copper-clad laminate, wherein 0.1 g to 5% by weight of the total amount of the resin varnish is added as an anti-settling agent that is a fine powder of g or more.
ることを特徴とする請求項１記載の銅張積層板の製造方
法。2. The method for producing a copper-clad laminate according to claim 1, wherein the anti-settling agent is fumed silica.
ているヒュームドシリカであることを特徴とする請求項
２記載の銅張積層板の製造方法。3. The method for manufacturing a copper clad laminate according to claim 2, wherein the fumed silica is a fumed silica that has been subjected to a hydrophobic treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6058694A JPH07266499A (en) | 1994-03-30 | 1994-03-30 | Manufacture of copper-clad laminated plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6058694A JPH07266499A (en) | 1994-03-30 | 1994-03-30 | Manufacture of copper-clad laminated plate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07266499A true JPH07266499A (en) | 1995-10-17 |
Family
ID=13146501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6058694A Withdrawn JPH07266499A (en) | 1994-03-30 | 1994-03-30 | Manufacture of copper-clad laminated plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07266499A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6674137B2 (en) | 2000-12-01 | 2004-01-06 | Nec Corporation | Semiconductor device and its manufacturing method |
| JP2007056098A (en) * | 2005-08-23 | 2007-03-08 | Asahi Organic Chem Ind Co Ltd | Resin composition for producing foam, foam production method using the composition, and foam |
| JP2010254807A (en) * | 2009-04-24 | 2010-11-11 | Panasonic Electric Works Co Ltd | Thermosetting resin composition, prepreg, composite laminate, metal-foil-clad laminate, circuit board, and circuit board for led mounting |
| US8821755B2 (en) | 2011-03-28 | 2014-09-02 | Sumitomo Chemical Company, Limited | Liquid composition containing liquid crystal polyester |
-
1994
- 1994-03-30 JP JP6058694A patent/JPH07266499A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6674137B2 (en) | 2000-12-01 | 2004-01-06 | Nec Corporation | Semiconductor device and its manufacturing method |
| JP2007056098A (en) * | 2005-08-23 | 2007-03-08 | Asahi Organic Chem Ind Co Ltd | Resin composition for producing foam, foam production method using the composition, and foam |
| JP2010254807A (en) * | 2009-04-24 | 2010-11-11 | Panasonic Electric Works Co Ltd | Thermosetting resin composition, prepreg, composite laminate, metal-foil-clad laminate, circuit board, and circuit board for led mounting |
| US8821755B2 (en) | 2011-03-28 | 2014-09-02 | Sumitomo Chemical Company, Limited | Liquid composition containing liquid crystal polyester |
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| A300 | Withdrawal of application because of no request for examination |
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