JP2001138426A - Laminate and method of manufacturing the same - Google Patents
Laminate and method of manufacturing the sameInfo
- Publication number
- JP2001138426A JP2001138426A JP32617099A JP32617099A JP2001138426A JP 2001138426 A JP2001138426 A JP 2001138426A JP 32617099 A JP32617099 A JP 32617099A JP 32617099 A JP32617099 A JP 32617099A JP 2001138426 A JP2001138426 A JP 2001138426A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- laminate
- matrix resin
- prepreg
- base material
- 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 abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 126
- 239000011347 resin Substances 0.000 claims abstract description 126
- 239000011159 matrix material Substances 0.000 claims abstract description 57
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 55
- 238000012545 processing Methods 0.000 claims abstract description 28
- 239000003365 glass fiber Substances 0.000 claims abstract description 20
- 238000010030 laminating Methods 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims description 22
- 239000003822 epoxy resin Substances 0.000 claims description 21
- 229920000647 polyepoxide Polymers 0.000 claims description 21
- 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 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 10
- 125000004386 diacrylate group Chemical group 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 125000003827 glycol group Chemical group 0.000 claims description 3
- 238000007731 hot pressing Methods 0.000 claims description 3
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 38
- 230000035939 shock Effects 0.000 abstract description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 16
- 229910000679 solder Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 230000032798 delamination Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 238000005553 drilling Methods 0.000 description 11
- 150000001412 amines Chemical class 0.000 description 7
- -1 glycol acrylate-modified bisphenol Chemical class 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 230000007547 defect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 3
- QUXLCYFNVNNRBE-UHFFFAOYSA-N 6-methylpyridin-2-amine Chemical compound CC1=CC=CC(N)=N1 QUXLCYFNVNNRBE-UHFFFAOYSA-N 0.000 description 2
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000005482 strain hardening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- NKYUHMVMZRRVSC-UHFFFAOYSA-N aniline propan-1-amine Chemical compound NC1=CC=CC=C1.NCCC NKYUHMVMZRRVSC-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 238000013441 quality evaluation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ガラス繊維からな
る補強基材にマトリクス樹脂を含浸させたプリプレグを
用いて積層成形することで得られる積層体およびその製
造方法において，特に補強基材を構成する繊維が低弾性
樹脂で被覆されている積層体およびその製造方法に関す
るものである。The present invention relates to a laminate obtained by laminating and molding a prepreg in which a matrix resin is impregnated with a reinforcing substrate made of glass fiber, and a method for producing the same. The present invention relates to a laminate in which fibers to be coated are coated with a low elasticity resin and a method for producing the same.
【０００２】[0002]
【従来の技術】ガラス繊維を補強基材としたプリプレグ
からなる積層体では、一般にガラス繊維とマトリクス樹
脂の接着力が問題となるため、カップリング剤を処理し
て補強基材の表面にカップリング剤の吸着層を形成する
方法が採られている。（例えば特開平４−１９２４８
９）すなわち、補強基材とマトリクス樹脂の間に吸着層
を形成させることにより、吸着層と補強基材及びマトリ
クス樹脂の各々が化学的に結合し、補強基材とマトリク
ス樹脂の接着性が改善されるものとなっている。2. Description of the Related Art In general, in a laminate made of a prepreg using glass fiber as a reinforcing base material, the adhesive strength between the glass fiber and the matrix resin becomes a problem. A method of forming an adsorbing layer of the agent has been adopted. (For example, Japanese Patent Application Laid-Open No.
9) That is, by forming an adsorbing layer between the reinforcing base material and the matrix resin, the adsorbing layer, the reinforcing base material and the matrix resin are chemically bonded, and the adhesion between the reinforcing base material and the matrix resin is improved. It is something to be done.
【０００３】しかしながら，従来のプリント積層基板を
始めとする積層体においては，はんだ耐熱試験やＰＣＴ
試験などの熱的衝撃が負荷される品質評価試験におい
て，層間剥離やミーズリングとよばれるガラスクロス経
糸と緯糸の交叉部での剥離が生じることがあり、特に多
層基板の場合には層間剥離による製品の信頼性低下が問
題になることがあった。However, in the case of a conventional printed circuit board and other laminates, solder heat resistance tests and PCT
In a quality evaluation test in which a thermal shock is applied, such as a test, delamination or peeling may occur at the intersection of glass cloth warps and wefts, which is referred to as measling. There was a case where the reliability of the product deteriorated.
【０００４】さらに，従来のガラス繊維を補強材とした
プリプレグからなる積層体では、ＩＣなどの部品実装用
の穴あけ加工に際して，補強材とマトリクス樹脂の接着
性が、ドリル加工のような機械加工に耐えうる程度の強
度を有していないため、加工時に、繊維束内部に図６に
示すようなマイクロクラックが発生することがあった。
このようなマイクロクラックを有する状態でめっきを行
うと，めっき液がマイクロクラックにより生じた空隙に
浸透するため，不要な導通回路が形成されることにな
り，製品の特性不良の原因のひとつとなる。このような
問題は，プリント配線基板の極薄化ニーズの伸長によ
り，より顕在化する可能性がある。Further, in a conventional laminate made of a prepreg using glass fiber as a reinforcing material, the adhesiveness between the reinforcing material and the matrix resin is reduced by machining such as drilling at the time of drilling for mounting components such as ICs. Since the fiber bundle does not have enough strength to withstand, microcracks as shown in FIG. 6 may be generated inside the fiber bundle during processing.
If plating is carried out in the presence of such microcracks, the plating solution penetrates into the voids created by the microcracks, thus creating an unnecessary conductive circuit, which is one of the causes of product characteristic defects. . Such a problem may become more apparent due to growing needs for ultra-thin printed wiring boards.
【０００５】[0005]
【発明が解決しようとする課題】本発明は，上述したよ
うな従来技術の欠点を解決し，従来よりも耐熱的衝撃
性、ドリル加工性およびレーザ加工性に優れた積層体及
びその製造方法を提供することを目的とする。SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks of the prior art and provides a laminate having excellent heat shock resistance, drill workability and laser workability, and a method of manufacturing the same. The purpose is to provide.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するた
め、本願の発明者らは、補強基材にガラス繊維を用いた
ときに生じるこのようなマイクロクラック発生は、はん
だ浴への浸漬等の熱的衝撃負荷あるいはドリル加工等の
機械的加工負荷により補強基材とマトリクス樹脂の線膨
張率の差異により界面に応力が発生するためであり、従
来のカップリング剤処理による化学的結合力では、この
ような内部応力に耐えられないためであると考え、その
対策について鋭意研究を重ねた結果、補強基材とマトリ
クス樹脂の間に、内部応力を吸収できるような弾性率の
低い材料から成る層を形成することが有効であるという
ことを見出し、この知見に基づいて本発明を完成した。In order to achieve the above-mentioned object, the inventors of the present application have found that the occurrence of such microcracks when glass fibers are used for the reinforcing substrate is caused by immersion in a solder bath or the like. This is because stress is generated at the interface due to the difference in the coefficient of linear expansion between the reinforcing substrate and the matrix resin due to thermal shock load or mechanical processing load such as drilling. We thought that it was not possible to withstand such internal stress, and as a result of intensive research on the countermeasures, a layer made of a material with a low elastic modulus capable of absorbing internal stress was placed between the reinforcing base material and the matrix resin. Was found to be effective, and the present invention was completed based on this finding.
【０００７】すなわち本発明は、補強基材となるガラス
繊維にマトリクス樹脂を含浸させたプリプレグを用いて
積層成形することで得られ積層体およびその製造方法に
おいて，特に補強基材を構成する繊維が低弾性樹脂で覆
われている積層体およびその製造方法を提供するもので
ある。以下本発明を詳しく説明する。That is, the present invention relates to a laminate obtained by laminating a glass fiber serving as a reinforcing base material using a prepreg impregnated with a matrix resin, and a method for producing the same. It is intended to provide a laminate covered with a low elasticity resin and a method for producing the same. Hereinafter, the present invention will be described in detail.
【０００８】本発明の請求項１に係る積層体は、補強基
材の表面がマトリクス樹脂の７０％以下の弾性率を有す
る低弾性樹脂で被覆されていることを特徴とするもので
ある。[0008] The laminate according to claim 1 of the present invention is characterized in that the surface of the reinforcing substrate is covered with a low elastic resin having an elastic modulus of 70% or less of the matrix resin.
【０００９】このような積層体によれば、マトリクス樹
脂と補強基材の間に低弾性樹脂を介した構造になるた
め、はんだ浴への浸漬等の熱的衝撃負荷やドリル加工等
の機械的加工負荷時に、補強基材とマトリクス樹脂の線
膨張率の差異により界面に発生する応力が緩和される。According to such a laminate, a low-elastic resin is interposed between the matrix resin and the reinforcing base material, so that a thermal shock load such as immersion in a solder bath or a mechanical process such as drilling is performed. The stress generated at the interface due to the difference in the linear expansion coefficient between the reinforcing base material and the matrix resin during the processing load is reduced.
【００１０】また請求項２に係る積層体は、低弾性樹脂
の引張弾性率が１．０ＧＰａ以下あるいは引張破断ひず
みが２０％以上のいずれかであって、マトリクス樹脂の
引張弾性率が１．５ＧＰａ以上あるいは引張破断ひずみ
が１５％以下のいずれかあることを特徴とするものであ
る。According to a second aspect of the present invention, the low modulus resin has a tensile modulus of 1.0 GPa or less or a tensile breaking strain of 20% or more, and the matrix resin has a tensile modulus of 1.5 GPa or less. It is characterized in that the tensile strain at break is at least 15% or less.
【００１１】このような積層体によれば、熱的衝撃負荷
や機械的加工負荷時に発生する界面の応力が特に有効に
緩和されるので、ミーズリングや層間剥離等の補強基材
とマトリクス樹脂との熱膨張率の差異により発生する不
良の防止効果が顕著である。According to such a laminate, the stress at the interface generated during a thermal shock load or a mechanical processing load is particularly effectively relieved. The effect of preventing defects caused by the difference in thermal expansion coefficient is remarkable.
【００１２】また請求項３に係る積層体は、低弾性樹脂
がグリコールアクリレートで変性されたビスフェノール
A型エポキシ樹脂であることを特徴とするものである。Further, according to a third aspect of the present invention, there is provided a laminate wherein the low elasticity resin is modified with glycol acrylate.
It is an A-type epoxy resin.
【００１３】このような積層体によれば、低弾性樹脂が
１．０ＧＰａ以下あるいは引張破断ひずみが２０％以上
のいずれかの特性を示すため、熱的衝撃負荷や機械的加
工負荷時に発生する界面の応力が特に有効に緩和され
る。According to such a laminate, the low-elasticity resin exhibits a characteristic of 1.0 GPa or less or a tensile breaking strain of 20% or more. Is particularly effectively alleviated.
【００１４】また請求項４に係る積層体は、低弾性樹脂
であるビスフェノールA型エポキシ樹脂の主剤が，ポリ
エチレングリコール２００ジアクリレートとの混合比を
変えて変性したものであることを特徴とするものであ
る。A laminate according to a fourth aspect is characterized in that the main component of the bisphenol A type epoxy resin, which is a low elasticity resin, is modified by changing the mixing ratio with polyethylene glycol 200 diacrylate. It is.
【００１５】このような積層体によれば、ビスフェノー
ルA型エポキシ樹脂の主剤とポリエチレングリコール２
００ジアクリレートの混合比を変えることにより、低弾
性樹脂の引張特性を制御することができるので、補強基
材やマトリクス樹脂の剛性、降伏応力、ひずみ硬化係数
等の弾塑性特性の変更に対する自由度が大きくなる。According to such a laminate, the main component of bisphenol A type epoxy resin and polyethylene glycol 2
Since the tensile properties of the low elasticity resin can be controlled by changing the mixing ratio of the 00 diacrylate, the degree of freedom for changing the elasto-plastic properties such as the rigidity, the yield stress, and the strain hardening coefficient of the reinforcing base material and the matrix resin can be controlled. Becomes larger.
【００１６】また請求項５に係る積層体は、低弾性樹脂
の補強基材の表面への付着率が０．１％以上３．５％以
であることを特徴とするものである。The laminate according to claim 5 is characterized in that the adhesion rate of the low elasticity resin to the surface of the reinforcing substrate is 0.1% or more and 3.5% or less.
【００１７】このような積層体によれば、付着率が０.
１％以下のときに発生する、機械的加工によるマイクロ
クラックを低減・防止することができると共に、３.５
％以上のときに発生する層間剥離等のはんだ耐熱性の低
下をも防止することができる。According to such a laminate, the adhesion rate is equal to 0.1.
It is possible to reduce and prevent micro-cracks caused by mechanical processing, which occur when the content is 1% or less, and to reduce 3.5.
% Or lowering of the solder heat resistance, such as delamination, which occurs when the content is not less than%.
【００１８】また請求項６に係る積層体は、積層体に加
工を施す場合であって、加工時に損傷が生じやすい部位
に前記プリプレグを配することを特徴とするものであ
る。[0018] Further, the laminated body according to claim 6 is a case where the laminated body is processed, wherein the prepreg is arranged in a portion where damage is likely to occur during the processing.
【００１９】このような積層体によれば、加工時に損傷
が生じやすい部位に、熱的衝撃や機械的加工が負荷され
た前記プリプレグを配するので、熱的衝撃や機械的加工
負荷時に発生するミーズリングや層間剥離、マイクロク
ラックの発生を減少もしくは防止することができるとと
もに、低弾性樹脂の添加による積層体としての耐熱性低
下を最小限に抑えることができる。According to such a laminate, the prepreg loaded with thermal shock or mechanical processing is arranged at a portion where damage is likely to occur during processing, so that the prepreg is generated at the time of thermal shock or mechanical processing load. The occurrence of measling, delamination, and microcracks can be reduced or prevented, and the decrease in heat resistance of the laminate due to the addition of a low-elastic resin can be minimized.
【００２０】また請求項７に係る積層体は、積層体をプ
リント配線基板に用いることを特徴とするものである。The laminate according to claim 7 is characterized in that the laminate is used for a printed wiring board.
【００２１】このような積層体によれば、プリント配線
基板の製造工程において加わる、電子部品実装部位確保
のためのドリル穴あけなどの機械加工時や、レーザー加
工を始めとする高エネルギー加工時に発生する、補強基
材とマトリクス樹脂の接着性に起因する種々の不良を低
減・防止させることができるので、製品の信頼性を高め
ることができる。According to such a laminated body, it occurs at the time of mechanical processing such as drilling for securing an electronic component mounting portion, which is added in the manufacturing process of a printed wiring board, or at the time of high energy processing such as laser processing. In addition, since various defects caused by the adhesion between the reinforcing base material and the matrix resin can be reduced or prevented, the reliability of the product can be improved.
【００２２】また請求項８に係る積層体の製造方法は、
プリプレグを形成した後、プリプレグを積層してホット
プレスを行うことにより積層体を形成する方法におい
て、マトリクス樹脂に対して弾性率の小さいあるいは引
張破断ひずみの大きい樹脂でガラス繊維からなる補強基
材を被覆する工程と、前記低弾性樹脂を硬化させる工程
と、前記補強基材間に前記マトリクス樹脂を含浸させる
工程と、前記マトリクス樹脂を硬化させる工程とを含む
工程でプリプレグを製造することを特徴とするものであ
る。[0022] The method of manufacturing a laminate according to claim 8 is characterized in that:
After forming the prepreg, in a method of forming a laminate by laminating the prepreg and performing hot pressing, a reinforcing base material made of glass fiber with a resin having a small elastic modulus or a large tensile breaking strain with respect to a matrix resin is used. A step of coating, a step of curing the low elasticity resin, a step of impregnating the matrix resin between the reinforcing base materials, and a step of curing the matrix resin, wherein the prepreg is manufactured by a step including: Is what you do.
【００２３】このような積層体の製造方法によれば、熱
的衝撃負荷や機械的加工負荷時に発生する界面の応力が
有効に緩和される積層体を連続的に製造することができ
る。According to such a method of manufacturing a laminate, it is possible to continuously produce a laminate in which the interface stress generated during a thermal shock load or a mechanical processing load is effectively alleviated.
【００２４】[0024]
【発明の実施の形態】以下、本発明の実施の形態を実施
例、比較例により詳細に説明するが、本発明はこれらに
よって限定されるものではない。本発明に係る積層体の
実施例を図１を参照して説明する。図１（ａ）は多数の
ガラス繊維１１から構成される複数のガラス繊維束１２
が経糸と緯糸が交叉するように積層されて織布状になっ
ている補強基材にマトリクス樹脂３が含浸された積層体
の断面図を示したものである。この補強基材の表面に
は、図１（ｂ）に示すように、低弾性樹脂２の層が形成
されており、マトリクス樹脂３と補強基材間に低弾性樹
脂２を介した構造となっている。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below in detail with reference to Examples and Comparative Examples, but the present invention is not limited by these. An embodiment of a laminate according to the present invention will be described with reference to FIG. FIG. 1A shows a plurality of glass fiber bundles 12 composed of many glass fibers 11.
FIG. 1 is a cross-sectional view of a laminate in which a matrix resin 3 is impregnated into a woven fabric-like reinforcing substrate in which warps and wefts are laminated so as to cross each other. As shown in FIG. 1B, a layer of the low elastic resin 2 is formed on the surface of the reinforcing base material, and the low elastic resin 2 is interposed between the matrix resin 3 and the reinforcing base material. ing.
【００２５】本発明で用いるマトリクス樹脂としては特
に限定されず、一般的にプリプレグのマトリクス樹脂と
して使用されてきたものが使用可能である。しかし、積
層体成形の容易さ、硬化温度、及びその他の要求物性等
の観点からエポキシ樹脂、ポリイミド樹脂、ビニルエス
テル樹脂、フェノール樹脂が好ましい。The matrix resin used in the present invention is not particularly limited, and those generally used as prepreg matrix resins can be used. However, an epoxy resin, a polyimide resin, a vinyl ester resin, and a phenol resin are preferable from the viewpoints of ease of molding the laminate, curing temperature, and other required physical properties.
【００２６】また、本発明に係る積層体をプリント配線
基板に用いる場合には、マトリクス樹脂として、ビスフ
ェノール型エポキシ樹脂および少量の多官能エポキシ樹
脂を含むエポキシ樹脂および必要に応じて臭素化フェノ
ール性化合物と、硬化剤および硬化促進剤とを含み、例
えばビスフェノール型エポキシ樹脂を主成分として多官
能エポキシ樹脂を少量含むものなど２種以上のエポキシ
樹脂を含むものも好適に使用される。When the laminate according to the present invention is used for a printed wiring board, an epoxy resin containing a bisphenol-type epoxy resin and a small amount of a polyfunctional epoxy resin and, if necessary, a brominated phenolic compound as a matrix resin. And a curing agent and a curing accelerator, for example, those containing two or more epoxy resins such as those containing a bisphenol type epoxy resin as a main component and a small amount of a polyfunctional epoxy resin are also preferably used.
【００２７】本発明で用いる低弾性樹脂はマトリクス樹
脂の７０％以下の弾性率であればよく、その範囲内では
特に限定されないが、補強基材及びマトリクス樹脂との
接着性等の観点からエポキシ樹脂が好ましい。これら以
外にもポリイミド樹脂、ビニルエステル樹脂、フェノー
ル樹脂を用いても本発明の効果を得ることができる。The low elasticity resin used in the present invention is not particularly limited as long as it has an elastic modulus of 70% or less of the matrix resin, but is not particularly limited within the range, but from the viewpoint of adhesion to the reinforcing base material and the matrix resin, etc. Is preferred. In addition to these, the effects of the present invention can be obtained by using a polyimide resin, a vinyl ester resin, or a phenol resin.
【００２８】さらに、マトリクス樹脂と低弾性樹脂の組
み合わせは、低弾性樹脂の引張弾性率が１．０ＧＰａ以
下あるいは引張破断ひずみが２０％以上のいずれかであ
って、マトリクス樹脂の引張弾性率が１．５ＧＰａ以上
あるいは引張破断ひずみが１５％以下のいずれかあれば
よいが、低弾性樹脂の引張弾性率が０．５ＧＰａ以下あ
るいは引張破断ひずみが４０％以上のいずれかであっ
て、マトリクス樹脂の引張弾性率が２．５ＧＰａ以上あ
るいは引張破断ひずみが１０％以下のいずれかあれば好
ましく、低弾性樹脂の引張弾性率が０．３ＧＰａ以下あ
るいは引張破断ひずみが６０％以上のいずれかであっ
て、マトリクス樹脂の引張弾性率が３．５ＧＰａ以上あ
るいは引張破断ひずみが５％以下のいずれかであればさ
らに好ましい。Further, in the combination of the matrix resin and the low elastic resin, the low elastic resin has a tensile elastic modulus of 1.0 GPa or less or a tensile breaking strain of 20% or more, and the matrix resin has a tensile elastic modulus of 1% or less. It is sufficient that the tensile modulus of the low elasticity resin is 0.5 GPa or less or the tensile breaking strain is 40% or more, and the tensile strength of the matrix resin is not less than 0.5 GPa or 15% or less. It is preferable that the modulus of elasticity is 2.5 GPa or more or the tensile strain at break is 10% or less, and the tensile modulus of the low elasticity resin is 0.3 GPa or less or the tensile strain at break is 60% or more. More preferably, the resin has a tensile modulus of 3.5 GPa or more or a tensile breaking strain of 5% or less.
【００２９】また、マトリクス樹脂と低弾性樹脂の組み
合わせは、低弾性樹脂の弾性率がマトリクス樹脂の弾性
率の７０％以上の場合、上述したような本発明の効果が
安定して得られないことが実験的に確認された。さら
に、硬化後も固化せずにゲル状にしかならないような樹
脂を低弾性樹脂として用いた場合にも、マトリクス樹脂
の含浸時に溶媒によって補強基材表面から除去されて、
所望の付着率が得られないことが確認された。Further, the combination of the matrix resin and the low elastic resin is such that when the elastic modulus of the low elastic resin is 70% or more of the elastic modulus of the matrix resin, the above-described effects of the present invention cannot be stably obtained. Was confirmed experimentally. Furthermore, even if a resin that does not solidify even after curing and becomes a gel state is used as the low elasticity resin, it is removed from the surface of the reinforcing base material by the solvent during the impregnation of the matrix resin,
It was confirmed that the desired adhesion rate could not be obtained.
【００３０】本発明に係る補強基材の形態としては、繊
布、不繊布、マットが好ましい。以下、本発明に係る積
層体の製造方法を詳述する。まず、硬化剤としてアミン
系硬化剤を含有するグリコールアクリレート変性ビスフ
ェノールA型エポキシ樹脂をメチルエチルケトン（ＭＥ
Ｋ）に溶かし込んだ溶液に、ガラス繊維の織布である補
強基材を浸漬し、含浸させた後、５０〜８０℃、好まし
くは６０〜７０℃で１０〜６０分間、好ましくは２０〜
３０分間乾燥させて溶媒成分の揮発及び低弾性樹脂の硬
化を行い、補強基材表面に低弾性樹脂層を形成させる。The form of the reinforcing substrate according to the present invention is preferably a woven cloth, a non-woven cloth, or a mat. Hereinafter, the method for producing a laminate according to the present invention will be described in detail. First, a glycol acrylate-modified bisphenol A-type epoxy resin containing an amine-based curing agent as a curing agent was added to methyl ethyl ketone (ME
After immersing a reinforcing substrate, which is a woven glass fiber fabric, in the solution dissolved in K) and impregnating the same, it is heated at 50 to 80 ° C., preferably 60 to 70 ° C. for 10 to 60 minutes, preferably 20 to 60 ° C.
After drying for 30 minutes, the solvent component is volatilized and the low-elastic resin is cured to form a low-elastic resin layer on the surface of the reinforcing substrate.
【００３１】得られた補強基材をさらに、硬化剤として
アミン系硬化剤を含有するグリコールアクリレート変性
ビスフェノールA型エポキシ樹脂を有機溶媒に溶かし込
んだ溶液に浸漬し，含浸させた後、８０〜１３０℃、好
ましくは１００〜１２０℃で１０〜４０分間、好ましく
は２０〜３０分間乾燥させて溶媒成分を揮発及びマトリ
クス樹脂の硬化を行い、プリプレグ化する。このプリプ
レグを複数枚重ねて、加熱加圧して積層一体化させ、積
層体を得る。The obtained reinforcing base material is further immersed in a solution obtained by dissolving a glycol acrylate-modified bisphenol A type epoxy resin containing an amine curing agent as a curing agent in an organic solvent and impregnated. C., preferably at 100 to 120.degree. C. for 10 to 40 minutes, preferably 20 to 30 minutes to volatilize the solvent component and harden the matrix resin to prepare a prepreg. A plurality of the prepregs are stacked and laminated under heat and pressure to obtain a laminate.
【００３２】（実施例１）硬化剤としてアミン系硬化剤
（１、２−ジアミノプロパンと２−アミノ−６−メチル
ピリジンの重量比５０：５０の混合物）を２５ｐｈｒ含
有するグリコールアクリレート変性ビスフェノールA型
エポキシ樹脂（油化シェルエポキシ製エピコート８７
１）をメチルエチルケトン（ＭＥＫ）に溶かし込んで１
ｗｔ％濃度にした溶液に、ガラス繊維の織布である補強
基材を浸漬・含浸させた後、６５℃で２５分間乾燥させ
て溶媒成分の揮発及び低弾性樹脂の硬化を行い、補強基
材表面に低弾性樹脂層を形成させる。Example 1 Glycol acrylate-modified bisphenol A type containing 25 phr of an amine curing agent (a mixture of 1,2-diaminopropane and 2-amino-6-methylpyridine at a weight ratio of 50:50) as a curing agent Epoxy resin (oil coat shell epicoat 87
1) is dissolved in methyl ethyl ketone (MEK) to give 1
After immersing and impregnating a reinforcing substrate, which is a glass fiber woven fabric, in a solution having a concentration of wt%, the substrate is dried at 65 ° C. for 25 minutes to volatilize a solvent component and cure the low elasticity resin. A low elastic resin layer is formed on the surface.
【００３３】得られた補強基材をさらに、硬化剤として
アミン系硬化剤（アミノプロパンアニリン，広栄化学工
業製ＫＣ１１１８）を２３．２ｐｈｒ含有するグリコー
ルアクリレート変性ビスフェノールA型エポキシ樹脂
（油化シェルエポキシ製エピコート８２８）をメチルエ
チルケトンに溶かし込んで５１ｗｔ％濃度にした溶液に
浸漬・含浸させた後、１００〜１２０℃、２４分間乾燥
させて溶媒成分の揮発及びマトリクス樹脂の硬化を行
い、厚さ０．１８ｍｍのプリプレグを得た。このプリプ
レグを８枚重ねて、加熱加圧（８０℃−５分、０．５Ｍ
Ｐａ ＋８０℃−５５分、４．０ＭＰａ ＋１２０℃−
６０分、４．０ＭＰａ）して積層一体化させ、厚さ１．
６ｍｍの積層体を得た。The obtained reinforcing base material is further used as a curing agent, and a glycol acrylate-modified bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy) containing 23.2 phr of an amine curing agent (aminopropane aniline, KC1118 manufactured by Koei Chemical Industry Co., Ltd.) is used. Epicoat 828) is dissolved in methyl ethyl ketone, immersed and impregnated in a solution having a concentration of 51 wt%, and then dried at 100 to 120 ° C. for 24 minutes to volatilize the solvent component and cure the matrix resin, and have a thickness of 0.18 mm. Prepreg was obtained. Eight sheets of this prepreg are stacked and heated and pressed (80 ° C.-5 minutes, 0.5M
Pa + 80 ° C-55 minutes, 4.0MPa + 120 ° C-
60 minutes, 4.0 MPa) to be laminated and integrated to a thickness of 1.
A 6 mm laminate was obtained.
【００３４】（比較例１）硬化剤としてアミン系硬化剤
（アミノプロパンアニリン，広栄化学工業製ＫＣ１１１
８）を２３．２ｐｈｒ含有するグリコールアクリレート
変性ビスフェノールA型エポキシ樹脂（油化シェルエポ
キシ製エピコート８２８）をメチルエチルケトン（ＭＥ
Ｋ）に溶かし込んで１．０ｗｔ％濃度にした溶液に、ガ
ラス繊維の織布である補強基材を浸漬し、含浸させた
後、６５℃で２５分間乾燥させて溶媒成分の揮発及び低
弾性樹脂の硬化を行い、厚さ０．１８ｍｍのプリプレグ
を得た。このプリプレグを８枚重ねて、加熱加圧（８０
℃−５分、０．５ＭＰａ ＋８０℃−５５分、 ４．０
ＭＰａ ＋１２０℃−６０分、４．０ＭＰａ）して積層
一体化させ、厚さ１．６ｍｍの積層体を得た。(Comparative Example 1) Amine-based curing agent (aminopropaneaniline, KC111 manufactured by Koei Chemical Industry Co., Ltd.) as a curing agent
8) containing 23.2 phr of a glycol acrylate-modified bisphenol A type epoxy resin (Epicoat 828 made by Yuka Shell Epoxy) in methyl ethyl ketone (ME
A reinforcing substrate, which is a woven fabric of glass fiber, is immersed and impregnated in a solution having a concentration of 1.0 wt% dissolved in K) and then dried at 65 ° C. for 25 minutes to volatilize the solvent component and reduce elasticity. The resin was cured to obtain a prepreg having a thickness of 0.18 mm. Eight prepregs are stacked and heated and pressed (80
C-5 minutes, 0.5MPa + 80C-55 minutes, 4.0
(MPa + 120 ° C. for 60 minutes, 4.0 MPa) to perform lamination and integration to obtain a 1.6 mm-thick laminate.
【００３５】実施例１，比較例１の各積層体に対して，
はんだ耐熱性（層間剥離，ミーズリング発生）およびド
リル加工性（マイクロクラック発生）を調べた。得られ
た結果を表１に示す。なお、ドリル加工性については、
３枚重ねの積層体に対して、直径φ０．４ｍｍ，長さ
６．５ｍｍ，刃長０．１１０〜０．１１５ｍｍ，刃幅
０．０２０〜０．０２５ｍｍのドリルを用い、回転数６
００００〜８００００ｒｐｍ、送り速度０．０１５〜
０．０２０ｍｍ／ｒｅｖの条件で試験をおこなった。ま
た、はんだ耐熱性については、２６０℃の溶融はんだ浴
上に積層体を浮かせ、積層体に白化が発生するまでの時
間を測定した。For each of the laminates of Example 1 and Comparative Example 1,
Solder heat resistance (delamination, measling occurred) and drill workability (microcracking occurred) were examined. Table 1 shows the obtained results. In addition, about the drill workability,
A drill having a diameter of 0.4 mm, a length of 6.5 mm, a blade length of 0.110 to 0.115 mm, and a blade width of 0.020 to 0.025 mm was used for a three-layered laminate, and the number of rotations was 6
0000-80000 rpm, feed rate 0.015-
The test was performed under the condition of 0.020 mm / rev. Regarding the solder heat resistance, the time required for the laminate to float on the molten solder bath at 260 ° C. and for whitening to occur in the laminate was measured.
【００３６】[0036]
【表１】 表１の結果から，比較例１の積層体に対して実施例１の
積層体はドリル加工性および耐熱性に優れおり、補強基
材とマトリクス樹脂の界面に低弾性樹脂層を介在させる
ことにより、ミーズリングや層間剥離等の熱的衝撃負荷
時の不良を防止することができ、また、機械的な加工に
より衝撃が負荷された場合でもマイクロクラックの発生
を減少あるいは防止できることが確認された。[Table 1] From the results in Table 1, it can be seen that the laminate of Example 1 is superior to the laminate of Comparative Example 1 in drilling workability and heat resistance, and that the low elastic resin layer is interposed at the interface between the reinforcing base material and the matrix resin. It was confirmed that defects during thermal shock load such as measling and delamination can be prevented, and that microcracks can be reduced or prevented even when a shock is applied by mechanical processing.
【００３７】比較例１の積層体の耐熱試験時における補
強基材とマトリクス樹脂との接合不良個所を観察した結
果の模式図を、図２に示す。図２から、積層体の外層側
に特に集中してミーズリングとマイクロクラックによる
層間剥離が発生することが確認された。FIG. 2 is a schematic view showing the result of observing defective bonding between the reinforcing base material and the matrix resin during the heat resistance test of the laminate of Comparative Example 1. From FIG. 2, it was confirmed that delamination due to measling and microcracks occurred particularly concentrated on the outer layer side of the laminate.
【００３８】さらに、実施例１，比較例１の各積層体に
対して、積層体温度温度が常温から２５０℃の間で曲げ
強度を測定した。得られた結果を図３に示す。曲げ試験
は大気雰囲気中で、各雰囲気温度で積層体を十分放置し
た後に３点曲げ試験（曲げ試験条件；評点間距離：４５
ｍｍ、試験速度：１ｍｍ／ｍｉｎ）により行った。Further, the bending strength of each of the laminates of Example 1 and Comparative Example 1 was measured when the laminate temperature was between room temperature and 250 ° C. The results obtained are shown in FIG. The bending test was performed in a three-point bending test (bending test conditions; distance between evaluation points: 45) after the laminate was sufficiently left at each atmospheric temperature in the air atmosphere.
mm, test speed: 1 mm / min).
【００３９】図３の結果から、同一雰囲気温度では、比
較例１の方が実施例１よりも曲げ強度が大きく、補強基
材表面に低弾性樹脂層を形成させると、耐熱性がやや低
下することが確認された。From the results shown in FIG. 3, it can be seen that, at the same ambient temperature, Comparative Example 1 has higher flexural strength than Example 1, and when a low-elastic resin layer is formed on the surface of the reinforcing base material, the heat resistance slightly decreases. It was confirmed that.
【００４０】（実施例２）外層側の第１・２・７・８層
に実施例１で得られるプリプレグを、内層側の第３・４
・５・６層に比較例１で得られるプリプレグを配する構
成となるように、プリプレグを８枚重ねて、実施例１、
比較例１と同様の条件で加熱加圧して積層一体化させ、
厚さ１．６ｍｍの積層体を得た。(Example 2) The prepreg obtained in Example 1 was placed on the first, second, second and third layers on the outer layer side and the third and fourth layers on the inner layer side.
Eight prepregs were stacked so that the prepreg obtained in Comparative Example 1 was arranged in 5.6 layers,
Under the same conditions as in Comparative Example 1, heat and pressure were applied to laminate and integrate,
A laminate having a thickness of 1.6 mm was obtained.
【００４１】実施例２の積層体に対しても、実施例１，
比較例１と同様の試験条件ではんだ耐熱性およびドリル
加工性を調べた。得られた結果を表１に示す。表１の結
果から、実施例２の積層体では，実施例１および比較例
１の積層体に比べてはんだ耐熱性が向上し、加工時に補
強基材とマトリクス樹脂の接着性に不良が生じやすい箇
所に実施例１の積層体を配すれば、実施例１の積層体の
ドリル加工性を維持したまま、実施例１よりも耐熱性が
向上することが確認された。また、はんだ耐熱性試験後
の実施例２の積層体を観察した結果、図２で観察された
ような外層側の層間剥離やミーズリングはほとんど認め
られなかった。The laminated body of the second embodiment is also used in the first and second embodiments.
Under the same test conditions as in Comparative Example 1, solder heat resistance and drill workability were examined. Table 1 shows the obtained results. From the results shown in Table 1, the laminate of Example 2 has improved solder heat resistance as compared with the laminates of Example 1 and Comparative Example 1, and tends to cause poor adhesion between the reinforcing base material and the matrix resin during processing. It was confirmed that when the laminate of Example 1 was disposed at the location, the heat resistance was improved as compared with Example 1 while maintaining the drill workability of the laminate of Example 1. Further, as a result of observing the laminate of Example 2 after the solder heat resistance test, almost no delamination or measling on the outer layer side as observed in FIG. 2 was observed.
【００４２】（実施例３〜６）硬化剤としてアミン系硬
化剤（１、２−ジアミノプロパンと２−アミノ−６−メ
チルピリジンの重量比５０：５０の混合物）を２５ｐｈ
ｒ含有するグリコールアクリレート変性ビスフェノール
A型エポキシ樹脂の主剤であるエピコート８２８とポリ
エチレングリコール（ＰＥＧ）２００ジアクリレートと
の混合比を表２に示すような条件で配合した場合の低弾
性樹脂の引張特性をそれぞれ実施例３〜６として、その
測定結果を表２に、そのときの引張応力-変位線図を図
４に示す。(Examples 3 to 6) 25 ph of an amine curing agent (a mixture of 1,2-diaminopropane and 2-amino-6-methylpyridine in a weight ratio of 50:50) was used as a curing agent.
r-containing glycol acrylate modified bisphenol
The tensile properties of the low elasticity resin when the mixing ratio of Epicoat 828, which is the main component of the A-type epoxy resin, and polyethylene glycol (PEG) 200 diacrylate were mixed under the conditions shown in Table 2 were set as Examples 3 to 6, respectively. Table 2 shows the measurement results, and FIG. 4 shows a tensile stress-displacement diagram at that time.
【００４３】[0043]
【表２】 表２及び図４の結果から、エピコート８２８とＰＥＧ２
００ジアクリレートの比率を変更することで樹脂の引張
特性を制御することができるため、低弾性樹脂として用
いる場合、マトリクス樹脂や補強基材の材質に応じて、
また積層体の用途や耐熱性や発生する応力分布等の使用
環境に応じて、適宜その特性を変更して繊維／樹脂界面
の特性を制御することが可能であることが確認された。[Table 2] From the results in Table 2 and FIG. 4, it can be seen that Epikote 828 and PEG2
Since the tensile properties of the resin can be controlled by changing the ratio of the 00 diacrylate, when used as a low elasticity resin, depending on the material of the matrix resin or the reinforcing base material,
In addition, it was confirmed that the characteristics of the fiber / resin interface can be controlled by appropriately changing the characteristics according to the use environment of the laminate, the heat resistance, and the use environment such as the generated stress distribution.
【００４４】（実施例７〜１０、比較例２〜５）硬化剤
としてアミン系硬化剤（１、２−ジアミノプロパンと２
−アミノ−６−メチルピリジンの重量比５０：５０の混
合物）を２５ｐｈｒ含有するグリコールアクリレート変
性ビスフェノールA型エポキシ樹脂（油化シェルエポキ
シ製エピコート８７１）を溶媒（Ｍ ＥＫ）に溶かし込
んで、表３に示すような溶液濃度にした溶液に、ガラス
繊維の繊布を浸漬し、含浸させた後、実施例１と同様の
方法で積層体を作製した。各条件での積層体のドリル加
工性、はんだ耐熱性の評価を実施例１の記載と同様の方
法で行った。評価結果を表３に示す。なお、各溶液濃度
での付着率は、表面に低弾性樹脂層を被覆させる前後の
補強基材の重量を測定し、得られた測定値より補強基材
１ｇ当たりの低弾性樹脂の付着量を算出することにより
求めた。(Examples 7 to 10, Comparative Examples 2 to 5) As the curing agent, an amine curing agent (1,2-diaminopropane and 2
Glycol acrylate-modified bisphenol A type epoxy resin (Epicoat 871 manufactured by Yuka Shell Epoxy) containing 25 phr of a mixture of -amino-6-methylpyridine at a weight ratio of 50:50) was dissolved in a solvent (MEK). A glass fiber fabric was immersed and impregnated in a solution having a solution concentration as shown in Table 2, and a laminate was produced in the same manner as in Example 1. Evaluation of drill workability and solder heat resistance of the laminate under each condition was performed in the same manner as described in Example 1. Table 3 shows the evaluation results. The adhesion rate at each solution concentration was determined by measuring the weight of the reinforcing substrate before and after coating the surface with the low elastic resin layer, and determining the amount of the low elastic resin adhering per 1 g of the reinforcing substrate from the measured values. It was determined by calculation.
【００４５】[0045]
【表３】 表３の結果から、溶液濃度が増加するにしたがい付着率
は単調に増加して、付着率が０．１％を超えるとマイク
ロクラックや層間剥離が次第に消滅してゆき、０．４％
以上になるとこれらの不良は殆ど認められなくなるとと
もに、ミーズリング発生までの時間も長くなりはんだ耐
熱性が向上するが、付着率がさらに増加し、２．０％を
超えるとミーズリング発生までの時間が次第に短くな
り、３．５％以上になると層間剥離が再び発生すること
が確認された。[Table 3] From the results in Table 3, it can be seen that as the solution concentration increases, the adhesion ratio monotonously increases, and when the adhesion ratio exceeds 0.1%, microcracks and delamination gradually disappear, and the ratio increases by 0.4%.
Above the above, these defects are hardly recognized and the time until the occurrence of the measling is increased, and the solder heat resistance is improved. However, the adhesion rate further increases. Was gradually shortened, and when it became 3.5% or more, it was confirmed that delamination occurred again.
【００４６】図５はこの実施の形態におけるプリプレグ
の製造を行う装置の概略を示す説明図である。図５に示
すように、このプリプレグの製造装置は、補強基材を連
続的に供給するための巻出しユニット２１、補強基材の
切り換え時に補強基材の供給を止めずに連続運転を可能
にするために設けられている巻き出しユニット２２，熱
硬化性樹脂を主成分とする低弾性樹脂を有機溶剤で溶か
したものが供給されている含浸漕２３、含浸した低弾性
樹脂を乾燥・硬化させるためのヒートユニット２４、熱
硬化性樹脂を主成分とするマトリクス樹脂を有機溶剤で
溶かしたものが供給されている含浸漕２５、含浸した低
弾性樹脂を乾燥・硬化させるためのヒートユニット２
６、得られたプリプレグを連続して巻き取られるように
構成されている巻き取りユニット２７から構成されてい
る。FIG. 5 is an explanatory view schematically showing an apparatus for manufacturing a prepreg according to this embodiment. As shown in FIG. 5, the prepreg manufacturing apparatus enables the unwinding unit 21 for continuously supplying the reinforcing base material and continuous operation without stopping the supply of the reinforcing base material when switching the reinforcing base material. Unwinding unit 22, provided with a low-elastic resin mainly composed of a thermosetting resin dissolved in an organic solvent, and an impregnating tank 23 supplied with the low-elastic resin, and drying and curing the impregnated low-elastic resin. Unit 24 for supplying a matrix resin containing a thermosetting resin as a main component dissolved in an organic solvent, and a heating unit 2 for drying and curing the impregnated low elastic resin.
6. It is composed of a winding unit 27 configured to continuously wind the obtained prepreg.
【００４７】図５に示した装置によるプリプレグ製造方
法は、以下の（ａ）〜（ｆ）の各工程を順に行うよう構
成されている。 （ａ）巻き出しユニット２２で補強基材を巻き出す工程 （ｂ）含浸漕２３に貯蔵されているマトリクス樹脂に対
して弾性率の小さいあるいは引張破断ひずみの大きい低
弾性樹脂にガラス繊維からなる補強基材を浸漬し、含浸
させる工程 （ｃ）ヒートユニット２４で低弾性樹脂を乾燥・硬化さ
せる工程 （ｄ）含浸漕２５に貯蔵されているマトリクス樹脂に補
強基材間を浸漬し、含浸させる工程 （ｅ）ヒートユニット２６でマトリクス樹脂を乾燥・硬
化させる工程 （ｆ）巻き取りユニット２７でプリプレグを巻き取り若
しくは切断する工程 得られたプリプレグを積層し、直圧式プレス機により加
熱加圧を行うことで積層体が形成される。例えば、積層
したプリプレグの上下面に銅箔を配した状態で加熱加圧
を行うと、銅張り積層板となり、プリント配線基板用積
層体として用いられる。The prepreg manufacturing method using the apparatus shown in FIG. 5 is configured to sequentially perform the following steps (a) to (f). (A) Step of unwinding the reinforcing base material by the unwinding unit 22 (b) Reinforcement made of glass fiber to a low elastic resin having a small elastic modulus or a large tensile breaking strain with respect to the matrix resin stored in the impregnation tank 23 Step of dipping and impregnating the base material (c) Step of drying and hardening the low elasticity resin with the heat unit 24 (d) Step of dipping and impregnating the matrix resin stored in the impregnation tank 25 between the reinforcing base materials (E) Step of drying and curing the matrix resin in the heat unit 26 (f) Step of winding or cutting the prepreg in the winding unit 27 Laminating the obtained prepregs and performing heating and pressing with a direct pressure press machine Thus, a laminate is formed. For example, when heating and pressing are performed in a state where copper foil is arranged on the upper and lower surfaces of the laminated prepreg, a copper-clad laminate is obtained, which is used as a laminate for a printed wiring board.
【００４８】[0048]
【発明の効果】上記のように本発明の請求項１に係る積
層体は、補強基材表面がマトリクス樹脂の70％以下の低
い弾性率を有する低弾性樹脂で被覆されており、さらに
低弾性樹脂がマトリクス樹脂で覆われていることによ
り、マトリクス樹脂と補強基材の間に低弾性樹脂を介し
た構造になるため、熱的衝撃が負荷されても応力を緩和
できるため、ミーズリングや層間剥離等の現象を防止す
ることができる。また、ドリル加工のような機械的な加
工により衝撃が負荷された場合でも同様のメカニズムに
より低弾性樹脂層でエネルギー吸収され、加工時のマイ
クロクラックの発生を低減あるいは防止することができ
る。As described above, in the laminate according to the first aspect of the present invention, the surface of the reinforcing base material is coated with a low elastic resin having a low elastic modulus of 70% or less of the matrix resin, Since the resin is covered with the matrix resin, the structure has a low elasticity resin between the matrix resin and the reinforcing base material, so that stress can be relieved even when a thermal shock is applied. A phenomenon such as peeling can be prevented. Even when an impact is applied by mechanical processing such as drilling, energy is absorbed by the low elastic resin layer by the same mechanism, and the occurrence of microcracks during processing can be reduced or prevented.
【００４９】また請求項２の発明は、低弾性樹脂の引張
弾性率が１．０ＧＰａ以下あるいは引張破断ひずみが２
０％以上のいずれかであって、マトリクス樹脂の引張弾
性率が１．５ＧＰａ以上あるいは引張破断ひずみが１５
％以下のいずれかの特性を有するものであるため、熱的
衝撃負荷や機械的加工負荷時に発生する界面の応力が特
に有効に緩和されるので、熱的衝撃負荷時のミーズリン
グや層間剥離等の現象の防止やドリル加工等の機械加工
負荷時のマイクロクラックの発生を低減あるいは防止す
ることができる。Further, according to the invention of claim 2, the low elastic resin has a tensile modulus of 1.0 GPa or less or a tensile breaking strain of 2 GPa or less.
0% or more, and the tensile elastic modulus of the matrix resin is 1.5 GPa or more or the tensile breaking strain is 15% or more.
% Or less, the interface stress generated during thermal shock load or mechanical processing load is particularly effectively relieved, such as measling and delamination during thermal shock load. And the occurrence of microcracks at the time of machining load such as drilling can be reduced or prevented.
【００５０】また請求項３の発明は、低弾性樹脂はグリ
コールアクリレートで変性されたビスフェノールA型エ
ポキシ樹脂であるので、低弾性樹脂が１．０ＧＰａ以下
あるいは引張破断ひずみが２０％以上のいずれかの特性
を示すため、熱的衝撃や機械的加工負荷時に発生する界
面の応力が特に有効に緩和され、熱的衝撃負荷時のミー
ズリングや層間剥離等の現象の防止やドリル加工等の機
械加工負荷時のマイクロクラックの発生を減少あるいは
防止することができる。According to the third aspect of the present invention, the low elasticity resin is a bisphenol A type epoxy resin modified with glycol acrylate, so that the low elasticity resin is not more than 1.0 GPa or has a tensile breaking strain of not less than 20%. Because of its characteristics, the stress at the interface generated during thermal shock or mechanical processing load is particularly effectively relieved, preventing phenomena such as measling and delamination during thermal shock load, and mechanical processing load such as drilling. The occurrence of microcracks at the time can be reduced or prevented.
【００５１】また請求項４の発明は、前記ビスフェノー
ルA型エポキシ樹脂の主剤は，ポリエチレングリコール
２００ジアクリレートの混合比を変えて変性したもので
あるので、低弾性樹脂の引張特性を制御することができ
るので、補強基材やマトリクス樹脂の剛性、降伏応力、
ひずみ硬化係数等の弾塑性特性の変更に対する自由度が
大きくなる。According to a fourth aspect of the present invention, since the main component of the bisphenol A type epoxy resin is modified by changing the mixing ratio of polyethylene glycol 200 diacrylate, it is possible to control the tensile properties of the low elasticity resin. Can be used, the rigidity, yield stress,
The degree of freedom for changing the elasto-plastic properties such as the strain hardening coefficient is increased.
【００５２】また請求項５の発明は、前記低弾性樹脂の
前記補強基材表面への付着率が０．１％以上３．５％以
下，好ましくは０．４％以上２．０％以下であるので、
付着率が０．１％以下のときのようなドリル加工による
マイクロクラックの発生を減少あるいは防止することが
でき、付着率３．５％以上のときのような，はんだ耐熱
性の低下による層間剥離の発生を減少もしくは防止する
ことができる。According to a fifth aspect of the present invention, the rate of adhesion of the low elasticity resin to the surface of the reinforcing substrate is 0.1% or more and 3.5% or less, preferably 0.4% or more and 2.0% or less. Because there is
It is possible to reduce or prevent the occurrence of microcracks due to drilling when the adhesion rate is 0.1% or less, and delamination due to a decrease in solder heat resistance when the adhesion rate is 3.5% or more. Can be reduced or prevented.
【００５３】また請求項６の発明は、積層板に加工を施
す場合であって、加工時に損傷が生じやすい部位に前記
プリプレグを配するので、熱的衝撃や機械的加工による
衝撃負荷時に発生するミーズリングや層間剥離、マイク
ロクラックの発生を減少もしくは防止することができる
とともに、低弾性樹脂の添加による積層体としての耐熱
性低下を最小限に抑えることができる。According to a sixth aspect of the present invention, the prepreg is disposed in a portion where the laminate is liable to be damaged during the processing, so that the prepreg is generated at the time of thermal shock or impact load due to mechanical processing. The occurrence of measling, delamination, and microcracks can be reduced or prevented, and the decrease in heat resistance of the laminate due to the addition of a low-elastic resin can be minimized.
【００５４】また請求項７の発明は、前記積層体をプリ
ント配線基板に用いることで、プリント配線基板の製造
工程において加わる、電子部品実装部位確保のためのド
リル穴あけなどの機械加工時や、レーザー加工を始めと
する高エネルギー加工時に発生する、補強基材とマトリ
クス樹脂の接着性に起因する種々の不良を低減・防止さ
せることができるので、製品の信頼性を高めることがで
きる。The invention according to claim 7 is characterized in that the laminated body is used for a printed wiring board, so that it can be used for machining such as drilling for securing an electronic component mounting portion, which is added in a manufacturing process of the printed wiring board, or for laser processing. Since various defects caused by the adhesion between the reinforcing base material and the matrix resin, which are generated at the time of high energy processing such as processing, can be reduced and prevented, the reliability of the product can be improved.
【００５５】また請求項８の発明は、プリプレグを形成
した後、前記プリプレグを積層してホットプレスを行う
ことにより積層体を成形する方法において、マトリクス
樹脂に対して弾性率の小さいあるいは引張破断ひずみの
大きい低弾性樹脂でガラス繊維からなる補強基材を被覆
する工程と、前記低弾性樹脂を硬化させる工程と、前記
補強基材間に前記マトリクス樹脂を含浸させる工程と、
前記マトリクス樹脂を硬化させる工程とを含む工程でプ
リプレグを製造するので、熱的衝撃負荷や機械的加工負
荷時に発生する界面の応力が有効に緩和される積層体を
連続的に製造することができる。According to a further aspect of the present invention, there is provided a method for forming a laminate by forming a prepreg, then laminating the prepreg and performing hot pressing to form a laminate. A step of coating a reinforcing substrate made of glass fiber with a large low elastic resin, a step of curing the low elastic resin, and a step of impregnating the matrix resin between the reinforcing substrates,
Since the prepreg is manufactured in the step including the step of curing the matrix resin, it is possible to continuously manufacture a laminate in which the interface stress generated during thermal shock load or mechanical processing load is effectively relaxed. .
【図１】本発明の実施の形態における積層体の構成を概
略示す説明図である。FIG. 1 is an explanatory diagram schematically showing a configuration of a laminate according to an embodiment of the present invention.
【図２】本発明の実施の形態における積層体の構成を概
略示す説明図である。比較例１の積層体におけるはんだ
耐熱試験時のミーズリング発生箇所を概略示す説明図で
ある。FIG. 2 is an explanatory view schematically showing a configuration of a laminated body according to the embodiment of the present invention. FIG. 5 is an explanatory view schematically showing a location where a measling occurs in a solder heat resistance test in the laminate of Comparative Example 1.
【図３】本発明における実施の形態における積層体の曲
げ強度の温度依存性を比較したグラフ図である。FIG. 3 is a graph comparing the temperature dependence of the bending strength of the laminate in the embodiment of the present invention.
【図４】引張応力-変位線図に対するエピコート８２８
とＰＥＧ２００ジアクリレートとの混合比の影響を示す
グラフ図である。FIG. 4: Epicoat 828 for tensile stress-displacement diagram
FIG. 4 is a graph showing the effect of the mixing ratio between PEG 200 diacrylate and PEG 200.
【図５】本発明の実施の形態におけるプリプレグの製造
を行う装置の構成を概略示す正面図である。FIG. 5 is a front view schematically showing a configuration of an apparatus for manufacturing a prepreg according to the embodiment of the present invention.
【図６】従来例の積層体の構成を概略示す説明図であ
る。FIG. 6 is an explanatory view schematically showing a configuration of a conventional laminated body.
１ 補強基材 ２ 低弾性樹脂 ３ マトリクス樹脂 11 ガラス繊維 12 繊維束 21 巻出しユニット 22 アキュムレータユニット 23 含浸漕 24 ヒートユニット 25 含浸漕 26 ヒートユニット 27 巻き取りユニット 100 マイクロクラック DESCRIPTION OF SYMBOLS 1 Reinforcement base material 2 Low elastic resin 3 Matrix resin 11 Glass fiber 12 Fiber bundle 21 Unwinding unit 22 Accumulator unit 23 Impregnation tank 24 Heat unit 25 Impregnation tank 26 Heat unit 27 Winding unit 100 Micro crack
───────────────────────────────────────────────────── フロントページの続き (72)発明者 桝井 幹生 大阪府門真市大字門真1048番地松下電工株 式会社内 (72)発明者 東 啓二 大阪府門真市大字門真1048番地松下電工株 式会社内 Ｆターム(参考） 4F072 AB09 AC12 AD13 AD23 AD28 AD33 AD38 AD45 AD51 AH21 AL12 AL13 4F100 AB17B AB33B AG00A AK25A AK53A AK53K AL06A AT00B BA02 BA10A BA10B DG11A DH01A GB43 JK07A JK10 JL01 YY00A ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Mikio Masui 1048 Kadoma Kadoma, Osaka Pref. Matsushita Electric Works, Ltd. Terms (reference) 4F072 AB09 AC12 AD13 AD23 AD28 AD33 AD38 AD45 AD51 AH21 AL12 AL13 4F100 AB17B AB33B AG00A AK25A AK53A AK53K AL06A AT00B BA02 BA10A BA10B DG11A DH01A GB43 JK07A JK10 JL01 YY00A
Claims (8)
樹脂を含浸させたプリプレグを積層した積層体におい
て、前記補強基材表面が前記マトリクス樹脂の７０％以
下の弾性率を有する低弾性樹脂で被覆されていることを
特徴とする積層体。1. A laminate in which a prepreg in which a matrix resin is impregnated with a reinforcing substrate made of glass fiber is laminated, wherein the surface of the reinforcing substrate is coated with a low elastic resin having an elastic modulus of 70% or less of the matrix resin. A laminate characterized in that:
ａ以下あるいは引張破断ひずみが２０％以上のいずれか
であって、前記マトリクス樹脂の引張弾性率が１．５Ｇ
Ｐａ以上あるいは引張破断ひずみが１５％以下のいずれ
かの特性を有することを特徴とする請求項１に記載の積
層体。2. The low elastic resin has a tensile modulus of 1.0 GP.
a or a tensile breaking strain of 20% or more, and the matrix resin has a tensile modulus of 1.5 G
The laminate according to claim 1, wherein the laminate has a property of not less than Pa or not more than 15% of tensile breaking strain.
で変性されたビスフェノールA型エポキシ樹脂であるこ
とを特徴とする請求項１または２に記載の積層体。3. The laminate according to claim 1, wherein the low elasticity resin is a bisphenol A type epoxy resin modified with glycol acrylate.
剤は，ポリエチレングリコール２００ジアクリレートと
の混合比を変えて変性したものであることを特徴とする
請求項３に記載の積層体。4. The laminate according to claim 3, wherein the main component of the bisphenol A type epoxy resin is modified by changing the mixing ratio with polyethylene glycol 200 diacrylate.
着率が０．１％以上３．５％以下であることを特徴とす
る請求項１乃至４に記載の積層体。5. The laminate according to claim 1, wherein an adhesion ratio of the low elastic resin to the surface of the reinforcing substrate is 0.1% or more and 3.5% or less.
に損傷が生じやすい部位に前記プリプレグを配すること
を特徴とする請求項１乃至５に記載の積層体。6. The laminate according to claim 1, wherein the prepreg is arranged at a position where the laminate is likely to be damaged during the processing.
とを特徴とする請求項１乃至６に記載の積層体。7. The laminate according to claim 1, wherein the laminate is used for a printed wiring board.
を積層してホットプレスを行うことにより積層体を成形
する方法において、前記プリプレグの製造方法は、マト
リクス樹脂に対して弾性率の小さいああるいは引張破断
ひずみの大きい樹脂でガラス繊維からなる補強基材を被
覆する工程と、前記低弾性樹脂を硬化させる工程と、前
記補強基材間に前記マトリクス樹脂を含浸させる工程
と、前記マトリクス樹脂を硬化させる工程とを含むこと
を特徴とする積層体の製造方法。8. A method of forming a laminate by forming a prepreg, then laminating the prepreg and performing hot pressing, wherein the method of manufacturing the prepreg has a low elastic modulus or a tensile strength with respect to a matrix resin. A step of coating a reinforcing substrate made of glass fiber with a resin having a large breaking strain, a step of curing the low elastic resin, a step of impregnating the matrix resin between the reinforcing substrates, and curing the matrix resin And a method for producing a laminate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32617099A JP2001138426A (en) | 1999-11-16 | 1999-11-16 | Laminate and method of manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32617099A JP2001138426A (en) | 1999-11-16 | 1999-11-16 | Laminate and method of manufacturing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001138426A true JP2001138426A (en) | 2001-05-22 |
Family
ID=18184837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32617099A Pending JP2001138426A (en) | 1999-11-16 | 1999-11-16 | Laminate and method of manufacturing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001138426A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003056622A (en) * | 2001-08-15 | 2003-02-26 | Nippon Kokan Light Steel Kk | Damping material and damper using it |
| JP2003105707A (en) * | 2001-09-28 | 2003-04-09 | Showa Highpolymer Co Ltd | Resin composition for road and its constructing method and pavement structure |
| JP2016079173A (en) * | 2014-10-15 | 2016-05-16 | 日本合成化学工業株式会社 | New pyridine-based compound, curing agent for anion curable compound therewith, curable composition and hardened material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05105778A (en) * | 1991-10-18 | 1993-04-27 | Shin Kobe Electric Mach Co Ltd | Laminated board manufacturing method |
| JPH05271442A (en) * | 1992-03-25 | 1993-10-19 | Shin Kobe Electric Mach Co Ltd | Laminated board manufacturing method |
| JPH0732541A (en) * | 1993-07-23 | 1995-02-03 | Shin Kobe Electric Mach Co Ltd | Manufacturing method of metal foil clad laminate |
-
1999
- 1999-11-16 JP JP32617099A patent/JP2001138426A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05105778A (en) * | 1991-10-18 | 1993-04-27 | Shin Kobe Electric Mach Co Ltd | Laminated board manufacturing method |
| JPH05271442A (en) * | 1992-03-25 | 1993-10-19 | Shin Kobe Electric Mach Co Ltd | Laminated board manufacturing method |
| JPH0732541A (en) * | 1993-07-23 | 1995-02-03 | Shin Kobe Electric Mach Co Ltd | Manufacturing method of metal foil clad laminate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003056622A (en) * | 2001-08-15 | 2003-02-26 | Nippon Kokan Light Steel Kk | Damping material and damper using it |
| JP2003105707A (en) * | 2001-09-28 | 2003-04-09 | Showa Highpolymer Co Ltd | Resin composition for road and its constructing method and pavement structure |
| JP2016079173A (en) * | 2014-10-15 | 2016-05-16 | 日本合成化学工業株式会社 | New pyridine-based compound, curing agent for anion curable compound therewith, curable composition and hardened material |
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