JPH0793496B2 - Copper foil resin adhesive layer for copper clad laminates - Google Patents
Copper foil resin adhesive layer for copper clad laminatesInfo
- Publication number
- JPH0793496B2 JPH0793496B2 JP2266837A JP26683790A JPH0793496B2 JP H0793496 B2 JPH0793496 B2 JP H0793496B2 JP 2266837 A JP2266837 A JP 2266837A JP 26683790 A JP26683790 A JP 26683790A JP H0793496 B2 JPH0793496 B2 JP H0793496B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- copper
- copper foil
- adhesive layer
- clad laminate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920005989 resin Polymers 0.000 title claims description 38
- 239000011347 resin Substances 0.000 title claims description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 23
- 239000011889 copper foil Substances 0.000 title claims description 15
- 229910052802 copper Inorganic materials 0.000 title claims description 8
- 239000010949 copper Substances 0.000 title claims description 8
- 239000012790 adhesive layer Substances 0.000 title claims description 4
- 239000010410 layer Substances 0.000 claims description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 10
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- 239000013034 phenoxy resin Substances 0.000 claims description 3
- 229920006287 phenoxy resin Polymers 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 229920001225 polyester resin Polymers 0.000 claims description 3
- 239000004645 polyester resin Substances 0.000 claims description 3
- 238000004080 punching Methods 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920003987 resole Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Manufacturing Of Printed Wiring (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、打抜加工性に優れた紙基材銅張積層板用樹脂
接着層に関する。TECHNICAL FIELD The present invention relates to a resin adhesive layer for a paper-based copper-clad laminate excellent in punching workability.
（従来の技術） 最近、電子機器の軽、薄、短、小化に伴い、1.78mmピッ
チ、1.50mmピッチのIC穴あるいはコネクタ穴を室温で打
抜き可能なMCL（銅張積層板）が必要となっている。(Prior Art) Recently, with the lightness, thinness, shortness, and miniaturization of electronic devices, MCL (copper clad laminate) capable of punching 1.78 mm pitch, 1.50 mm pitch IC holes or connector holes at room temperature is required. Has become.
従来、打抜き加工性を良くするためには、繊維基材に含
浸する熱硬化性樹脂を可撓化する方法、又は低弾性紙基
材を利用する方法がある。Conventionally, in order to improve punching workability, there is a method of making a thermosetting resin impregnated into a fiber base material flexible or a method of using a low elastic paper base material.
（発明が解決しようとする課題） 上記によって樹脂を可撓化すると、打抜き加工性とIC
穴、コネクタ穴間の耐クラック性は向上するが、耐熱
性、耐湿性、耐銀マイグレーション性、耐電食性、耐溶
剤性は低下する問題がある。(Problems to be solved by the invention) When the resin is made flexible by the above, punching workability and IC
Although crack resistance between the holes and the connector holes is improved, there is a problem that heat resistance, moisture resistance, silver migration resistance, electrolytic corrosion resistance, and solvent resistance are lowered.
低弾性紙基材を利用すると、反り特性と寸法特性が低下
する問題がある。The use of a low-elasticity paper substrate has a problem that warp characteristics and dimensional characteristics deteriorate.
本発明は、打抜き加工性に優れ、かつ他の特性が低下し
ない銅張積層板を提供することを目的とする。It is an object of the present invention to provide a copper clad laminate having excellent punching workability and having no deterioration in other properties.
（課題を解決するための手段） 上記の目的を達成するために、本発明は、プリプレグを
重ねさらにその外側に銅箔を重ねて加熱加圧成形する紙
基材銅張積層板において、銅箔とプリプレグとの間にポ
リビニルブチラール、ポリブタジエン、ポリエステル樹
脂、フェノキシ樹脂のうち少なくとも１つ以上を用いレ
ゾール型フェノールホルマリン樹脂と組合せた樹脂層を
設け、その樹脂層の加熱加圧成形後の破断歪みが20℃で
1.2％以上であることを特徴とする。(Means for Solving the Problems) In order to achieve the above object, the present invention provides a paper-based copper-clad laminate in which a prepreg is further laminated and a copper foil is further laminated on the outer side thereof under heat and pressure to form a copper foil. And a prepreg are provided with a resin layer in which at least one of polyvinyl butyral, polybutadiene, polyester resin, and phenoxy resin is used in combination with a resole-type phenol formalin resin, and the rupture strain of the resin layer after heat-press molding is high. At 20 ℃
It is characterized by being 1.2% or more.
銅箔とプリプレグとの間に形成する樹脂層は、銅箔用接
着剤又は樹脂シートとする。使用する樹脂は、ポリビニ
ルブチラール、ポリブタジエン、ポリエステル樹脂、フ
ェノキシ樹脂のうち少なくとも１つ以上を用いレゾール
型フェノールホルマリン樹脂と組合せたものとする。さ
らにこの樹脂層には、エポキシ樹脂、フェノール樹脂、
メラミン樹脂、尿素樹脂等を樹脂層の加熱加圧成形後の
破断歪みが20℃で1.2％以上となるようにする限り併用
してもよい。又、樹脂層の成形後における応力ー歪曲線
の下降伏点が存在するように、樹脂層に用いる樹脂を選
択し或るいは変性することも打抜き加工性を良くする。
物質に一定の方法で応力を加えて変形させるとき、応力
が小さいときには弾性的変形を示すが、応力がある限度
を越えたとき応力を僅かに増加しただけで歪（伸び、変
形）が急激に大きくなることを降伏という。縦軸に荷
重、横軸に歪を取るとき荷重が小さい間は荷重が増加す
るとともに歪も比例的に増加する。しかし、荷重がある
一定の限度を越えると比例性が失われる。さらに荷重を
増すと材料の中に滑り現象が起こり、塑性変形を生じる
ようになる。その上荷重を増すと歪が急激に増加するよ
うになる。荷重の最大値を降伏点と呼び、降伏点を過ぎ
ると荷重がいったん低下し、その後は一定の応力のもと
で歪だけが増加する。この場合、荷重の最大値を上降伏
点、最大値を通りいったん低下したところを下降伏点と
いう。こういう荷重（応力）−歪（伸び）を示す材料
は、一般に軟らかくて強靭（粘い）な材料や粘り強い強
靭な材料で示される。The resin layer formed between the copper foil and the prepreg is a copper foil adhesive or a resin sheet. The resin used is at least one of polyvinyl butyral, polybutadiene, polyester resin, and phenoxy resin, and is used in combination with a resol-type phenol formalin resin. Furthermore, in this resin layer, epoxy resin, phenol resin,
Melamine resin, urea resin and the like may be used together as long as the breaking strain of the resin layer after heating and pressurizing is 1.2% or more at 20 ° C. Further, the punching workability is also improved by selecting or modifying the resin used for the resin layer so that the stress-strain curve has a falling yield point after the resin layer is molded.
When a material is deformed by applying a certain amount of stress, it exhibits elastic deformation when the stress is small, but when the stress exceeds a certain limit, the stress (extension, deformation) suddenly increases with only a slight increase in the stress. The increase in size is called surrender. When the load is taken on the vertical axis and the strain is taken on the horizontal axis, the load increases and the strain increases proportionally while the load is small. However, when the load exceeds a certain limit, proportionality is lost. When the load is further increased, a slip phenomenon occurs in the material, which causes plastic deformation. Moreover, when the load is increased, the strain increases rapidly. The maximum value of the load is called the yield point, and once the yield point is exceeded, the load drops once and then only the strain increases under constant stress. In this case, the maximum value of the load is called the upper yield point, and the point where the load passes the maximum value and is once decreased is called the lower yield point. The material exhibiting such load (stress) -strain (elongation) is generally represented by a soft and tough (tough) material or a tenacious and tough material.
上記の樹脂を溶剤溶液として銅箔に塗布し乾燥して接着
剤付き銅箔とする。プリプレグと接着剤付き銅箔を積層
し、加熱加圧成形して銅張積層板とする。The above resin is applied as a solvent solution to a copper foil and dried to obtain a copper foil with an adhesive. A prepreg and an adhesive-attached copper foil are laminated and heat-pressed to form a copper-clad laminate.
又、上記樹脂を予めシートとした後、銅箔とプリプレグ
の間に重ね、その他上記と同様にして銅張積層板とす
る。In addition, after the above resin is formed into a sheet in advance, it is laminated between the copper foil and the prepreg, and otherwise the same as above, to obtain a copper clad laminate.
（作用） 室温で打抜き加工する時にはクラックをおこしやすい。
クラックは、表層部の破断歪みが大きいとおきにくいこ
とになる。(Function) Cracks are likely to occur when punching at room temperature.
Cracks are less likely to occur if the surface layer portion has a large breaking strain.
本発明によって、表層部に樹脂層を設け、これによって
打抜き時の歪みを低減し、さらに破断歪みが大きい樹脂
を選ぶと、クラックが発生しにくい。成形後の樹脂層の
破断歪みが20℃で1.2％以上とすると耐クラック性は向
上し、さらに2.0％以上とすると著しく向上する。According to the present invention, when a resin layer is provided on the surface layer portion to reduce the distortion at the time of punching and to select a resin having a large breaking strain, cracks are less likely to occur. When the breaking strain of the resin layer after molding is 1.2% or more at 20 ° C., the crack resistance is improved, and when it is 2.0% or more, the crack resistance is remarkably improved.
又、成形後の樹脂層の応力−歪み曲線に下降伏点がある
と、樹脂層が打抜き時の歪を吸収することになる。If the stress-strain curve of the resin layer after molding has a descending yield point, the resin layer absorbs the strain during punching.
（実施例） （実施例１） ポリビニルブチラール（積水化学製、BXー１）150重量
部（以下部と略称）、レゾール型フェノールホルマリン
樹脂（日立化成製、UP−13N）50部、不飽和ポリエステ
ル樹脂（日立化成製、ポリセット）100部をアセトンに
溶かし、固形分18重量％の接着剤を得た。この接着剤を
35μｍの銅箔（日本電解製）に固形分約30g/m2の割合で
塗布乾燥した後、プリプレグ（フェノール樹脂含浸紙）
と共に常法によって加熱加圧して銅張積層板を得た。別
に、上記の接着剤用組成物を型で加熱加圧して樹脂板を
得た。得た銅張積層板の特性と樹脂板の引張試験結果を
表１に示す。(Example) (Example 1) Polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., BX-1) 150 parts by weight (abbreviated as "part" below), resol type phenol formalin resin (manufactured by Hitachi Chemical, UP-13N) 50 parts, unsaturated polyester 100 parts of resin (manufactured by Hitachi Chemical, Polyset) was dissolved in acetone to obtain an adhesive having a solid content of 18% by weight. This glue
35 μm copper foil (manufactured by Nippon Denshoku Co., Ltd.) is coated and dried at a solid content of about 30 g / m 2 , and then prepreg (phenol resin impregnated paper)
Together with this, a copper clad laminate was obtained by heating and pressurizing by a conventional method. Separately, the above adhesive composition was heated and pressed in a mold to obtain a resin plate. Table 1 shows the properties of the obtained copper-clad laminate and the results of the tensile test of the resin plate.
（実施例２） ポリビニルブチラール100部、レゾール型フェノールホ
ルマリン樹脂50部、不飽和ポリエステル樹脂70部をアセ
トンに溶かし、固形分18重量％の接着剤を得た。以下、
実施例１と同様にして銅張積層板を、接着剤組成物で樹
脂板を得た。(Example 2) 100 parts of polyvinyl butyral, 50 parts of resol type phenol formalin resin and 70 parts of unsaturated polyester resin were dissolved in acetone to obtain an adhesive having a solid content of 18% by weight. Less than,
A copper clad laminate was obtained in the same manner as in Example 1 to obtain a resin plate using the adhesive composition.
（比較例） ポリビニルブチラール100部、レゾール型フェノールホ
ルマリン樹脂50部をアセトンに溶かし、固形分18重量％
の接着剤を得た。以下、実施例１と同様にして銅張積層
板を、又接着剤組成物で樹脂板を得た。試験結果を表１
に示す。(Comparative Example) 100 parts of polyvinyl butyral and 50 parts of resol-type phenol-formalin resin were dissolved in acetone to give a solid content of 18% by weight.
The adhesive of was obtained. Thereafter, a copper clad laminate and a resin plate were obtained from the adhesive composition in the same manner as in Example 1. Table 1 shows the test results
Shown in.
（試験） 引張試験は、20℃で引張速度50mm/分とし、伸び計を用
いて測定した。(Test) The tensile test was carried out at 20 ° C. with a tensile speed of 50 mm / min and was measured using an extensometer.
打抜き加工性は、20℃、80トンプレス、穴間ピッチ1.78
mmで打抜いた時のクラック、剥離、目白の有無を示し、
◎は著しく良好、○は良好、△はやや悪い、×は不良状
態を示す。Punching workability is 20 ℃, 80 tons press, hole pitch 1.78
Indicates the presence or absence of cracks, peeling, and whitening when punched in mm,
⊚ markedly good, ◯ good, Δ slightly bad, and × bad.
（発明の効果） 本発明によって、銅箔に接する樹脂層の加熱加圧成形後
の破断歪みが20℃で1.2％以上即ち実施例１、２では、
表１に示すように打抜き加工性が良い。2.2％の場合は
待に優れている。 (Effects of the Invention) According to the present invention, the rupture strain of the resin layer in contact with the copper foil after heat-pressing is 1.2% or more at 20 ° C.
As shown in Table 1, the punching workability is good. 2.2% is excellent for waiting.
これに反して、比較例のように1.0％の場合はクラック
を生ずる。On the contrary, in the case of 1.0% as in the comparative example, cracking occurs.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 斉藤 清 茨城県下館市大字小川1500番地 日立化成 工業株式会社下館工場内 (72)発明者 木村 裕之 茨城県下館市大字小川1500番地 日立化成 工業株式会社下館工場内 (72)発明者 奈良部 嘉行 茨城県下館市大字小川1500番地 日立化成 工業株式会社下館工場内 (56)参考文献 特開 昭58−204072（ＪＰ，Ａ) 特開 平１−237132（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kiyoshi Saito 1500 Ogawa, Shimodate, Ibaraki Shimodate, Hitachi Chemical Co., Ltd. Shimodate factory (72) Hiroyuki Kimura 1500, Ogawa, Shimodate, Ibaraki Hitachi Chemical Co., Ltd. Shimodate Factory (72) Inventor Yoshiyuki Narabe 1500 Ogawa, Shimodate City, Ibaraki Hitachi Chemical Co., Ltd. Shimodate Factory (56) Reference JP-A-58-204072 (JP, A) JP-A-1-237132 (JP, A)
Claims (2)
重ねて加熱加圧成形する紙基材銅張積層板において、銅
箔とプリプレグとの間にポリビニルブチラール、ポリブ
タジエン、ポリエステル樹脂、フェノキシ樹脂のうち少
なくとも１つ以上を用いレゾール型フェノールホルマリ
ン樹脂と組合せた樹脂層を設け、その樹脂層の加熱加圧
成形後の破断歪みが20℃で1.2％以上であることを特徴
とする銅張積層板用銅箔樹脂接着層。1. A paper-based copper-clad laminate in which a copper foil is further laminated on the outer surface of a prepreg and heat-pressed, and polyvinyl butyral, polybutadiene, polyester resin, or phenoxy resin is provided between the copper foil and the prepreg. A copper clad laminate characterized in that at least one or more of the above are provided with a resin layer in combination with a resol-type phenol formalin resin, and the strain at break after heat and pressure molding of the resin layer is 1.2% or more at 20 ° C. Copper foil resin adhesive layer for boards.
伏点が存在することを特徴とする請求項１記載の銅張積
層板用銅箔樹脂接着層。2. The copper foil resin adhesive layer for a copper-clad laminate according to claim 1, wherein a tensile stress-strain curve of the resin layer after molding has a descending yield point.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2266837A JPH0793496B2 (en) | 1990-10-04 | 1990-10-04 | Copper foil resin adhesive layer for copper clad laminates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2266837A JPH0793496B2 (en) | 1990-10-04 | 1990-10-04 | Copper foil resin adhesive layer for copper clad laminates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04144187A JPH04144187A (en) | 1992-05-18 |
| JPH0793496B2 true JPH0793496B2 (en) | 1995-10-09 |
Family
ID=17436351
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2266837A Expired - Fee Related JPH0793496B2 (en) | 1990-10-04 | 1990-10-04 | Copper foil resin adhesive layer for copper clad laminates |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0793496B2 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003105707A (en) * | 2001-09-28 | 2003-04-09 | Showa Highpolymer Co Ltd | Resin composition for road and its constructing method and pavement structure |
| US9079378B2 (en) | 2009-03-31 | 2015-07-14 | Jx Nippon Mining & Metals Corporation | Electromagnetic shielding material and method of producing electromagnetic shielding material |
| WO2011004664A1 (en) * | 2009-07-07 | 2011-01-13 | 日鉱金属株式会社 | Copper foil composite |
| JP5325175B2 (en) | 2010-07-15 | 2013-10-23 | Ｊｘ日鉱日石金属株式会社 | Copper foil composite and method for producing molded body |
| CN103501997B (en) | 2011-05-13 | 2015-11-25 | Jx日矿日石金属株式会社 | Copper foil composite and for its Copper Foil and formed body and manufacture method thereof |
| JP5822838B2 (en) | 2012-01-13 | 2015-11-24 | Jx日鉱日石金属株式会社 | Copper foil composite, molded body and method for producing the same |
| CN104080605B (en) | 2012-01-13 | 2016-08-24 | Jx日矿日石金属株式会社 | Copper foil composite and formed body and manufacture method thereof |
| WO2017154167A1 (en) * | 2016-03-10 | 2017-09-14 | 三井金属鉱業株式会社 | Multilayer laminate plate and production method for multilayered printed wiring board using same |
| JP6953438B2 (en) * | 2016-12-28 | 2021-10-27 | 日鉄ケミカル＆マテリアル株式会社 | Metal-fiber reinforced resin material composite, its manufacturing method and adhesive sheet |
| CN111655475B (en) * | 2018-04-03 | 2023-01-06 | 日本制铁株式会社 | Metal-carbon fiber reinforced resin material composite and method for producing metal-carbon fiber reinforced resin material composite |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58204072A (en) * | 1982-05-21 | 1983-11-28 | Toshiba Chem Corp | Adhesive resin composition for copper clad laminate |
| JPH01237132A (en) * | 1988-03-18 | 1989-09-21 | Sumitomo Bakelite Co Ltd | Manufacture of heat-curable resin copper-clad laminate |
-
1990
- 1990-10-04 JP JP2266837A patent/JPH0793496B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04144187A (en) | 1992-05-18 |
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| LAPS | Cancellation because of no payment of annual fees |