JP2006290978A - Aromatic polyamide film and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aromatic polyamide film suitably usable as a plastic material used for a solder application such as a flexible circuit board and a TAB (tape automated bonding) tape substrate. <P>SOLUTION: The aromatic polyamide film is a monolayer or laminated film containing a metal or a metal compound and an aromatic polyamide as main components, and has at least one layer containing ≥10 and ≤70 wt.% metal selected from aluminum, vanadium, iron, nickel, copper, palladium and manganese, or metal compound thereof. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an aromatic polyamide film that can be suitably used as a plastic material used for soldering such as a flexible circuit board and a TAB tape substrate, and a method for producing the same.

  In the electric and electronic industries, the use of flexible printed circuit boards is increasing due to the reduction in size and weight of equipment and the advancement of required functions. A general configuration of a flexible printed circuit board is one in which an electric circuit is formed on one or both sides of a substrate film, and a cover film or an insulating resist is laminated on the circuit. Conventionally, a polyimide film or a polyester film is used as a substrate film. When solder resistance is required, it is necessary to handle the film at a high temperature of about 260 ° C., and a polyimide film having excellent heat resistance is mainly used. ing. However, it is difficult to reduce the thickness of a polyimide film from the viewpoints of mechanical strength and bending resistance, and therefore it is difficult to meet the demand for further miniaturization and weight reduction of equipment.

  The aromatic polyamide film has heat resistance next to polyimide and has high rigidity, so that it is easy to make a thin film, and it is expected to realize a flexible printed circuit board that is superior not only in performance but also in cost. An example of a flexible printed circuit board using an aromatic polyamide film is described in Patent Document 1. However, the film has insufficient solder heat resistance, and when used at a high temperature such as a solder application, the flatness such as curl may be deteriorated.

  On the other hand, in the synthesis of aromatic polyamide, the addition of a metal compound is widely performed, but most of them are addition of an alkali metal or alkaline earth metal halogen salt as a polymer dissolution aid, or The purpose is to add particles as an easy-to-lubricant, and no examples have been found in which mechanical and thermal properties are improved by the metal contained in the film.

  Patent Document 2 discloses that an alkali metal or alkaline earth metal halogen salt is added as a dissolution aid. This is effective in improving the solubility during polymerization, but the metal flows out in the washing step after spinning, hardly remains in the molded product, and is ineffective in improving heat resistance.

  Patent Document 3 has a layer containing metal ions selected from Group Ia (Group 1), Group IIa (Group 2), Group IIIa (Group 3), and 2 ppm or more and 2,000 ppm or less to prevent charging. In addition, Patent Document 4 discloses a technique for imparting easy slipperiness to a film by adding particles, but heat resistance is not improved even if these metals are used.

Patent Document 5 discloses that by containing a metal or a metal compound in an aromatic polyamide in a proportion of 0.5% by weight or more and 10% by weight or less based on a polymer, tensile modulus and tensile elongation are high, and surface roughness is further increased. It is disclosed to obtain a low film. However, although the film obtained by the invention has improved tensile elastic modulus, tensile elongation and surface smoothness, it cannot be said that the heat resistance is sufficient, and the flatness deteriorates due to the temperature applied in the process when used in soldering. There was a problem to do.
JP-A-6-350210 Japanese Examined Patent Publication No. 4-23007 JP-A-8-225664 JP 2001-273623 A JP 2004-269555 A

  The present invention has been achieved as a result of studying the solution of the problems in the prior art described above as an issue. That is, an object of the present invention is to provide a thin aromatic polyamide film having solder heat resistance.

  The object includes aromatic polyamide and at least one metal or metal compound selected from the group consisting of aluminum, vanadium, iron, nickel, copper, palladium and manganese, and the total content of these metals and metal compounds Is achieved by an aromatic polyamide film having at least one layer of 10 wt% or more and 70 wt% or less.

  Since the aromatic polyamide film of the present invention is a thin film and has solder heat resistance, it can be suitably used as a plastic material used for soldering such as a flexible circuit board and a TAB tape board.

  The aromatic polyamide film of the present invention contains at least one metal or metal compound selected from the group consisting of aluminum, vanadium, iron, nickel, copper, palladium and manganese, and its total content (metal content relative to film weight) (Amount + content of metal compound) of at least one layer of 10 wt% or more and 70 wt% or less. In order to further improve heat resistance, the total content is more preferably 12% by weight to 60% by weight, further preferably 15% by weight to 50% by weight, and more preferably 15% by weight to 30% by weight. . If it is less than 10% by weight, sufficient heat resistance cannot be obtained, and planarity may be lowered when used for soldering. On the other hand, if it exceeds 70% by weight, the raw material solution cannot be uniformly mixed with metal or metal compound, and film formation may be difficult. Even in the case where a film is obtained, the mechanical strength and elongation of the film may be reduced due to the agglomerated metal or metal compound, and the film may be easily broken and productivity may be reduced. The amount of metal contained can be quantified by flameless atomic absorption spectrophotometry or ICP-MS method. Further, the valence of the contained metal can be determined by an X-ray photoelectron spectrometer (ESCA). Therefore, when the metal compound contained in the film is a metal oxide, the amount of the metal compound can be calculated from these results. In the case of other than an oxide, the amount of the metal compound may be determined after identifying the metal compound using an X-ray diffractometer or the like.

  The aromatic polyamide film of the present invention is preferably 1% or less of the absolute value of the dimensional change rate of the sample from 25 ° C. to 260 ° C. More preferably, it is 0.8% or less, More preferably, it is 0.5% or less. If it exceeds 1%, the planarity may deteriorate when used for soldering. Even if the planarity does not deteriorate, the circuit may be disconnected due to a dimensional change. Furthermore, lead-free solder may be used in recent years due to environmental considerations. In this case, the heat resistance required for the film is even higher, and the absolute value of the dimensional change rate from 25 ° C. to 280 ° C. is 1% or less. It is preferable. In order to reduce the dimensional change rate of the film, it is effective to contain at least one metal or metal compound selected from the group consisting of aluminum, vanadium, iron, nickel, copper, palladium and manganese in the film. . In particular, the inclusion of copper or copper oxide is preferable because it is effective in reducing the dimensional change rate and improving the heat resistance.

  In this case, it is preferable that the film has at least one layer containing copper or copper oxide, and the total content of these copper and copper oxide is 15 wt% or more and 50 wt% or less.

  The dimensional change rate can be measured using, for example, TMA, SS6000 (manufactured by Seiko Instruments Inc.).

  It is preferable that the aromatic polyamide of the present invention has a structure represented by chemical formula (I) and chemical formula (II) because it can be dissolved in a polar solvent and it is easy to contain a metal or a metal compound in the film.

X: Arbitrary halogen atom The aromatic polyamide film of the present invention has a Young's modulus (tensile modulus) in at least one direction of 10 to 20 GPa, and can resist the force applied during use during processing. This is preferable because the properties are further improved. Further, when the Young's modulus in at least one direction is 10 GPa or more, the film can be thinned.

  If the Young's modulus in all directions is less than 10 GPa, deformation may occur during processing when the thin film is formed. On the other hand, if the Young's modulus exceeds 20 GPa, the toughness of the film decreases, and film formation and processing may be difficult. The Young's modulus in at least one direction is more preferably 11 to 20 GPa, and further preferably 12 to 20 GPa.

  In the aromatic polyamide film of the present invention, it is particularly preferable that the longitudinal direction and the width direction are 10 GPa or more, and that the Young's modulus in all directions is 10 GPa or more.

  The Young's modulus can be measured using, for example, Robot Tensilon RTA-100 (manufactured by Orientec). The measurement conditions are a sample width of 10 mm, a sample length of 50 mm, a tensile speed of 300 mm / min, 23 ° C., and 65% RH.

The aromatic polyamide film of the present invention has a moisture absorption rate at 25 ° C./75 RH% of 5% or less, more preferably 4% or less, and even more preferably 2% or less. This is preferable because the change in the number is reduced. The moisture absorption here is measured by the method described below. First, about 0.5g of the film was sampled and heated for 3 hours at 120 ° C for dehumidification. Then, the temperature was lowered to 25 ° C so as not to absorb moisture. (The weight at this time is defined as W ₀ ). Then, allowed to stand 25 ° C. 48 hours under an atmosphere of 75 RH%, the subsequent weight was measured, this as W _1, determine the moisture absorption using the following equation.

Moisture absorption rate (%) = ((W ₁ −W ₀ ) / W ₀ ) × 100
In addition, although the one where a moisture absorption is lower is preferable, realistically, a minimum is about 0.03%.

  Further, the aromatic polyamide film of the present invention has a elongation at break in at least one direction of 5 to 200%, more preferably 10 to 100% in the measurement based on JIS-C2318. This is preferable because breakage is reduced.

  The aromatic polyamide film of the present invention preferably has a relative dielectric constant of 4 or less at 1 kHz. More preferably, it is 3.5 or less, and most preferably 2 or less. Since the relative dielectric constant is small, signal delay can be reduced when the film of the present invention is used as an electronic circuit board.

  The film of the present invention can be produced, for example, by the following method, but the present invention is not limited to this.

  As a method for obtaining the aromatic polyamide, various methods used for the aromatic polyamide can be used. For example, a low temperature solution polymerization method, an interfacial polymerization method, a melt polymerization method, a solid phase polymerization method and the like can be used. When it is obtained from a low temperature solution polymerization method, ie, acid dichloride and diamines, they are synthesized in an aprotic organic polar solvent. The reaction between isocyanate and carboxylic acid is carried out in an aprotic organic polar solvent in the presence of a catalyst. At this time, in order to suppress the formation of low molecular weight substances, mixing of water and other substances that inhibit the reaction should be avoided, and it is preferable to take efficient stirring means.

  Examples of the aprotic polar solvent used in the production of the aromatic polymer of the present invention include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, and formamides such as N, N-dimethylformamide and N, N-diethylformamide. Solvents, acetamide solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m- Alternatively, phenolic solvents such as p-cresol, xylenol, halogenated phenol, catechol, hexamethylphosphoramide, γ-butyrolactone, etc. can be mentioned, and these are preferably used alone or as a mixture. Toluene's The use of such aromatic hydrocarbons are also possible.

  The intrinsic viscosity of the polymer (value measured at 30 ° C. in a 100 ml solution of 0.5 g of polymer in sulfuric acid) is preferably 0.5 or more.

  It is also possible to add an inorganic salt such as calcium chloride, magnesium chloride, lithium chloride, lithium nitrate, lithium bromide or the like as a dissolution aid to the polymer stock solution for obtaining a molded body. As the inorganic salt, halogen salts of Group 1 (alkali metal) and Group 2 (alkaline earth metal) are preferable.

  When aromatic diacid chloride and aromatic diamine are used as monomers, hydrogen chloride is by-produced. When neutralizing this, a cation, hydroxide ion or carbonate ion of Group I or Group II of the Periodic Table is used. Inorganic neutralizers represented by salts composed of anions such as ethylene oxide, propylene oxide, ammonia, triethylamine, triethanolamine, and diethanolamine are used. Further, for the purpose of improving the humidity characteristics of the base film, benzoyl chloride, phthalic anhydride, acetic chloride, aniline, etc. may be added to the polymerized system to block the end of the polymer.

  As the polymer stock solution, the neutralized polymer solution may be used as it is, or a polymer once isolated and then redissolved in an organic solvent may be used.

  A metal compound is added to the polymer stock solution and dissolved to obtain a film-forming stock solution. Examples of the addition method include direct addition of powder or a metal compound in a solution state, dispersion in a solvent and addition in a solution or slurry state, and the addition method is not limited.

  The polymer concentration in the stock solution is preferably 2 to 40% by weight, more preferably 5 to 35% by weight, and particularly preferably 10 to 25% by weight. If it falls below this range, it is necessary to take a large amount of discharge, which is economically disadvantageous. If it exceeds this range, it may be difficult to obtain a thin fibrous molded body or a thin film-shaped molded body due to the discharge amount or solution viscosity. .

  As a method for incorporating a metal or a metal compound in an aromatic polyamide film, there are no particular limitations such as a method of adding metal or metal compound particles in advance to a raw material before polymerization, a method of adding to a polymer stock solution after polymerization and stirring and mixing. Not. In particular, it is preferable to dissolve a metal or metal compound precursor in a polymer solution and form particles in the film forming process, because the particle size distribution of the generated particles becomes small. Furthermore, when the average particle diameter of the formed metal or metal compound particles is 0.001 to 10 nm, a film excellent in mechanical strength and surface smoothness can be obtained.

  The metal compound used as a precursor for particle generation is dissolved in an aromatic polyamide solution, and further decomposed by heating and / or chemical methods (chemical reaction) at a temperature of 400 ° C. or less to convert into metal or metal compound particles. What can be done is preferred.

  Examples of the metal compound as the precursor include metal acetylacetonate (metal pentanedione complex), metal carboxylate, metal nitrate, metal oxyhydrochloride, metal chloride and the like. Examples of the metal alkoxide include copper dimethoxide and aluminum triisopropoxide, but are not limited thereto.

  In the present invention, as the metal acetylacetonate, aluminum (III) acetylacetonate, palladium (II) acetylacetonate, copper (II) acetylacetonate, iron (III) acetylacetonate, manganese (III) acetylacetonate, Although nickel (II) acetylacetonate, vanadium oxide (IV) acetylacetonate, etc. are mentioned, it is not limited to this. When metal acetylacetonate is added and heated to the decomposition point temperature or higher, 2,4-pentanedione is eliminated, and metal or metal oxide particles can be formed.

  The content of the metal or metal compound may be adjusted so that the content of the metal or metal compound is 10% by weight or more and 70% by weight or less based on the film weight in the layer. When the amount (or addition amount) increases, and particularly when the content exceeds 20% by weight, it may be difficult to obtain a uniform film-forming stock solution. In such a case, it is effective to mix a metal or metal compound with a solvent at one end and then mix and stir with the polymer solution, and to set the temperature during stirring to 80 ° C. to 150 ° C. Furthermore, pressurization may be performed to prevent the solvent from volatilizing at a high temperature.

  The film-forming stock solution prepared as described above is formed into a film by a dry method, a dry-wet method, a wet method, a semi-dry semi-wet method, etc., but a dry-wet method is preferable in terms of easy control of the surface form. Hereinafter, a dry and wet method will be described as an example.

  The stock solution is extruded from a die onto a support such as a drum or an endless belt to form a thin film, and then the solvent is scattered from the thin film layer to dry the thin film. The drying temperature is preferably 100 ° C. or higher and 210 ° C. or lower, and more preferably 120 ° C. or higher and 190 ° C. or lower. The drying time is preferably from 0.5 minutes to 12 minutes, and more preferably from 1 minute to 10 minutes.

  Next, the film after the dry process is peeled off from the support and introduced into the wet process, and desalting, desolvation, and the like are performed. The polymer concentration when peeling the film from the support is preferably 30% by weight or more and 60% by weight or less, and more preferably 40% by weight or more and 50% by weight or less. If the polymer concentration is less than 30% by weight, the film may be insufficiently self-supporting and may be easily broken, and if it exceeds 60% by weight, stretching may not be performed sufficiently.

  The aromatic polyamide film of the present invention is preferably stretched in the longitudinal direction of the film in the state of a gel film while being peeled from the support and introduced into the wet process. The draw ratio is preferably 1.05 to 4 times, more preferably 1.05 to 2 times. If the draw ratio in the longitudinal direction is less than 1.05, the Young's modulus in the longitudinal direction may be insufficient, and if it exceeds 4 times, a brittle film with low elongation may be obtained.

  The film that has undergone the wet process is dried in the width direction of the film after drying the moisture. The stretching temperature is preferably 150 ° C. or higher and 400 ° C. or lower, more preferably 200 ° C. or higher and 350 ° C. or lower, and still more preferably 220 ° C. or higher and 280 ° C. or lower. If the stretching temperature is lower than this range, the film may be easily broken during stretching and the curl may be increased. On the other hand, if it is too high, the molecules are difficult to align and the Young's modulus may decrease.

  The draw ratio in the width direction is preferably 0.8 to 4 times, more preferably 1 to 2 times. If the draw ratio in the width direction is less than 0.8 times, the Young's modulus in the width direction may be insufficient. If it exceeds 4 times, the film will have a low elongation and the Young's modulus in the longitudinal direction will be greatly reduced. There is.

  The draw ratio is 0.8 to 8 times in terms of area ratio (area ratio is defined by a value obtained by dividing the film area after stretching by the area of the film before stretching. 1 or less means relaxation). Among these, it is preferable that the film has a mechanical property excellent in the range of 1.2 times or more and 6 times or less because it can stably form a film.

  Heat treatment is performed during or after stretching of the film, and the heat treatment temperature is preferably in the range of 150 ° C. or higher and 400 ° C. or lower. More preferably, it is 180 degreeC or more and 320 degrees C or less, More preferably, it is 200 degreeC or more and 260 degrees C or less. When the heat treatment temperature is lower than 150 ° C., the Young's modulus of the film may be lowered. On the other hand, when the temperature exceeds 400 ° C., the crystallization of the film proceeds so much that the film may be hard and brittle.

  In addition, when using a method in which a metal or a metal compound precursor is dissolved in a polymer solution and particles are formed in the film forming process as a method for incorporating a metal or a metal compound in an aromatic polyamide film In this heat treatment step, particles of metal or metal compound may be generated. The temperature at which the precursor changes to metal or metal compound particles varies depending on the type of metal used, and the heat treatment temperature should be selected as appropriate. Is more preferable, and more preferably 250 ° C. or higher.

  Further, it is effective to gradually cool the film after stretching or heat treatment, and it is effective to cool at a rate of 50 ° C./second or less.

  The film of the present invention may be a single layer film or a laminated film. In particular, when the content of the metal and the metal compound is increased, the film surface may be roughened by the aggregated particles. However, a layer containing 5% by weight or less of the metal and the metal compound is formed on at least one side of the layer containing the metal and the metal compound. Lamination is preferable because the surface smoothness of the lamination surface can be improved. Lamination is also an effective means when high insulation is required for the film. In addition, 0 weight% may be sufficient as content of the metal and metal compound in said lamination | stacking.

  In addition, the metal or metal compound in the above stack is preferably at least one element selected from the group consisting of aluminum, vanadium, iron, nickel, copper, palladium, and manganese.

  In the case of a laminated film, for example, in the case of two layers, at least one selected from the group consisting of aluminum, vanadium, iron, nickel, copper, palladium, and manganese is divided into two parts by dividing the polymerized aromatic polyamide solution. The seed metal or metal compound is added and then laminated. The same applies to the case of three or more layers. As a method of laminating, for example, laminating in a die, laminating in a composite tube, or a method of once forming one layer and forming another layer thereon may be used.

The aromatic polyamide film of the present invention may contain 10% by weight or less of an inorganic or organic additive for the purpose of surface formation, processability improvement and the like. The additives for the purpose of surfacing _{example, SiO 2, TiO 2, Al} 2 O 3 in the inorganic _{particles, CaSO 4, BaSO 4, CaCO} 3, carbon black, carbon nanotube, fullerene, zeolite, other metallic powder Etc. Preferred organic particles include, for example, particles made of an organic polymer such as crosslinked polyvinylbenzene, crosslinked acrylic, crosslinked polystyrene, polyester particles, polyimide particles, polyamide particles, and fluororesin particles, or the above organic polymer on the surface. Inorganic particles that have been subjected to treatment such as coating may be mentioned.

  However, the method for obtaining the aromatic polyamide film of the present invention is not limited to the above method.

  Since the aromatic polyamide film of the present invention is a thin film and has solder heat resistance, it can be suitably used as a base film for flexible circuit boards and TAB tapes.

  Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited thereto.

  The physical property measuring method and the effect evaluating method of the present invention are as follows.

(1) Film thickness Five points were measured using a micro thickness meter (manufactured by Anritsu Co., Ltd.), and an average value was obtained.

(2) Dimensional change Measured at 25 ° C. to 400 ° C. at a rate of temperature increase of 10 ° C./minute using TMA, SS6000 (Seiko Instruments Inc.) for a film that was allowed to stand at a temperature of 23 ° C. and relative humidity of 65% for 24 hours The absolute value of the sample dimensional change rate with respect to the initial length of the sample at each temperature was obtained. The weight during measurement was 120 g / mm ² , the initial length of the sample was 15 mm, and the width was 4 mm. The maximum value of the dimensional change rate from 25 ° C. to 260 ° C. is shown in the table.

(3) Valence of metal or metal compound The arbitrary place of the film was observed with the X-ray photoelectron spectrometer (ESCA).

Equipment: ESCALAB220iXL
Excitation X-ray: monochromatic AlKα1,2 line (1486.6eV)
X-ray diameter: 1mm
X-ray output: 10kV 20mA
Photoelectron escape angle: 90 ° (detection depth: 10 nm)
Data processing: C1s main peak position was adjusted to 284.6 eV. 9-point smoothing
The valence of the metal was determined from the peak of each element.

(4) Metal content 0.7 g of a film was precisely weighed and heated to 550 ° C. or more in a platinum crucible to be incinerated. The ash was dissolved in nitric acid and hydrofluoric acid and then made up to a constant volume with dilute nitric acid. This constant volume solution was quantified by ICP emission spectrometry or atomic absorption spectrophotometry.

(5) Solder flatness evaluation In accordance with JIS-C-6471 (1990), the solder resistance was adjusted at 105 ° C for 1 hour and then floated in a 260 ° C solder bath for 5 seconds to perform a solder test.

  The sample used was a film cut into a 50 mm square.

  Compare the appearance (flatness) of the film after the solder test with the blank in Reference Example 1. If the flatness of the blank is equal to or less than x, the flatness is better compared to the blank. However, those with curls and undulations were evaluated as △.

(6) Solder dimensional stability evaluation In accordance with JIS-C-6471 (1990), the solder resistance was adjusted at 105 ° C. for 1 hour and then floated in a 260 ° C. solder bath for 5 seconds to perform a solder test.

  As a sample, a film was cut into a square of 50 mm and a solder test was performed.

The dimensions of two adjacent sides of the film after the solder test were measured, and the average value of the dimensional change (L ₁ (mm)) was determined. The dimensional change rate (T (%)) was calculated by the following formula and evaluated according to the following criteria.

T (%) = (| 50−L ₁ | / 50) × 100
○: T <3
Δ: 3 ≦ T <5
×: 5 ≦ T
(Reference Example 1)
A 200 ml four-necked flask equipped with a stirrer was charged with 6.060 g of 2-chloro-1,4-phenylenediamine, 1.502 g of 4,4′-diaminodiphenyl ether and 129.5 ml of N-methyl-2-pyrrolidone under a nitrogen atmosphere. The mixture was stirred under ice cooling. After 10 to 30 minutes, 11.693 g of 2-chloroterephthalic acid dichloride was added in five portions. After further stirring for 1 hour, hydrogen chloride generated by the reaction was neutralized with 3.512 g of lithium carbonate to obtain a transparent polymer solution a.

  A part of the obtained polymer solution was taken on a glass plate, and a uniform film was formed using a bar coater. This was heated at 120 ° C. for 7 minutes to obtain a self-holding film. The obtained film was peeled off from the glass plate, fixed to a metal frame, washed with running water for 10 minutes, and further heat treated at 300 ° C. for 1 minute to obtain an aromatic polyamide film. The physical properties and evaluation results of the obtained film are shown in Table 1. The end of the sample after the solder test was curled, and the area of the portion maintaining the flatness was about 70%. The dimensional change rate was 5%.

Example 1
100 g of the polymer solution a obtained in Reference Example 1 was placed in a 300 ml separable flask equipped with another stirrer, 5 g of copper acetylacetonate was added, and the mixture was stirred at 60 ° C. for 2 hours.

  A part of the obtained polymer solution was taken on a glass plate, and a uniform film was formed using a bar coater. This was heated at 120 ° C. for 7 minutes to obtain a self-holding film. The obtained film was peeled off from the glass plate, fixed to a metal frame, washed with running water for 10 minutes, and further heat treated at 300 ° C. for 1 minute to obtain an aromatic polyamide film. The physical properties and evaluation results of the obtained film are shown in Table 1. In addition, it was confirmed by ESCA analysis that copper acetylacetonate was changed to divalent copper oxide fine particles. The sample after the solder test had good flatness and dimensional stability.

(Example 2)
100 g of the polymer solution a obtained in Reference Example 1 was placed in a 300 ml separable flask equipped with another stirrer, 3 g of copper acetylacetonate was added, and the mixture was stirred at 60 ° C. for 2 hours.

  A part of the obtained polymer solution was taken on a glass plate, and a uniform film was formed using a bar coater. This was heated at 120 ° C. for 7 minutes to obtain a self-holding film. The obtained film was peeled off from the glass plate, fixed to a metal frame, washed with running water for 10 minutes, and further heat treated at 300 ° C. for 1 minute to obtain an aromatic polyamide film. The physical properties and evaluation results of the obtained film are shown in Table 1. The sample after the solder test was slightly deteriorated in flatness, but had good dimensional stability.

(Example 3)
100 g of the polymer solution a obtained in Reference Example 1 was placed in a 300 ml separable flask equipped with another stirrer, 5 g of nickel acetylacetonate was added, and the mixture was stirred at 60 ° C. for 2 hours.

  A part of the obtained polymer solution was taken on a glass plate, and a uniform film was formed using a bar coater. This was heated at 120 ° C. for 7 minutes to obtain a self-holding film. The obtained film was peeled off from the glass plate, fixed to a metal frame, washed with running water for 10 minutes, and further heat treated at 300 ° C. for 1 minute to obtain an aromatic polyamide film. The physical properties and evaluation results of the obtained film are shown in Table 1. The sample after the solder test was slightly deteriorated in flatness, but had good dimensional stability.

Example 4
100 g of the polymer solution a obtained in Reference Example 1 was placed in a 300 ml separable flask equipped with another stirrer, 5 g of manganese acetylacetonate was added, and the mixture was stirred at 60 ° C. for 2 hours.

  A part of the obtained polymer solution was taken on a glass plate, and a uniform film was formed using a bar coater. This was heated at 120 ° C. for 7 minutes to obtain a self-holding film. The obtained film was peeled off from the glass plate, fixed to a metal frame, washed with running water for 10 minutes, and further heat treated at 300 ° C. for 1 minute to obtain an aromatic polyamide film. The physical properties and evaluation results of the obtained film are shown in Table 1. The sample after the solder test was slightly deteriorated in flatness, but had good dimensional stability.

(Example 5)
100 g of the polymer solution a obtained in Reference Example 1 was placed in a 300 ml separable flask equipped with another stirrer, and 1.6 g of copper (II) oxide powder having a particle size of 50 μm was added, and 2 at 60 ° C. Stir for hours.

  A part of the obtained polymer solution was taken on a glass plate, and a uniform film was formed using a bar coater. This was heated at 120 ° C. for 7 minutes to obtain a self-holding film. The obtained film was peeled off from the glass plate, fixed to a metal frame, washed with running water for 10 minutes, and further heat treated at 300 ° C. for 1 minute to obtain an aromatic polyamide film. The physical properties and evaluation results of the obtained film are shown in Table 1. The sample after the solder test was slightly deteriorated in both flatness and dimensional stability.

(Example 6)
100 g of the polymer solution a obtained in Reference Example 1 was put into a 300 ml separable flask equipped with another stirrer, and 14 g of copper acetylacetonate was mixed with 14 ml of N-methyl-2-pyrrolidone and added. Stir at 90 ° C. for 2 hours.

  A part of the obtained polymer solution was taken on a glass plate, and a uniform film was formed using a bar coater. This was heated at 120 ° C. for 7 minutes to obtain a self-holding film. The obtained film was peeled off from the glass plate, fixed to a metal frame, washed with running water for 10 minutes, and further heat treated at 300 ° C. for 1 minute to obtain an aromatic polyamide film. The physical properties and evaluation results of the obtained film are shown in Table 1. The sample after the solder test had good flatness and dimensional stability.

(Example 7)
100 g of the polymer solution a obtained in Reference Example 1 was put into a 300 ml separable flask equipped with another stirrer, and 20 g of copper acetylacetonate was mixed with 20 ml of N-methyl-2-pyrrolidone and added. Stir at 90 ° C. for 2 hours.

  A part of the obtained polymer solution was taken on a glass plate, and a uniform film was formed using a bar coater. This was heated at 120 ° C. for 7 minutes to obtain a self-holding film. The obtained film was peeled off from the glass plate, fixed to a metal frame, washed with running water for 10 minutes, and further heat treated at 300 ° C. for 1 minute to obtain an aromatic polyamide film. The physical properties and evaluation results of the obtained film are shown in Table 1. The sample after the solder test was slightly deteriorated in flatness, but had good dimensional stability.

(Comparative Example 1)
100 g of the polymer solution a obtained in Reference Example 1 was placed in a 300 ml separable flask equipped with another stirrer, 1 g of copper acetylacetonate was added, and the mixture was stirred at 60 ° C. for 2 hours.

  A part of the obtained polymer solution was taken on a glass plate, and a uniform film was formed using a bar coater. This was heated at 120 ° C. for 7 minutes to obtain a self-holding film. The obtained film was peeled off from the glass plate, fixed to a metal frame, washed with running water for 10 minutes, and further heat treated at 300 ° C. for 1 minute to obtain an aromatic polyamide film. The physical properties and evaluation results of the obtained film are shown in Table 1. In the sample after the solder test, the flatness was deteriorated, and the dimensional change rate was slightly deteriorated to 4%.

(Comparative Example 2)
100 g of the polymer solution a obtained in Reference Example 1 was placed in a 300 ml separable flask equipped with another stirrer, and 25 g of copper acetylacetonate was mixed with 25 ml of N-methyl-2-pyrrolidone and added. Stirring was carried out at 90 ° C. for 20 hours. However, since the amount added was large, a uniform polymer solution could not be obtained and film formation could not be performed.

Claims (8)

An aromatic polyamide and at least one metal or metal compound selected from the group consisting of aluminum, vanadium, iron, nickel, copper, palladium and manganese, and the total content of these metals and metal compounds is 10% by weight An aromatic polyamide film having at least one layer of 70% by weight or less. The aromatic polyamide film according to claim 1, comprising at least one layer containing copper or copper oxide, wherein the total content of these copper and copper oxide is 15 wt% or more and 50 wt% or less. The aromatic polyamide film according to claim 1 or 2, wherein an absolute value of a dimensional change rate from 25 ° C to 260 ° C is 1% or less. An aromatic polyamide and at least one metal or metal compound selected from the group consisting of aluminum, vanadium, iron, nickel, copper, palladium and manganese, and the total content of these metals and metal compounds is 5% by weight The aromatic polyamide film in any one of Claims 1-3 formed by laminating | stacking the layer which is the following. The aromatic polyamide film according to claim 1, wherein the aromatic polyamide has a structure represented by chemical formula (I) and chemical formula (II).

X: Any halogen atom The method for producing an aromatic polyamide film according to any one of claims 1 to 5, wherein after dissolving the metal compound in the polyamide solution, metal particles or metal compound particles are produced by heating and / or chemical reaction. The method for producing an aromatic polyamide film according to claim 6, wherein the metal compound dissolved in the polyamide solution is metal acetylacetonate. A flexible circuit board comprising a conductive layer provided on at least one surface of the aromatic polyamide film according to claim 1.