JPH0634434B2 - Circuit board - Google Patents
Circuit boardInfo
- Publication number
- JPH0634434B2 JPH0634434B2 JP62253128A JP25312887A JPH0634434B2 JP H0634434 B2 JPH0634434 B2 JP H0634434B2 JP 62253128 A JP62253128 A JP 62253128A JP 25312887 A JP25312887 A JP 25312887A JP H0634434 B2 JPH0634434 B2 JP H0634434B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- pps
- circuit board
- paper
- polyphenylene sulfide
- 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 - Lifetime
Links
Landscapes
- Laminated Bodies (AREA)
Description
【発明の詳細な説明】 [産業上の利用分野] この発明は、ポリフェニレンスルフィドフィルム上に金
属や導電性塗料等により電気回路が形成された回路基板
に関する。TECHNICAL FIELD The present invention relates to a circuit board in which an electric circuit is formed on a polyphenylene sulfide film by a metal, a conductive paint or the like.
[従来技術及びその欠点] 従来より、フレキシブル回路基板としてポリエステルフ
ィルムに銅箔等を接着したものが用いられている。しか
しながら、これは耐熱性に劣るという欠点を有する。こ
の問題を解決するために、例えば特公昭61-53880に記載
されているように、2軸配向ポリフェニレンスルフィル
ドフィルムを基板としたフレキブル回路基板が提案され
ている。この2軸配向ホリフェニレンスルフィド系回路
基板は耐熱性に優れ、寸法安定性、機械的特性にも優れ
るが、ポリフェニレンスルフィドフィルム上に接着剤で
銅等の金属層を貼着し、接着剤を約150 ℃程度の温度下
で熱硬化させると、金属層とポリフェニレンスルフィド
フィルムとの熱膨張係数の差により、回路基板がそって
しまうという問題がある。硬化温度の低い接着剤を用い
ても、回路基板は多かれ少なかれ他の配線と結合されね
ばらなず、ここで一般に使用されるハンダ浴に回路基板
を浮かべるとやはり回路基板がそってしまう。[Prior Art and its Defects] Conventionally, a flexible circuit board in which a copper foil or the like is adhered to a polyester film has been used. However, this has the disadvantage of poor heat resistance. In order to solve this problem, a flexible circuit board using a biaxially oriented polyphenylene sulfide filled film as a substrate has been proposed, for example, as described in JP-B-61-53880. This biaxially oriented phenylene sulfide circuit board has excellent heat resistance, dimensional stability, and mechanical properties, but a metal layer such as copper is adhered onto the polyphenylene sulfide film with an adhesive, When heat-cured at a temperature of about 150 ° C., there is a problem that the circuit board is warped due to the difference in thermal expansion coefficient between the metal layer and the polyphenylene sulfide film. Even if an adhesive having a low curing temperature is used, the circuit board must be bonded to other wiring more or less, and when the circuit board is floated on the solder bath generally used here, the circuit board is also warped.
[発明が解決しようとする問題点] この発明の目的は、ハンダ浴に浮かべた際にもそること
がなく、かつ耐熱性、寸法安定性、機械特性に優れた回
路基板を提供することである。[Problems to be Solved by the Invention] An object of the present invention is to provide a circuit board which does not warp when floated in a solder bath and has excellent heat resistance, dimensional stability, and mechanical properties. .
[問題点を解決するための手段] 本願発明者らは、鋭意研究の結果、2軸配向ポリフェニ
レンスルフィドフィルムと特定の熱膨張係数を有する繊
維シートとの積層体のポリフェニレンスルフィドフィル
ム側に回路を形成すると、ハンダ浴に浮かべた際にも回
路基板がそらないことを見出し、この発明を完成した。[Means for Solving the Problems] As a result of earnest research, the inventors of the present application formed a circuit on the polyphenylene sulfide film side of a laminate of a biaxially oriented polyphenylene sulfide film and a fiber sheet having a specific thermal expansion coefficient. Then, they found that the circuit board did not warp when floated in a solder bath, and completed the present invention.
すなわち、この発明は、2軸配向ポリフェニレンスルフ
ィドフィルムと、300 ℃で不融で、かつ100 ℃から200
℃の熱膨張係数が50x10-61/℃以下の繊維シートとを積
層した積層体の2軸配向ポリフェニレンスルフィドフィ
ルム側に電気回路を形成して成る回路基板を提供する。That is, the present invention is a biaxially oriented polyphenylene sulfide film that is infusible at 300 ° C and is from 100 ° C to 200 ° C.
Provided is a circuit board formed by forming an electric circuit on the biaxially oriented polyphenylene sulfide film side of a laminated body in which a fiber sheet having a thermal expansion coefficient at 50 ° C. of 50 × 10 −6 1 / ° C. or less is laminated.
[発明の効果] この発明の回路基板は、接着剤の硬化時にもハンダ浴に
浮かべた時にも実質的にそらず、また、ポリフェニレン
スルフィドの性質上、耐熱性、寸法安定性及び機械的特
性に優れている。[Effects of the Invention] The circuit board of the present invention does not substantially bend when the adhesive is cured or floated in a solder bath, and due to the property of polyphenylene sulfide, it has excellent heat resistance, dimensional stability, and mechanical properties. Are better.
[発明の具体的説明] 本発明において、2軸配向ポリフェニレンスルフィドフ
ィルム(以下、PPS−BOと省略することがある)と
は、ポリフェニレンスルフィドを主成分とする樹脂組成
物を、溶融成形してシート状とし、2軸延伸、熱処理し
てなるフィルムである。[Detailed Description of the Invention] In the present invention, a biaxially oriented polyphenylene sulfide film (hereinafter, sometimes abbreviated as PPS-BO) is a sheet obtained by melt-molding a resin composition containing polyphenylene sulfide as a main component. It is a film obtained by biaxial stretching and heat treatment.
該フィルムの配向度は、広角X線回折で2θ=20〜2
1度の結晶ピークについて求めた配向度OFがEnd 方向
及びEdge方向で0.07〜0.50、Through 方向で0.60〜1.00
の範囲にあることが好ましい。The degree of orientation of the film is 2θ = 20 to 2 in wide angle X-ray diffraction.
The orientation degree OF obtained for the 1-degree crystal peak is 0.07 to 0.50 in the End direction and Edge direction, and 0.60 to 1.00 in the Through direction.
It is preferably in the range of.
該フィルムの厚さは3〜200μmの範囲が好ましい。The thickness of the film is preferably in the range of 3 to 200 μm.
本発明において、ポリフェニレンスルフィドを主成分と
する樹脂組成物とは、ポリフェニレンスルフィドを70
重量%以上、好ましくは90重量%以上含む組成物をい
う。In the present invention, the resin composition containing polyphenylene sulfide as a main component means polyphenylene sulfide of 70% or less.
A composition containing at least 90% by weight, preferably at least 90% by weight.
ポリフェニレンスルフィドの含有量が70重量%未満で
は、組成物としての結晶性、熱転移度等が低くなり、該
組成物から成るフィルムの特長である耐熱性、寸法安定
性、機械的特性等を損なう。When the content of polyphenylene sulfide is less than 70% by weight, the composition has a low crystallinity, a thermal transition degree, etc., and the heat resistance, dimensional stability, mechanical properties, etc., which are the features of the film made of the composition, are impaired. .
該組成物は、これから成形されるフィルムの耐熱性、寸
法安定性、機械的特性等に悪影響を与えないならば、3
0重量%以下の範囲でポリフェニレンスルフィド以外の
ポリマー、無機又は有機のフィラー、滑剤、着色剤、紫
外線吸収剤等を含んでいても差支えない。If the composition does not adversely affect the heat resistance, dimensional stability, mechanical properties, etc. of the film to be molded, it is 3
Polymers other than polyphenylene sulfide, inorganic or organic fillers, lubricants, colorants, ultraviolet absorbers and the like may be contained in an amount of 0% by weight or less.
該樹脂組成物の溶融粘度は、温度300 ℃、剪断速度200
1/sec.のもとで500 〜12000 ポイズ(より好ましくは70
0 〜10000 ポイズ)の範囲がフィルムの成形性の点で好
ましい。The melt viscosity of the resin composition has a temperature of 300 ° C. and a shear rate of 200.
500-12000 poise (more preferably 70
The range of 0 to 10,000 poise) is preferable from the viewpoint of film formability.
本発明においてポリフェニレンスルフィド(以下PPS
と省略することがある)とは、繰り返し単位の70モル
%以上(好ましくは85モル%以上)が構成式 で示される構成単位から成る重合体をいう。かかる成分
が70モル%未満ではポリマーの結晶性、熱転移温度等
が低くなり、ポリフェニレンスルフィドを主成分とする
樹脂組成物から成るフィルムの特長である耐熱性、寸法
安定性、機械的特性等を損なう。In the present invention, polyphenylene sulfide (hereinafter referred to as PPS
May be omitted) means that 70 mol% or more (preferably 85 mol% or more) of the repeating unit is a constituent formula. A polymer comprising a structural unit represented by If the amount of such components is less than 70 mol%, the crystallinity of the polymer, the heat transition temperature, etc. are lowered, and the heat resistance, dimensional stability, mechanical properties, etc., which are the features of the film made of the resin composition containing polyphenylene sulfide as the main component, Spoil.
繰り返し単位の30モル%未満、好ましくは15モル%
未満であれば共重合可能なスルフィド結合を含有する単
位が含まれていても差支えない。Less than 30 mol% of repeating units, preferably 15 mol%
If it is less than the above, it does not matter even if a unit containing a copolymerizable sulfide bond is included.
本発明において用いられる繊維シートとは、紙、不織
布、織布等の総称で、セルロース繊維をベースとした天
然紙が好ましく、市販の紙をそのまま用いることができ
る。繊維シートは300 ℃で不融で、かつ、100 ℃〜200
℃における熱膨張係数が50x10-61/℃以下、好ましくは
30x10-61/℃以下である。300 ℃で不融とは、300 ℃の
ハンダに30秒間浮かべて溶融しないことを意味する。
また、熱膨張係数は、後で詳述する方法により、天秤法
で、200 ℃まで昇温した後、100 ℃まで降温し、その降
温時の温度変化に対する繊維シートの寸法変化量から求
めた値である。繊維シートの厚さは5μmないし200 μ
mが好ましい。また、繊維シートには例えば酸化アルミ
ニウム、酸化ケイ素等のような無機物が含まれていても
よい。さらに、回路基板に透孔を設けた際に透孔の内壁
がケバ立つことを防止するために繊維シートに樹脂を含
浸し又はこれでコーティングしてもよい。The fiber sheet used in the present invention is a general term for paper, non-woven fabric, woven fabric, etc., and natural paper based on cellulose fiber is preferable, and commercially available paper can be used as it is. The fibrous sheet is infusible at 300 ° C and is between 100 ° C and 200 ° C.
Coefficient of thermal expansion at ℃ is less than 50 × 10 -6 1 / ℃, preferably
It is not more than 30 × 10 -6 1 / ° C. Infusible at 300 ° C. means that it does not melt by floating in solder at 300 ° C. for 30 seconds.
The coefficient of thermal expansion is a value obtained from the dimensional change amount of the fiber sheet with respect to the temperature change at the time of the temperature decrease by the balance method after raising the temperature to 200 ° C and then decreasing the temperature to 100 ° C by the method described in detail later. Is. The thickness of fiber sheet is 5μm to 200μ
m is preferred. In addition, the fiber sheet may contain an inorganic substance such as aluminum oxide or silicon oxide. Further, the fiber sheet may be impregnated with resin or coated with resin in order to prevent the inner wall of the through hole from being fluffed when the through hole is provided in the circuit board.
本発明の回路基板では、ポリフェニレンスルフィドフィ
ルムと繊維シートの積層体のポリフェニレンスルフィド
フィルム側に回路基板が形成されている。すなわち、繊
維シート(Bμm)/PPSフィルム(Aμm)/回路の構成
を有する。回路が繊維シート側に形成されるとそりを低
下させる効果が得られない。また、ポリフェニレンスル
フィドを省略して繊維シート上に回路を形成したものは
100 ℃で長時間放置すると繊維シートが劣化し、また、
機械的強度、耐電圧の信頼性に乏しい。In the circuit board of the present invention, the circuit board is formed on the polyphenylene sulfide film side of the laminate of the polyphenylene sulfide film and the fiber sheet. That is, it has a structure of fiber sheet (B μm) / PPS film (A μm) / circuit. When the circuit is formed on the fiber sheet side, the effect of reducing the warp cannot be obtained. In addition, the one in which the circuit is formed on the fiber sheet by omitting polyphenylene sulfide is
The fiber sheet deteriorates when left at 100 ° C for a long time.
Poor reliability of mechanical strength and withstand voltage.
積層体を構成するポリフェニレンスルフィド(Aμm)と
繊維シート(Bμm)の厚さの比率A/Bは繊維シートの
熱膨張係数によって異なるが、A/Bがあまりにも小さ
いと機械強度が低下し、また逆にあまりにも大きいと回
路基板のそりが大きくなり、ハンダ耐熱性を向上させる
効果が小さくなるので、特に限定されないが0.1 ないし
4.0 が好ましい。The thickness ratio A / B of the polyphenylene sulfide (Aμm) and the fiber sheet (Bμm) that make up the laminate differ depending on the thermal expansion coefficient of the fiber sheet, but if A / B is too small, the mechanical strength decreases, and On the other hand, if it is too large, the warp of the circuit board becomes large, and the effect of improving the heat resistance of the solder becomes small.
4.0 is preferred.
PPSフィルム/繊維シート積層体の厚さは10μmな
いし200 μmが好ましい。The thickness of the PPS film / fiber sheet laminate is preferably 10 μm to 200 μm.
上述した本発明の回路基板の繊維シート側にさらにポリ
フェニレンスルフィドフィルムを積層して、PPSフィ
ルム(Aμm)/繊維シート(Bμm)/PPSフィルム(A′
μm)/回路という構成にしてもよい。この場合のPP
Sフィルムの厚さの和と繊維シートの厚さの比率(A+
A′)/Bは、繊維シートの熱膨張係数によって異なるが、
値があまりにも小さいと機械強度が低下し、また逆にあ
まりにも大きいと回路基板のそりが大きくなり、ハンダ
耐熱性を向上させる効果が小さくなるので、特に限定さ
れないが0.1 ないし4.0 が好ましい。また、この場合も
積層体の厚さは10μmないし200 μmが好ましい。By further laminating a polyphenylene sulfide film on the fiber sheet side of the circuit board of the present invention described above, a PPS film (A μm) / fiber sheet (B μm) / PPS film (A ′)
(μm) / circuit. PP in this case
Ratio of sum of S film thickness and fiber sheet thickness (A +
A ′) / B depends on the coefficient of thermal expansion of the fiber sheet,
If the value is too small, the mechanical strength is lowered, and conversely, if it is too large, the warp of the circuit board becomes large, and the effect of improving the solder heat resistance becomes small, so that it is not particularly limited, but 0.1 to 4.0 is preferable. Also in this case, the thickness of the laminate is preferably 10 μm to 200 μm.
また、上述したPPSフィルム(Aμm)/繊維シート(B
μm)/PPSフィルム(A′μm)/回路の、回路が形成
されていないPPSフィルム上に第2の回路を形成して
回路/PPSフィルム(Aμm)/繊維シート(Bμm)/P
PSフィルム(A′μm)/回路という構成にしてもよ
い。この場合の各層の厚さや比や積層体の厚さの好まし
い範囲は上記と同様である。In addition, the PPS film (A μm) / fiber sheet (B
μm) / PPS film (A′μm) / circuit, a second circuit is formed on the PPS film on which no circuit is formed, and the circuit / PPS film (A μm) / fiber sheet (B μm) / P is formed.
You may make it the structure of PS film (A'micrometer) / circuit. In this case, the preferable ranges of the thickness and ratio of each layer and the thickness of the laminated body are the same as above.
ポリフェニレンスルフィドフィルム上の電気回路は、例
えば銅、アルミニウム等の金属箔又は蒸着膜のような金
属層や導電性塗料等により形成することができる。The electric circuit on the polyphenylene sulfide film can be formed by a metal foil such as copper or aluminum, or a metal layer such as a vapor deposition film, a conductive paint, or the like.
この発明の回路基板は、例えば以下の方法により製造す
ることができる。The circuit board of the present invention can be manufactured, for example, by the following method.
本発明に用いるポリフェニレンスルフィドは、硫化アル
カリとパラジハロベンゼンとを極性溶媒中に高温高圧下
に反応させて得られる。特に硫化ナトリウムとパラジク
ロルベンゼンをN−メチルピロリドン等のアミド系高沸
点極性溶媒中で反応させるのが好ましい。この場合、重
合度を調整するために、カ性アルカリ、カルボン酸アル
カリ金属塩等のいわゆる重合助剤を添加して230 ℃〜28
0 ℃で反応させるのが最も好ましい。重合系内の圧力及
び重合時間は使用する助剤の種類や量及び所望する重合
度等によって適宜決定する。得られた粉状又は粒状のポ
リマーを、水及び/又は溶媒で洗浄して、副生塩、重合
助剤、未反応モノマー等を分離する。The polyphenylene sulfide used in the present invention can be obtained by reacting an alkali sulfide and paradihalobenzene in a polar solvent at high temperature and high pressure. In particular, it is preferable to react sodium sulfide and paradichlorobenzene in an amide-based high-boiling polar solvent such as N-methylpyrrolidone. In this case, in order to adjust the degree of polymerization, a so-called polymerization aid such as caustic alkali and alkali metal carboxylic acid is added to the composition at 230 ° C to 28 ° C.
Most preferably, the reaction is carried out at 0 ° C. The pressure in the polymerization system and the polymerization time are appropriately determined depending on the kind and amount of the auxiliary agent used, the desired degree of polymerization and the like. The obtained powdery or granular polymer is washed with water and / or a solvent to separate by-product salts, polymerization aids, unreacted monomers and the like.
このポリマーを2軸配向フィルムに成形するには、押出
機により溶融された該樹脂を口金から定量的に金属ドラ
ムの上にキャスティングし、急速冷却することによって
無配向、非晶状態のシートを得て、該シートを周知の方
法で2軸延伸、熱処理する。延伸は長手方向、幅方向と
も90〜110 ℃で3.0 倍〜4.5 倍の範囲で行なう。熱処
理は240 ℃〜融点の範囲で、定長又は15%以下の制限
収縮下に1〜60秒間行なう。さらに、該フィルムの熱
的寸法安定性を向上させるために、一方向又は二方向に
リラックスしてもよい。なお、後の工程において繊維シ
ートと接着する際の接着性を向上させる目的で、コロナ
放電処理やプラズマ処理等の表面処理をフィルムに施し
ておくことが好ましい。To form this polymer into a biaxially oriented film, the resin melted by an extruder is quantitatively cast from a die onto a metal drum and rapidly cooled to obtain a non-oriented, amorphous sheet. Then, the sheet is biaxially stretched and heat treated by a known method. Stretching is performed at 90 to 110 ° C. in the longitudinal direction and the width direction in the range of 3.0 to 4.5 times. The heat treatment is performed in the range of 240 ° C. to the melting point for 1 to 60 seconds under a constant length or a limited shrinkage of 15% or less. Further, it may be relaxed in one or two directions to improve the thermal dimensional stability of the film. The film is preferably subjected to a surface treatment such as a corona discharge treatment or a plasma treatment for the purpose of improving the adhesiveness when it is adhered to the fiber sheet in a later step.
一方、市販の天然紙のような、上記した繊維シートを準
備する。On the other hand, the above-mentioned fiber sheet such as commercially available natural paper is prepared.
次に、上述のようにして得たポリフェニレンスルフィド
フィルムと繊維シートとを接着剤で接着する。接着剤は
特に限定されないが、耐熱性及び作業性から考えて熱硬
化型の溶剤系が好ましく、例えばウレタン系、エポキシ
系、アクリル系、シリコーン系接着剤等を挙げることが
できる。Next, the polyphenylene sulfide film obtained as described above and the fiber sheet are bonded with an adhesive. The adhesive is not particularly limited, but thermosetting solvent-based adhesives are preferable from the viewpoint of heat resistance and workability, and examples thereof include urethane-based, epoxy-based, acrylic-based, and silicone-based adhesives.
次に積層方法は、2軸配向ポリフェニレンスルフィドフ
ィルム(又は繊維シート)の片面に接着剤を塗布し、乾
燥した後、加熱ロール又は加熱プレスで繊維シート(又
はポリフェニレンスルフィドフィルム)を貼り合せる。
このようにして得られる積層体の繊維シート側にさらに
第2のポリフェニレンスルフィドフィルムを貼り合せる
場合にも、上記と同様に行なうことができる。また、接
着剤の塗布の方法としては、グラビアロール法、リバー
スロールコータ法、ダイコータ法等の周知の方法を採用
することができる。バッチ式で行なう場合には、メタリ
ングバー、アプリケータ、ガラス棒等で接着剤を塗布す
ることができる。塗布後の溶剤の乾燥は、用いる溶剤の
種類により異なり、通常は溶剤の沸点付近の温度で残存
溶剤が完全になくなる条件が選ばれる。又、貼り合せの
条件は、温度50℃〜200℃ 、線圧1〜50kg/cm の範
囲で行なうのがよい。また、必要に応じて接着剤の硬化
を行なう。硬化条件は接着剤の種類や組成、厚みによっ
て異なるが、常温ないし200 ℃で0.5 時間〜100 時間の
範囲内が好ましい。Next, in the laminating method, an adhesive is applied to one side of the biaxially oriented polyphenylene sulfide film (or fiber sheet), dried, and then the fiber sheet (or polyphenylene sulfide film) is laminated with a heating roll or a heating press.
When the second polyphenylene sulfide film is further attached to the fiber sheet side of the thus obtained laminate, the same operation as above can be performed. As a method of applying the adhesive, a well-known method such as a gravure roll method, a reverse roll coater method, a die coater method can be adopted. When the batch method is used, the adhesive can be applied with a metering bar, an applicator, a glass rod or the like. Drying of the solvent after coating varies depending on the type of solvent used, and usually, conditions are selected in which the residual solvent completely disappears at a temperature near the boiling point of the solvent. The bonding conditions are preferably 50 ° C. to 200 ° C. and linear pressure of 1 to 50 kg / cm. Also, the adhesive is cured as necessary. The curing conditions vary depending on the type and composition of the adhesive and the thickness, but it is preferably within the range of 0.5 hours to 100 hours at room temperature to 200 ° C.
次にこのようにして得た積層体のポリフェニレンスルフ
ィドフィルム上に電気回路を形成する。金属層で電気回
路を形成する場合には、特に限定されないが、通常、上
記と同様にして金属箔を上記積層体のポリフェニレンス
ルフィドフィルム上に貼り合せた後、又は蒸着膜を形成
した後、周知の方法により金属箔又は蒸着膜をエッチン
グする。導電性塗料で回路を形成する場合には、一般的
に周知のスクリーン印刷法が用いられる。導電性塗料の
硬化方法は、通常、180 ℃〜250 ℃の温度で1分〜2時
間が好ましい。Next, an electric circuit is formed on the polyphenylene sulfide film of the laminate thus obtained. In the case of forming an electric circuit with a metal layer, it is not particularly limited, but usually, after bonding a metal foil on the polyphenylene sulfide film of the above-mentioned laminate in the same manner as described above, or after forming a vapor deposition film, it is well known. The metal foil or the vapor deposition film is etched by the method of 1. When forming a circuit with a conductive paint, a generally known screen printing method is used. The method for curing the conductive paint is usually preferably at a temperature of 180 ° C to 250 ° C for 1 minute to 2 hours.
次に本発明に関する特性の測定方法及び効果の評価方法
についてまとめて記載する。Next, the method of measuring the characteristics and the method of evaluating the effects relating to the present invention will be described collectively.
(1) 300 ℃での溶融状態の評価 300 ℃(±5℃以下の精度)のハンダ液面に30秒間浮
かべた時の溶融状態を目視で観察する。(1) Evaluation of molten state at 300 ° C Visually observe the molten state when floated on the solder surface of 300 ° C (accuracy of ± 5 ° C or less) for 30 seconds.
(2) 熱膨張係数 差動トランスと加熱炉を組み込んだ天秤を用い、200 ℃
まで昇温した後、100 ℃まで降温し、その降温時の温度
変化に対する試料の寸法変化量をプロットし、その勾配
より求める。試料のサイズは50 mm x 5 mmとし、0.2 g/
5 mm幅の荷重を加えて測定する。(2) Coefficient of thermal expansion 200 ° C
After the temperature has risen to 100 ° C, the temperature is lowered to 100 ° C, and the dimensional change of the sample is plotted against the temperature change during the temperature drop, and the slope is determined. The sample size is 50 mm x 5 mm, 0.2 g /
Measure with a load of 5 mm width.
(3) 2軸配向ポリフェニレンスルフィドフィルムの配向
度 各試料の延伸方向をそろえて厚み1mm、幅1mm、長さ1
0mmの短冊状に成型(成型時の各フィルムの固定はコロ
ジオンの5%酢酸アミル溶液を用いた)し、フィルムの
膜面に沿ってX線を入射(Edge及びEnd 方向)してプレ
ート写真を撮影した。X線発生装置は理学電機製、D-3F
型装置を用い、40 kV-20 mA でNiフィルターを通したCu
-Kα線をX線源とした。(3) Degree of orientation of biaxially oriented polyphenylene sulfide film Aligning the stretching direction of each sample, thickness 1mm, width 1mm, length 1
Molded into a strip of 0 mm (fixing each film at the time of molding with 5% amyl acetate solution of collodion), incident X-rays along the film surface of the film (in the Edge and End directions), and take a plate photograph. I took a picture. The X-ray generator is Rigaku Denki, D-3F
Cu filtered through Ni filter at 40 kV-20 mA using
-Kα ray was used as the X-ray source.
試料−フィルム間距離は41mmでコダックノンスクリー
ンタイプフィルムを用い多重露出(15分及び30分)
法を採用した。次にプレート写真上の(200) ピースの強
度をφ=0゜(赤道線上)10゜、20゜、30゜の位
置で写真の中心から半径方向にデンシトメーターを走査
し、黒化度Iを読み取り各試料の配向度(OF)を OF=I(φ=30゜)/I(φ=0゜) と定義した。Sample-to-film distance is 41 mm, multiple exposure (15 and 30 minutes) using Kodak non-screen type film
Adopted the law. Then, the intensity of the (200) piece on the plate photograph was scanned at 0 = 0 ° (on the equator line) at 10 °, 20 °, and 30 ° with a densitometer in the radial direction from the center of the photograph, and the blackening degree I was measured. Was read and the orientation degree (OF) of each sample was defined as OF = I (φ = 30 °) / I (φ = 0 °).
ここで、I(φ=30゜)は30゜の走査の最大強度、
I(φ=0゜)は赤道線走査の最大強度である。なおI
(φ=0゜)はφ=0゜とφ=180゜、I(φ=30
゜)はφ=30゜とφ=150゜の強度の平均値を用い
た。デンシトメーターの測定条件は次のようである。Where I (φ = 30 °) is the maximum intensity of the 30 ° scan,
I (φ = 0 °) is the maximum intensity of the equatorial line scan. I
(Φ = 0 °) is φ = 0 ° and φ = 180 °, I (φ = 30
The average value of the strengths of φ = 30 ° and φ = 150 ° was used for (°). The measurement conditions of the densitometer are as follows.
装置は小西六写真工業製サクラマイクロデンシトメータ
ーモデルPDM-5 タイプAを使用し、測定濃度範囲は0.0
〜4.0D(最小測定面積4μm2換算)、光学系倍率10
0倍でスリット幅1μm、高さ10μmを使用し、フィ
ルム移動速度50μm/秒でチャート速度は1mm/ 秒で
ある。The equipment uses Sakura Microdensitometer model PDM-5 type A made by Konishi Rokusha Kogyo Co., Ltd.
~ 4.0D (minimum measurement area 4μm 2 conversion), optical system magnification 10
At 0 times, a slit width of 1 μm and a height of 10 μm are used, and the film moving speed is 50 μm / sec and the chart speed is 1 mm / sec.
(4) ハンダ耐熱性 各温度(±5℃以下の精度)に設定したハンダ液面に電
気回路面が接するように20秒間浮かべて取り出す。そ
の時の基板の平面性の悪化したハンダの温度で表わし
た。(4) Solder heat resistance Float for 20 seconds so that the electric circuit surface is in contact with the solder liquid surface set to each temperature (accuracy of ± 5 ° C or less) and take out. It is represented by the temperature of the solder at which the flatness of the substrate deteriorates.
(5) 耐屈曲回数(MIT) 金属層から成る電気回路を塩化第2鉄水溶液でエッチン
グし、120 ℃で50時間エージングした後、ASTM-D-217
6-63T に準じて測定した。(5) Bending Resistance (MIT) An electric circuit consisting of a metal layer was etched with an aqueous solution of ferric chloride and aged at 120 ° C for 50 hours, and then ASTM-D-217.
Measured according to 6-63T.
(6) そり度 銅箔を用いたフレキシブル配線基板は、50mm x 50 mm
にサンプリングし、120 ℃で5分間エージングした。そ
りが発生しているサンプルの一片をガラス板にセロテー
プで固定することによりそれと対称の片がそり上る。そ
のそり上った辺から垂直下のガラス板までの距離をそり
度(mm)とした。(6) Warpage The flexible wiring board using copper foil is 50 mm x 50 mm.
Samples were sampled and aged at 120 ° C for 5 minutes. By fixing one piece of the sample in which the warpage has occurred to the glass plate with cellophane tape, a piece symmetrical with that is raised. The warp degree (mm) was defined as the distance from the warped side to the vertically lower glass plate.
一方、導電性塗料(「ハイソール」KO-0107東レ株式会
社製)を用いたフレキシブル配線基板は、200 ℃、10
分の条件で該塗料を硬化させた後、銅箔を用いた場合と
同様の方法で測定した。On the other hand, a flexible wiring board using a conductive paint (“Hisole” KO-0107 Toray Industries, Inc.)
After the paint was cured under the condition of minutes, the measurement was performed in the same manner as in the case of using the copper foil.
(7) 表面電気抵抗値 荷重500gの4cm角型電極で測定した表面抵抗(Ω/□)
で表示した。(7) Surface electric resistance value Surface resistance (Ω / □) measured with a 4 cm square electrode with a load of 500 g.
Displayed in.
[発明の実施例] 次に本発明の実施例及び比較例を示し、この発明の効果
を具体的に説明する。[Examples of the Invention] Next, the effects of the present invention will be specifically described by showing Examples of the present invention and Comparative Examples.
実施例1 (1) 本発明に用いるPPS−BOの調製 (a)PPSポリマーの調製 オートクレーブに硫化ナトリウム32.6 kg(250モル、結
晶水40重量%を含む)、水酸化ナトリウム100 g、安
息香酸ナトリウム36.1 kg(250モル)、及びN−メチル−
2−ピロリドン(以下NMPと略称する。)79.2 kg を
仕込みかくはんしながら徐々に205 ℃まで昇温し、水6.
9 kgを含む留出液7.0 を除去した。残留混合物に1,4-
ジクロルベンゼン37.5 kg(255モル)及びNMP20.0 kg
を加え、265 ℃で4時間加熱した。反応生成物を熱湯で
8回洗浄し、溶融粘度2900ポイズ、非ニュートン係数1.
17、ガラス転移点91℃、融点285℃の高重合度ポリ
フェニレンスルフィド21.1 kg (収率78%)を得た。Example 1 (1) Preparation of PPS-BO used in the present invention (a) Preparation of PPS polymer Sodium sulfide 32.6 kg (including 250 mol and 40% by weight of water of crystallization), 100 g of sodium hydroxide, and sodium benzoate were added to an autoclave. 36.1 kg (250 mol), and N-methyl-
2-Pyrrolidone (hereinafter referred to as NMP) 79.2 kg was charged and the temperature was gradually raised to 205 ° C while stirring, and water was added 6.
Distillate 7.0 containing 9 kg was removed. 1,4-to the residual mixture
Dichlorobenzene 37.5 kg (255 mol) and NMP 20.0 kg
Was added and heated at 265 ° C. for 4 hours. The reaction product was washed 8 times with hot water, melt viscosity 2900 poise, non-Newton coefficient 1.
17, 21.1 kg (yield 78%) of highly polymerized polyphenylene sulfide having a glass transition point of 91 ° C. and a melting point of 285 ° C. was obtained.
(b)溶融成形 上記(a)で得られた組成物を180 ℃で2時間、減圧下
で乾燥した後、該組成物に滑剤として、ステアリン酸カ
ルシウム粉末を0.1 重量%添加し、ミキサーでかくはん
混合した後、直径40mmのエクストルーダのホッパに投
入した。310 ℃で溶融された該組成物を長さ250 mm、間
隙1.5 mmの直線状のリップを有する口金から押出し、表
面温度を30℃に保った金属ドラム上にキャストして冷
却固化した。(B) Melt molding After drying the composition obtained in (a) above under reduced pressure at 180 ° C. for 2 hours, 0.1% by weight of calcium stearate powder as a lubricant was added to the composition and stirred by a mixer. After that, it was put into a hopper of an extruder having a diameter of 40 mm. The composition melted at 310 ° C. was extruded from a die having a straight lip having a length of 250 mm and a gap of 1.5 mm, cast on a metal drum whose surface temperature was kept at 30 ° C., and solidified by cooling.
得られたフィルムは、幅が230 mm、厚さ380 μm、密度
1.315 の未延伸フィルムであった。The film obtained has a width of 230 mm, a thickness of 380 μm and a density.
It was an unstretched film of 1.315.
(c)2軸延伸、熱処理 上記(b)で得られたフィルムをロール群から成る縦延
伸装置によって、フィルムの長手方向に延伸温度98℃
で3.9 倍に延伸し、続いてフィルムをテンタに供給し、
延伸温度98℃で幅方向に3.7 倍延伸し、さらに同一テ
ンタ内に後続する熱処理室で270 ℃、10秒間の熱処理
をして、2軸配向フィルムを得た。さらに、該フィルム
をフリー状態で250 ℃2分間強制収縮させた。さらに該
フィルムの片面に6000 J/m2のコロナ放電処理を施し、
このフィルムをPPS−BO−1(厚さ25μm)とす
る。(C) Biaxial stretching, heat treatment The film obtained in (b) above is stretched at a temperature of 98 ° C. in the longitudinal direction of the film by a longitudinal stretching device consisting of rolls.
Stretching to 3.9 times with, then feeding the film to the tenter,
The film was stretched 3.7 times in the width direction at a stretching temperature of 98 ° C. and further heat-treated at 270 ° C. for 10 seconds in the subsequent heat treatment chamber in the same tenter to obtain a biaxially oriented film. Further, the film was forcibly contracted for 2 minutes at 250 ° C. in a free state. Furthermore, a 6000 J / m 2 corona discharge treatment is applied to one side of the film,
This film is named PPS-BO-1 (thickness 25 μm).
(2) 本発明に用いる繊維シートの準備 市販のクラフト紙(厚さ100 μm)を用いた(紙−1と
する)。この紙は300 ℃で全く溶融せず、熱膨張係数は
9 x 10-6/℃であった。(2) Preparation of fiber sheet used in the present invention Commercially available kraft paper (thickness 100 µm) was used (referred to as Paper-1). This paper does not melt at 300 ℃ and has a coefficient of thermal expansion
It was 9 x 10 -6 / ° C.
(3) 接着剤の調製 市販のエポキシ系接着剤である「ケミットエポキシ TE
5920」(東レ株式会社製)を用いた。この接着剤の主剤
と硬化剤の混合比を主剤/硬化剤=100/15とし、メタノ
ール/トルエンの混合溶剤で30重量%になるように調
整した。(3) Preparation of adhesive "Chemit Epoxy TE" which is a commercially available epoxy adhesive
5920 "(manufactured by Toray Industries, Inc.) was used. The mixing ratio of the main agent and the curing agent of this adhesive was set to the main agent / curing agent = 100/15, and the mixture was adjusted to 30% by weight with a mixed solvent of methanol / toluene.
(4) 積層体の調製 PPS−BO−1のコロナ処理面にグラビアロール法で
先に調製した接着剤をコーティングした。溶剤の乾燥条
件は100 ℃で3分間であり、接着剤の厚みは硬化後で1
0μmになるよう調整した。続いて後続するロールラミ
ネータで紙−1と貼り合せた。貼り合せの条件は温度12
0 ℃、線圧3 kg/cmとした。得られた積層体は150 ℃で
60分間硬化させた(積層体−1とする)。(4) Preparation of Laminated Body The corona-treated surface of PPS-BO-1 was coated with the adhesive previously prepared by the gravure roll method. The solvent is dried at 100 ° C for 3 minutes, and the thickness of the adhesive is 1 after curing.
It was adjusted to be 0 μm. Then, it was attached to Paper-1 by the following roll laminator. The bonding conditions are temperature 12
The temperature was 0 ° C and the linear pressure was 3 kg / cm. The obtained laminated body was cured at 150 ° C. for 60 minutes (referred to as laminated body-1).
次にもう1層のPPS−BO−1のコロナ処理面に上記
の条件で接着剤をコーティングし、先に得られたPPS
−BO−1/紙/−1の紙−1の側に上記の条件で貼り
合せた。得られた積層体を150 ℃で60分間硬化させた
(積層体−2)。Next, the corona-treated surface of another layer of PPS-BO-1 was coated with the adhesive under the above conditions, and the PPS obtained above was obtained.
-BO-1 / Paper / Paper-1 was attached to the side of Paper-1 under the above conditions. The obtained laminate was cured at 150 ° C. for 60 minutes (laminate-2).
(5) 回路基板の調製 積層体−1のPPS−BO−1側及び積層体−2の片面
に6000 J/m2のコロナ処理を行ない該処理面に接着剤を
介して厚さ35μmの電解銅箔を積層した。使用した接
着剤は、先の積層体の作製に用いたものと同じであり、
塗布厚みは硬化後で10μmになるよう調整し、貼り合
せ及び硬化の条件は先の積層体の作製の場合と同じであ
った。得られた2種類の銅貼り品は、5mmの間隔で5mm
幅に、かつ碁盤の目に銅が残るようにエッチングした。
このようにして得られた回路基板を基板−1及び基板−
2とする。(5) Preparation of Circuit Board Corona treatment of 6000 J / m 2 was performed on the PPS-BO-1 side of laminate-1 and one side of laminate-2, and the treated surface was electrolyzed to a thickness of 35 μm via an adhesive. Copper foil was laminated. The adhesive used was the same as that used to make the previous laminate,
The coating thickness was adjusted to be 10 μm after curing, and the conditions for bonding and curing were the same as in the case of producing the above-mentioned laminate. The two types of copper-bonded products obtained are 5 mm apart at intervals of 5 mm.
The width was etched and copper was left on the board.
The circuit board thus obtained is used as the board-1 and the board-
Set to 2.
また、先に得られた積層体−1のPPS−BO−1側及
び積層体−2の片面に圧力0.6 mmHgの二酸化炭素ガス中
で、印加電圧2KV、処理速度0.25 m/分の条件でプラ
ズマ処理を行ない、該処理面に導電性塗料([ハイソー
ル」K0-0107 東レ株式会社製)を8μmの厚さに塗布
し、200℃、10分の条件で硬化させた。該導電性塗料
の表面電気抵抗値は8 x 10-1Ω/□であった。得られた
回路基板を基板−3、基板−4とする。Further, on the PPS-BO-1 side of the laminate 1 obtained above and on one surface of the laminate 2 in a carbon dioxide gas with a pressure of 0.6 mmHg, plasma was applied under the conditions of an applied voltage of 2 KV and a treatment speed of 0.25 m / min. After the treatment, a conductive paint ([Hisol] K0-0107 Toray Co., Ltd.) was applied to the treated surface to a thickness of 8 μm and cured under conditions of 200 ° C. and 10 minutes. The surface electric resistance value of the conductive paint was 8 × 10 −1 Ω / □. The obtained circuit boards are referred to as board-3 and board-4.
(6) 比較例1〜5 実施例1と同様にして、厚さ100 μmのPPS−BOを
作製した(PPS−BO−2とする)。PPS−BO−
2に実施例1の条件で銅箔を用いた回路基板を作製した
(比較例1)。(6) Comparative Examples 1 to 5 PPS-BO having a thickness of 100 μm was manufactured in the same manner as in Example 1 (referred to as PPS-BO-2). PPS-BO-
In 2, the circuit board using the copper foil was prepared under the conditions of Example 1 (Comparative Example 1).
さらに、実施例1で使用した紙−1も同様の回路基板を
作製した(比較例2)。Further, a similar circuit board was produced using the paper-1 used in Example 1 (Comparative Example 2).
さらに、実施例1で作製した積層体−1の紙−1側に銅
箔を用いた回路基板を作製した(比較例−3)。Furthermore, a circuit board using a copper foil was prepared on the paper-1 side of the laminate-1 prepared in Example 1 (Comparative Example-3).
次に上記のPPS−BO−2及び積層体−1の紙側に実
施例1と同様に導電性塗料を用いた回路基板を作製した
(PPS−BO−2を用いたものを比較例4、積層体−
1を用いたものを比較例5とする)。Next, on the paper side of the above PPS-BO-2 and the laminate-1, a circuit board using a conductive coating material was produced in the same manner as in Example 1 (Comparative Example 4, using PPS-BO-2 was used. Laminated body
1 is used as Comparative Example 5).
(7) 評価 第1表に銅箔を用いた回路基板の評価結果を示す。本発
明の回路基板は、PPS−BO単体のものに比べて、そ
りが著しく小さく(ほとんどフラット)、かつハンダ耐
熱性が一段と優れていることがわかる。また、PPSフ
ィルムの融点近くまでハンダの温度を上昇させたが平面
性が急激に悪化することはなかった。一方、紙をベース
とした回路基板は、銅を内側(PPS−BO単体とは逆
の方向)に大きくそる。また、120 ℃で50時間放置し
た後の機械的強度が非常に悪い。また、PPS−BOと
紙の2層体の紙側に銅箔を用いた回路を形成すると、そ
りの点で不利であることがわかる。(7) Evaluation Table 1 shows the evaluation results of the circuit board using the copper foil. It can be seen that the circuit board of the present invention has significantly smaller warp (almost flat) and more excellent solder heat resistance than the PPS-BO alone. Further, the temperature of the solder was raised to near the melting point of the PPS film, but the flatness did not deteriorate sharply. On the other hand, in a paper-based circuit board, copper is largely bent inward (opposite direction to that of a single PPS-BO). In addition, the mechanical strength after standing for 50 hours at 120 ° C is extremely poor. Further, it can be seen that forming a circuit using a copper foil on the paper side of the two-layered body of PPS-BO and paper is disadvantageous in terms of warpage.
第2表に導電性塗料を用いた回路基板の評価結果を示
す。そりの状態は、銅箔を用いた場合と同傾向にある。Table 2 shows the evaluation results of the circuit board using the conductive paint. The state of warpage tends to be the same as when copper foil is used.
実施例2 (1) 回路基板の作製 実施例1で作製した基板−2のもう一方の面に実施例1
の条件で銅箔を用いた回路を作製した(基板−5とす
る)。 Example 2 (1) Fabrication of Circuit Board Example 1 was formed on the other surface of the substrate-2 fabricated in Example 1.
A circuit using a copper foil was produced under the conditions (referred to as substrate-5).
比較のために上記比較例1のもう一方の面にも同様の回
路基板を作製した(比較例6とする)。For comparison, a similar circuit board was prepared on the other surface of Comparative Example 1 (referred to as Comparative Example 6).
(2) 評価 第3表に評価結果を示す。本発明の回路基板(回路/PPS
/BO/紙/PPS-BO/回路)は、PPS−BO単体のものに比
べてそり状態は変わらないもののハンダ耐熱性が一段と
向上しているのがわかる。(2) Evaluation Table 3 shows the evaluation results. Circuit board of the present invention (circuit / PPS
It can be seen that the / BO / paper / PPS-BO / circuit) has the same warped state as that of the PPS-BO alone, but the solder heat resistance is further improved.
実施例3 (1) PPS−BOの作製 実施例1と同様にして12μmと50μmのPPS−B
Oを作製した(12μmのものをPPS−BO−3、5
0μmのものをPPS−BO−4とする)。 Example 3 (1) Preparation of PPS-BO In the same manner as in Example 1, 12 μm and 50 μm PPS-B.
O was prepared (12 μm of PPS-BO-3, 5
The one having a thickness of 0 μm is designated as PPS-BO-4).
(2) 紙の準備 下記の5種類の紙を準備した。(2) Preparation of paper The following 5 kinds of paper were prepared.
紙−2:コイル絶縁紙、厚さ25μm 紙−3:NF−7(白)[四国製紙(株)]、厚さ70
μm 紙−4:耐油紙[四国製紙(株)]、厚さ55μm 紙−5:研磨紙用原紙C.W.S−BM、厚さ130 μm 紙−6:セラフォームM-20[四国製紙(株)]、厚さ8
0μm 上記の紙は全て300 ℃で溶融せず、熱膨張係数も本発明
の範囲であった。Paper-2: Coil insulation paper, thickness 25 μm Paper-3: NF-7 (white) [Shikoku Paper Co., Ltd.], thickness 70
μm Paper-4: Oil resistant paper [Shikoku Paper Co., Ltd.], thickness 55 μm Paper-5: Base paper for abrasive paper C.I. W. S-BM, thickness 130 μm Paper-6: Ceraform M-20 [Shikoku Paper Co., Ltd.], thickness 8
0 μm All the above papers did not melt at 300 ° C., and the coefficient of thermal expansion was within the range of the present invention.
(3) 回路基板の作製 上記のPPS−BO(PPS−BO−3、PPS−BO
−4)と実施例1で作製したPPS−BO−1と上記の
紙(紙−2〜紙−6)とを組み合せて10種類の積層体
を作製した。積層体の構成は全てPPS−BO/紙/P
PS−BOとした。また、積層の条件は、実施例1の条
件を用いた。次いで、得られた10種類の積層体の片面
に実施例1と同様の条件で金箔を用いた回路を形成した
(基板−6〜基板−15)。(3) Preparation of circuit board PPS-BO (PPS-BO-3, PPS-BO)
-4), PPS-BO-1 produced in Example 1 and the above-mentioned papers (paper-2 to paper-6) were combined to produce 10 kinds of laminates. Laminates are all PPS-BO / paper / P
It was PS-BO. Moreover, the conditions of Example 1 were used for the lamination conditions. Next, a circuit using a gold foil was formed on one surface of each of the obtained 10 types of laminates under the same conditions as in Example 1 (Substrate-6 to Substrate-15).
(4) 評価 第4表に評価結果を示す。本発明で言う熱膨張係数が大
きくなると、回路基板のそりの状態が大きくなることが
わかる。ハンダ耐熱性は全て優れていた。(4) Evaluation Table 4 shows the evaluation results. It can be seen that the warped state of the circuit board increases as the coefficient of thermal expansion referred to in the present invention increases. Solder heat resistance was all excellent.
比較例7 実施例1の方法で、25μm厚みの未延伸フィルムを作
成した(PPS−NO−1とする。)。また、該未延伸
フィルムを270℃の温度で3分間熱処理した。その時
のフィルムの密度は1.358であった(PPS−NO
−2とする。)。 Comparative Example 7 An unstretched film having a thickness of 25 μm was prepared by the method of Example 1 (referred to as PPS-NO-1). Further, the unstretched film was heat-treated at a temperature of 270 ° C. for 3 minutes. The density of the film at that time was 1.358 (PPS-NO
-2. ).
上記2種のフィルムを各々実施例1の条件で繊維シート
の両面に積層した。更に実施例1と同様の方法で回路基
板を作成した。PPS−NO−1を用いたものを基板−
16、PPS−NO−2を用いたものを基板−17とす
る。The above two kinds of films were laminated on both surfaces of the fiber sheet under the conditions of Example 1. Further, a circuit board was prepared in the same manner as in Example 1. Substrate using PPS-NO-1
16. A substrate using PPS-NO-2 is referred to as Substrate-17.
第5表に評価結果を示す。第1表の実施例1の結果と比
較すると、熱処理していない未延伸フィルムを用いた基
板−16はハンダ耐熱温度が低く、熱処理した未延伸フ
ィルムを用いた基板−17は機械的強度が悪いことが判
る。従って、未延伸フィルムでは本発明の目的を達成で
きない。Table 5 shows the evaluation results. Comparing with the results of Example 1 in Table 1, the substrate-16 using the unstretched film that has not been heat-treated has a low soldering heat resistance temperature, and the substrate-17 using the heat-treated unstretched film has poor mechanical strength. I understand. Therefore, the unstretched film cannot achieve the object of the present invention.
Claims (2)
ムと、300 ℃で不融で、かつ100 ℃から200 ℃の熱膨張
係数が50x10-61/℃以下の繊維シートとを積層した積層
体の2軸配向ポリフェニレンスルフィドフィルム側に電
気回路を形成して成る回路基板。1. A biaxial laminate comprising a biaxially oriented polyphenylene sulfide film and a fiber sheet which is infusible at 300 ° C. and has a coefficient of thermal expansion of 100 ° C. to 200 ° C. of 50 × 10 −6 1 / ° C. or less. A circuit board formed by forming an electric circuit on the oriented polyphenylene sulfide film side.
第1項記載の回路基板。2. The circuit board according to claim 1, wherein the fiber sheet is paper.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62253128A JPH0634434B2 (en) | 1987-10-07 | 1987-10-07 | Circuit board |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62253128A JPH0634434B2 (en) | 1987-10-07 | 1987-10-07 | Circuit board |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0195585A JPH0195585A (en) | 1989-04-13 |
JPH0634434B2 true JPH0634434B2 (en) | 1994-05-02 |
Family
ID=17246892
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62253128A Expired - Lifetime JPH0634434B2 (en) | 1987-10-07 | 1987-10-07 | Circuit board |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0634434B2 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69427258T2 (en) * | 1993-03-31 | 2001-12-06 | Toray Industries, Inc. | FIBERBOARD IMPREGNATED WITH RESIN |
JP2011140150A (en) * | 2010-01-06 | 2011-07-21 | Toray Ind Inc | Laminate |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS593991A (en) * | 1982-06-29 | 1984-01-10 | 東レ株式会社 | Printed circuit board |
-
1987
- 1987-10-07 JP JP62253128A patent/JPH0634434B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH0195585A (en) | 1989-04-13 |
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