JPH08118543A - Production of copper clad laminated sheet - Google Patents
Production of copper clad laminated sheetInfo
- Publication number
- JPH08118543A JPH08118543A JP6265027A JP26502794A JPH08118543A JP H08118543 A JPH08118543 A JP H08118543A JP 6265027 A JP6265027 A JP 6265027A JP 26502794 A JP26502794 A JP 26502794A JP H08118543 A JPH08118543 A JP H08118543A
- Authority
- JP
- Japan
- Prior art keywords
- resin varnish
- resin
- impregnated
- copper
- surface layer
- 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
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
用されるプリント配線板等の材料である銅張り積層板に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copper-clad laminate which is a material for printed wiring boards and the like used in electric and electronic equipment.
【０００２】[0002]
【従来の技術】ラジカル重合型熱硬化性樹脂を含む樹脂
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り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を切断することなく一体化でき、ロ
スを少なくして製造できる等の多くの利点がある。そし
て、特公平５−２９５４８号に示されているように、上
記ラジカル重合型熱硬化性樹脂として、ビニルエステル
を含有する樹脂を使用すれば耐熱性、耐水性、電気特
性、パンチング加工性等の優れた銅張り積層板を製造で
きることが知られている。2. Description of the Related Art It is known to produce a copper clad laminate using an impregnated product obtained by impregnating a glass substrate with a resin varnish containing a radical-polymerizable thermosetting resin. 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 cross-linked and cured to produce a copper-clad laminate. Is common. Then, according to the manufacturing method using the 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. Therefore, there are many advantages such that the long glass base material and the long copper foil can be integrated without cutting and the manufacturing can be performed with less loss. And, as shown in Japanese Patent Publication No. 5-29548, if a resin containing vinyl ester is used as the radical polymerization type thermosetting resin, heat resistance, water resistance, electrical characteristics, punching workability, etc. It is known that excellent copper clad laminates can be produced.
【０００３】しかし、銅張り積層板が、ラジカル重合型
熱硬化性樹脂及び無機充填材を含む樹脂ワニスをガラス
不織布に含浸した含浸品をコア材とし、その両外面にラ
ジカル重合型熱硬化性樹脂を含む樹脂ワニスをガラスク
ロスに含浸した含浸品を表層材として積層し、さらにそ
の少なくとも一方の表面に銅箔を積層した後、加熱硬化
させて一体化したものである場合には、銅張り積層板を
プリント配線板に加工した場合、そりが発生しやすいと
いう問題があった。However, the copper-clad laminate has a core material which is an impregnated product obtained by impregnating a glass nonwoven fabric with a resin varnish containing a radical polymerization type thermosetting resin and an inorganic filler, and has a radical polymerization type thermosetting resin on both outer surfaces thereof. When a glass cloth is impregnated with a resin varnish containing a layered product as a surface layer material, a copper foil is further laminated on at least one surface of the layered product, and then heat-cured to form an integrated body. When the board is processed into a printed wiring board, there is a problem that warpage is likely to occur.
【０００４】[0004]
【発明が解決しようとする課題】上記の事情に鑑み、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
含む樹脂ワニスをガラス不織布に含浸した含浸品をコア
材とし、その両外面にラジカル重合型熱硬化性樹脂を含
む樹脂ワニスをガラスクロスに含浸した含浸品を表層材
として積層し、さらにその少なくとも一方の表面に銅箔
を積層した後、加熱硬化させて一体化した銅張り積層板
の加工時のそりを低減できる、銅張り積層板の製造方法
を提供することを目的としている。SUMMARY OF THE INVENTION In view of the above circumstances, the present invention has a core material which is an impregnated product obtained by impregnating a glass nonwoven fabric with a resin varnish containing a radical polymerization type thermosetting resin and an inorganic filler. A layer of impregnated product in which a glass cloth is impregnated with a resin varnish containing a radical-polymerizable thermosetting resin is laminated as a surface layer material, and then copper foil is laminated on at least one surface of the layer, and then heat cured to form an integrated copper clad. It is an object of the present invention to provide a method for manufacturing a copper-clad laminate, which can reduce warpage during processing of the laminate.
【０００５】[0005]
【課題を解決するための手段】請求項１に係る発明の銅
張り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む樹脂ワニスをガラス不織布に含浸
した含浸品をコア材とし、その両外面にラジカル重合型
熱硬化性樹脂を含む樹脂ワニスをガラスクロスに含浸し
た含浸品を表層材として積層し、さらにその少なくとも
一方の表面に銅箔を積層した後、加熱硬化させる銅張り
積層板の製造方法において、コア材に使用する樹脂ワニ
スの粘度（ηB ）と、表層材に使用する樹脂ワニスの粘
度（ηA）の比がηB ／ηA ＞５であることを特徴とし
ている。According to a first aspect of the present invention, there is provided a method for manufacturing a copper-clad laminate, which comprises an impregnated product obtained by impregnating a glass nonwoven fabric with a resin varnish containing a radical polymerization type thermosetting resin and an inorganic filler. As a surface material, the impregnated product obtained by impregnating glass cloth with a resin varnish containing a radical polymerization type thermosetting resin on both outer surfaces is laminated as a surface layer material, and a copper foil is further laminated on at least one surface of the material, followed by heat curing. In the method of manufacturing a copper-clad laminate, the ratio of the viscosity (η B ) of the resin varnish used for the core material to the viscosity (η A ) of the resin varnish used for the surface layer material is η B / η A > 5. Is characterized by.
【０００６】請求項２に係る発明の銅張り積層板の製造
方法は、ラジカル重合型熱硬化性樹脂及び無機充填材を
含む樹脂ワニスをガラス不織布に含浸した含浸品をコア
材とし、その両外面にラジカル重合型熱硬化性樹脂を含
む樹脂ワニスをガラスクロスに含浸した含浸品を表層材
として積層し、さらにその少なくとも一方の表面に銅箔
を積層した後、加熱硬化させる銅張り積層板の製造方法
において、表層材及び／またはコア材が、紫外線照射に
よりプレキュアされていることを特徴としている。According to a second aspect of the present invention, there is provided a method for producing a copper-clad laminate, wherein a glass nonwoven fabric is impregnated with a resin varnish containing a radical polymerization type thermosetting resin and an inorganic filler, and the core material is used as the core material. Manufacture of a copper clad laminate in which a resin varnish containing a radical polymerization type thermosetting resin is impregnated into a glass cloth as a surface layer material, and a copper foil is further laminated on at least one surface of the impregnated product, followed by heat curing. The method is characterized in that the surface layer material and / or the core material is pre-cured by ultraviolet irradiation.
【０００７】請求項３に係る発明の銅張り積層板の製造
方法は、ラジカル重合型熱硬化性樹脂及び無機充填材を
含む樹脂ワニスをガラス不織布に含浸した含浸品をコア
材とし、その両外面にラジカル重合型熱硬化性樹脂を含
む樹脂ワニスをガラスクロスに含浸した含浸品を表層材
として積層し、さらにその少なくとも一方の表面に銅箔
を積層した後、加熱硬化させる銅張り積層板の製造方法
において、コア材と表層材の積層物に紫外線を照射して
プレキュアし、次いで銅箔を積層することを特徴として
いる。According to a third aspect of the present invention, there is provided a copper clad laminate manufacturing method, wherein a glass nonwoven fabric is impregnated with a resin varnish containing a radical polymerization type thermosetting resin and an inorganic filler, and the core material is used as the core material. Manufacture of a copper clad laminate in which a resin varnish containing a radical polymerization type thermosetting resin is impregnated into a glass cloth as a surface layer material, and a copper foil is further laminated on at least one surface of the impregnated product, followed by heat curing. The method is characterized in that a laminate of the core material and the surface layer material is irradiated with ultraviolet rays to be pre-cured, and then a copper foil is laminated.
【０００８】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、積層板の厚さ方向の樹脂成分の構成が
測定位置によって不均一になっていることが原因の一つ
であることを見出した。そして、この樹脂成分の構成が
位置によって不均一となる原因は、ガラス基材に含浸さ
れた樹脂ワニスが積層工程や加熱硬化させる工程におい
て大きく流動するためと考え、樹脂ワニスの流動を防止
する手段について検討を行い、本発明を完成するに到っ
たものである。以下、本発明を詳細に説明する。As a result of examining the cause of the warpage, the present inventors have found that one of the causes is that the composition of the resin component in the thickness direction of the laminate is nonuniform depending on the measurement position. I found it. The reason why the structure of the resin component becomes non-uniform depending on the position is that the resin varnish impregnated in the glass substrate largely flows in the laminating step and the step of heating and curing, and means for preventing the flow of the resin varnish The present invention has been completed and the present invention has been completed. Hereinafter, the present invention will be described in detail.
【０００９】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、ビニル
エステル樹脂、不飽和ポリエステル樹脂等が例示でき
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やエポキシ樹脂等
の付加型熱硬化性樹脂を含有させることも可能である。
さらに、コア材に使用する樹脂ワニスは、寸法変化挙動
の安定化のために無機充填材を含有していて、この無機
充填材としては、特に限定するものではないが、水酸化
アルミニウム、タルク、ガラス粉等が例示できる。さら
に、本発明でコア材または表層材に使用する樹脂ワニス
には各種添加剤、例えば硬化触媒、難燃剤、無機充填
材、カップリンング剤等が、必要に応じて、添加されて
いても差し支えない。The radical polymerization type thermosetting resin used in the present invention is not particularly limited, but vinyl ester resin, unsaturated polyester resin and the like can be exemplified. Further, the resin varnish of the present invention may contain a radical-polymerizable thermosetting resin together with a radical-polymerizable monomer such as styrene, diallyl phthalate or methacrylic acid, or an addition-type thermosetting resin such as an epoxy resin. Is.
Furthermore, the resin varnish used for the core material contains an inorganic filler for stabilizing the dimensional change behavior.The inorganic filler is not particularly limited, but aluminum hydroxide, talc, Glass powder etc. can be illustrated. Further, various additives such as a curing catalyst, a flame retardant, an inorganic filler, and a coupling agent may be added to the resin varnish used for the core material or the surface layer material in the present invention, if necessary. Absent.
【００１０】本発明で使用するガラス不織布及びガラス
クロスについては、電気用途に使用可能な絶縁性を有し
ているものであればよく、特に限定はない。なお、ガラ
ス不織布とは、当然のことながら、織られることなく得
られた布を指しており、ガラスぺーパー、ガラスマット
等と表現される場合もある。The glass nonwoven fabric and the glass cloth used in the present invention are not particularly limited as long as they have an insulating property that can be used for electrical applications. The glass nonwoven fabric naturally refers to a cloth obtained without being woven, and may be expressed as a glass paper, a glass mat, or the like.
【００１１】請求項１に係る発明の銅張り積層板の製造
方法は、樹脂ワニスの粘度を調製することにより、積層
工程や加熱硬化させる工程における樹脂ワニスの過剰な
流動を防止するものである。すなわち、コア材に使用す
る樹脂ワニスの粘度（ηB ）と、表層材に使用する樹脂
ワニスの粘度（ηA ）の比をηB ／ηA ＞５とすること
が重要である。そして、ηB ／ηA ＞１０であれば樹脂
ワニスの過剰な流動を防止するのに、さらに好ましい。
なお、ワニスの粘度を測定する温度は本発明では３０℃
である。ηB ／ηA ≦５の場合は、積層工程や加熱硬化
させる工程においてコア材に使用する樹脂ワニスと表層
材に使用する樹脂ワニスが厚み方向に不均一に混合し、
その結果、厚み方向の樹脂成分の構成が位置によって異
なるという現象が生じる。樹脂ワニスの粘度調製は、使
用する樹脂の種類、分子量、ラジカル重合性単量体や各
種添加剤の種類、量等により、また、積層板に要求され
る特性とのバランスを考慮しながら実施される。樹脂ワ
ニスの粘度の絶対値については、特に限定するものでは
ないが、高すぎる場合はガラス不織布やガラスクロスへ
の樹脂ワニスの含浸が不十分となり、積層板の特性を損
なうため通常１００００ｃｐｓまでで行うことが好まし
い。In the method for producing a copper-clad laminate according to the first aspect of the present invention, the viscosity of the resin varnish is adjusted to prevent excessive flow of the resin varnish in the laminating step and the heat curing step. That is, it is important to set the ratio of the viscosity (η B ) of the resin varnish used for the core material to the viscosity (η A ) of the resin varnish used for the surface layer material to η B / η A > 5. Further, if η B / η A > 10, it is more preferable to prevent excessive flow of the resin varnish.
The temperature at which the viscosity of the varnish is measured is 30 ° C. in the present invention.
Is. In the case of η B / η A ≦ 5, the resin varnish used for the core material and the resin varnish used for the surface layer material are unevenly mixed in the thickness direction in the laminating step and the heat curing step,
As a result, a phenomenon occurs in which the composition of the resin component in the thickness direction varies depending on the position. The viscosity of the resin varnish is adjusted depending on the type and molecular weight of the resin used, the type and amount of the radical-polymerizable monomer and various additives, and the balance with the properties required for the laminate. It The absolute value of the viscosity of the resin varnish is not particularly limited, but when it is too high, impregnation of the glass woven fabric or glass cloth with the resin varnish becomes insufficient and the properties of the laminate are impaired. It is preferable.
【００１２】請求項２及び請求項３に係る発明の銅張り
積層板の製造方法では、ガラス基材へ含浸された樹脂ワ
ニスに紫外線を照射してプレキュアすることで、樹脂ワ
ニスの過剰な流動を防止する。紫外線照射装置として
は、通常の高圧水銀灯、超高圧水銀灯、水銀／金属ハラ
イド灯、キセノン灯、カーボンアーク灯等が使用でき
る。一方、樹脂ワニスとしては、必須ではないが樹脂ワ
ニス中に光重合触媒を加えて使用すると短時間のプレキ
ュアで目的達成可能となり好都合である。光重合触媒と
してはベンゾインエーテル系、ベンゾフェノン系、アセ
トフェノン系等のカルボニル化合物やスルフィド系、キ
ノン系、アゾ系、スルホクロリド系の化合物など近紫外
域の光でラジカルを発生するものであればすべて使用で
きる。プレキュアの程度については紫外線が照射された
含浸品の表面が僅かに流動性を維持している程度が好ま
しい。プレキュアが過剰であると含浸品同士、あるいは
含浸品と銅箔との接着性が低下する。このプレキュアの
程度は照射する紫外線の強度、光重合触媒の種類、量等
により調製される。プレキュアを実施する段階は、樹脂
ワニスをガラス基材に含浸する含浸工程の後であって、
含浸品を積層し、さらに銅箔を配し積層するまでの工程
の間であればよいが、含浸品の積層工程中に発生する樹
脂ワニスの流動が大きい場合には、含浸工程の直後に行
うことが好ましい。また、その実施方法は下記のいずれ
の方法でもよい。 表層材のみに紫外線照射をし、プレキュアする。 コア材のみに紫外線照射をし、プレキュアする。 表層材及びコア材に紫外線照射をし、プレキュアす
る。 コア材と表層材の積層物に紫外線を照射してプレキュ
アする。In the method for producing a copper-clad laminate according to the second and third aspects of the present invention, the resin varnish impregnated in the glass substrate is irradiated with ultraviolet rays to be pre-cured to prevent excessive flow of the resin varnish. To prevent. As the ultraviolet irradiation device, a normal high pressure mercury lamp, an ultrahigh pressure mercury lamp, a mercury / metal halide lamp, a xenon lamp, a carbon arc lamp or the like can be used. On the other hand, the resin varnish is not essential, but it is convenient to use the resin varnish by adding a photopolymerization catalyst so that the object can be achieved by pre-cure in a short time. As photopolymerization catalysts, use all carbonyl compounds such as benzoin ether-based, benzophenone-based, acetophenone-based, sulfide-based, quinone-based, azo-based, and sulfochloride-based compounds that generate radicals in the near-ultraviolet region. it can. The degree of pre-cure is preferably such that the surface of the impregnated product irradiated with ultraviolet rays maintains a slight fluidity. If the pre-cure is excessive, the adhesiveness between the impregnated products or between the impregnated product and the copper foil will decrease. The degree of this precure is adjusted depending on the intensity of ultraviolet rays to be irradiated, the type and amount of the photopolymerization catalyst, and the like. The step of performing pre-cure is after the impregnation step of impregnating the glass substrate with the resin varnish,
It may be during the process of laminating the impregnated product and further disposing the copper foil and laminating, but when the flow of the resin varnish generated during the laminating process of the impregnated product is large, it is performed immediately after the impregnation process. It is preferable. In addition, the method of implementation may be any of the following methods. Precure by irradiating only the surface layer material with ultraviolet rays. Precure the core material by irradiating it with ultraviolet light. The surface material and the core material are irradiated with ultraviolet rays and pre-cured. The laminate of the core material and the surface material is irradiated with ultraviolet rays to be pre-cured.
【００１３】なお、この請求項２及び請求項３に係る発
明の銅張り積層板の製造方法では、コア材に使用する樹
脂ワニスの粘度（ηB ）と、表層材に使用する樹脂ワニ
スの粘度（ηA ）の比については、請求項１のような特
別な制限を満たす必要はない。In the method for manufacturing a copper clad laminate according to the second and third aspects of the invention, the viscosity (η B ) of the resin varnish used for the core material and the viscosity of the resin varnish used for the surface layer material are Regarding the ratio of (η A ), it is not necessary to satisfy the special limitation as in claim 1.
【００１４】[0014]
【作用】本発明では、コア材に使用する樹脂ワニスの粘
度（ηB ）と、表層材に使用する樹脂ワニスの粘度（η
A ）の比をηB ／ηA ＞５とするか、もしくは、ガラス
基材へ含浸された樹脂ワニスに紫外線を照射してプレキ
ュアすることで、積層工程及び／または加熱工程での樹
脂ワニスの過剰な流動を防止して、一体化された銅張り
積層板の厚さ方向の樹脂成分の構成が位置によって異な
るという現象の発生を防止する。In the present invention, the viscosity (η B ) of the resin varnish used for the core material and the viscosity (η B ) of the resin varnish used for the surface layer material
The ratio of A ) is η B / η A > 5, or the resin varnish impregnated in the glass substrate is irradiated with ultraviolet rays to be pre-cured, whereby the resin varnish in the laminating step and / or the heating step is Excessive flow is prevented, and the phenomenon that the composition of the resin component in the thickness direction of the integrated copper-clad laminate differs depending on the position is prevented.
【００１５】[0015]
【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.
【００１６】表１に示すように原材料を配合し、ディス
パーで十分に攪拌して樹脂ワニスを作製した。表１に示
す原材料の詳細は以下の通りである。Raw materials were blended as shown in Table 1 and sufficiently stirred with a disper to prepare a resin varnish. Details of the raw materials shown in Table 1 are as follows.
【００１７】ビニルエステル樹脂としては昭和高分子
（株）製の品番Ｓ５１０を使用し、無機充填材の一種で
ある水酸化アルミニウムとしては、住友化学工業（株）
製の品番Ｃ−３０３を使用し、無機充填材の一種である
カオリンクレーとしては竹原化学工業（株）製の商品名
グロマックスＬＬを使用した。また、熱重合触媒として
クメンハイドロパーオキサイド（以下ＣＨＰと略す）を
使用し、光重合触媒としてチバガイギー社製の商品名イ
ルガキュアーＩ−６５１（以下Ｉ−６５１と略す）を使
用した。また紫外線照射には、１ＫＷの超高圧水銀灯を
使用した。Product number S510 manufactured by Showa High Polymer Co., Ltd. is used as the vinyl ester resin, and aluminum hydroxide, which is one of the inorganic fillers, is manufactured by Sumitomo Chemical Co., Ltd.
The product number C-303 manufactured by Takehara Chemical Industry Co., Ltd. was used as the kaolin clay, which is a kind of inorganic filler. Further, cumene hydroperoxide (hereinafter abbreviated as CHP) was used as a thermal polymerization catalyst, and Irgacure I-651 (hereinafter abbreviated as I-651) manufactured by Ciba-Geigy was used as a photopolymerization catalyst. A 1 KW ultra-high pressure mercury lamp was used for ultraviolet irradiation.
【００１８】（実施例１）表１記載の樹脂ワニスＡ１を
厚さ２００μｍの平織りガラスクロス（大きさ３００ｍ
ｍ×３００ｍｍ）に、また同表記載の樹脂ワニスＢ１を
厚さ３７０μｍのガラス不織布（大きさ３００ｍｍ×３
００ｍｍ）にそれぞれ含浸して含浸品を得た。得られた
ガラス不織布基材の含浸品３枚を重ねてコア材とし、そ
の上下にガラスクロス基材の含浸品を表層材として各１
枚積層し、さらに、この積層物の上下の表面にそれぞれ
厚さ１８μｍ銅箔を配したものを、所定間隙に調製した
２本のロールの間を通した。次いで得られた積層物を２
枚の金属プレートの間にはさみ、平置きの状態で１１０
℃で６０分間加熱して硬化させ、厚み１．６ｍｍの銅張
り積層板を作製した。なお、表１に示す樹脂ワニスの粘
度から明らかなように、本実施例の場合のコア材に使用
した樹脂ワニスＢ１の粘度（ηB1）と、表層材に使用す
る樹脂ワニスＡ１の粘度（ηA1）の比は約１７であっ
た。Example 1 A resin varnish A1 shown in Table 1 was used as a plain weave glass cloth having a thickness of 200 μm (size 300 m).
m × 300 mm) and the resin varnish B1 shown in the same table, and a glass nonwoven fabric having a thickness of 370 μm (size: 300 mm × 3)
00 mm) were each impregnated to obtain an impregnated product. Three pieces of the impregnated products of the glass non-woven fabric base materials are stacked to form a core material, and the impregnated products of the glass cloth base material are used as the surface layer material one above and one below the core material.
A sheet was laminated, and a copper foil having a thickness of 18 μm was arranged on each of the upper and lower surfaces of the laminate, and the copper foil was passed between two rolls having a predetermined gap. The resulting laminate is then 2
It is sandwiched between two metal plates and placed 110
It was heated at 60 ° C. for 60 minutes to be hardened to produce a copper-clad laminate having a thickness of 1.6 mm. As is clear from the viscosity of the resin varnish shown in Table 1, the viscosity (η B1 ) of the resin varnish B1 used as the core material and the viscosity (η B1 of the resin varnish A1 used as the surface layer material in this example. The ratio of A1 ) was about 17.
【００１９】（実施例２）樹脂ワニスＢ１の代わりに表
１記載の樹脂ワニスＢ２を使用した以外は実施例１と同
様にして、厚み１．６ｍｍの銅張り積層板を作製した。
なお、表１に示す樹脂ワニスの粘度から明らかなよう
に、本実施例の場合のコア材に使用した樹脂ワニスＢ２
の粘度（ηB2）と、表層材に使用する樹脂ワニスＡ１の
粘度（ηA1）の比は７．３であった。(Example 2) A copper-clad laminate having a thickness of 1.6 mm was produced in the same manner as in Example 1 except that the resin varnish B2 shown in Table 1 was used instead of the resin varnish B1.
As is clear from the viscosity of the resin varnish shown in Table 1, the resin varnish B2 used as the core material in the present example.
Viscosity (eta B2) of the ratio of the viscosity (eta A1) of the resin varnish A1 used for the surface layer material was 7.3.
【００２０】（比較例１）樹脂ワニスＢ１の代わりに表
１記載の樹脂ワニスＢ３を使用した以外は実施例１と同
様にして、厚み１．６ｍｍの銅張り積層板を作製した。
なお、表１に示す樹脂ワニスの粘度から明らかなよう
に、本実施例の場合のコア材に使用した樹脂ワニスＢ３
の粘度（ηB3）と、表層材に使用する樹脂ワニスＡ１の
粘度（ηA1）の比は４．３であった。Comparative Example 1 A copper-clad laminate having a thickness of 1.6 mm was produced in the same manner as in Example 1 except that the resin varnish B3 shown in Table 1 was used instead of the resin varnish B1.
As is clear from the viscosity of the resin varnish shown in Table 1, the resin varnish B3 used as the core material in the present example.
The ratio of the viscosity (η B3 ) of the resin varnish A1 used for the surface layer material (η A1 ) was 4.3.
【００２１】（実施例３）表１記載の樹脂ワニスＡ２を
厚さ２００μｍの平織りガラスクロス（大きさ３００ｍ
ｍ×３００ｍｍ）に含浸した後、含浸品から約１０ｃｍ
離れた距離から６０秒間紫外線を含浸品の一方の面に照
射してプレキュアを行い、プレキュアした含浸品を得
た。また、表１記載の樹脂ワニスＢ４を厚さ３７０μｍ
のガラス不織布（大きさ３００ｍｍ×３００ｍｍ）に含
浸して含浸品を得た。得られたガラス不織布基材の含浸
品３枚を重ねてコア材とし、その上下に前記プレキュア
したガラスクロス基材の含浸品を表層材として各１枚積
層し、さらに、この積層物の上下の表面にそれぞれ厚さ
１８μｍ銅箔を配したものを、所定間隙に調製した２本
のロールの間を通した。次いで得られた積層物を２枚の
金属プレートの間にはさみ、平置きの状態で１１０℃で
６０分間加熱して硬化させ、厚み１．６ｍｍの銅張り積
層板を作製した。Example 3 A resin varnish A2 shown in Table 1 was used as a plain weave glass cloth having a thickness of 200 μm (size 300 m).
m × 300mm), then about 10cm from the impregnated product
Precuring was performed by irradiating one surface of the impregnated product with ultraviolet rays for 60 seconds from a distance to obtain a precured impregnated product. In addition, the resin varnish B4 shown in Table 1 has a thickness of 370 μm.
The glass non-woven fabric (size 300 mm × 300 mm) was impregnated to obtain an impregnated product. Three pieces of the obtained impregnated product of the glass nonwoven fabric base material are laminated to form a core material, and one of the pre-cured impregnated product of the glass cloth base material is laminated on each as a surface layer material. A copper foil having a thickness of 18 μm on each surface was passed between two rolls prepared with a predetermined gap. Then, the obtained laminate was sandwiched between two metal plates and heated in a flat state at 110 ° C. for 60 minutes to be hardened to produce a copper-clad laminate having a thickness of 1.6 mm.
【００２２】（実施例４）表１記載の樹脂ワニスＢ４を
厚さ３７０μｍのガラス不織布（大きさ３００ｍｍ×３
００ｍｍ）に含浸したものを３枚重ね合わせ、次いで、
この積層物の両表面からそれぞれ約１０ｃｍ離れた距離
から４５秒間紫外線を積層物の両方の面にに照射してプ
レキュアを行い、プレキュアした積層物を得た。また、
表１記載の樹脂ワニスＡ２を厚さ２００μｍの平織りガ
ラスクロス（大きさ３００ｍｍ×３００ｍｍ）に含浸し
て含浸品を得た。前記で得られたガラス不織布基材の含
浸品３枚を積層してプレキュアした積層物をコア材と
し、その上下に前記のガラスクロス基材の含浸品を表層
材として各１枚積層し、さらに、この積層物の上下の表
面にそれぞれ厚さ１８μｍ銅箔を配したものを、所定間
隙に調製した２本のロールの間を通した。次いで得られ
た積層物を２枚の金属プレートの間にはさみ、平置きの
状態で１１０℃で６０分間加熱して硬化させ、厚み１．
６ｍｍの銅張り積層板を作製した。Example 4 The resin varnish B4 shown in Table 1 was used as a glass non-woven fabric having a thickness of 370 μm (size: 300 mm × 3).
00mm) impregnated three pieces, and then
Precuring was performed by irradiating both surfaces of the laminate with ultraviolet light for 45 seconds from a distance of about 10 cm from each surface of the laminate to obtain a precured laminate. Also,
The resin varnish A2 shown in Table 1 was impregnated into a 200 μm thick plain woven glass cloth (size: 300 mm × 300 mm) to obtain an impregnated product. Three pieces of the impregnated product of the glass non-woven fabric substrate obtained above were laminated and pre-cured as a core material, and one sheet each of the impregnated product of the glass cloth substrate as a surface layer material was laminated above and below the core material. A copper foil having a thickness of 18 μm disposed on each of the upper and lower surfaces of this laminate was passed between two rolls having a predetermined gap. Then, the obtained laminate was sandwiched between two metal plates and heated in a flat state at 110 ° C. for 60 minutes to be cured, and the thickness was 1.
A 6 mm copper-clad laminate was prepared.
【００２３】（実施例５）表１記載の樹脂ワニスＡ２を
厚さ２００μｍの平織りガラスクロス（大きさ３００ｍ
ｍ×３００ｍｍ）に含浸した後、含浸品から約１０ｃｍ
離れた距離から６０秒間紫外線を含浸品の一方の面に照
射してプレキュアを行い、プレキュアした含浸品を得
た。また、表１記載の樹脂ワニスＢ４を厚さ３７０μｍ
のガラス不織布（大きさ３００ｍｍ×３００ｍｍ）に含
浸したものを３枚重ね合わせ、次いで、この積層物の両
表面からそれぞれ約１０ｃｍ離れた距離から４５秒間紫
外線を積層物の両方の面にに照射してプレキュアを行
い、プレキュアした積層物を得た。得られたガラス不織
布基材の含浸品３枚を積層してプレキュアした積層物を
コア材とし、その上下に前記プレキュアしたガラスクロ
ス基材の含浸品を表層材として各１枚積層し、さらに、
この積層物の上下の表面にそれぞれ厚さ１８μｍ銅箔を
配したものを、所定間隙に調製した２本のロールの間を
通した。次いで得られた積層物を２枚の金属プレートの
間にはさみ、平置きの状態で１１０℃で６０分間加熱し
て硬化させ、厚み１．６ｍｍの銅張り積層板を作製し
た。Example 5 A resin varnish A2 shown in Table 1 was used as a plain weave glass cloth having a thickness of 200 μm (size 300 m).
m × 300mm), then about 10cm from the impregnated product
Precuring was performed by irradiating one surface of the impregnated product with ultraviolet rays for 60 seconds from a distance to obtain a precured impregnated product. In addition, the resin varnish B4 shown in Table 1 has a thickness of 370 μm.
Of the glass nonwoven fabric (size: 300 mm x 300 mm) impregnated with each other are overlapped, and then both surfaces of the laminate are irradiated with ultraviolet rays for 45 seconds from a distance of about 10 cm from each surface of the laminate. Was pre-cured to obtain a pre-cured laminate. Three sheets of the obtained impregnated glass non-woven fabric substrate were laminated and pre-cured as a core material, and one sheet each of the pre-cured glass cloth substrate impregnated article was laminated as a surface layer material, and further,
A copper foil having a thickness of 18 μm on each of the upper and lower surfaces of this laminate was passed between two rolls having a predetermined gap. Then, the obtained laminate was sandwiched between two metal plates and heated in a flat state at 110 ° C. for 60 minutes to be hardened to produce a copper-clad laminate having a thickness of 1.6 mm.
【００２４】（実施例６）表１記載の樹脂ワニスＡ２を
厚さ２００μｍの平織りガラスクロス（大きさ３００ｍ
ｍ×３００ｍｍ）に含浸して含浸品を得た。また、表１
記載の樹脂ワニスＢ４を厚さ３７０μｍのガラス不織布
（大きさ３００ｍｍ×３００ｍｍ）に含浸して含浸品を
得た。次に、得られたガラス不織布基材の含浸品３枚を
重ねてコア材とし、その上下に前記のガラスクロス基材
の含浸品を表層材として各１枚積層し、得られた積層物
の両表面からそれぞれ約１０ｃｍ離れた距離から４５秒
間紫外線を積層物の両方の面にに照射してプレキュアを
行い、プレキュアした積層物を得た。さらに、この積層
物の上下の表面にそれぞれ厚さ１８μｍ銅箔を配したも
のを、所定間隙に調製した２本のロールの間を通した。
次いで得られた積層物を２枚の金属プレートの間にはさ
み、平置きの状態で１１０℃で６０分間加熱して硬化さ
せ、厚み１．６ｍｍの銅張り積層板を作製した。Example 6 A resin varnish A2 shown in Table 1 was used as a plain weave glass cloth having a thickness of 200 μm (size 300 m).
m × 300 mm) to obtain an impregnated product. Table 1
A glass woven fabric (size: 300 mm × 300 mm) having a thickness of 370 μm was impregnated with the described resin varnish B4 to obtain an impregnated product. Next, three pieces of the glass impregnated product obtained by impregnating the glass non-woven fabric are stacked to form a core material, and the impregnated product of the glass cloth substrate is laminated on each of the upper and lower parts as a surface layer material to form a core material. Precuring was performed by irradiating both surfaces of the laminate with ultraviolet light for 45 seconds from a distance of about 10 cm from each surface to obtain a precured laminate. Further, the upper and lower surfaces of this laminate, on each of which a copper foil having a thickness of 18 μm was arranged, were passed between two rolls having a predetermined gap.
Then, the obtained laminate was sandwiched between two metal plates and heated in a flat state at 110 ° C. for 60 minutes to be hardened to produce a copper-clad laminate having a thickness of 1.6 mm.
【００２５】（比較例２）表１記載の樹脂ワニスＡ２を
厚さ２００μｍの平織りガラスクロス（大きさ３００ｍ
ｍ×３００ｍｍ）に含浸して含浸品を得た。また、表１
記載の樹脂ワニスＢ４を厚さ３７０μｍのガラス不織布
（大きさ３００ｍｍ×３００ｍｍ）に含浸して含浸品を
得た。得られたガラス不織布基材の含浸品３枚を重ねて
コア材とし、その上下に前記のガラスクロス基材の含浸
品を表層材として各１枚積層し、さらに、この積層物の
上下の表面にそれぞれ厚さ１８μｍ銅箔を配したもの
を、所定間隙に調製した２本のロールの間を通した。次
いで得られた積層物を２枚の金属プレートの間にはさ
み、平置きの状態で１１０℃で６０分間加熱して硬化さ
せ、厚み１．６ｍｍの銅張り積層板を作製した。COMPARATIVE EXAMPLE 2 A resin varnish A2 shown in Table 1 was used as a plain weave glass cloth having a thickness of 200 μm (size 300 m).
m × 300 mm) to obtain an impregnated product. Table 1
A glass woven fabric (size: 300 mm × 300 mm) having a thickness of 370 μm was impregnated with the described resin varnish B4 to obtain an impregnated product. Three pieces of the impregnated product of the obtained glass nonwoven fabric base material are stacked to form a core material, and one of the impregnated product of the glass cloth base material is laminated on the upper and lower sides thereof as a surface layer material, and the upper and lower surfaces of the laminate are further laminated. An 18 μm-thick copper foil was placed on each of the sheets and passed through two rolls prepared with a predetermined gap. Then, the obtained laminate was sandwiched between two metal plates and heated in a flat state at 110 ° C. for 60 minutes to be hardened to produce a copper-clad laminate having a thickness of 1.6 mm.
【００２６】上記の各実施例及び各比較例で得られた銅
張積層板を２５０ｍｍ×２５０ｍｍに切断し、全面エッ
チングをして銅箔を除去し、さらに、１７０℃に加熱し
たオーブン中に吊り下げた状態で入れ、３０分間熱処理
し、次いで、吊り下げた状態で取り出して室温まで冷却
した。得られた熱処理した積層板をガラスの平板状に平
置きし、最大持ち上がり量をそり量として測定した。ま
た、それぞれの銅張積層板について、絶縁抵抗、半田耐
熱性及び曲げ強度の測定をＪＩＳ Ｃ−６４８１に準じ
て行った。以上の測定結果を表２に示す。The copper clad laminates obtained in each of the above Examples and Comparative Examples were cut into 250 mm × 250 mm, the entire surface was etched to remove the copper foil, and the copper clad laminate was hung in an oven heated to 170 ° C. It was put in the lowered state, heat-treated for 30 minutes, taken out in the suspended state, and cooled to room temperature. The heat-treated laminated plate thus obtained was placed flat on a flat glass plate, and the maximum lift amount was measured as the warp amount. Further, with respect to each copper-clad laminate, the insulation resistance, solder heat resistance and bending strength were measured according to JIS C-6481. Table 2 shows the above measurement results.
【００２７】表２にみるように、本発明の実施例はすべ
て、比較例１及び比較例２よりもそり量が少ないことが
確認され、また、絶縁抵抗、半田耐熱性及び曲げ強度に
ついての性能の低下も生じていないことが確認された。As shown in Table 2, all the examples of the present invention were confirmed to have a smaller amount of warpage than Comparative Examples 1 and 2, and the performances of insulation resistance, solder heat resistance and bending strength were confirmed. It was confirmed that there was no decrease in
【００２８】[0028]
【表１】 [Table 1]
【００２９】[0029]
【表２】 [Table 2]
【００３０】[0030]
【発明の効果】請求項１〜請求項３に係る発明の銅張積
層板の製造方法によれば、ラジカル重合型熱硬化性樹脂
及び無機充填材を含む樹脂ワニスをガラス不織布に含浸
した含浸品をコア材とし、その両外面にラジカル重合型
熱硬化性樹脂を含む樹脂ワニスをガラスクロスに含浸し
た含浸品を表層材として積層し、さらにその少なくとも
一方の表面に銅箔を積層した後、加熱硬化させて一体化
した銅張り積層板について、加工時のそりを低減するこ
とができる。そりの発生が少ない銅張り積層板を使用す
れば、プリント配線板の製造工程及び実装工程における
トラブルが少なくなるので、本発明の製造方法による銅
張積層板は好適に利用できる。According to the method for producing a copper clad laminate of the present invention according to claims 1 to 3, an impregnated product obtained by impregnating a glass nonwoven fabric with a resin varnish containing a radical polymerization type thermosetting resin and an inorganic filler. As a core material, laminated on both outer surfaces of the impregnated product obtained by impregnating a glass cloth with a resin varnish containing a radical polymerization type thermosetting resin as a surface layer material, and further laminating a copper foil on at least one surface thereof, followed by heating. With respect to the copper-clad laminate that is hardened and integrated, warpage during processing can be reduced. If a copper-clad laminate with less warpage is used, troubles in the manufacturing process and mounting process of the printed wiring board are reduced, so that the copper-clad laminate according to the manufacturing method of the present invention can be preferably used.
───────────────────────────────────────────────────── 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 Ｂ３２Ｂ 31/04 9349−4Ｆ 31/12 9349−4Ｆ Ｈ０５Ｋ 1/03 ６３０ Ｆ 7511−4Ｅ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display location B32B 31/04 9349-4F 31/12 9349-4F H05K 1/03 630 F 7511-4E
Claims (3)
填材を含む樹脂ワニスをガラス不織布に含浸した含浸品
をコア材とし、その両外面にラジカル重合型熱硬化性樹
脂を含む樹脂ワニスをガラスクロスに含浸した含浸品を
表層材として積層し、さらにその少なくとも一方の表面
に銅箔を積層した後、加熱硬化させる銅張り積層板の製
造方法において、コア材に使用する樹脂ワニスの粘度
（ηB ）と、表層材に使用する樹脂ワニスの粘度
（ηA ）の比がηB ／ηA ＞５であることを特徴とする
銅張り積層板の製造方法。1. An impregnated product obtained by impregnating a glass nonwoven fabric with a resin varnish containing a radical polymerization type thermosetting resin and an inorganic filler is used as a core material, and a resin varnish containing a radical polymerization type thermosetting resin is formed on both outer surfaces of the glass. The impregnated product impregnated in the cloth is laminated as a surface layer material, and after further laminating a copper foil on at least one surface of the cloth, in a method for producing a copper-clad laminate that is heat-cured, the viscosity of the resin varnish (η B ) and the viscosity (η A ) of the resin varnish used for the surface layer material is η B / η A > 5, a method for producing a copper-clad laminate.
填材を含む樹脂ワニスをガラス不織布に含浸した含浸品
をコア材とし、その両外面にラジカル重合型熱硬化性樹
脂を含む樹脂ワニスをガラスクロスに含浸した含浸品を
表層材として積層し、さらにその少なくとも一方の表面
に銅箔を積層した後、加熱硬化させる銅張り積層板の製
造方法において、表層材及び／またはコア材が、紫外線
照射によりプレキュアされていることを特徴とする銅張
り積層板の製造方法。2. An impregnated product obtained by impregnating a glass nonwoven fabric with a resin varnish containing a radical polymerization type thermosetting resin and an inorganic filler is used as a core material, and a resin varnish containing a radical polymerization type thermosetting resin is formed on both outer surfaces of the glass material. In the method for producing a copper-clad laminate, in which impregnated products impregnated with a cloth are laminated as a surface layer material, copper foil is further laminated on at least one surface of the cloth, and the resulting material is heated and cured, the surface layer material and / or the core material is irradiated with ultraviolet rays. A method for producing a copper-clad laminate, characterized in that it is pre-cured.
填材を含む樹脂ワニスをガラス不織布に含浸した含浸品
をコア材とし、その両外面にラジカル重合型熱硬化性樹
脂を含む樹脂ワニスをガラスクロスに含浸した含浸品を
表層材として積層し、さらにその少なくとも一方の表面
に銅箔を積層した後、加熱硬化させる銅張り積層板の製
造方法において、コア材と表層材の積層物に紫外線を照
射してプレキュアし、次いで銅箔を積層することを特徴
とする銅張り積層板の製造方法。3. A glass woven resin varnish containing a radical polymerization type thermosetting resin on both outer surfaces of the core material, which is an impregnated product obtained by impregnating a glass nonwoven fabric with a resin varnish containing a radical polymerization type thermosetting resin and an inorganic filler. The impregnated product impregnated in the cloth is laminated as a surface layer material, and after further laminating a copper foil on at least one surface of the cloth, in the method for producing a copper-clad laminate which is heat-cured, ultraviolet rays are applied to the laminate of the core material and the surface layer material. A method for producing a copper-clad laminate, which comprises irradiating and pre-curing, and then laminating copper foil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6265027A JP2988280B2 (en) | 1994-10-28 | 1994-10-28 | Manufacturing method of copper-clad laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6265027A JP2988280B2 (en) | 1994-10-28 | 1994-10-28 | Manufacturing method of copper-clad laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08118543A true JPH08118543A (en) | 1996-05-14 |
| JP2988280B2 JP2988280B2 (en) | 1999-12-13 |
Family
ID=17411569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6265027A Expired - Fee Related JP2988280B2 (en) | 1994-10-28 | 1994-10-28 | Manufacturing method of copper-clad laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2988280B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09109322A (en) * | 1995-10-23 | 1997-04-28 | Matsushita Electric Works Ltd | Manufacture of laminated board |
| US7091716B2 (en) | 2002-02-25 | 2006-08-15 | Fujitsu Limited | Multilayer wiring board, manufacturing method therefor and test apparatus thereof |
| JP2012126104A (en) * | 2010-12-17 | 2012-07-05 | Panasonic Corp | Copper-clad laminate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04272845A (en) * | 1991-02-28 | 1992-09-29 | Dainippon Ink & Chem Inc | Manufacture of laminated board |
| JPH0557828A (en) * | 1991-08-30 | 1993-03-09 | Dainippon Ink & Chem Inc | Manufacture of laminated sheet and epoxy-based resin composition |
-
1994
- 1994-10-28 JP JP6265027A patent/JP2988280B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04272845A (en) * | 1991-02-28 | 1992-09-29 | Dainippon Ink & Chem Inc | Manufacture of laminated board |
| JPH0557828A (en) * | 1991-08-30 | 1993-03-09 | Dainippon Ink & Chem Inc | Manufacture of laminated sheet and epoxy-based resin composition |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09109322A (en) * | 1995-10-23 | 1997-04-28 | Matsushita Electric Works Ltd | Manufacture of laminated board |
| US7091716B2 (en) | 2002-02-25 | 2006-08-15 | Fujitsu Limited | Multilayer wiring board, manufacturing method therefor and test apparatus thereof |
| US7284311B2 (en) | 2002-02-25 | 2007-10-23 | Fujitsu Limited | Multilayer wiring board, manufacturing method therefor and test apparatus thereof |
| JP2012126104A (en) * | 2010-12-17 | 2012-07-05 | Panasonic Corp | Copper-clad laminate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2988280B2 (en) | 1999-12-13 |
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