JPH05110218A - Renewable laminated board and printed board using it - Google Patents
Renewable laminated board and printed board using itInfo
- Publication number
- JPH05110218A JPH05110218A JP29192391A JP29192391A JPH05110218A JP H05110218 A JPH05110218 A JP H05110218A JP 29192391 A JP29192391 A JP 29192391A JP 29192391 A JP29192391 A JP 29192391A JP H05110218 A JPH05110218 A JP H05110218A
- Authority
- JP
- Japan
- Prior art keywords
- polyimide
- synthetic resin
- board
- recyclable
- laminated
- 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
Landscapes
- Laminated Bodies (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
(57)【要約】
【目的】 はんだ耐熱性を有し、かつリサイクル可能な
積層板、プリント配線板を提供する。
【構成】 電気絶縁層と導電層からなる積層板において
電気絶縁層の合成樹脂成分としてガラス転移温度が２６
０℃以上で、溶媒に可溶な合成樹脂を用いるリサイクル
可能な積層板。及び当該積層板を用いるプリント配線
板。合成樹脂の例としては、ポリイミド、フッ素化ポリ
イミド、特にジアミン成分として、２，２′−ビス（ト
リフルオロメチル）−４，４′−ジアミノビフェニルを
用いたポリイミドが挙げられる。
【効果】 リサイクルが可能であり、環境保護及び省資
源に有用なものである。(57) [Abstract] [Purpose] To provide a laminated board and a printed wiring board which have solder heat resistance and are recyclable. [Structure] In a laminated plate composed of an electric insulating layer and a conductive layer, a glass transition temperature of 26
A recyclable laminated board that uses a solvent-soluble synthetic resin at 0 ° C or higher. And a printed wiring board using the laminate. Examples of the synthetic resin include polyimide, fluorinated polyimide, and particularly polyimide using 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl as a diamine component. [Effect] It is recyclable and useful for environmental protection and resource saving.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐熱性に優れかつリサ
イクル可能な積層板及びプリント配線板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated board and a printed wiring board which have excellent heat resistance and can be recycled.
【０００２】[0002]
【従来の技術】プリント配線板としては、配線構造から
片面板、両面板、多層板の３種類があり、主に銅張り積
層板から製造されている。銅張り積層板には、紙基材フ
ェノール樹脂銅張り積層板、紙基材エポキシ樹脂銅張り
積層板、ガラス基材エポキシ樹脂銅張り積層板、ポリイ
ミド銅張り積層板などがある。また最近では高周波用の
低誘電率積層板としてフッ素系樹脂を用いた積層板も製
造されている。従来の積層板及びプリント配線板に使用
する合成樹脂を選定する基準としては耐熱性、寸法安定
性、低誘電率性、低価格などであったが、これからは、
別の観点からの基準が重要になってくるものと思われ
る。それは地球環境又は地球資源の観点からの基準でリ
サイクル性である。この基準からみた場合これまで用い
られているフェノール樹脂、エポキシ樹脂、熱硬化型ポ
リイミド、フッ素系樹脂は、いずれも溶媒に不溶であ
り、また熱にも溶融せず、リサイクル化は困難である。
更に廃棄物処理も難しく、今後問題になってくるものと
予想される。またポリエーテルイミドなどの熱可塑性ポ
リイミドは熱に溶融し、溶媒に溶けるという性質を持っ
ていてリサイクル可能であるが、ガラス転移温度が２６
０℃未満であり、耐熱性に問題がある。2. Description of the Related Art There are three types of printed wiring boards, from a wiring structure to a single-sided board, a double-sided board, and a multilayer board, which are mainly manufactured from copper-clad laminates. Examples of the copper-clad laminate include a paper-based phenol resin copper-clad laminate, a paper-based epoxy resin copper-clad laminate, a glass-based epoxy resin copper-clad laminate, and a polyimide copper-clad laminate. Recently, a laminated plate using a fluororesin has been manufactured as a low dielectric constant laminated plate for high frequencies. Heat resistance, dimensional stability, low dielectric constant, low price, etc. were the criteria for selecting synthetic resins used for conventional laminated boards and printed wiring boards, but from now on,
It seems that criteria from a different perspective will become important. It is recyclable by the standards of the global environment or global resources. From this point of view, all of the phenol resins, epoxy resins, thermosetting polyimides, and fluororesins that have been used so far are insoluble in solvents and do not melt with heat, and are difficult to recycle.
Furthermore, waste treatment is difficult and is expected to become a problem in the future. In addition, thermoplastic polyimides such as polyetherimide have the property of being melted by heat and dissolving in a solvent and thus recyclable, but have a glass transition temperature of 26%.
Since it is less than 0 ° C, there is a problem in heat resistance.
【０００３】[0003]
【発明が解決しようとする課題】本発明はかかる実情に
かんがみ、はんだ耐熱性を有し、かつリサイクル可能な
積層板、プリント配線板を提供することを目的とする。SUMMARY OF THE INVENTION In consideration of such circumstances, an object of the present invention is to provide a laminated board and a printed wiring board which have solder heat resistance and can be recycled.
【０００４】[0004]
【課題を解決するための手段】本発明を概説すれば、本
発明の第１の発明は、電気絶縁層と導電層からなる積層
板において電気絶縁層の合成樹脂成分としてガラス転移
温度が２６０℃以上で、溶媒に可溶な合成樹脂を用いる
ことを特徴とする。そして、本発明の第２の発明は、電
気絶縁層と導電層からなる積層板から製造されるプリン
ト配線板において電気絶縁層の合成樹脂成分としてガラ
ス転移温度が２６０℃以上で溶媒に可溶な合成樹脂を用
いた積層板をもちいることを特徴とする。The first aspect of the present invention is to provide a laminated plate comprising an electric insulating layer and a conductive layer having a glass transition temperature of 260 ° C. as a synthetic resin component of the electric insulating layer. The above is characterized by using a synthetic resin soluble in a solvent. A second invention of the present invention is a printed wiring board manufactured from a laminate comprising an electric insulating layer and a conductive layer, which has a glass transition temperature of 260 ° C. or higher and is soluble in a solvent as a synthetic resin component of the electric insulating layer. It is characterized by using a laminated plate using a synthetic resin.
【０００５】本発明者らは、上記課題を解決するため鋭
意研究を行った結果、本発明を完成するに至った。The present inventors have completed the present invention as a result of intensive research to solve the above problems.
【０００６】本発明で用いられる導電層としては銅、ア
ルミニウム、ニッケル、銀、金、鉄等の板又は箔が挙げ
られるが、好ましくは銅箔である。The conductive layer used in the present invention may be a plate or foil made of copper, aluminum, nickel, silver, gold, iron or the like, preferably copper foil.
【０００７】また本発明で用いられる合成樹脂は、ガラ
ス転移温度が２６０℃以上あり、溶媒に可溶でリサイク
ル性があるものならすべて使用できる。例えばある種の
ポリエステルイミド、ポリアミドイミド、ポリイミド、
フッ素化ポリイミドなどである。特に好ましいのは、下
記の構造式（化１）で示されるフッ素化ジアミンを合成
原料としたフッ素化ポリイミド、フッ素化ポリイミド共
重合体、フッ素化ポリイミド混合物である。Any synthetic resin having a glass transition temperature of 260 ° C. or higher, soluble in a solvent and recyclable can be used as the synthetic resin used in the present invention. For example, some polyester imides, polyamide imides, polyimides,
Examples include fluorinated polyimide. Particularly preferred are fluorinated polyimides, fluorinated polyimide copolymers, and fluorinated polyimide mixtures using the fluorinated diamine represented by the following structural formula (Formula 1) as a synthetic raw material.
【０００８】[0008]
【化１】 [Chemical 1]
【０００９】これらのフッ素化ポリイミド等の前駆体で
あるポリアミド酸の製造方法は、通常のポリアミド酸の
製造条件と同じでよく、上記のフッ素化ジアミンとテト
ラカルボン酸成分を一般的にはＮ−メチル−２−ピロリ
ドン、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）、
Ｎ，Ｎ−ジメチルホルムアミドなどの極性有機溶媒中で
反応させる。本発明においてはジアミンまたテトラカル
ボン酸成分共単一化合物で用いるばかりでなく、複数の
ジアミン、テトラカルボン酸成分を混合して用いる場合
がある。その場合は、複数又は単一のジアミンのモル数
の合計と複数又は単一のテトラカルボン酸成分のモル数
の合計が等しいかほぼ等しくなるようにする。またポリ
アミド酸溶液からポリイミド溶液を製造するためにはポ
リアミド酸溶液を１５０〜２００℃で加熱すればよい。The method for producing the polyamic acid, which is a precursor of these fluorinated polyimides, may be the same as the ordinary production conditions for the polyamic acid, and the fluorinated diamine and the tetracarboxylic acid component are generally N-containing. Methyl-2-pyrrolidone, N, N-dimethylacetamide (DMAc),
The reaction is carried out in a polar organic solvent such as N, N-dimethylformamide. In the present invention, not only a diamine or a tetracarboxylic acid component is used as a single compound, but a plurality of diamine and tetracarboxylic acid components may be mixed and used. In that case, the total number of moles of a plurality or single diamine and the total number of moles of a plurality or single tetracarboxylic acid component are equal or nearly equal. In order to produce a polyimide solution from a polyamic acid solution, the polyamic acid solution may be heated at 150 to 200 ° C.
【００１０】本発明における電気絶縁層としては、基材
に合成樹脂を含浸させたプリプレグを用いてもよく、又
は合成樹脂単体、又は合成樹脂に充てん材等を添加した
ものを用いてもよい。As the electrical insulating layer in the present invention, a prepreg in which a base material is impregnated with a synthetic resin may be used, or a synthetic resin alone or a synthetic resin to which a filler or the like is added may be used.
【００１１】基材としては、一般に積層材料に使用され
ているものがほとんど使用できる。例えば、ＳｉＯ2 、
Ａｌ2 Ｏ3 等を成分とするＥガラス、Ｓガラス、Ｄガラ
ス及び石英を使用したＱガラス等の各種ガラスクロス及
びシート等が使用できる。また充てん材としては、アル
ミナ、シリカ、ベリリア、窒化ホウ素等の粉末を使用す
ることができる。As the base material, most of those generally used for laminated materials can be used. For example, SiO 2 ,
Various glass cloths and sheets such as E glass, S glass, D glass and Q glass using quartz, which contain Al 2 O 3 etc., can be used. Further, as the filler, powder of alumina, silica, beryllia, boron nitride or the like can be used.
【００１２】合成樹脂がプリプレグの場合は、例えば金
属板の片側又は両側にプリプレグを必要に枚数だけ重
ね、更にその外側に銅箔を重ね、加熱・加圧することに
より、積層板が得られる。更にこの積層板を通常の配線
板製造工程により、プリント配線板を製造することがで
きる。When the synthetic resin is a prepreg, a laminated plate can be obtained, for example, by laminating a required number of prepregs on one side or both sides of a metal plate, further laminating copper foil on the outer side, and heating and pressing. Further, a printed wiring board can be manufactured from this laminated board by a normal wiring board manufacturing process.
【００１３】[0013]
【実施例】以下、実施例により本発明について詳細に説
明するが、本発明はこれらの実施例に限定されるもので
はない。The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
【００１４】実施例１ 三角フラスコに２，２−ビス（３，４−ジカルボキシフ
ェニル）ヘキサフルオロプロパン二無水物４．４４２ｇ
と前記式（化１）で表される２，２′−ビス（トリフル
オロメチル）−４，４′−ジアミノビフェニル３．２０
２ｇ及びＮ−メチル−２−ピロリドン４０ｇを入れた。
これを室温、乾燥窒素気流中で４８時間かくはんした
後、１８０℃で３時間加熱かくはんし、イミド化を行っ
た。このポリイミド溶液を水の中へ少しずつ滴下したと
ころ、白色固体が析出した。これをろ過後乾燥し、ポリ
イミド固形物を得た。このポリイミド固形物を酢酸エチ
ルに溶解し、ポリイミド溶液を得た。補強材のガラスク
ロスに含浸させ、１５０℃で３０分間乾燥させ、プリプ
レグを得た。このプリプレグ１０枚の上下に銅箔を重ね
てプレス成形（圧力：４０kgf ／cm2 、温度：３５０
℃、時間：２時間）により銅張り積層板を得た。この銅
張り積層板を３００℃のオーブンの中に１日間放置し、
観察を行った結果異常は全く認められなかった。また使
用したポリイミドの熱的特性を測定したところ、このポ
リイミドのガラス転移温度は３３５℃であった。次にこ
の銅張り積層板を、Ｎ−メチル−２−ピロリドン中に浸
漬し、１００℃で３時間加熱したところ、ポリイミドは
溶解し、ガラスクロス、銅箔が分離できた。更にポリイ
ミドのＮ−メチル−２−ピロリドン溶液を、水の中に滴
下し、ポリイミド固形物を回収することができた。回収
したポリイミド固形物を用いて再度同様の方法により銅
張り積層板を作製することができた。Example 1 4.442 g of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride in an Erlenmeyer flask
And 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl represented by the above formula (Formula 1) 3.20
2 g and 40 g of N-methyl-2-pyrrolidone were added.
This was stirred at room temperature in a stream of dry nitrogen for 48 hours and then heated at 180 ° C. for 3 hours to carry out imidization. When this polyimide solution was dropped into water little by little, a white solid was deposited. This was filtered and dried to obtain a polyimide solid. This polyimide solid was dissolved in ethyl acetate to obtain a polyimide solution. A glass cloth as a reinforcing material was impregnated and dried at 150 ° C. for 30 minutes to obtain a prepreg. Copper foils are laminated on the top and bottom of 10 sheets of this prepreg and press-formed (pressure: 40 kgf / cm 2 , temperature: 350
C, time: 2 hours) to obtain a copper-clad laminate. Leave this copper clad laminate in an oven at 300 ° C for 1 day,
As a result of observation, no abnormality was recognized. When the thermal characteristics of the polyimide used were measured, the glass transition temperature of this polyimide was 335 ° C. Next, when this copper-clad laminate was immersed in N-methyl-2-pyrrolidone and heated at 100 ° C. for 3 hours, the polyimide was dissolved and the glass cloth and the copper foil could be separated. Furthermore, the N-methyl-2-pyrrolidone solution of polyimide was dropped into water, and the polyimide solid could be recovered. A copper-clad laminate could be manufactured again by the same method using the recovered polyimide solid matter.
【００１５】実施例２ 実施例１で２，２−ビス（３，４−ジカルボキシフェニ
ル）ヘキサフルオロプロパン４．４４２ｇの代りに２，
２−ビス（３，４−ジカルボキシフェニル）ヘキサフル
オロプロパン３．９９８ｇと無水ピロメリット酸二無水
物０．２１８ｇを加え、同様の操作を行い銅張り積層板
が得られた。この銅張り積層板を３００℃のオーブンの
中に１日間放置し、観察を行った結果異常は全く認めら
れなかった。また使用したポリイミドの熱的特性を測定
したところ、このポリイミドのガラス転移温度は３４３
℃であった。次にこの銅張り積層板を、Ｎ−メチル−２
−ピロリドン中に浸漬し、１００℃で３時間加熱したと
ころ、ポリイミドは溶解し、ガラスクロス、銅箔が分離
できた。更にポリイミドのＮ−メチル−２−ピロリドン
溶液を、水の中に滴下し、ポリイミド固形物を回収する
ことができた。回収したポリイミド固形物を用いて再度
同様の方法により銅張り積層板を作製することができ
た。Example 2 In Example 1, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane was replaced with 2,442 instead of 4,442 g.
2-Bis (3,4-dicarboxyphenyl) hexafluoropropane (3.998 g) and pyromellitic dianhydride (0.218 g) were added, and the same operation was performed to obtain a copper-clad laminate. The copper-clad laminate was left in an oven at 300 ° C. for 1 day and observed, and no abnormality was found. Also, when the thermal characteristics of the polyimide used were measured, the glass transition temperature of this polyimide was 343.
It was ℃. Next, this copper-clad laminate is treated with N-methyl-2.
When immersed in pyrrolidone and heated at 100 ° C. for 3 hours, the polyimide was dissolved and the glass cloth and copper foil could be separated. Furthermore, the N-methyl-2-pyrrolidone solution of polyimide was dropped into water, and the polyimide solid could be recovered. A copper-clad laminate could be manufactured again by the same method using the recovered polyimide solid matter.
【００１６】実施例３ 実施例１で作製した積層板を使用し、一般に用いられて
いるサブトラクト法でプリント配線板を作製した。まず
銅張り積層板に印刷合せ用穴明けを行った。次に表面に
エッチングレジストを印刷した後裏面にエッチングレジ
ストを印刷した。次にエッチングを行った後エッチング
レジストをはく離して回路を形成した。このようにして
非スルーホール両面プリント配線板を作製した。作製し
たプリント配線板をＮ−メチル−２−ピロリドン中に浸
漬し、１００℃で３時間加熱したところ、ポリイミドは
溶解し、ガラスクロス、銅箔が分離できた。更にポリイ
ミドのＮ−メチル−２−ピロリドン溶液を、水の中に滴
下し、ポリイミド固形物を回収することができた。Example 3 Using the laminated board prepared in Example 1, a printed wiring board was prepared by a generally used subtraction method. First, the copper-clad laminate was perforated for printing. Next, an etching resist was printed on the front surface and then an etching resist was printed on the back surface. Next, after etching was performed, the etching resist was peeled off to form a circuit. In this way, a non-through hole double-sided printed wiring board was produced. When the produced printed wiring board was immersed in N-methyl-2-pyrrolidone and heated at 100 ° C. for 3 hours, the polyimide was dissolved and the glass cloth and the copper foil could be separated. Furthermore, the N-methyl-2-pyrrolidone solution of polyimide was dropped into water, and the polyimide solid could be recovered.
【００１７】[0017]
【発明の効果】以上説明したように、本発明による積層
板、プリント配線板は、はんだ耐熱性を有しかつリサイ
クルが可能であり、環境保護及び省資源に有用なもので
ある。As described above, the laminated board and the printed wiring board according to the present invention have solder heat resistance and can be recycled, and are useful for environmental protection and resource saving.
Claims (5)
いて、電気絶縁層の合成樹脂成分としてガラス転移温度
が２６０℃以上で、溶媒に可溶な合成樹脂を用いること
を特徴とするリサイクル可能な積層板。1. A recyclable laminate, comprising a synthetic resin component having a glass transition temperature of 260 ° C. or higher and a solvent-soluble synthetic resin, as a synthetic resin component of the electrical insulating layer, in a laminate comprising an electrically insulating layer and a conductive layer. Laminated board.
０℃以上で、溶媒に可溶なポリイミドを用いる請求項１
に記載のリサイクル可能な積層板。2. The synthetic resin has a glass transition temperature of 26.
A polyimide soluble in a solvent at 0 ° C. or higher is used.
The recyclable laminate described in.
０℃以上で、溶媒に可溶なフッ素化ポリイミドを用いる
請求項１に記載のリサイクル可能な積層板。3. A synthetic resin having a glass transition temperature of 26.
The recyclable laminate according to claim 1, wherein a fluorinated polyimide soluble in a solvent at 0 ° C or higher is used.
１）： 【化１】 で表されるフッ素化ジアミンを合成原料の一つとし、か
つ溶媒可溶であるポリイミド、ポリイミド共重合体、ポ
リイミド混合物を用いる請求項１に記載のリサイクル可
能な積層板。4. The following structural formula (Formula 1) as a synthetic resin: The recyclable laminate according to claim 1, wherein the fluorinated diamine represented by the formula (1) is used as a synthetic raw material, and a solvent-soluble polyimide, polyimide copolymer, or polyimide mixture is used.
板を用いることを特徴とするプリント配線板。5. A printed wiring board using the recyclable laminate according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29192391A JPH05110218A (en) | 1991-10-14 | 1991-10-14 | Renewable laminated board and printed board using it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29192391A JPH05110218A (en) | 1991-10-14 | 1991-10-14 | Renewable laminated board and printed board using it |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05110218A true JPH05110218A (en) | 1993-04-30 |
Family
ID=17775219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29192391A Pending JPH05110218A (en) | 1991-10-14 | 1991-10-14 | Renewable laminated board and printed board using it |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05110218A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5819731A (en) * | 1997-01-03 | 1998-10-13 | Minnesota Mining And Manufacturing Company | Face mask having a combination adjustable ear loop and drop down band |
| WO2003051628A1 (en) * | 2001-12-17 | 2003-06-26 | Suzuka Fuji Xerox Co., Ltd. | Composite resin molding and process for producing the same |
| WO2004035307A1 (en) * | 2002-09-11 | 2004-04-29 | Amt Laboratory Co., Ltd. | Film multilayer body and flexible circuit board |
| JP2004130748A (en) * | 2002-10-15 | 2004-04-30 | Mitsui Chemicals Inc | Laminated body |
| US6949289B1 (en) | 1998-03-03 | 2005-09-27 | Ppg Industries Ohio, Inc. | Impregnated glass fiber strands and products including the same |
| US7354641B2 (en) | 2004-10-12 | 2008-04-08 | Ppg Industries Ohio, Inc. | Resin compatible yarn binder and uses thereof |
| JP2010155360A (en) * | 2008-12-26 | 2010-07-15 | Nippon Steel Chem Co Ltd | Laminate for wiring board, having transparent insulating resin layer |
| JP2010201625A (en) * | 2009-02-27 | 2010-09-16 | Nippon Steel Chem Co Ltd | Laminate for flexible substrate and thermally conductive polyimide film |
-
1991
- 1991-10-14 JP JP29192391A patent/JPH05110218A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5819731A (en) * | 1997-01-03 | 1998-10-13 | Minnesota Mining And Manufacturing Company | Face mask having a combination adjustable ear loop and drop down band |
| US6095143A (en) * | 1997-01-03 | 2000-08-01 | Minnesota Mining And Manufacturing Company | Face mask having a combination adjustable ear loop and drop down band |
| US6949289B1 (en) | 1998-03-03 | 2005-09-27 | Ppg Industries Ohio, Inc. | Impregnated glass fiber strands and products including the same |
| WO2003051628A1 (en) * | 2001-12-17 | 2003-06-26 | Suzuka Fuji Xerox Co., Ltd. | Composite resin molding and process for producing the same |
| WO2004035307A1 (en) * | 2002-09-11 | 2004-04-29 | Amt Laboratory Co., Ltd. | Film multilayer body and flexible circuit board |
| JP2004130748A (en) * | 2002-10-15 | 2004-04-30 | Mitsui Chemicals Inc | Laminated body |
| US7354641B2 (en) | 2004-10-12 | 2008-04-08 | Ppg Industries Ohio, Inc. | Resin compatible yarn binder and uses thereof |
| JP2010155360A (en) * | 2008-12-26 | 2010-07-15 | Nippon Steel Chem Co Ltd | Laminate for wiring board, having transparent insulating resin layer |
| JP2010201625A (en) * | 2009-02-27 | 2010-09-16 | Nippon Steel Chem Co Ltd | Laminate for flexible substrate and thermally conductive polyimide film |
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