JP2014189605A - Polyarylate resin film and capacitor employing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyarylate resin film excellent in mechanical characteristics and electrical characteristics.SOLUTION: A polyarylate resin film comprises one or more divalent phenol residues selected from a group including the specified general formula (i) and an aromatic dicarboxylic acid residue. The polyarylate resin film is obtained from a polyarylate resin having a glass transformation temperature of 200°C or more.

Description

  The present invention relates to a polyarylate resin film excellent in mechanical properties and electrical properties.

  Conventionally, plastics have been used as insulating members for capacitor dielectrics, motors, transformers, and the like, taking advantage of their electrical insulating properties. In particular, with the development of electronic devices and the like in recent years, film capacitors are often used as materials that are inexpensive and easy to manufacture. There are various types of plastics used in film capacitors. However, due to the downsizing of electronic equipment and the increase in capacity of capacitors, the usage environment has become high, and even under such conditions, the electrical characteristics are stable over a long period of time. It is required to be. For example, it is disclosed to use a blend of various polyesters or a film made of a polymer alloy such as polyester and polycarbonate (Patent Documents 1 and 2). In addition, a method of blending an amorphous high heat resistant resin such as polyetherimide with a polyphenyl sulfide resin is also disclosed (Patent Document 3). Both are aimed at improving the performance of the capacitor by improving the processability of the film.

  Polyarylate resins are well known as engineering plastics that are transparent, have high heat resistance, and have excellent mechanical properties such as impact strength and dimensional stability. Such polyarylate resin has solubility in various solvents and excellent electrical properties (insulating properties, dielectric properties, etc.), and is used as a film for capacitors. However, the electrical properties of the conventional polyarylate resin are insufficient for high temperature use and large capacity (Patent Document 4).

Japanese Patent Publication No. 7-21070 Special table 2011-516680 gazette JP 2001-261959 A Japanese Patent Application Laid-Open No. 51-39796

  An object of the present invention is to provide a polyarylate resin film excellent in mechanical properties and electrical properties.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the gist of the present invention is as follows.
(1) A polyarylate resin comprising an aromatic dicarboxylic acid residue and at least one dihydric phenol residue selected from the following general formulas (i) to (iv), and having a glass transition temperature of 200 ° C. or higher. A polyarylate resin film obtained more.
In the general formula (i), R ¹ , R ² , R ³ and R ⁴ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a nitro group, and the hydrocarbon group has 1 to 20 carbon atoms. Selected from the group consisting of an aliphatic group having 3 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms.
In general formula (ii), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a nitro group, and the hydrocarbon group has 1 to 20 carbon atoms. Selected from the group consisting of an aliphatic group, an alicyclic group having 3 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms, and R ¹⁵ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. , An alkenyl group, or a phenyl group.
In the general formula (iii), R ²¹ , R ²² , R ²³ and R ²⁴ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a nitro group, and the hydrocarbon group has 1 to 20 carbon atoms. Selected from the group consisting of an aliphatic group having 3 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms, and R ²⁵ and R ²⁶ are each independently a hydrogen atom or carbon number 1 Selected from the group consisting of -20 aliphatic hydrocarbon groups, alicyclic hydrocarbon groups having 1-20 carbon atoms, aromatic hydrocarbon groups having 1-20 carbon atoms, and halogenated alkyl groups, and k is 2-12. Is an integer.
In the general formula (iv), R ³¹ , R ³² , R ³³ and R ³⁴ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a nitro group, and the hydrocarbon group has 1 to 20 carbon atoms. Selected from the group consisting of an aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and R ³⁵ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. Selected from the group consisting of an alicyclic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 1 to 20 carbon atoms, and a halogenated alkyl group, and R ³⁶ is an aromatic hydrocarbon having 1 to 20 carbon atoms. Selected from the group consisting of groups.
(2) The polyarylate resin film according to (1), which has a thickness of 0.5 to 1500 μm.
(3) The polyarylate resin film according to (1) or (2), wherein the elongation at break is 5% or more.
(4) The polyarylate resin film according to (1) to (3), wherein a metal vapor deposition layer is formed on one or both sides of the film.
(5) A polyarylate resin comprising an aromatic dicarboxylic acid residue and one or more dihydric phenol residues selected from the following general formulas (i) to (iv), an organic solvent having a boiling point of less than 115 ° C The method for producing a polyarylate resin film according to any one of (1) to (4), wherein the polyarylate resin film is formed by flowing and drying after being dissolved in the solution.
In the general formula (i), R ¹ , R ² , R ³ and R ⁴ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a nitro group, and the hydrocarbon group has 1 to 20 carbon atoms. Selected from the group consisting of an aliphatic group having 3 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms.
In general formula (ii), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a nitro group, and the hydrocarbon group has 1 to 20 carbon atoms. Selected from the group consisting of an aliphatic group, an alicyclic group having 3 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms, and R ¹⁵ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. , An alkenyl group, or a phenyl group.
In the general formula (iii), R ²¹ , R ²² , R ²³ and R ²⁴ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a nitro group, and the hydrocarbon group has 1 to 20 carbon atoms. Selected from the group consisting of an aliphatic group having 3 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms, and R ²⁵ and R ²⁶ are each independently a hydrogen atom or carbon number 1 Selected from the group consisting of -20 aliphatic hydrocarbon groups, alicyclic hydrocarbon groups having 1-20 carbon atoms, aromatic hydrocarbon groups having 1-20 carbon atoms, and halogenated alkyl groups, and k is 2-12. Is an integer.
In the general formula (iv), R ³¹ , R ³² , R ³³ and R ³⁴ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a nitro group, and the hydrocarbon group has 1 to 20 carbon atoms. Selected from the group consisting of an aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and R ³⁵ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. Selected from the group consisting of an alicyclic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 1 to 20 carbon atoms, and a halogenated alkyl group, and R ³⁶ is an aromatic hydrocarbon having 1 to 20 carbon atoms. Selected from the group consisting of groups.
(6) The polyarylate resin film according to (5), wherein an organic solvent having a boiling point of less than 115 ° C. is used and drying is performed in a temperature range not exceeding (glass transition temperature−80 ° C.) of the polyarylate resin to be used. Manufacturing method.
(7) A capacitor using the polyarylate resin film of (1) to (5).

  According to the present invention, a polyarylate resin film excellent in mechanical properties and electrical properties can be obtained.

  Hereinafter, the present invention will be described in detail.

  The polyarylate resin used in the present invention is an aromatic polyester polymer composed of an aromatic dicarboxylic acid residue and a dihydric phenol residue, and is produced by methods such as solution polymerization, melt polymerization, and interfacial polymerization. Further, it is preferably an amorphous polyarylate resin that does not crystallize even when it is gradually cooled from a molten state or when it is heat-treated at a temperature exceeding the glass transition temperature. Whether or not the material is amorphous may be confirmed by a known method such as differential scanning calorimetry (DSC) or dynamic viscoelasticity measurement.

  Further, the glass transition temperature of the polyarylate resin needs to be 200 ° C. or higher, preferably 210 ° C. or higher, more preferably 220 ° C. or higher. When the glass transition temperature is 200 ° C. or higher, not only the heat resistance is excellent, but also the dielectric breakdown strength important as a characteristic of the insulating material is large. When the glass transition temperature is less than 200 ° C., the dielectric breakdown strength is not sufficiently increased.

  Examples of the acid component for introducing the aromatic dicarboxylic acid residue include terephthalic acid, isophthalic acid, phthalic acid, chlorophthalic acid, nitrophthalic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2 , 7-Naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, methyl terephthalic acid, 4,4'-biphenyldicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 4,4'-diphenylether dicarboxylic acid, 4,4 ' -Diphenylmethane dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, 4,4'-diphenylisopropylidenedicarboxylic acid, 1,2-bis (4-carboxyphenoxy) ethane, 5-sodium sulfoisophthalic acid and the like. Among these, terephthalic acid and isophthalic acid are preferable, and in view of mechanical properties and moldability, it is particularly preferable to use a mixture of both. In this case, the mixing molar ratio is arbitrary in the range of terephthalic acid / isophthalic acid = 80/20 to 20/80 (mol%), preferably 70/30 to 25/75 (mol%), more preferably When the range is 60/40 to 30/70 (mol%), the resulting polyarylate resin is likely to be amorphous.

  Moreover, you may use aliphatic dicarboxylic acids in the range which does not impair the characteristic and effect of this invention. The aliphatic dicarboxylic acids are not particularly limited, and examples thereof include dicarboxymethylcyclohexane, cyclohexanedicarboxylic acid, adipic acid, sebacic acid, glutaric acid, and dodecanedioic acid.

  As a bisphenol component for introducing a dihydric phenol residue, those represented by the following general formulas (i) to (iv) must be used. By using these bisphenols, the resulting polyarylate resin has a glass transition temperature of 200 ° C. or higher, and is excellent in mechanical properties and electrical properties. In the present invention, these compounds may be used alone or in combination of two or more.

The compound represented by the general formula (i) is as follows.
In the general formula (i), R ¹ , R ² , R ³ and R ⁴ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a nitro group, and the hydrocarbon group has 1 to 20 carbon atoms. Selected from the group consisting of an aliphatic group having 3 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms.

  Examples of the bisphenol for introducing the structure represented by the general formula (i) include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, Examples include 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene, and the like. These compounds may be used alone or in combination of two or more.

The compound represented by the general formula (ii) is as follows.
In general formula (ii), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a nitro group, and the hydrocarbon group has 1 to 20 carbon atoms. Selected from the group consisting of an aliphatic group, an alicyclic group having 3 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms, and R ¹⁵ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. , An alkenyl group, or a phenyl group.

  Examples of the bisphenol for introducing the structure represented by the general formula (ii) include 3,3-bis (4-hydroxyphenyl) phthalimidine, N-phenyl-3,3-bis (4-hydroxyphenyl) phthalimidine, N-methyl-3,3-bis (4-hydroxyphenyl) phthalimidine, N-ethyl-3,3-bis (4-hydroxyphenyl) phthalimidine and the like can be mentioned. These compounds may be used alone or in combination of two or more.

The compound represented by the general formula (iii) is as follows.
In the general formula (iii), R ²¹ , R ²² , R ²³ and R ²⁴ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a nitro group, and the hydrocarbon group has 1 to 20 carbon atoms. Selected from the group consisting of an aliphatic group having 3 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms, and R ²⁵ and R ²⁶ are each independently a hydrogen atom or carbon number 1 Selected from the group consisting of -20 aliphatic hydrocarbon groups, alicyclic hydrocarbon groups having 1-20 carbon atoms, aromatic hydrocarbon groups having 1-20 carbon atoms, and halogenated alkyl groups, and k is 2-12. Is an integer.

  The bisphenol for introducing the structure represented by the general formula (iii) is, for example, a bisphenol having a cycloalkylidene group, and specific examples thereof include 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1 -Bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-phenylphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclopentane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclo Pentane, 1,1-bis (4-hydroxy-3-phenylphenyl) cyclopentane, , 1-bis (4-hydroxyphenyl) cyclododecane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclododecane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclododecane 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) -3,3,5-trimethylcyclohexane, 1,1 -Bis (4-hydroxy-3,5-dimethylphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxy-3-phenylphenyl) -3,3,5-trimethylcyclohexane and the like Can be mentioned. These compounds may be used alone or in combination of two or more.

The compound represented by the general formula (iv) is as follows.
In the general formula (iv), R ³¹ , R ³² , R ³³ and R ³⁴ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a nitro group, and the hydrocarbon group has 1 to 20 carbon atoms. Selected from the group consisting of an aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and R ³⁵ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. Selected from the group consisting of an alicyclic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 1 to 20 carbon atoms, and a halogenated alkyl group, and R ³⁶ is an aromatic hydrocarbon having 1 to 20 carbon atoms. Selected from the group consisting of groups.

  Examples of the bisphenol for introducing the structure represented by the general formula (iv) include bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxy-3-methylphenyl) phenylmethane, and bis (4-hydroxy-). 3,5-dimethylphenyl) phenylmethane, bis (4-hydroxy-3-phenylphenyl) phenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxy) -3-methylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-phenylphenyl) Examples include -1-phenylethane. These compounds may be used alone or in combination of two or more.

In addition, bisphenols, dihydroxybenzenes and aliphatic glycols represented by the general formula (v) different from the structures represented by the general formulas (i) to (iv) may be used as long as the characteristics and effects of the present invention are not impaired. it can.
In the general formula (v), R ³¹ , R ³² , R ³³ and R ³⁴ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a nitro group, and the hydrocarbon group has 1 to 20 carbon atoms. Are selected from the group consisting of an aliphatic group having 3 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms.

  The bisphenol represented by the general formula (v) may contain a dihydric phenol residue, dihydroxybenzene residue or aliphatic glycol residue different from the general formulas (i) to (iv), and specific examples thereof. For example, 4,4′-dihydroxydiphenylmethane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2- (4-hydroxyphenyl) propane (hereinafter sometimes referred to as bisphenol A), 2, 2- (4-hydroxyphenyl) butane, 2,2,-(4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis ( 4-hydroxy-3-methylphenyl) butane, 2,2-bis (4-hydroxy-3-methylphenyl) -4-methylpentane, 2,2-bis 4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) butane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl)- 4-pentane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane and the like can be mentioned. Examples of dihydroxybenzenes include hydroquinone, resorcinol, catechol and the like. Aliphatic glycols include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, nonanediol, decanediol, cyclohexanedimethanol, ethylene oxide adduct of bisphenol A, propylene oxide adduct, and ethylene oxide of bisphenol S. Additives can be mentioned. These can be used by mixing with the bisphenol components represented by the general formulas (i) to (iv), and although the glass transition temperature of the resulting polyarylate resin is lowered, the mechanical properties are improved. -Bis (4-hydroxyphenyl) propane is particularly preferred.

  The blending amount of the dihydric phenol residue, dihydroxybenzene residue or aliphatic glycol residue different from the structure represented by the general formulas (i) to (iv) is such that the glass transition temperature of the resulting polyarylate resin is less than 200 ° C. Unless it becomes, it will not specifically limit. Although the glass transition temperature differs depending on the dihydric phenol to be combined, it cannot be determined unconditionally. However, an example of the blending amount of the dihydric phenol having the structure represented by the general formula (v) It is 5 to 75 mol%, preferably 5 to 70 mol%, more preferably 5 to 60 mol%.

  In the polyarylate resin used in the present invention, in addition to the aromatic dicarboxylic acid residue and the dihydric phenol residue, a monofunctional carboxylic acid residue, a monofunctional phenol residue, or a monofunctional alcohol residue is used as a molecular weight modifier. be able to. Examples of the monofunctional carboxylic acid residue include acetic acid, propionic acid, octanoic acid, cyclohexanecarboxylic acid, benzoic acid, toluic acid, p-tert-butylbenzoic acid, p-methoxyphenylacetic acid and the like. Examples of the monofunctional phenol residue include phenol, cresol, p-tert-butylphenol, nonylphenol, o-phenylphenol, cumylphenol, and the like. Examples of the monofunctional alcohol residue include methanol, ethanol, n-propanol, isopropanol, n-butanol, pentanol, hexanol, dodecyl alcohol, stearyl alcohol, benzyl alcohol, phenethyl alcohol and the like.

  In addition, the polyarylate resin used in the present invention is not necessarily a linear polyarylate, and can be copolymerized with a polyhydric phenol. The amount of polyhydric phenol used for copolymerization can be appropriately adjusted according to the required characteristics.

The inherent viscosity (η _inh ) of the polyarylate resin used in the present invention is preferably 0.40 to 1.20 dl / g, and more preferably 0.45 to 1.10 dl / g. Inherent viscosity (η _inh ) is one of the indicators of the molecular weight of the polymer. In the present invention, when it is less than 0.40 dl / g, the mechanical properties of the polyarylate resin are inferior, and 1.20 dl / g. Exceeding this is not preferable because the processability when forming a polyarylate resin film may deteriorate.

  In the present invention, examples of the method for polymerizing the polyarylate resin include an interfacial polymerization method, a solution polymerization method, a melt polymerization method, and the like, among which the interfacial polymerization method is preferable. According to the interfacial polymerization method, the reaction is faster than the solution polymerization method or the melt polymerization method, and a high molecular weight polyarylate resin can be easily obtained. The interfacial polymerization method is a polymerization method that can easily control the molecular weight of the resulting polyarylate resin and can impart excellent low impurity properties and transparency. Below, the manufacturing method of polyarylate resin by the general interfacial polymerization method is explained in full detail.

  The interfacial polymerization method includes an aqueous phase in which dihydric phenols are dissolved in an alkaline aqueous solution, and an organic phase in which dicarboxylic acid dihalide, which is a raw material for introducing a dicarboxylic acid residue, is dissolved in an organic solvent insoluble in water. By mixing in the presence of a catalyst. This method of interfacial polymerization is described in W.W. M.M. EARECKSON, J.A. Poly. Sci. XL399 (1959) and Japanese Patent Publication No. 40-1959.

  The interfacial polymerization method will be described in detail below. First, an alkaline aqueous solution of a desired dihydric phenol is prepared as the aqueous phase, and then a polymerization catalyst and, if necessary, a molecular weight adjusting agent (end-capping agent) are added. Separately, an organic phase is prepared by dissolving an aromatic dicarboxylic acid dihalide, which is a raw material for introducing an aromatic dicarboxylic acid residue, in an organic solvent for preparing an organic phase described later. Thereafter, an aqueous alkali solution as an aqueous phase and an organic solvent solution as an organic phase are mixed and subjected to an interfacial polymerization reaction while stirring at 25 ° C. or lower for 30 minutes to 5 hours, whereby a high molecular weight polyarylate resin is added to the organic solvent. Therefore, after washing the organic solvent solution with pure water or ion-exchanged water, only the polyarylate resin can be obtained by distilling off the organic solvent.

  Examples of the alkali for preparing the alkaline aqueous solution include sodium hydroxide and potassium hydroxide. Of these, sodium hydroxide is preferable because it is economically advantageous and easy to treat the waste liquid.

  Polymerization catalysts include trimethylamine, triethylamine, tri-n-butylamine, trihexylamine, tridodecylamine, N, N-dimethylcyclohexylamine, tertiary amines such as pyridine, quinoline, dimethylaniline, trimethylbenzylammonium halide, tributyl. Quaternary ammonium salts such as benzylammonium halide, triethylbenzylammonium halide, tributylbenzylphosphonium halide, tetrabutylammonium halide, trimethylbenzylphosphonium halide, tributylbenzylphosphonium halide, triethylbenzylphosphonium halide, tetrabutylphosphonium halide, triphenylbenzyl Phosphonium halide, tetraphenylphosphonium halide, etc. Such as grade phosphonium salt and the like. Of these, tributylbenzylammonium halide, tetrabutylammonium halide, and tetrabutylphosphonium halide are preferred from the viewpoint of fast reaction rate and minimizing hydrolysis of aromatic dicarboxylic acid halide.

  Examples of the solvent for obtaining the organic phase include a solvent that is incompatible with water and dissolves the polyarylate resin. Specifically, dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, o-dichlorobenzene, m-dichlorobenzene, Examples include chlorinated solvents such as p-dichlorobenzene, aromatic hydrocarbon solvents such as toluene, benzene, and xylene, and tetrahydrofuran. Among these, non-flammable and easy to handle even if the production equipment is not explosion-proof. Is preferable from the viewpoint of good.

  In the case of producing a polyarylate resin by a solution polymerization method, a dihydric phenol compound and an aromatic dicarboxylic acid dihalide are dissolved in an organic solvent, stirred, and reacted at 2 to 80 ° C. In the case of producing by melt polymerization, first, dihydric phenol is reacted with an organic carboxylic acid anhydride such as acetic anhydride at 100 to 200 ° C. to obtain a diesterified product of dihydric phenol, and then aromatic dicarboxylic acid. A polyarylate resin can be obtained by evaporating the organic carboxylic acid produced as a by-product while causing a transesterification reaction by raising the temperature to 300 to 360 ° C. under reduced pressure while stirring.

  The carboxyl value of the polyarylate resin used in the present invention is preferably 100 mol / ton or less, more preferably 50 mol / ton or less, more preferably 30 mol or less, because it affects electric characteristics such as arc discharge resistance and dielectric constant. It is more preferable to make it less than / ton. The carboxyl value of the polyarylate resin can be measured by a known method such as neutralization titration.

  The amount of residual alkali metal in the polyarylate resin used in the present invention is preferably less than 50 ppm. If the amount of residual alkali metal is 50 ppm or more, the above-described electrical characteristics tend to be deteriorated, which is not preferable. The amount of residual alkali metal in the polyarylate resin can be quantified using a known method such as ion chromatography analysis, atomic absorption spectrometry, or plasma emission spectroscopy.

  The amount of the catalyst such as quaternary ammonium salt and quaternary phosphonium salt remaining in the polyarylate resin used in the present invention is preferably less than 200 ppm, more preferably less than 100 ppm. If the remaining catalyst is 200 ppm or more, the dielectric breakdown strength tends to decrease, such being undesirable. Catalysts such as quaternary ammonium salts and quaternary phosphonium salts remaining in the polyarylate resin can be quantified using a gas chromatographic method.

  In order to obtain the polyarylate resin film of the present invention, a film production method such as a melt extrusion method or a casting method can be employed, and it is not particularly limited. One example will be described below.

  In the melt extrusion method, the dried polyarylate resin was put into an extruder set and adjusted to a temperature higher by 100 to 180 ° C., preferably 110 to 170 ° C. than its glass transition temperature, and allowed to melt and then passed through a filter. Thereafter, the molten polymer is discharged into a sheet using a die of a T die, and is cooled and solidified on a cooling drum to obtain a polyarylate resin film. Since the polyarylate resin film thus obtained has a thickness of several tens to 1,000 μm, it is stretched to obtain a polyarylate resin film of several μm to several tens μm that can be suitably used as a film capacitor. It can also be processed.

The casting method is a so-called solution casting method, in which a polyarylate resin is dissolved in an organic solvent, and the organic solvent solution is applied onto a metal drum or belt, or a film substrate made of a resin different from the polyarylate resin. Then, the polyarylate resin film can be obtained by distilling off the organic solvent and peeling it off from the substrate.

  In the production method of these polyarylate resin films, the casting method is preferred. In the case of the melt extrusion method, the higher the glass transition temperature of the polyarylate resin, the higher the processing temperature during extrusion, but the processing temperature may be equal to or higher than the decomposition start temperature of the polyarylate resin. It is not preferable. In contrast, the casting method does not depend much on the glass transition temperature of the polyarylate resin and can handle organic solvent solutions in the temperature range from room temperature to several tens of degrees Celsius. It does not have to be. In addition, in the melt extrusion method, it is difficult to obtain a thin polyarylate resin film only by extrusion molding. However, in the case of the casting method, the concentration of the organic solvent solution and the thickness when coating it are adjusted. Thus, the thickness can be controlled, and as a result, a thin polyarylate resin film having a thickness of several μm can be produced relatively easily.

  The organic solvent used in the solution casting method is not particularly limited. For example, methylene chloride (boiling point 40 ° C), chloroform (boiling point 61 ° C), chlorobenzene (boiling point 131 ° C), 1,2-dichlorobenzene (boiling point 180 ° C). ) And other halogen solvents such as toluene (boiling point 110 ° C.), xylene (144 ° C.), cyclohexanone (boiling point 156 ° C.), tetrahydrofuran (boiling point 66 ° C.), 1,3-dioxane (boiling point 105). ° C), 1,4-dioxane (boiling point 101 ° C), 1,3-dioxolane (boiling point 75 ° C), N-methylpyrrolidone (boiling point 202 ° C), N, N-dimethylacetamide (165 ° C), dimethylformamide (boiling point) 153 ° C.), diethylene glycol dimethyl ether (boiling point 162 ° C.), propylene glycol monomer Non-halogenated solvents such as ethers (boiling point 121 ° C.) and the like.

  Among these, toluene (boiling point 110 ° C.), tetrahydrofuran (boiling point 66 ° C.), 1,3-dioxane (boiling point 105 ° C.), 1,3-dioxolane (boiling point), which is a non-halogen solvent and has a boiling point of less than 115 ° C. 75 ° C.) is preferred, and tetrahydrofuran (boiling point 66 ° C.) and 1,3-dioxolane (boiling point 75 ° C.) which are non-halogen solvents and have a boiling point of less than 100 ° C. are more preferred. From the viewpoint of solubility, tetrahydrofuran (Boiling point 66 ° C.) and 1,3-dioxolane (boiling point 75 ° C.) are particularly preferred.

  When forming a polyarylate resin film by the solution casting method, dissolve the polyarylate resin in the above organic solvent and apply it to a metal drum, belt, etc., and then remove the organic solvent in a drying step to peel it off from the substrate. By doing so, a polyarylate resin film can be obtained, but sufficient control of the drying temperature in the drying process will affect the mechanical properties of the resulting polyarylate resin film, particularly the tensile elongation at break and surface appearance. Important to give.

In the present invention, an organic solvent having a boiling point of less than 115 ° C. is used for forming a polyarylate resin film by a solution casting method, and the polyarylate resin film is dried within a temperature range not exceeding the (glass transition temperature−80 ° C.) of the polyarylate resin to be used. It is particularly preferable to carry out.
For example, when a film is formed using a polyarylate resin having a glass transition temperature of 240 ° C. and methylene chloride having a boiling point of 40 ° C., the solution cast film is first preliminarily dried and pressed at a temperature of less than 40 ° C. The method of drying on the conditions which heat up in steps of 40 degreeC, 60 degreeC, and 80 degreeC is mentioned.
By setting the temperature below the boiling point of the organic solvent using the drying temperature as the starting temperature, the organic solvent gradually evaporates from the solution-cast film, and drying can be performed without impairing the smoothness of the film surface. On the other hand, when the temperature exceeding the boiling point of the organic solvent is set as the starting temperature, volatilization of the organic solvent starts abruptly, resulting in unevenness and smoothness may be impaired. Further, by increasing the temperature stepwise, the internal stress associated with the drying of the polyarylate resin film accompanying a drastic change in the drying temperature can be reduced. Furthermore, by setting the temperature exceeding the boiling point and not exceeding the (glass transition temperature−100 ° C.) of the polyarylate resin to be used as the upper limit temperature for drying, the minimum amount of heat required for drying the organic solvent. Efficient drying. On the other hand, drying beyond the range of (glass transition temperature-100 ° C) of the polyarylate resin can reduce the residual amount of the organic solvent, but tends to reduce the tensile elongation at break of the obtained polyarylate resin film. There is.

  Specific examples of the drying of the polyarylate resin film vary depending on the organic solvent used and the drying equipment, but in the first drying step, preliminary drying is performed at a temperature below the boiling point of the organic solvent, and the organic solvent contained in the polyarylate resin film After the amount is less than 23% by mass, preferably less than 20% by mass, more preferably less than 18% by mass, the second drying step exceeds the drying temperature of the first step, and the glass transition temperature of the polyarylate resin. After the treatment at a temperature below, the organic solvent content in the polyarylate resin film is less than 3% by mass, preferably less than 1% by mass, and more preferably less than 0.5% by mass. When the organic solvent content is 3% by mass or more, the properties of the polyarylate resin film surface are deteriorated, which adversely affects the surface treatment and the like. The content of the organic solvent remaining in the polyarylate resin film of the present invention can be quantified using a known method such as heat loss or gas chromatography. In the case of measuring by weight loss by heating, quantification is possible by processing for about 0.5 to 1 h at a temperature lower than the glass transition temperature of the obtained polyarylate resin film.

  When an organic solvent having a boiling point exceeding 100 ° C. is used as the organic solvent, even if the drying temperature is lower than the boiling point of toluene, it takes as little time as possible and takes sufficient time. Since drying can suppress rapid evaporation of the organic solvent, the surface appearance of the resulting polyarylate resin film can reduce defects such as bubbles and blisters. On the other hand, when an organic solvent having a boiling point of less than 100 ° C., such as tetrahydrofuran, is used as the organic solvent, it can be set at a higher temperature within a range not exceeding the boiling point and can be dried in a short time.

  In the second drying step, it is necessary to be lower than the glass transition temperature of the polyarylate resin, preferably 50 to 150 ° C. lower than the glass transition temperature, and 80 to 120 ° C. lower than the glass transition temperature. More preferably. When drying is performed at a high temperature exceeding a predetermined drying temperature, the resulting polyarylate resin film not only is inferior in dimensional stability, but also tends to decrease mechanical properties, particularly tensile elongation at break. Decrease in tensile elongation at break is due to the risk of breakage in post-processing steps described later, for example, processing by roll-to-roll such as vapor deposition, or when the final product is rolled up with a polyarylate resin film. There are concerns about cracks and breakage, and it may affect the product characteristics of the final product, which is not preferable.

  The heat loss of the polyarylate resin film of the present invention at 200 ° C. × 0.5 h is preferably less than 1% by mass, more preferably less than 0.5% by mass, and less than 0.3% by mass. More preferably. The loss on heating is mainly due to the organic solvent remaining inside the film when the polyarylate resin film is formed. Therefore, it can be considered that the loss on heating and the amount of the remaining organic solvent are equal. By increasing the heat loss, the dielectric breakdown voltage of the resulting polyarylate resin film tends to decrease.

  The polyarylate resin film of the present invention may further contain ceramic particles. Examples of ceramic particles that can be used include titanium oxide, magnesium titanate, magnesium silicate, zinc titanate, bismuth titanate, lanthanum oxide, calcium titanate, strontium titanate, barium titanate, and calcium carbonate. . Among these, ceramic particles having a dielectric constant of 10 or more are preferable. The average particle size of the ceramic particles is preferably about several hundred nm to 1 μm. These can be used alone or in combination of two or more. The method of dispersing the ceramic particles in the polyarylate resin is not particularly limited, but the method of dispersing the ceramic particles in the polyarylate resin by melt kneading in advance, the polyarylate resin used when forming a film by the solution casting method And a method of dispersing in the solvent solution.

  The polyarylate resin film in the present invention may be a single layer or multiple layers, but the content of ceramic particles in the film is preferably 5 to 50% by volume. For example, when used as a film for a capacitor, if the content of ceramic particles is less than 5% by volume, a significant improvement in the dielectric constant of the film cannot be obtained, and if it exceeds 50% by volume, The stretchability of the polyarylate resin film is extremely lowered, and it becomes difficult to stably produce the stretched film. In order to prevent troubles such as film breakage at the time of stretching or to improve the uniformity of the film surface, it is effective to reduce the content of ceramic particles in the film surface layer with a multilayer structure. In the solution casting method, the tensile elongation at break of the resulting polyarylate resin film is lowered.

  Moreover, it can also be set as the polyarylate resin film which laminated | stacked the ceramic particle layer by apply | coating and drying the slurry solution which disperse | distributed the ceramic particle on the polyarylate resin film. At that time, the coating thickness after drying is preferably 1 μm in order to suppress peeling of the ceramic particle layer and deterioration of workability.

  The thickness of the polyarylate resin film of the present invention is not particularly limited, but is 0.5 to 1500 μm, preferably 0.5 to 500 μm, more preferably 0.5 to 150 μm, most preferably. 0.5 to 50 μm.

  The tensile elongation at break of the film comprising the polyarylate resin of the present invention is slightly different depending on the type of polyarylate resin to be obtained, but the dihydric phenol component constituting the polyarylate resin is described in the general formula (i) When used alone, the tensile elongation at break is preferably 8% or more, more preferably 9% or more, and even more preferably 10% or more. When the compounds described in general formula (ii) or (iii) are used alone, the tensile elongation at break is preferably 10% or more, more preferably 15% or more, and 20% or more. Is more preferable. When the compound represented by the general formula (iv) is used alone, the tensile elongation at break is preferably 50% or more, more preferably 65% or more, and further preferably 70% or more. Further, when (i) to (v) are used in combination, the tensile elongation at break is preferably 10% or more, more preferably 20% or more, and further preferably 30% or more. . When adjusting the thickness of the polyarylate resin film to be obtained, it is preferable that the thickness is not deviated significantly from the tensile elongation at break.

  The dielectric breakdown voltage of the film comprising the polyarylate resin of the present invention is slightly different depending on the type of the polyarylate resin to be obtained, but the dihydric phenol component constituting the polyarylate resin is represented by the general formula (i), (ii) ) Or (iii) when used alone, the dielectric breakdown voltage is preferably 230 kV / mm or more, more preferably 250 kV / mm or more, and 270 kV / mm or more. Further preferred. When the compound represented by the general formula (iv) is used alone, the dielectric breakdown voltage is preferably 250 kV / mm or more, more preferably 270 kV / mm or more, and 290 kV / mm or more. Further preferred. Further, when (i) to (v) are used in combination, the dielectric breakdown voltage is preferably 210 kV / mm or more, more preferably 230% or more, and further preferably 250% or more. preferable. When adjusting the thickness of the polyarylate resin film to be obtained, it is preferable to perform the adjustment within a range not greatly deviating from the dielectric breakdown voltage.

  Using the polyarylate resin film of the present invention having a metal layer formed on at least one surface, a film capacitor can be obtained by a known method such as a winding method or a lamination method. The metal phase is used as an electrode of a capacitor, and can be produced by, for example, laminating a metal thin film by a method such as vacuum deposition or sputtering, or laminating a separately prepared metal foil. Examples of the metal for forming the metal thin film include, but are not limited to, aluminum, zinc, tin, titanium, nickel, and alloys thereof.

  Next, a method for producing a capacitor using the polyarylate resin film of the present invention will be described. When a metal foil is used as the internal electrode of the capacitor, the metal foil and the polyarylate resin of the present invention are alternately overlapped and wound by, for example, a foil protruding method or a tab insertion method during winding. Then, the polyarylate resin film and the electrode are alternately overlapped and wound so that the electrode can be drawn out to obtain a capacitor element or a capacitor mother element.

  When a metal thin film is used as the internal electrode of the capacitor, the metal thin film is first formed on the above-described polyarylate resin film of the present invention. As a method for forming the metal thin film, a vapor deposition method is preferable. The metal to be deposited is preferably a metal mainly composed of aluminum. When the metal thin film is formed, the adhesion between the metal thin film and the film can be improved in advance by a treatment such as corona discharge treatment or plasma treatment on the film surface on the metal thin film formation side. When forming the metal thin film or after forming the metal thin film, a portion where the metal thin film is not formed (hereinafter referred to as a non-thin film forming portion) is often provided so that the counter electrode is not short-circuited. When obtaining a wound type capacitor, slit a thin tape so that a non-thin film forming part comes to one end of the metal thin film forming film and overlap two sheets, or double-sided metal thin film forming film and non-metal thin film forming In many cases, individual elements are wound individually by overlapping films. After press-molding the capacitor mother element obtained as described above, a capacitor can be obtained through an external electrode attaching step, a lead wire attaching step, an exterior step, and the like. The capacitor using the polyarylate resin film of the present invention can be used for both AC and DC applications.

1. Measurement Method According to the following method, measurement of resin properties and evaluation of film performance were performed.

(1) Inherent viscosity of polyarylate resin (η _inh )
Based on the relative viscosity (η _rel ) measured at a concentration of 1 g / dl and a temperature of 25 ° C., using a mixed solution of phenol / 1,1,2,2-tetrachloroethane = 60/40 using an Ubbelohde type viscosity tube. Calculated by the following formula and expressed in units of dl / g.
Inherent viscosity (η _inh ) = Ln (η _rel ) / c
η _rel : relative viscosity, c: concentration (g / dl)

(2) Glass transition temperature Using a differential scanning calorimeter (trade name “DSC7”, manufactured by PerkinElmer Co., Ltd.), the temperature was increased from 40 ° C. to 340 ° C. at a rate of temperature increase of 20 ° C./min. The onset temperature of the discontinuous change derived from the glass transition temperature in the curve was taken as the glass transition temperature.

(3) Heat loss The obtained polyarylate resin film was heat-treated at 200 ° C. for 0.5 h, and the heat loss was calculated from the mass difference before and after the heat treatment according to the following formula. The weight loss by heating refers to the content of the organic solvent remaining in the substantially obtained polyarylate resin film.
Heat loss (mass%) = (mass before heating−mass after heating) / mass before heating × 100

(4) Tensile properties Tensile strength and tensile elongation at break were measured according to JIS K7127. Using a tensile tester, the sample is pulled at a speed of 200 mm / min, and the strength (value obtained by dividing the tensile load value by the cross-sectional area of the test piece) and the elongation when the sample is cut (ruptured) are obtained. The tensile elongation is calculated by the following formula.
Elongation rate (%) = (L-Lo) / Lo
Lo: sample length before test, L: sample length at break

(5) Dielectric breakdown voltage (BDV)
It measured based on JIS C2151. Using a DC withstand voltage tester in an atmosphere of 100 ° C., using a cylinder with a diameter of 25 mm as the upper electrode and a cylinder with a diameter of 25 mm as the lower electrode, increasing the voltage at a boosting rate of 1 kV / sec and causing a breakdown (unit) : KV) and the film thickness (unit: mm), the dielectric breakdown voltage (unit: kV / mm) was calculated.

(6) Dielectric constant, dielectric loss tangent Based on JIS C2151, the dielectric constant and dielectric loss tangent at 23 degreeC and 1 kHz were measured.

Example 1
1.2 L of water was put in a reaction vessel equipped with a stirrer, 0.79 mol of sodium hydroxide, 0.194 mol of 9,9-bis (4-hydroxyphenyl) fluorene (hereinafter referred to as BPF) which is a dihydric phenol, As a molecular weight regulator, 0.0116 mol of p-tert-butylphenol (hereinafter referred to as PTBP) was dissolved, 0.0013 mol of a polymerization catalyst (tributylbenzylammonium chloride) was added, and the mixture was vigorously stirred. In another container, 0.100 mol of terephthalic acid chloride (hereinafter referred to as TPC) and 0.100 mol of isophthalic acid chloride (hereinafter referred to as IPC) were weighed and dissolved in 0.7 L of methylene chloride.
This methylene chloride solution was mixed with the previously prepared aqueous alkaline solution to be stirred to initiate polymerization. The polymerization reaction temperature was adjusted to about 20 ° C. Polymerization is carried out for 2 hours by stirring. Thereafter, stirring is stopped and the reaction solution is allowed to stand to separate the aqueous phase and the organic phase. Only the aqueous phase is withdrawn from the reaction vessel, and 2 g of acetic acid is added to the remaining organic phase. Added. Then, 1.5 L of water was added, and the mixture was stirred for 30 minutes. This washing operation was repeated until the electric conductivity of the water phase after washing was 50 μS / cm or less. The methylene chloride is evaporated while the obtained organic phase is gradually put into a 50 ° C. hot water tank equipped with a homomixer to precipitate a powdered polymer, which is taken out and dehydrated and dried. Arylate resin was obtained.
The resulting polyarylate resin had an inherent viscosity of 0.49 dl / g. When DSC measurement was performed, no crystal melting peak was observed, and the glass transition temperature was 320 ° C.
Next, the polyarylate resin was dissolved in methylene chloride to a concentration of 10% by mass, and this solution was used to form a 100 μm-thick coating film on a polyethylene terephthalate (PET) substrate using an applicator. 1 hour until the coating film spontaneously peeled off from the base material in the environment of the above, after leaving to stand and drying, only the peeled coating film was put in a vacuum dryer, 40 ° C. × 0.5 h, 60 ° C. × 0.5 h, 80 ° C. The temperature was increased stepwise to x 0.5 h and the resultant was dried to obtain a polyarylate resin film having a thickness of about 10 μm. About the obtained polyarylate resin film, it processed on 200 degreeC x 0.5 h conditions, and calculated | required the heat loss. The loss on heating was 0.2% by mass. Thereafter, tensile properties, dielectric breakdown voltage, dielectric constant and dielectric loss tangent of the obtained polyarylate resin film were measured. The results are shown in Table 1.

Example 2
A polyarylate resin was obtained in the same manner as in Example 1 except that 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter referred to as BCF) was used as the dihydric phenol. This polyarylate resin had an inherent viscosity of 0.49 dl / g. When DSC measurement was performed, no crystal melting peak was observed, and the glass transition temperature was 285 ° C. A polyarylate resin film having a thickness of about 10 μm was obtained from the obtained polyarylate resin in the same manner as in Example 1. About the obtained polyarylate resin film, it processed on 200 degreeC x 0.5 h conditions, and calculated | required the heat loss. The loss on heating was 0.2% by mass. Thereafter, tensile properties, dielectric breakdown voltage, dielectric constant and dielectric loss tangent of the obtained polyarylate resin film were measured. The results are shown in Table 1.

Example 3
A polyarylate resin was obtained in the same manner as in Example 1 except that 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene (hereinafter referred to as BXF) was used as the dihydric phenol. This polyarylate resin had an inherent viscosity of 0.47 dl / g. When DSC measurement was performed, no crystal melting peak was observed, and the glass transition temperature was 305 ° C. A polyarylate resin film having a thickness of about 10 μm was obtained from the obtained polyarylate resin in the same manner as in Example 1. About the obtained polyarylate resin film, it processed on 200 degreeC x 0.5 h conditions, and calculated | required the heat loss. The loss on heating was 0.2% by mass. Thereafter, tensile properties, dielectric breakdown voltage, dielectric constant and dielectric loss tangent of the obtained polyarylate resin film were measured. The results are shown in Table 1.

Example 4
A polyphenol was obtained in the same manner as in Example 1 except that N-phenyl-3,3-bis (4-hydroxyphenyl) phthalimidine (hereinafter referred to as PPPBP) was used as the dihydric phenol and the amount of sodium hydroxide added was 0.79 mol. Arylate resin was obtained. This polyarylate resin had an inherent viscosity of 0.49 dl / g. When DSC measurement was performed, no crystal melting peak was observed, and the glass transition temperature was 300 ° C. A polyarylate resin film having a thickness of about 10 μm was obtained from the obtained polyarylate resin in the same manner as in Example 1. About the obtained polyarylate resin film, it processed on 200 degreeC x 0.5 h conditions, and calculated | required the heat loss. The loss on heating was 0.2% by mass. Thereafter, tensile properties, dielectric breakdown voltage, dielectric constant and dielectric loss tangent of the obtained polyarylate resin film were measured. The results are shown in Table 1.

Example 5
A polyarylate resin was obtained in the same manner as in Example 1 except that 1,1-bis (4-hydroxyphenyl) cyclohexane (hereinafter referred to as BPZ) was used as the dihydric phenol and the amount of sodium hydroxide added was 0.71 mol. It was. This polyarylate resin had an inherent viscosity of 0.49 dl / g. When DSC measurement was performed, no crystal melting peak was observed, and the glass transition temperature was 210 ° C. A polyarylate resin film having a thickness of about 10 μm was obtained from the obtained polyarylate resin in the same manner as in Example 1. About the obtained polyarylate resin film, it processed on 200 degreeC x 0.5 h conditions, and calculated | required the heat loss. The loss on heating was 0.2% by mass. Thereafter, tensile properties, dielectric breakdown voltage, dielectric constant and dielectric loss tangent of the obtained polyarylate resin film were measured. The results are shown in Table 1.

Example 6
A polyarylate resin was obtained in the same manner as in Example 4 except that 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter referred to as BPTMC) was used as the dihydric phenol. This polyarylate resin had an inherent viscosity of 0.49 dl / g. When DSC measurement was performed, no crystal melting peak was observed, and the glass transition temperature was 255 ° C. A polyarylate resin film having a thickness of about 10 μm was obtained from the obtained polyarylate resin in the same manner as in Example 1. About the obtained polyarylate resin film, it processed on 200 degreeC x 0.5 h conditions, and calculated | required the heat loss. The loss on heating was 0.2% by mass. Thereafter, tensile properties, dielectric breakdown voltage, dielectric constant and dielectric loss tangent of the obtained polyarylate resin film were measured. The results are shown in Table 1.

Example 7
A polyphenol was obtained in the same manner as in Example 1 except that 1,1-bis (4-hydroxyphenyl) -1-phenylethane (hereinafter referred to as BPAP) was used as the dihydric phenol and the amount of sodium hydroxide added was 0.48 mol. Arylate resin was obtained. This polyarylate resin had an inherent viscosity of 0.49 dl / g. When DSC measurement was performed, no crystal melting peak was observed, and the glass transition temperature was 240 ° C. A polyarylate resin film having a thickness of about 10 μm was obtained from the obtained polyarylate resin in the same manner as in Example 1. About the obtained polyarylate resin film, it processed on 200 degreeC x 0.5 h conditions, and calculated | required the heat loss. The loss on heating was 0.2% by mass. Thereafter, tensile properties, dielectric breakdown voltage, dielectric constant and dielectric loss tangent of the obtained polyarylate resin film were measured. The results are shown in Table 1.

Examples 8 and 9
A polyarylate resin was obtained in the same manner as in Example 7 except that the blending of BPAP and PTBP was as described in Table 1. This polyarylate resin did not show a crystal melting peak by DSC measurement. Table 1 shows the inherent viscosity and glass transition temperature of these polyarylate resins. A polyarylate resin film having a thickness of about 10 μm was obtained from the obtained polyarylate resin in the same manner as in Example 1. About the obtained polyarylate resin film, it processed on 200 degreeC x 0.5 h conditions, and calculated | required the heat loss. The loss on heating was 0.2% by mass. Thereafter, tensile properties, dielectric breakdown voltage, dielectric constant and dielectric loss tangent of the obtained polyarylate resin film were measured. The results are shown in Table 1.

Examples 10 and 11
A polyarylate resin was obtained in the same manner as in Example 7 except that the composition of TPC and IPC was changed to that shown in Table 1. This polyarylate resin did not show a crystal melting peak by DSC measurement. Table 1 shows the inherent viscosity and glass transition temperature of these polyarylate resins. A polyarylate resin film having a thickness of about 10 μm was obtained from the obtained polyarylate resin in the same manner as in Example 1. About the obtained polyarylate resin film, it processed on 200 degreeC x 0.5 h conditions, and calculated | required the heat loss. The loss on heating was 0.2% by mass. Thereafter, tensile properties, dielectric breakdown voltage, dielectric constant and dielectric loss tangent of the obtained polyarylate resin film were measured. The results are shown in Table 1.

Comparative Example 1
A polyarylate resin was obtained in the same manner as in Example 1 except that 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as BPA) was used as the dihydric phenol. This polyarylate resin had an inherent viscosity of 0.49 dl / g. When DSC measurement was performed, no crystal melting peak was observed, and the glass transition temperature was 190 ° C. A polyarylate resin film having a thickness of about 10 μm was obtained from the obtained polyarylate resin in the same manner as in Example 1. About the obtained polyarylate resin film, it processed on 200 degreeC x 0.5 h conditions, and calculated | required the heat loss. The loss on heating was 0.2% by mass. Thereafter, tensile properties, dielectric breakdown voltage, dielectric constant and dielectric loss tangent of the obtained polyarylate resin film were measured. The results are shown in Table 2.

Comparative Example 2
A polyarylate resin was obtained in the same manner as in Example 1 except that 2,2-bis (4-hydroxy-3-methylphenyl) propane (hereinafter referred to as BCA) was used as the dihydric phenol. This polyarylate resin had an inherent viscosity of 0.49 dl / g. When DSC measurement was performed, no crystal melting peak was observed, and the glass transition temperature was 185 ° C. A polyarylate resin film having a thickness of about 10 μm was obtained from the obtained polyarylate resin in the same manner as in Example 1. About the obtained polyarylate resin film, it processed on 200 degreeC x 0.5 h conditions, and calculated | required the heat loss. The loss on heating was 0.2% by mass. Thereafter, tensile properties, dielectric breakdown voltage, dielectric constant and dielectric loss tangent of the obtained polyarylate resin film were measured. The results are shown in Table 2.

Examples 12-21
A polyarylate resin was obtained in the same manner as in Example 1 except that the two types of dihydric phenols shown in Table 3 and their blending amounts and sodium hydroxide blending amounts were used. These polyarylate resins did not show a crystal melting peak by DSC measurement. Table 3 shows the inherent viscosity and glass transition temperature of these polyarylate resins. A polyarylate resin film having a thickness of about 10 μm was obtained from the obtained polyarylate resin in the same manner as in Example 1. About the obtained polyarylate resin film, it processed on 200 degreeC x 0.5 h conditions, and calculated | required the heat loss. The loss on heating was 0.2% by mass. Thereafter, tensile properties, dielectric breakdown voltage, dielectric constant and dielectric loss tangent of the obtained polyarylate resin film were measured. The results are shown in Table 3.

Example 22
A 20 μm coating film was formed from a 5 mass% methylene chloride solution in which the polyarylate resin obtained in Example 7 was dissolved. Thereafter, a polyarylate resin film having a thickness of 1 μm was obtained by the same operation as in Example 7. It was. About the obtained polyarylate resin film, it processed on 200 degreeC x 0.5 h conditions, and calculated | required the heat loss. The loss on heating was 0.2% by mass. Thereafter, tensile properties, dielectric breakdown voltage, dielectric constant and dielectric loss tangent of the obtained polyarylate resin film were measured. The results are shown in Table 4.

Example 23
A 500 μm-thick coating film was formed from a 20 mass% methylene chloride solution in which the polyarylate resin obtained in Example 7 was dissolved. Thereafter, a polyarylate resin film having a thickness of about 100 μm was prepared by the same operation as in Example 7. Obtained. About the obtained polyarylate resin film, it processed on 200 degreeC x 0.5 h conditions, and calculated | required the heat loss. The loss on heating was 0.2% by mass. Thereafter, tensile properties, dielectric breakdown voltage, dielectric constant and dielectric loss tangent of the obtained polyarylate resin film were measured. The results are shown in Table 4.

Example 24
A 100 μm coating film was formed from a 10% by mass methylene chloride solution in which the polyarylate resin obtained in Example 7 was dissolved, and was allowed to stand and dry in an environment of about 23 ° C. until the coating film naturally separated from the substrate. Then, only the peeled coating film was put into a vacuum dryer and 40 ° C. × 0.5 h, 60 ° C. × 0.5 h, 80 ° C. × 0.5 h, 100 ° C. × 0.5 h, 150 ° C. × 0.5 h, 200 The polyarylate resin film having a thickness of about 10 μm was obtained by raising the temperature stepwise to ℃ × 0.5h and drying. About the obtained polyarylate resin film, it processed on 200 degreeC x 0.5 h conditions, and calculated | required the heat loss. The loss on heating was 0.1% by mass. Thereafter, tensile properties, dielectric breakdown voltage, dielectric constant and dielectric loss tangent of the obtained polyarylate resin film were measured. The results are shown in Table 4.

Example 25
The polyarylate resin obtained in Example 7 was dissolved in tetrahydrofuran (hereinafter referred to as THF) so as to have a concentration of 10% by mass, a 100 μm coating film was formed from this solution, and the coating film was formed under an environment of about 23 ° C. After standing and drying until it spontaneously peels off from the material, only the peeled coating film is put in a vacuum dryer, and the temperature is raised stepwise to 40 ° C. × 0.5 h, 60 ° C. × 0.5 h, 80 ° C. × 0.5 h. And dried to obtain a polyarylate resin film having a thickness of about 10 μm. The obtained polyarylate resin film was cut into two, and one was treated under the conditions of 200 ° C. × 0.5 h to determine the loss on heating. The loss on heating was 1.0% by mass. The other was further dried at 100 ° C. × 0.5 h and treated under the conditions of 200 ° C. × 0.5 h to determine the heat loss. The loss on heating was 0.3% by mass.
Thereafter, the tensile properties, dielectric breakdown voltage, dielectric constant and dielectric loss tangent of the polyarylate resin film which had been dried to 100 ° C. × 0.5 h were measured. The results are shown in Table 4.

Example 26
The polyarylate resin obtained in Example 7 was dissolved in toluene so as to have a concentration of 10% by mass, a 100 μm coating film was formed from this solution, and the coating film spontaneously peeled from the substrate in an environment of about 23 ° C. After standing and drying, only the peeled coating film is put into a vacuum dryer and gradually raised to 40 ° C. × 0.5 h, 60 ° C. × 0.5 h, 80 ° C. × 0.5 h, 100 ° C. × 0.5 h. A polyarylate resin film having a thickness of about 10 μm was obtained by heating and drying. About the obtained polyarylate resin film, it processed on 200 degreeC x 0.5 h conditions, and calculated | required the heat loss. The loss on heating was 0.8% by mass. Thereafter, tensile properties, dielectric breakdown voltage, dielectric constant and dielectric loss tangent of the obtained polyarylate resin film were measured. The results are shown in Table 4.

Example 27
The polyarylate resin obtained in Example 7 was dissolved in toluene so as to have a concentration of 10% by mass, a 100 μm coating film was formed from this solution, and the coating film spontaneously peeled from the substrate in an environment of about 23 ° C. After standing and drying, only the peeled coating film is put in a vacuum dryer and 40 ° C. × 0.5 h, 60 ° C. × 0.5 h, 80 ° C. × 0.5 h, 100 ° C. × 0.5 h, 120 ° C. × 0 The polyarylate resin film having a thickness of about 10 μm was obtained by raising the temperature stepwise to 0.5 h and drying. About the obtained polyarylate resin film, it processed on 200 degreeC x 0.5 h conditions, and calculated | required the heat loss. The loss on heating was 0.8% by mass. Thereafter, tensile properties, dielectric breakdown voltage, dielectric constant and dielectric loss tangent of the obtained polyarylate resin film were measured. The results are shown in Table 4.

Example 28
The polyarylate resin obtained in Example 7 was dissolved in N-methylpyrrolidone (hereinafter referred to as NMP) so as to have a concentration of 10% by mass, and a 100 μm coating film was formed from this solution. After standing and drying until the film spontaneously peeled off from the substrate, only the peeled coating film was put in a vacuum dryer and 40 ° C. × 0.5 h, 60 ° C. × 0.5 h, 80 ° C. × 0.5 h, 100 × The polyarylate resin film having a thickness of about 10 μm was obtained by raising the temperature in steps of 0.5 h and 120 ° C. × 0.5 h and drying. The obtained polyarylate resin film was cut into two, and one was treated under the conditions of 200 ° C. × 0.5 h to determine the loss on heating. The loss on heating was 2.0% by mass. The other was further dried at 140 ° C. × 0.5 h and 160 ° C. × 0.5 h, and treated under the conditions of 200 ° C. × 0.5 h to determine the loss on heating. The loss on heating was 0.8% by mass. The tensile properties, dielectric breakdown voltage, dielectric constant and dielectric loss tangent of the polyarylate resin film which had been dried to 160 ° C. × 0.5 h were measured. The results are shown in Table 4.

  Since Examples 1 to 28 satisfied the requirements of the present invention, they were polyarylate resin films excellent in both mechanical properties and electrical properties.

  In particular, since Example 22 was a polyarylate resin film having a thickness of 1 μm, the tensile elongation at break was larger and the dielectric breakdown voltage was higher than in Example 7. Since Example 23 was a polyarylate resin film having a thickness of 100 μm, the tensile fracture elongation was small and the dielectric breakdown voltage was small as compared with Example 7, but it had practical performance.

  In Example 24, the upper limit of the drying temperature was 200 ° C, and the temperature difference from the glass transition temperature of 240 ° C of the polyarylate resin used was 40 ° C. Although having practical performance, the tensile elongation at break was lower than that of Example 7. Further, the obtained film was easily curled when compared with the film obtained in Example 7, and was inferior in dimensional stability.

  In Example 25, THF (boiling point 66 ° C.) was used as a solvent, and drying was performed within a range not exceeding the boiling point. Therefore, a film excellent in surface condition could be obtained. However, it was necessary to make the drying temperature higher than Example 7 using methylene chloride as a solvent, and although it had practical performance, the tensile elongation at break was lower than that of Example 7.

  In Example 26, toluene (boiling point: 110 ° C.) was used as a solvent, the boiling point was not exceeded, and drying was performed up to 100 ° C. to obtain a film. However, it was necessary to make the drying temperature higher than in Example 7 using methylene chloride as a solvent, and although it had practical performance, the tensile strength and tensile elongation at break were lower than in Example 7. Moreover, since the loss on heating was 0.8% by mass, which was slightly higher than that of Example 7, the dielectric breakdown voltage was also slightly decreased.

  In Example 27, toluene (boiling point: 110 ° C.) was used as a solvent, the boiling point was exceeded, and drying was performed at an upper limit of 120 ° C. to obtain a film. The loss on heating decreased to 0.3% by mass, but the tensile elongation at break greatly decreased. Further, the surface shape was swelled more than the film obtained in Example 26, and the surface smoothness was inferior. There was no problem in practical use.

  In Example 28, NMP (boiling point 202 ° C.) was used as a solvent, the boiling point was not exceeded, and drying was performed up to 160 ° C. to obtain a film. The loss on heating was 0.8% by mass. Although both the tensile elongation at break and the breakdown voltage were greatly reduced, there was no problem in practical use.

Since Comparative Examples 1 and 2 used only BPA and BCA as dihydric phenols, respectively, the resulting polyarylate resin film had a low glass transition temperature and an inferior dielectric breakdown voltage.

Claims (7)

It is obtained from a polyarylate resin comprising an aromatic dicarboxylic acid residue and at least one dihydric phenol residue selected from the following general formulas (i) to (iv), and having a glass transition temperature of 200 ° C. or higher. Polyarylate resin film.
In the general formula (i), R ¹ , R ² , R ³ and R ⁴ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a nitro group, and the hydrocarbon group has 1 to 20 carbon atoms. Selected from the group consisting of an aliphatic group having 3 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms.
In general formula (ii), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a nitro group, and the hydrocarbon group has 1 to 20 carbon atoms. Selected from the group consisting of an aliphatic group, an alicyclic group having 3 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms, and R ¹⁵ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. , An alkenyl group, or a phenyl group.
In the general formula (iii), R ²¹ , R ²² , R ²³ and R ²⁴ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a nitro group, and the hydrocarbon group has 1 to 20 carbon atoms. Selected from the group consisting of an aliphatic group having 3 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms, and R ²⁵ and R ²⁶ are each independently a hydrogen atom or carbon number 1 Selected from the group consisting of -20 aliphatic hydrocarbon groups, alicyclic hydrocarbon groups having 1-20 carbon atoms, aromatic hydrocarbon groups having 1-20 carbon atoms, and halogenated alkyl groups, and k is 2-12. Is an integer.
In the general formula (iv), R ³¹ , R ³² , R ³³ and R ³⁴ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a nitro group, and the hydrocarbon group has 1 to 20 carbon atoms. Selected from the group consisting of an aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and R ³⁵ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. Selected from the group consisting of an alicyclic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 1 to 20 carbon atoms, and a halogenated alkyl group, and R ³⁶ is an aromatic hydrocarbon having 1 to 20 carbon atoms. Selected from the group consisting of groups.   2. The polyarylate resin film according to claim 1, which has a thickness of 0.5 to 1500 [mu] m.   The polyarylate resin film according to claim 1 or 2, wherein the elongation at break is 8% or more.   The polyarylate resin film according to claim 1, wherein a metal vapor-deposited layer is formed on one side or both sides of the film. A polyarylate resin composed of an aromatic dicarboxylic acid residue and one or more dihydric phenol residues selected from the following general formulas (i) to (iv) is dissolved in an organic solvent, and then fluent and dried. It forms by performing, The manufacturing method of the polyarylate resin film in any one of Claims 1-4 characterized by the above-mentioned.
In the general formula (i), R ¹ , R ² , R ³ and R ⁴ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a nitro group, and the hydrocarbon group has 1 to 20 carbon atoms. Selected from the group consisting of an aliphatic group having 3 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms.
In general formula (ii), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a nitro group, and the hydrocarbon group has 1 to 20 carbon atoms. Selected from the group consisting of an aliphatic group, an alicyclic group having 3 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms, and R ¹⁵ is hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. , An alkenyl group, or a phenyl group.
In the general formula (iii), R ²¹ , R ²² , R ²³ and R ²⁴ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a nitro group, and the hydrocarbon group has 1 to 20 carbon atoms. Selected from the group consisting of an aliphatic group having 3 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms, and R ²⁵ and R ²⁶ are each independently a hydrogen atom or carbon number 1 Selected from the group consisting of -20 aliphatic hydrocarbon groups, alicyclic hydrocarbon groups having 1-20 carbon atoms, aromatic hydrocarbon groups having 1-20 carbon atoms, and halogenated alkyl groups, and k is 2-12. Is an integer.
In the general formula (iv), R ³¹ , R ³² , R ³³ and R ³⁴ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and a nitro group, and the hydrocarbon group has 1 to 20 carbon atoms. Selected from the group consisting of an aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and R ³⁵ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. Selected from the group consisting of an alicyclic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 1 to 20 carbon atoms, and a halogenated alkyl group, and R ³⁶ is an aromatic hydrocarbon having 1 to 20 carbon atoms. Selected from the group consisting of groups.   6. The production of a polyarylate resin film according to claim 5, wherein an organic solvent having a boiling point of less than 115 ° C. is used and the polyarylate resin is dried in a temperature range not exceeding (glass transition temperature −80 ° C.) of the polyarylate resin to be used. Method. A capacitor using the polyarylate resin film according to claim 1.