JPH0665707B2 - Improved polyimide film - Google Patents
Improved polyimide filmInfo
- Publication number
- JPH0665707B2 JPH0665707B2 JP60209668A JP20966885A JPH0665707B2 JP H0665707 B2 JPH0665707 B2 JP H0665707B2 JP 60209668 A JP60209668 A JP 60209668A JP 20966885 A JP20966885 A JP 20966885A JP H0665707 B2 JPH0665707 B2 JP H0665707B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- polyimide film
- inorganic powder
- polyimide
- weight
- 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
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、全芳香族非熱可塑性ポリイミドフイルム（以
下、単にポリイミドフイルムと略記する）に関する、 更に詳しくは、無機微細粉体を添加することにより、表
面に微細な突起を発生させ、表面状態を制御し、フイル
ムの走行性及び接着性を改良したポリイミドフイルムに
関するものである。TECHNICAL FIELD The present invention relates to a wholly aromatic non-thermoplastic polyimide film (hereinafter simply referred to as a polyimide film), and more specifically to the addition of an inorganic fine powder. The present invention relates to a polyimide film in which fine projections are generated on the surface to control the surface condition and improve the running property and adhesiveness of the film.
（従来の技術と問題点） ポリイミドフイルムは、耐熱性、耐寒性、耐薬品性、電
気絶縁性、機械的強度その他優れた諸特性を有すること
が知られており、電気絶縁フイルム、断熱フイルム、フ
レキシブルプリント配線板のベースフイルム等に広く利
用されている。ポリイミドフイルムが、これらの用途に
用いられる際の重要な実用特性の一つは走行性（易滑
性）である。様々なフイルム加工工程において、フイル
ム支持体（例へば、ロール）とフイルムの易滑性、また
はフイルム同志の易滑性が確保されることにより、各工
程における操作性、取扱い性を向上させ、更にはフイル
ム上にシワ等の不良箇所の発生が回避できる。また一
方、ポリイミドフイルムの主要用途であるフレキシブル
プリント配線板用途においては、通常、種々の接着剤を
介して銅箔と接着されているが、ポリイミドフイルム
は、その化学構造及び高度の耐薬品（溶剤）安定性によ
り銅箔との接着性が不充分な場合が多く、現状ではポリ
イミドフイルムに表面処理（アルカル処理、コロナ処
理、サンドブラスト処理等）を施し、接着されている。(Conventional Technology and Problems) Polyimide film is known to have various excellent properties such as heat resistance, cold resistance, chemical resistance, electrical insulation, mechanical strength, etc., and electrical insulation film, heat insulation film, Widely used for base films of flexible printed wiring boards. One of the important practical properties when the polyimide film is used for these applications is the running property (slipperiness). In various film processing steps, the smoothness of the film support (eg, roll) and the film, or the smoothness of the same film is secured to improve the operability and handleability in each step. It is possible to avoid the occurrence of defective parts such as wrinkles on the film. On the other hand, in flexible printed wiring board applications, which are the main applications of polyimide films, they are usually bonded to copper foil through various adhesives, but polyimide films have a chemical structure and high chemical resistance (solvent). ) In many cases, the adhesiveness to the copper foil is insufficient due to stability, and at present, the polyimide film is subjected to surface treatment (alcal treatment, corona treatment, sandblast treatment, etc.) and adhered.
本発明者は、これらの市場要求に対し鋭意研究の結果、
走行性（易滑性）と接着性の改善を同時に達成した、改
良されたポリイミドフイルムを見出し、本発明に到達し
た。The present inventor, as a result of earnest research on these market requirements,
The present invention has been accomplished by finding an improved polyimide film which simultaneously achieves improvement in running property (slippery property) and adhesiveness.
従来のポリエステルフイルムにおける易滑化技術では、
不活性無機化合物（例えば、シリカ、クレイ、チタニア
等）や有機化合物（例えば、テレフタル酸カルシウム、
高融点ポリエステル）を添加するか、及び又は触媒残渣
を利用してフイルム表面に突起を形成する方法がとられ
ている。更には、不活性無機化合物等が添加されたポリ
エステルフイルムを加熱下に一軸方向又は二軸方向に延
伸し、表面に形成される突起の数を増加させ、また突起
の高さを調整している。これらの方法は、積極的に表面
に突起を発生させ、フイルム表面の摩擦係数を低減させ
ることにより、易滑化効果を得るものであるが、フイル
ム表面の摩擦係数の低減には表面に高く大きな突起を数
多く生成させることが有効である。この場合、無機又は
有機の微細粒子、もしくは触媒残渣粒子を樹脂に多量に
添加すればする程、表面上の突起の数は増えるが、その
反面フイルムの機械的強度の低下をまねき、フイルム品
質の不均一さを増加させるという問題点がある。In the conventional slipping technology for polyester film,
Inert inorganic compounds (eg silica, clay, titania, etc.) and organic compounds (eg calcium terephthalate,
A high melting point polyester) is added and / or a catalyst residue is used to form protrusions on the film surface. Furthermore, a polyester film to which an inert inorganic compound or the like is added is stretched uniaxially or biaxially under heating to increase the number of protrusions formed on the surface and adjust the height of the protrusions. . These methods obtain a slippery effect by positively generating protrusions on the surface and reducing the friction coefficient of the film surface, but in order to reduce the friction coefficient of the film surface, it is high and large. It is effective to generate many protrusions. In this case, the more inorganic or organic fine particles or catalyst residue particles are added to the resin, the more the number of protrusions on the surface increases, but on the other hand, the mechanical strength of the film is reduced and the film quality is reduced. There is a problem of increasing non-uniformity.
（問題点を解決するための手段） 本発明は、厳密に粒度の調整された粒径が１〜５μｍを
主体とした無機粉体を、フイルム樹脂中に樹脂重量当
り、0.1〜0.5重量％均一に分散させてなるポリイミドフ
イルムを内容とし、その機械的特性及びその他の物性を
低下させずに表面に制御された突起を発生させることを
見出し、電子関連部品の素材として高度の信頼性が要求
されるポリイミドフイルムの物性を維持したまま、フイ
ルム表面の摩擦係数を低減することによりフイルムの走
行性（易滑性）を改善し、更には微細な表面粗さの制御
を可能にし、ポリイミドフイルムを接着剤を介し銅箔と
接着した際の接着強度の向上を達成したものである。以
下に、本発明の詳細を説明する。(Means for Solving Problems) In the present invention, an inorganic powder whose particle size is strictly adjusted and whose particle size is 1 to 5 μm is uniformly contained in a film resin in an amount of 0.1 to 0.5% by weight based on the resin weight. It is found that the content of the polyimide film is a controlled protrusion on the surface without deteriorating its mechanical properties and other physical properties, and high reliability is required as a material for electronic parts. While maintaining the physical properties of the polyimide film, the friction coefficient of the film surface is reduced to improve the running property (easiness of sliding) of the film, and it is also possible to control the fine surface roughness and bond the polyimide film. The adhesive strength is improved when it is bonded to the copper foil via the agent. The details of the present invention will be described below.
従来のポリエステルフイルムにおける走行性改善技術で
は、前記した通り、不活性無機化合物（例えば、シリ
カ、クレイ、チタニア等）や有機化合物（例えば、テレ
フタル酸カルシウム、高融点ポリエステル）を添加する
か、又は（及び）触媒残渣を利用してフイルム表面に突
起を形成するのに対し、本発明は、表面の微細な突起、
または表面粗さを制御することに注目し、極めて粒度分
布の制御された無機粉体を用いることによりフイルム表
面に突起を形成すると共に、表面粗さを調整し、フイル
ム走行性と接着剤を介した銅箔との接着強度とを同時に
改善する利点を有する。In the conventional technology for improving the running property of a polyester film, as described above, an inert inorganic compound (eg, silica, clay, titania, etc.) or an organic compound (eg, calcium terephthalate, high melting point polyester) is added, or ( And) forming protrusions on the film surface using the catalyst residue, the present invention provides fine protrusions on the surface,
Or, paying attention to controlling the surface roughness, the protrusions are formed on the film surface by using the inorganic powder whose particle size distribution is extremely controlled, and the surface roughness is adjusted, and the film running property and the adhesive are used. It has the advantage of simultaneously improving the adhesive strength with the formed copper foil.
ポリエステルフイルムにおける表面上の突起の形成で
は、一軸または二軸方向の加熱下延伸により突起の増大
及び調整が行なわれるのに対し、本発明は、無延伸のポ
リイミドフイルム表面上の突起の制御が可能である。ま
た、その物性上、引裂抵抗（引きさき強度）が低いこと
が問題とされるポリイミドフイルムにおいて、無機粉体
を添加することは実質的に引裂開始点を形成することに
なり、フイルム物性の大巾な低下が懸念されるが、本発
明はフイルム物性に影響を与えず、かつ表面上の突起形
成に有効な添加粉体の粒度領域を見出し、該問題を解決
した。In the formation of projections on the surface of a polyester film, the projections are increased and adjusted by uniaxially or biaxially heating and stretching, whereas the present invention can control the projections on an unstretched polyimide film surface. Is. In addition, in a polyimide film, which has a problem of low tear resistance (pulling strength) due to its physical properties, the addition of an inorganic powder substantially forms a tear initiation point, and the physical properties of the film are large. The present invention has solved the problem by finding a grain size range of the added powder which does not affect the physical properties of the film and is effective for forming protrusions on the surface, although there is a concern that the width may decrease significantly.
本発明が適用できるポリイミドフイルムとは、芳香族テ
トラカルボン酸二無水物と芳香族ジアミンまたは、この
両者を主成分とする化学物質を、N,N−ジメチルホルム
アミド、N,N−ジメチルアセトアミド、ジメチルスルホ
オキサイド、ｎ−メチルピロリドの如き極性溶媒中で付
加重合されたワニス状ポリアミド酸溶液を用い、該ワニ
ス状ポリアミド酸溶液と無水酢酸を主成分とする脱水環
化試剤とを混合した後、支持体上に流延させ、支持体上
で予備乾燥の上、拘束下で高温加熱することにより、脱
溶媒とイミド環閉環を同時に進行させる化学的転化法に
より得られるフイルムである。また、該ワニス状ポリア
ミド酸溶液を該脱水環化試剤と反応させ、ワニス状態を
維持したままイミド環を完全または部分的に閉環させた
後、該ワニス状ポリイミド溶液を支持体上に流延し、支
持体上で予備乾燥の上、拘束下に高温加熱することによ
り、脱溶媒とイミド環閉環を行ない製膜されるフイルム
も、本発明の適用できるポリイミドフイルムに含まれ
る。The polyimide film to which the present invention can be applied is an aromatic tetracarboxylic dianhydride and an aromatic diamine, or a chemical substance containing both of them as main components, N, N-dimethylformamide, N, N-dimethylacetamide, and dimethyl. A varnish-like polyamic acid solution that has been addition-polymerized in a polar solvent such as sulfoxide or n-methylpyrrolide is used, and the varnish-like polyamic acid solution is mixed with a dehydration cyclization agent containing acetic anhydride as a main component, and then a support is prepared. The film is obtained by a chemical conversion method in which the solvent is cast and the imide ring is closed at the same time by casting on the support, predrying on the support, and heating at high temperature under restraint. Further, the varnish-like polyamic acid solution is reacted with the dehydration cyclization reagent to completely or partially close the imide ring while maintaining the varnish state, and then the varnish-like polyimide solution is cast on a support. The polyimide film to which the present invention can be applied also includes a film formed by carrying out desolvation and imide ring closure by predrying on a support and heating at a high temperature under restraint.
本発明のフイルム表面上に突起を形成させるために樹脂
に添加される無機微細粉体は、前記のポリイミドフイル
ム製造工程で接触する全ての化学物質に対して不活性で
あることが必要であり、また不溶である必要がある。本
発明者は鋭意検討の結果、IIa族のアルカリ土類金属（B
e,Mg,Ca,Sr及びRa）のオルトリン酸塩化合物が該ワニス
状組成物及びポリイミドフイルム中で化学的及び物理的
に安定であり、ポリイミドフイルムの諸物性に影響を与
えないことを見出した。更に好ましくは、IIa族のアル
カリ土類金属のオルトリン酸塩化合物粉体として第２リ
ン酸カルシウム無水物（CaHPO4）又は（及び）ピロリン
酸カルシウム（Ca2P2O7）を用いた場合が、該ワニス状
溶液及び該ポリイミドフイルム中での均一分散性が良好
である。即ち本発明において、該ワニス状溶液及び該ポ
リイミドフイルム中において化学的及び物理的に安定で
あり、また分散性が良好で極めて均一に分散し、更には
該ポリイミドフイルム製造工程中の全般を通じ化学的及
び物理的に安定である無機粉体を用いることが、ポリイ
ミドフイルムの諸物性に影響又は変化を与えず、ポリイ
ミドフイルム表面に微細な突起を形成するために必須で
ある。The inorganic fine powder added to the resin to form protrusions on the film surface of the present invention is required to be inert to all chemical substances contacted in the polyimide film manufacturing process, It must also be insoluble. As a result of diligent study, the present inventor has found that a group IIa alkaline earth metal (B
It was found that orthophosphate compounds (e, Mg, Ca, Sr and Ra) are chemically and physically stable in the varnish-like composition and the polyimide film and do not affect the physical properties of the polyimide film. . More preferably, when the dibasic calcium phosphate anhydrous (CaHPO 4 ) or (and) calcium pyrophosphate (Ca 2 P 2 O 7 ) is used as the group IIa alkaline earth metal orthophosphate compound powder, the varnish The uniform dispersibility in the solution and the polyimide film is good. That is, in the present invention, it is chemically and physically stable in the varnish-like solution and the polyimide film, has good dispersibility and is extremely uniformly dispersed, and further chemically throughout the polyimide film manufacturing process. It is essential to use a physically stable inorganic powder in order to form fine projections on the surface of the polyimide film without affecting or changing the physical properties of the polyimide film.
本発明における、ポリイミドフイルムの表面に突起を形
成するために添加される無機粉体の粒径は１〜５μｍを
主体としたものが採用される。１μｍ以上、５μｍ以下
の範囲にある場合、該ポリイミドフイルムの機械的物性
の低下を発生させず、任意に無機粉体の添加量を調節す
ることが出来、フイルム表面上の突起の形成（フイルム
表面粗さ）の微妙な制御が可能となる。即ち、通常7.5
μ〜125μの厚み範囲において用いられるポリイミドフ
イルムに対し、粒径が５μｍをこえて大きな粒径の無機
粒子を添加することは、フイルム表面上に突起を形成す
るには有効であるが、実質的にはフイルムに物理的損傷
を与えていることに等しくなり、フイルムの機械的強度
を低下させる。また粒径が１μｍ未満の無機粒子の添加
は、フイルムの機械的物性には影響が少ないが、表面上
に走行性（易滑性）及び接着性の改善に有効な大きさの
突起を形成することができず、粒径が１μｍ未満の粒度
の粒子を多量に含む無機粉体を用いる場合は不必要な添
加量の増大をまねく。In the present invention, the particle size of the inorganic powder added to form the protrusions on the surface of the polyimide film is mainly 1 to 5 μm. When the thickness is in the range of 1 μm or more and 5 μm or less, the mechanical properties of the polyimide film are not deteriorated, and the addition amount of the inorganic powder can be arbitrarily adjusted to form protrusions on the film surface (film surface). Delicate control of (roughness) is possible. That is, usually 7.5
The addition of inorganic particles with a particle size of more than 5 μm to the polyimide film used in the thickness range of μ to 125 μ is effective for forming protrusions on the film surface, but it is substantially effective. Is equivalent to physically damaging the film, reducing the mechanical strength of the film. Further, the addition of inorganic particles having a particle size of less than 1 μm has little effect on the mechanical properties of the film, but forms protrusions of a size effective on improving the running property (slippery property) and the adhesive property on the surface. However, when an inorganic powder containing a large amount of particles having a particle size of less than 1 μm is used, an unnecessary addition amount is increased.
本発明によれば、該ポリイミドフイルムに無機粉体を添
加する場合の添加量が、対フイルム樹脂重量当り、0.1
〜0.5重量％の範囲で添加する場合、走行性（易滑性）
及び接着性の向上に有効である。即ち無機粉体の添加量
が、対フイルム樹脂重量当り、0.1〜0.5重量％の範囲に
ある場合、該ポリイミドフイルムの諸特性に変化を与え
ず、フイルムの均一性を保持したまま、走行性（易滑
性）及び接着性の優れたポリイミドフイルムが得られ
る。無機粉体の添加量が、対フイルム樹脂重量当り、0.
1重量％未満の場合は、フイルム表面に形成される突起
の数が少なく、走行性（易滑性）及び接着性の改善効果
が低い。また、0.5重量％をこえた場合は、走行性（易
滑性）及び接着性の改善効果はあるが、フイルム樹脂中
での無機粉体の均一分散が困難となり、該ポリイミドフ
イルムの諸物性の均質性が損なわれる。According to the present invention, when the inorganic powder is added to the polyimide film, the addition amount is 0.1, based on the weight of the film resin.
When added in the range of ~ 0.5% by weight, the running property (slipperiness)
It is also effective in improving the adhesiveness. That is, when the amount of the inorganic powder added is in the range of 0.1 to 0.5% by weight based on the weight of the film resin, various properties of the polyimide film are not changed and the running property is maintained while maintaining the uniformity of the film. A polyimide film excellent in slipperiness) and adhesiveness can be obtained. The amount of inorganic powder added was 0, based on the weight of the film resin.
When it is less than 1% by weight, the number of projections formed on the film surface is small, and the effect of improving the running property (slippery property) and the adhesive property is low. Further, when it exceeds 0.5% by weight, there is an effect of improving runnability (sliding property) and adhesiveness, but it becomes difficult to uniformly disperse the inorganic powder in the film resin, and various physical properties of the polyimide film The homogeneity is impaired.
本発明において、実用特性として充分な走行性（易滑
性）が得られるのは、ASTM Ｄ−1894−63に基づく測定
で動摩擦係数が0.50以下の場合である。In the present invention, sufficient practical running characteristics (sliding property) can be obtained when the dynamic friction coefficient is 0.50 or less as measured by ASTM D-1894-63.
本発明においては、上記した無機粉体を添加することに
よりフイルム表面上に所望の突起が形成され、接着剤を
介して銅箔と接着された際の接着強度が向上する。フイ
ルム表面の表面粗さを中心線平均粗さ＜Ra＞で表わした
場合、無機粉体を添加しない場合のフイルムの表面粗さ
がRa＝0.006〜0.012μｍの範囲にあるのに対し、接着性
改善の効果が発現されるのは、無機粉体を添加し、フイ
ルム表面上に突起が形成されることによりフイルムの表
面粗さがRa≧0.018となつた場合であり、実用的に充分
な接着強度が得られるのはRa≧0.025μｍの場合であ
る。また、Ra値が大きくなると共に、接着性も向上する
が、Ra値が0.055μｍをこえると接着性の改善効果はそ
れ以上向上しにくくなる。フイルムの表面粗さは、添加
する無機粉体の量を調節することにより任意に制御でき
る。即ち、フイルム表面を無機粉体を添加することによ
り粗化することができ、サンドブラスト処理等で接着面
を粗化し、接着力を向上させている従来の方法と同等の
効果が得られる。また更に、フイルム表面を均一に粗化
するためには、極めて粒度分布の制御された無機粉体を
用いる必要がある。In the present invention, by adding the above-mentioned inorganic powder, desired projections are formed on the film surface, and the adhesive strength when bonded to the copper foil via the adhesive is improved. When the surface roughness of the film surface is expressed by the center line average roughness <Ra>, the film surface roughness without adding inorganic powder is in the range of Ra = 0.006 to 0.012 μm, while the adhesiveness is The improvement effect is exhibited when the surface roughness of the film is Ra ≧ 0.018 due to the addition of the inorganic powder and the formation of protrusions on the surface of the film. The strength is obtained when Ra ≧ 0.025 μm. Further, the Ra value increases and the adhesiveness improves, but when the Ra value exceeds 0.055 μm, the effect of improving the adhesiveness is further difficult to improve. The surface roughness of the film can be arbitrarily controlled by adjusting the amount of inorganic powder added. That is, the surface of the film can be roughened by adding an inorganic powder, and the same effect as the conventional method in which the adhesive surface is roughened by sandblasting or the like to improve the adhesive strength can be obtained. Furthermore, in order to uniformly roughen the film surface, it is necessary to use an inorganic powder having an extremely controlled particle size distribution.
本発明における物性測定法は次の通りである。The physical property measuring methods in the present invention are as follows.
（ａ） フイルム表面粗さの測定 JIS Ｂ−0601「表面あらさ」に基づき、触針式表面素
さ測定器で測定。Ra（中心線平均粗さ）値の測定の場合
のカツトオフ値は0.25mmである。(A) Measurement of film surface roughness Measured with a stylus type surface roughness measuring device based on JIS B-0601 "Surface roughness". The cut-off value for the measurement of Ra (center line average roughness) value is 0.25 mm.
（ｂ） フイルム機械強度（抗張力、伸び率） ASTM Ｄ−882−80に基づき、オートグラフ装置で測定
する。(B) Film mechanical strength (tensile strength, elongation) Measured by an autograph device according to ASTM D-882-80.
（ｃ） 摩擦係数（Uk:動摩擦係数） ASTM Ｄ−1894−63に基づき、フイルムの機械方向に測
定する。(C) Coefficient of friction (Uk: dynamic friction coefficient) Measured in the machine direction of the film based on ASTM D-1894-63.
（ｄ） 接着強度 JIS Ｃ−6481（1976）印刷回路用銅張積層板試験方法
5.7項ひきはがし試験に基づき、ポリイミドフイルムと
銅箔をエポキシ／ナイロン系接着剤で接着し、160℃で1
2時間硬化させた後、硬質板の上にフイルム面を固定
し、測定する。(D) Adhesive strength JIS C-6481 (1976) Test method for copper clad laminates for printed circuits
Section 5.7 Based on the peeling test, bond the polyimide film and copper foil with epoxy / nylon adhesive and
After curing for 2 hours, fix the film surface on the hard plate and measure.
（ｅ） 無機粉体の粒度分布 コールターカウンターTAII型を用い、電解質溶液（例え
ば、イソトン）中に粉体を分散させたものをアパチヤー
径、23μｍで測定。(E) Particle size distribution of inorganic powder: Coulter counter TAII type was used to measure powder having an aperture diameter of 23 μm, which was obtained by dispersing powder in an electrolyte solution (for example, Isoton).
（実施例） 以下、実施例により本発明を具体的に説明する。(Examples) Hereinafter, the present invention will be specifically described with reference to Examples.
比較例１ N,N−ジメチルホルムアミド中、ピロメリツト酸２無水
物と4,4′−ジアミノジフエニルエーテルとの概略等モ
ルを反応させ、ワニス状ポリアミド酸溶液を得た。然る
後、該ポリアミド酸溶液を連続製膜装置を用い、ポリイ
ミドに転化すると同時に乾燥固化し、ポリイミドフイル
ムとし、25μｍ公称厚みのポリイミドフイルムを得た。Comparative Example 1 In N, N-dimethylformamide, approximately equimolar amounts of pyromellitic acid dianhydride and 4,4'-diaminodiphenyl ether were reacted to obtain a varnish-like polyamic acid solution. Then, the polyamic acid solution was converted into polyimide using a continuous film forming apparatus and simultaneously dried and solidified to obtain a polyimide film, and a polyimide film having a nominal thickness of 25 μm was obtained.
実施例１〜２ 比較例１と同一の原料、同一の方法により得られたワニ
ス状ポリアミド酸溶液に、粒径において１μｍ未満及び
５μｍ以上が除去された平均粒径が25μｍの無水第２リ
ン酸カルシウム（CaHPO4）又はピロリン酸カルシウム
（Ca2P2O7）を、対フイルム樹脂重量当り、0.1重量％添
加し、充分に攪拌、分散させた後、比較例１と同一の方
法にて、25μｍ公称厚さのポリイミドフイルムを得た。Examples 1 and 2 Anhydrous dibasic calcium phosphate having an average particle size of 25 μm obtained by removing less than 1 μm and 5 μm or more in particle size in a varnish-like polyamic acid solution obtained by the same raw material and the same method as in Comparative Example 1 ( CaHPO 4 ) or calcium pyrophosphate (Ca 2 P 2 O 7 ) was added in an amount of 0.1% by weight based on the weight of the film resin, and the mixture was sufficiently stirred and dispersed. Thus, a polyimide film was obtained.
実施例３〜６ 比較例１と同一の原料及び実施例１と同一の無機粉体を
用い、ワニス状ポリアミド酸溶液に無機粉体を添加する
際の添加量を、対フイルム重量当り、0.2重量％及び0.5
重量％とし、比較例１と同じ方法で、それぞれ25μｍ公
称厚みのポリイミドフイルムを得た。Examples 3 to 6 Using the same raw materials as in Comparative Example 1 and the same inorganic powder as in Example 1, the addition amount when the inorganic powder was added to the varnish-like polyamic acid solution was 0.2% based on the weight of the film. % And 0.5
In the same manner as in Comparative Example 1, a polyimide film having a nominal thickness of 25 μm was obtained, in which the content of the polyimide film was 25 wt%.
比較例２〜３ 比較例１と同一の原料、同一の方法により得られたワニ
ス状ポリアミド酸溶液に粒度分布が0.1〜25μｍで平均
粒度が11.3〜12.0μｍの無水第２リン酸カルシウム（Ca
HPO4）又はピロリン酸カルシウム（Ca2P2O7）を、対フ
イルム樹脂重量当り、0.2重量％添加し、充分に攪拌、
分散させた後、比較例１と同一の方法にて25μｍ公称厚
さのポリイミドフイルムを得た。Comparative Examples 2-3 Anhydrous dibasic calcium phosphate (Ca) having a particle size distribution of 0.1 to 25 μm and an average particle size of 11.3 to 12.0 μm was added to a varnish-like polyamic acid solution obtained by the same raw material and the same method as in Comparative Example 1.
HPO 4 ) or calcium pyrophosphate (Ca 2 P 2 O 7 ) was added in an amount of 0.2% by weight based on the weight of the film resin, and the mixture was sufficiently stirred,
After being dispersed, a polyimide film having a nominal thickness of 25 μm was obtained by the same method as in Comparative Example 1.
比較例４〜５ 比較例１と同一の原料及び実施例１と同一の無機粉体を
用い、ワニス状ポリアミド酸溶液に粉体を添加する際の
添加量を、対フイルム重量当り、0.7重量％とし、比較
例１と同じ方法で、それぞれ25μｍ公称厚みのポリイミ
ドフイルムを得た。Comparative Examples 4 to 5 Using the same raw materials as in Comparative Example 1 and the same inorganic powder as in Example 1, the addition amount of the powder to the varnish-like polyamic acid solution was 0.7% by weight based on the weight of the film. In the same manner as in Comparative Example 1, polyimide films each having a nominal thickness of 25 μm were obtained.
実施例１〜６、比較例１〜５において、得られたポリイ
ミドフイルムの機械的物性、走行性及び接着性評価結果
を表１に示す。Table 1 shows the results of evaluation of mechanical properties, running properties and adhesiveness of the polyimide films obtained in Examples 1 to 6 and Comparative Examples 1 to 5.
（効果） 表１から明らかな通り、粒径が１〜５μｍを主体とした
無機粉体を対フイルム樹脂重量当り0.1〜0.5重量％含む
本発明のポリイミドフイルムは、ポリミイド固有の物性
を保持し、しかも表面を易滑性にして、接着性が顕著に
向上する。従つて、フレキシブルプリント配線板用途等
広い分野で好適に使用できる。(Effect) As is apparent from Table 1, the polyimide film of the present invention containing 0.1 to 0.5% by weight of the inorganic powder mainly having a particle size of 1 to 5 μm with respect to the film resin weight retains the physical properties peculiar to polymide, Moreover, the surface is made slippery, and the adhesiveness is remarkably improved. Therefore, it can be suitably used in a wide variety of fields such as flexible printed wiring board applications.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭59−108058（ＪＰ，Ａ) 特開 昭60−228557（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP 59-108058 (JP, A) JP 60-228557 (JP, A)
Claims (4)
を、対フイルム樹脂重量当り、0.1乃至0.5重量％含むこ
とを特徴とする全芳香族非熱可塑性ポリイミドフイル
ム。1. A wholly aromatic non-thermoplastic polyimide film comprising an inorganic powder mainly having a particle size of 1 to 5 μm in an amount of 0.1 to 0.5% by weight based on the weight of the film resin.
オルトリン酸塩である特許請求の範囲第１項記載の全芳
香族非熱可塑性ポリイミドフイルム。2. The wholly aromatic non-thermoplastic polyimide film according to claim 1, wherein the inorganic powder is an orthophosphate of a Group IIa alkaline earth metal.
塩が第２リン酸カルシウム無水物（CaHPO4）である特許
請求の範囲第２項記載の全芳香族非熱可塑性ポリイミド
フイルム。3. A wholly aromatic non-thermoplastic polyimide film according to claim 2, wherein the group IIa alkaline earth metal orthophosphate is dicalcium phosphate anhydrous (CaHPO 4 ).
塩がピロリン酸カルシウム（Ca2P2O7）である特許請求
の範囲第２項記載の全芳香族非熱可塑性ポリイミドフイ
ルム。4. A wholly aromatic non-thermoplastic polyimide film as claimed in claim 2, wherein the group IIa alkaline earth metal orthophosphate is calcium pyrophosphate (Ca 2 P 2 O 7 ).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60209668A JPH0665707B2 (en) | 1985-09-20 | 1985-09-20 | Improved polyimide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60209668A JPH0665707B2 (en) | 1985-09-20 | 1985-09-20 | Improved polyimide film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6268852A JPS6268852A (en) | 1987-03-28 |
| JPH0665707B2 true JPH0665707B2 (en) | 1994-08-24 |
Family
ID=16576623
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60209668A Expired - Lifetime JPH0665707B2 (en) | 1985-09-20 | 1985-09-20 | Improved polyimide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0665707B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005268364A (en) * | 2004-03-17 | 2005-09-29 | Shindo Denshi Kogyo Kk | Flexible circuit board and method for fixing the same |
| US7658791B2 (en) * | 2004-11-17 | 2010-02-09 | Dai Nippon Toryo Co., Ltd. | Anticorrosive coating compositions |
| KR101137274B1 (en) | 2005-04-04 | 2012-04-20 | 우베 고산 가부시키가이샤 | Copper clad laminate |
| KR100839760B1 (en) * | 2006-02-06 | 2008-06-19 | 주식회사 엘지화학 | Copper clad laminate for chip on film |
| JP2010126634A (en) | 2008-11-27 | 2010-06-10 | Du Pont Toray Co Ltd | Polyimide film and method for producing the same |
| JP6423633B2 (en) | 2014-07-11 | 2018-11-14 | 東レ・デュポン株式会社 | Polyimide film for graphite sheet and method for producing the same |
| JP6735542B2 (en) | 2015-08-25 | 2020-08-05 | 東レ・デュポン株式会社 | Polyimide film and manufacturing method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59108058A (en) * | 1982-12-14 | 1984-06-22 | Toray Ind Inc | Polyester composition |
| JPS60228557A (en) * | 1984-04-27 | 1985-11-13 | Sumitomo Bakelite Co Ltd | Polyarylene polyether polyimide film |
-
1985
- 1985-09-20 JP JP60209668A patent/JPH0665707B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6268852A (en) | 1987-03-28 |
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