JPH11209687A - Resin for film formation, production thereof, and coating liquid obtained therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyarylate resin which has a high mol.wt. and is excellent in abrasion resistance and electrical properties by subjecting dicarboxylic halides dissolved in an org. solvent and a dihydric phenol dissolved in an aq. alkali soln. to interfacial polymn. in the presence of a specific catalyst. SOLUTION: A soln. of 10-90 mol.% terephthalic halide and 90-10 mol.% isophthalic halide in a water-immiscible org. solvent and a soln. of 2,2-bis(3- methyl-4-hydroxyphenyl)propane in an aq. alkali soln. are subjected to interfacial polymn. in the presence of a quaternary ammonium or phosphonium salt having at least three 3C or higher alkyl groups as a catalyst. Thus, a resin for film formation is obtd. as a polymn. product which is a polyarylate resin having an inherent viscosity (at 25 deg.C in 1,1,2,2-tetrachloroethane at a concn. of 1 g/dl) of 0.8 or higher and a carboxyl value of 20 mol/ton or lower.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin for forming a film comprising a polyarylate containing a specific dihydric phenol unit, having a high molecular weight, and having excellent electrical properties and abrasion resistance. The present invention relates to a production method capable of easily producing a resin, and a coating solution obtained by dissolving the resin in a solvent.

[0002]

2. Description of the Related Art Amorphous polyarylate comprising residues of 2,2-bis (4-hydroxyphenyl) propane (sometimes referred to as bisphenol A) and residues of terephthalic acid and isophthalic acid is used as an engineering plastic. It is already well known. Such polyarylate has high heat resistance, excellent mechanical strength and dimensional stability typified by impact strength, and is amorphous and transparent. Widely applied to

[0003] A polyarylate resin using bisphenol A as a dihydric phenol (hereinafter referred to as bisphenol A polyarylate) has good solubility in various solvents, and has good electrical properties (insulating properties, dielectric properties, dielectric properties). Properties, etc.), making use of its excellent abrasion resistance to electronic parts such as films for capacitors, and making use of abrasion resistance and scratch resistance to various films and coating resins of liquid crystal display devices. It is applied to applications for forming various coatings.

[0004] However, in fields where surface gloss such as a film is required, or in applications where a film is formed such as a coating material, the requirements for electrical properties and abrasion resistance of a resin are becoming increasingly severe. In response to the use of bisphenol A polyarylate, there have been applications where these properties are insufficient. Under these circumstances, there is a demand for a resin having further excellent electrical characteristics and wear resistance.

As a resin capable of solving such a problem, BP901605 discloses 2,2-bis (3-methyl-4-hydroxyphenyl) propane (sometimes referred to as bisphenol C). It is composed of terephthalic acid and has an intrinsic viscosity of 0.8 in tetrachloroethane.
4 is described. However, in the present invention, the abrasion resistance of this polymer is not mentioned, and the polyarylate described in the examples has only an acid component of terephthalic acid, so that it is brittle and inherently Since the viscosity was about 0.84, the abrasion resistance was insufficient.

Further, Japanese Patent Application Laid-Open No. 9-22126 discloses that, as an example, bisphenol C, terephthalic acid and isophthalic acid, each containing 1 g of tetrachloroethane.
/ Dl concentration at 25 ° C. of 0.833
An electrophotographic photoreceptor using polyarylate is described, and it is described that an electrophotographic photoreceptor using this polymer has excellent abrasion resistance, but still has a low molecular weight and is used for film formation. The resin had insufficient wear resistance. Further, the publication discloses an electrophotographic photosensitive member using a polyarylate having an inherent viscosity of 1.241 as a comparative example. Although the photosensitive member has excellent abrasion resistance, it has a problem in storage stability of a coating liquid. It has been pointed out that there is. Furthermore, since the polymer having an inherent viscosity of 1.241 was a polymer synthesized using tetramethylbenzylammonium chloride as a catalyst, it had a high carboxyl value and had a problem in electrical characteristics. Also, there was a problem in the storage stability of the coating liquid due to the high carboxyl value.

Under these circumstances, there has been a demand for a film-forming resin which is excellent in abrasion resistance and electrical properties and which has excellent storage stability when used as a coating liquid.

[0008]

SUMMARY OF THE INVENTION In view of the above situation, an object of the present invention is to contain a specific dihydric phenol unit, have a high molecular weight, and have more excellent abrasion resistance and electrical properties than conventional ones. Provision of a film-forming resin excellent in storage stability when used as a coating liquid, a method for producing a film-forming resin capable of easily obtaining such a resin, and a coating liquid excellent in storage stability In the offer.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to solve such problems, and as a result, by using a specific polymerization catalyst at the time of interfacial polymerization, bisphenol C
And a polyarylate consisting of terephthalic acid and isophthalic acid, and having a molecular weight not less than a specific value, and having a low carboxyl value. This polyarylate is known from conventional bisphenol A polyarylate as well as conventional polyarylate. The present inventors have found out that the abrasion resistance and the electrical properties are superior to those of bisphenol C polyarylate, and they are suitable as a resin for forming a film.

That is, the gist of the present invention is that, first, the dihydric phenol component forming the polyarylate is composed of 2,2-bis (3-methyl-4-hydroxyphenyl) propane and the dihydric carboxylic acid component is Terephthalic acid 10-90
Mol% and 90 to 10 mol% of isophthalic acid.
A polyarylate having an inherent viscosity of 0.85 or more at a concentration of 1 g / dl measured in 1,1,2,2-tetrachloroethane at a temperature of 0.degree. C. and a carboxyl number of 20 mol / ton or less. For forming a film.

Second, when a divalent carboxylic acid halide dissolved in an organic solvent incompatible with water is reacted with a divalent phenol dissolved in an aqueous alkali solution by an interfacial polymerization method to obtain a polyarylate, A method for producing a resin for forming a film, wherein a quaternary ammonium salt or a quaternary phosphonium salt having three or more alkyl groups having three or more carbon atoms is used as a catalyst.

Third, there is provided a coating liquid comprising the resin for forming a film and a solvent for dissolving the resin.

Further, in the resin for forming a film according to the present invention, the polyarylate having a residual sodium content of less than 10 ppm, and containing a quaternary ammonium salt or a quaternary phosphonium salt of the polyarylate measured by gas chromatography. Those having an amount of less than 100 ppm, especially 5 p
pm, phenolic hydroxyl value of the polyarylate is 30 mol / ton or less, and the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn in terms of polystyrene of the polyarylate is less than 3.0. , 2,2 as a dihydric phenol component forming a polyarylate
A dihydric phenol other than -bis (3-methyl-4-hydroxyphenyl) propane is 20 mol% or less,
Polyarylate-forming dihydric carboxylic acid component comprising equimolar terephthalic acid and isophthalic acid, polyarylate having an inherent viscosity of 1.0 to 2.5, polyarylate having a carboxyl number of 15 mol / It is a preferred embodiment to use one that is less than ton. Further, in the method for producing a resin for forming a film according to the present invention, a quaternary ammonium salt having a distribution ratio of not less than 2.0 × 10 ^{−2 and not} more than 2.5 as a catalyst in a water-chloroform system at 20 ° C. Is a preferred embodiment. Further, in the coating liquid of the present invention, a coating liquid in which the concentration of the film-forming resin is at least 10% by weight is a preferred embodiment.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The resin for forming a film of the present invention comprises polyarylate, and the dihydric phenol component forming this polyarylate is 2,2.
It consists of 2-bis (3-methyl-4-hydroxyphenyl) propane and the divalent carboxylic acid component is terephthalic acid 10
-90 mol% and 90-10 mol% isophthalic acid. This polyarylate is a dihydric phenol component,
2,2-bis (3-methyl-4-hydroxyphenyl)
It is possible to copolymerize less than 20 mol% of dihydric phenols other than propane (bisphenol C). If the amount of the dihydric phenol other than bisphenol C exceeds 20 mol%, the abrasion resistance of bisphenol C tends to decrease, which is not preferable.

Examples of dihydric phenols other than the copolymerizable bisphenol C include 2-methyl-4,4'-dihydroxybiphenyl, 3-methyl-4,4'-dihydroxybiphenyl and 2-chloro-4,4. '-Dihydroxybiphenyl, 3-chloro-4,4'-dihydroxybiphenyl, 3,3'-dimethyl-4,4'-dihydroxybiphenyl, 2,2'-dimethyl-4,4'-dihydroxybiphenyl, 2,3 '-Dimethyl-4,4'-dihydroxybiphenyl, 3,3'-dichloro-4,4'-
Dihydroxybiphenyl, 3,3'-di-tert-butyl-4,4'-dihydroxybiphenyl, 3,3'-
Dimethoxy-4,4'-dihydroxybiphenyl, 3,
3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, 3,3 ′, 5,5′-tetra-tert
-Butyl-4,4'-dihydroxybiphenyl, 3,
3 ′, 5,5′-tetrachloro-4,4′-dihydroxybiphenyl, 2,2′-dihydroxy-3,3′-dimethylbiphenyl,

3,3'-difluoro-4,4'-biphenol, 2,2'-dihydroxy-3,3 ', 5,5'
-Tetramethylbiphenyl, 3,3 ', 5,5'-tetrafluoro-4,4'-biphenol, 2,2', 3
3 ', 5,5'-hexamethyl-4,4'-biphenol, bis (4-hydroxyphenyl) methane, 1,1-
Bis (4-hydroxyphenyl) ethane, bis (4-methyl-2-hydroxyphenyl) methane, bis (3,5
-Dimethyl-4-hydroxyphenyl) methane, 1,1
-Bis (4-hydroxyphenyl) cyclohexane,
2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2 -Bis (3,5-dimethyl-
4-hydroxyphenyl) propane, 1,1-bis (4
-Hydroxyphenyl) -1-phenylethane, 1,1
-Bis (4-hydroxyphenyl) -2-ethylhexane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, bis (3-methyl-4-hydroxyphenyl) methane, 2,2-bis ( 4-hydroxyphenyl) butane,

1,1-bis (4-hydroxyphenyl)
-2-methylpropane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl) octane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 2,2- Screw (3
-Allyl-4-hydroxyphenyl) propane, 2,2
-Bis (3-isopropyl-4-hydroxyphenyl)
Propane, 2,2-bis (3-tert-butyl-4-
Hydroxyphenyl) propane, 2,2-bis (3-s
ec-butyl-4-hydroxyphenyl) propane,
1,1-bis (2-methyl-4-hydroxy-5-te
rt-butylphenyl) -2-methylpropane, 4,
4 '-[1,4-phenylene-bis (1-methylethylidene)] bis (3-methyl-4-hydroxyphenyl), 1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane, bis (2 -Hydroxyphenyl) methane, 2,4'-methylenebisphenol, bis (3-methyl-4-hydroxyphenyl) methane, 1,
1-bis (4-hydroxyphenyl) propane, 1,1
-Bis (2-hydroxy-5-methylphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -3-methyl-butane, bis (2-hydroxy-3,5-dimethylphenyl) methane, 1,1 -Bis (4-hydroxyphenyl) cyclopentane,

1,1-bis (3-methyl-4-hydroxyphenyl) cyclopentane, 3,3-bis (4-hydroxyphenyl) pentane, 3,3-bis (3-methyl-4-hydroxyphenyl) pentane , 3,3-bis (3,5-dimethyl-4-hydroxyphenyl) pentane, 2,2-bis (2-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxyphenyl) Nonane, 1,1-bis (3-methyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 2,2-bis (4- Hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (2-hydroxy-3-tert-butyl-5-methylphen) L) methane, bis (4-hydroxyphenyl) diphenylmethane, terpene diphenol, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (2-methyl-4-hydroxy- 5-tert-butylphenyl) -2-methylpropane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, bis (3,5-di-tert-butyl-4-hydroxyphenyl) methane, bis (3,5-di-sec-butyl-4
-Hydroxyphenyl) methane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (2-hydroxy-3,5-di-te
rt-butylphenyl) ethane, 1,1-bis (3-nonyl-4-hydroxyphenyl) methane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 1,1 -Bis (2-hydroxy-3,
5-di-tert-butyl-6-methylphenyl) methane,

1,1-bis (3-phenyl-4-hydroxyphenyl) -1-phenylethane, α, α'-bis (4-hydroxyphenyl) acetic acid butyl ester,
1-bis (3-fluoro-4-hydroxyphenyl) methane, bis (2-hydroxy-5-fluorophenyl)
Methane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 1,1-bis (3-fluoro-4
-Hydroxyphenyl) -1-phenylmethane, 1,1
-Bis (3-fluoro-4-hydroxyphenyl) -1
-(P-fluorophenyl) methane, 1,1-bis (4
-Hydroxyphenyl) -1- (p-fluorophenyl) methane, 2,2-bis (3-chloro-4-hydroxy-5-methylphenyl) propane, 2,2-bis (3,5-dichloro-4-) Hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 1,1-bis (3,5-dibromo-4-
Hydroxyphenyl) methane, 2,2-bis (3,5-
Dibromo-4-hydroxyphenyl) propane, 2,2
-Bis (3-nitro-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) dimethylsilane,
Bis (2,3,5-trimethyl-4-hydroxyphenyl) -1-phenylmethane, 2,2-bis (4-hydroxyphenyl) dodecane, 2,2-bis (3-methyl-
4-hydroxyphenyl) dodecane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) dodecane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3,5-di-tert-butyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (2-methyl-4-hydroxy-5-cyclohexylphenyl)-
2-methylpropane, 1,1-bis (2-hydroxy-
3,5-di-tert-butylphenyl) ethane,

2,2-bis (4-hydroxyphenyl)
Propanoic acid methyl ester, 2,2-bis (4-hydroxyphenyl) propanoic acid ethyl ester, 2,2 ′,
3,3 ′, 5,5′-hexamethyl-4,4′-biphenol, bis (2-hydroxyphenyl) methane, 2,
4'-methylenebisphenol, 1,2-bis (4-hydroxyphenyl) ethane, 2- (4-hydroxyphenyl) -2- (2-hydroxyphenyl) propane, bis (2-hydroxy-3-allylphenyl) methane ,
1,1-bis (2-hydroxy-3,5-dimethylphenyl) -2-methylpropane, 1,1-bis (2-hydroxy-5-tert-butylphenyl) ethane, bis (2-hydroxy-5 Phenylphenyl) methane,
1,1-bis (2-methyl-4-hydroxy-5-te
rt-butylphenyl) butane, bis (2-methyl-4)
-Hydroxy-5-cyclohexylphenyl) methane,
2,2-bis (4-hydroxyphenyl) pentadecane, 2,2-bis (3-methyl-4-hydroxyphenyl) pentadecane, 2,2-bis (3,5-dimethyl-
4-hydroxyphenyl) pentadecane, 1,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) ethane, bis (2-hydroxy-3,5-di-t
tert-butylphenyl) methane, 2,2-bis (3-
Styryl-4-hydroxyphenyl) propane, 1,1
-Bis (4-hydroxyphenyl) -1- (p-nitrophenyl) ethane, bis (3,5-difluoro-4-hydroxyphenyl) methane, bis (3,5-difluoro-4-hydroxyphenyl) -1- Phenylmethane, bis (3,5-difluoro-4-hydroxyphenyl) diphenylmethane, bis (3-fluoro-4-hydroxyphenyl) diphenylmethane,

2,2-bis (3-chloro-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -3,3-dimethyl-5-methyl-cyclohexane, 1,1-bis ( 4-hydroxyphenyl)-
3,3-dimethyl-5,5-dimethyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3
-Dimethyl-4-methyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3-dimethyl-5
-Ethyl-cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3-dimethyl-5-methyl-cyclopentane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) -3, 3-dimethyl-5-methyl-
Cyclohexane, 1,1-bis (3,5-diphenyl-
4-hydroxyphenyl) -3,3-dimethyl-5-methyl-cyclohexane, 1,1-bis (3-methyl-4
-Hydroxyphenyl) -3,3-dimethyl-5-methyl-cyclohexane, 1,1-bis (3-phenyl-4)
-Hydroxyphenyl) -3,3-dimethyl-5-methyl-cyclohexane, 1,1-bis (3,5-dichloro-4-hydroxyphenyl) -3,3-dimethyl-5-
Methyl-cyclohexane, 1,1-bis (3,5-dibromo-4-hydroxyphenyl) -3,3-dimethyl-
5-methyl-cyclohexane, 1,4-di (4-hydroxyphenyl) -p-menthane, 1,4-di (3-methyl-4-hydroxyphenyl) -p-menthane, 1,4
-Di (3,5-dimethyl-4-hydroxyphenyl)-
Terpene diphenols such as p-menthane and the like can be mentioned.

Particularly preferred dihydric phenols include:
2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z), 1,1-
Bis (4-hydroxyphenyl) -1-phenylethane (bisphenol AP) is mentioned.

In the present invention, the divalent carboxylic acid component forming a polyarylate is terephthalic acid 10 to 90.
It is a mixture of mol% and isophthalic acid of 90 to 10 mol%. If the terephthalic acid is less than 10 mol%, the storage stability of the coating solution tends to deteriorate, and if it exceeds 90 mol%, the abrasion resistance decreases. There is a tendency, and it is particularly preferable to use an equal mixture of terephthalic acid and isophthalic acid.

Further, the terminal of the polyarylate in the present invention may be sealed with a monovalent phenol, a monovalent acid chloride, a monovalent alcohol, a monovalent carboxylic acid or the like. Examples of the monovalent phenol include phenol, cresol, p-tert-butylphenol, and o-phenylphenol, and examples of the monovalent acid chloride include benzoic acid chloride, methanesulfonyl chloride, and phenyl chloroformate. And monohydric alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol,
Butanol, pentanol, hexanol, dodecyl alcohol, stearyl alcohol, benzyl alcohol, phenethyl alcohol, and the like.Examples of monovalent carboxylic acids include acetic acid, propionic acid, octanoic acid, cyclohexanecarboxylic acid, benzoic acid, toluic acid, and phenyl. Acetic acid, p-tert-butylbenzoic acid, p-methoxyphenylacetic acid and the like can be mentioned.

The molecular weight of the polyarylate is determined by using tetrachloroethane as a solvent for viscosity measurement at 25 ° C. and 1 g / d.
The inherent viscosity of the solution is 0.85 or more, preferably 1.0 to 2.5. The inherent viscosity is 0.
If it is less than 85, the abrasion resistance may be insufficient. On the other hand, if it exceeds 2.5, spinnability may occur or the viscosity of the solution to be adjusted during coating may increase, making it difficult to handle. This is not preferred because of the tendency. The molecular weight of the resin of the present invention can be controlled by the amount of the above-mentioned terminal blocking material added at the time of production.

In the molecular weight distribution of the polyarylate in the present invention, the value of Mw / Mn, which is the ratio of the weight average molecular weight Mw to the number average molecular weight Mn in terms of polystyrene, is preferably less than 3.0, more preferably 2.8 or less. If the value of Mw / Mn is 3.0 or more, the wear resistance tends to decrease due to the plasticizing effect of the low molecular weight component, which is not preferable.

It is essential that the carboxyl number of the polyarylate be 20 mol / ton or less. Since the carboxyl number affects electric characteristics such as arc resistance and dielectric constant, the carboxyl number is preferably 15 mol / ton or less. The carboxyl number of the resin can be measured by a known method such as neutralization titration using a potentiometric titrator. Since the carboxyl number affects the storage stability of a coating solution when a resin is dissolved in a solvent described below to form a coating solution,
It is necessary to make it 0 mol / ton or less. When the resin concentration of the coating liquid is as high as about 20% by weight and long-term storage stability is required, the concentration is preferably less than 15 mol / ton. The storage stability of the solution can be evaluated by dissolving the resin in the above-described solvent at a concentration of about 15 to 20% by weight, sealing the solvent so that the solvent does not evaporate, and storing at room temperature or a predetermined temperature. If the storage stability is poor, the solution becomes cloudy and the solid precipitates or thickens and gels over time.

The residual sodium content of polyarylate is 1
Preferably it is less than 0 ppm. If the amount of residual sodium is 10 ppm or more, the above-mentioned electric characteristics tend to deteriorate, which is not preferable. The amount of residual sodium in the resin can be quantified by using a known method such as ion chromatography, atomic absorption analysis, or plasma emission spectroscopy.

The terminal phenolic hydroxyl value of the polyarylate is preferably 30 mol / ton or less. If the phenolic hydroxyl value is more than 30 mol / ton, the electrical properties are lowered, and when heated, the phenolic hydroxyl groups are oxidized and the resin tends to be undesirably colored. The phenolic hydroxyl value of the resin is determined by the proton NM
It can be directly quantified by R.

Furthermore, the amount of the quaternary ammonium salt or quaternary phosphonium salt remaining in the polyarylate is 100 p when measured by gas chromatography.
pm, more preferably 5 pp
m. If the amount of the remaining quaternary ammonium salt or quaternary phosphonium salt is 100 ppm or more, the dielectric breakdown strength tends to decrease, which is not preferable.

As a method for producing a polyarylate for obtaining the resin for forming a film according to the present invention, a divalent carboxylic acid halide dissolved in an organic solvent incompatible with water and a divalent phenol dissolved in an aqueous alkali solution are used. And an interfacial polymerization method (WM EARCKSON J. Pol)
y. Sci. XL399 1959, Tokiko 40-1
959) is preferably employed. The interfacial polymerization method is faster in reaction than the solution polymerization method, so it is possible to minimize the hydrolysis of the acid halide, and particularly by selecting a polymerization catalyst described later, a high molecular weight as in the present invention. It is advantageous when obtaining a polymer.

The production method by the interfacial polymerization method will be described in more detail. An alkaline aqueous solution of a dihydric phenol is prepared,
Subsequently, a polymerization catalyst is added. Examples of the alkali that can be used here include sodium hydroxide and potassium hydroxide. The polymerization catalyst is not particularly limited as long as a polymer having a high molecular weight and a low carboxyl value can be obtained, but a quaternary ammonium salt or a quaternary phosphonium salt having three or more alkyl groups having three or more carbon atoms is preferable. It is preferable in that a polymer having a high molecular weight and a low carboxyl number is provided. A quaternary ammonium salt or quaternary phosphonium having two or less alkyl groups having three or more carbon atoms has a low polymerization rate and a high molecular weight polymer cannot be obtained. This is not preferred because of the tendency to occur. Considering the residual amount of the polymerization catalyst in the polymer as described above, a quaternary ammonium having a distribution ratio of 2.0 × 10 ⁻² or more and 1.5 or less at 20 ° C. in a water-chloroform system is used. Salts are more preferred because of their high polymerization rate and easy removal from the polymer solution after polymerization. When the distribution ratio is less than 2.0 × 10 ⁻² ,
The polymerization rate tends to be low, and if it exceeds 1.5, the lipophilicity tends to be high, so that removal from the polymer tends to be difficult.

Specific examples of the polymerization catalyst include tripropylbenzylammonium halide, tributylbenzylammonium halide, tributylmethylammonium halide, tetrabutylammonium halide, tetrabutylphosphonium halideium halide, and tributylbenzylammonium halide. The halide is not particularly limited, such as chlorine, bromine, and iodine.

On the other hand, a solvent which is not compatible with water and dissolves polyarylate, for example, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, 1,1,2,2-tetrachloroethane , 1,1,
The solution obtained by dissolving a divalent carboxylic acid halide in a chlorine-based solvent such as 1-trichloroethane, o-, m-, p-dichlorobenzene, or an aromatic hydrocarbon such as toluene, benzene, or xylene is used as the alkali solution. Mix. 2
The resin of the present invention can be obtained by carrying out the reaction with stirring at a temperature of 5 ° C. or lower for 1 hour to 5 hours. The resin for forming a film is substantially amorphous, has a high molecular weight, Polyarylate with excellent mechanical properties and abrasion resistance.

Further, since the resin for forming a film has high solubility in general-purpose solvents, it can be easily dissolved in the solvent to form a coating liquid. Solvents used when forming the coating liquid include methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene,
Examples thereof include chlorinated solvents such as 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, o-, m-, and p-dichlorobenzene, toluene, benzene, xylene, and tetrahydrofuran.

The coating liquid may contain various additives as necessary, and may be coated on a substrate, and the solvent may be removed to form a film, which may be used as a coating or as a film after peeling off the coating. Can be. When the coating liquid is used, the resin is at a concentration of at least about 10% by weight, preferably 15 to 20%.
It is preferable to completely dissolve at a concentration of about% by weight. If the concentration is less than 10% by weight, the coatability may be reduced or the film thickness when coated may be non-uniform.

Various antioxidants such as a hindered phenol type, a hindered amine type, a thioether type and a phosphorus type can be added to the resin for forming a film of the present invention as long as its properties are not impaired. In order to impart various performances, conductive fillers such as carbon black, acetylene black, Ketjen black, and metal powder, and various fillers such as silica and talc can be contained.

The resin for forming a film of the present invention is used as a resin for a binder or a resin for a film. The resin for coating is formed by a casting method as described above by a casting method, a melt extrusion method or a calender method. It can be used as an insulating material for electrical equipment such as motors, transformers, and generators, as a coating material for electric wires, or as a dielectric film material for capacitors and the like. And various substrates, etc.
It can be widely applied to electric and electronic materials.

[0039]

EXAMPLES Next, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these, and various modifications and applications are possible without departing from the spirit of the present invention. It is.

Example 1 100 parts by weight of 2,2-bis (3-methyl-4-hydroxyphenyl) propane was placed in a reaction vessel equipped with a stirrer.
p-tert-butylphenol (referred to as PTBP)
1.17 parts by weight, 40.98 parts by weight of sodium hydroxide,
0.82 parts by weight of tri-n-butylbenzylammonium chloride as a polymerization catalyst was charged and dissolved in 2720 parts by weight of water (aqueous phase). Separately, methylene chloride 202
79.99 parts by weight of a terephthalic acid chloride / isophthalic acid chloride = 1/1 mixture (abbreviated as MPC) was dissolved in 3 parts by weight (organic phase). This organic phase was added to the previously prepared aqueous phase under vigorous stirring, and a polymerization reaction was carried out at 20 ° C. for 3 hours. Thereafter, 15 parts by weight of acetic acid was added to stop the reaction, and an aqueous phase and an organic phase were separated. Washing and separation were repeated once for the organic phase with twice the volume of ion-exchanged water for the organic phase. When the electric conductivity of the washing water reached 20 μS, the washing was stopped. At 50 ° C., the washed organic phase was put into a hot water tank equipped with a homomixer, and methylene chloride was evaporated to obtain a powdery polymer. Thereafter, dehydration and drying were performed to obtain a resin for forming a film. The obtained film-forming resin is dissolved in methylene chloride so that the resin concentration becomes 15% by weight,
A coating solution was prepared.

Examples 2 to 17, Comparative Examples 1 to 3, 2,2-bis (3-methyl-4-hydroxyphenyl)
With respect to 100 parts by weight of propane, p-tert-butylphenol, sodium hydroxide, type and amount of polymerization catalyst, M
Example 1 except that the preparation of PC and the degree of washing of the organic phase were changed.
In the same manner as in the above, a film-forming resin was produced, and a coating liquid was prepared.

Comparative Examples 4 and 5 2,2-bis (3-methyl-4-hydroxyphenyl)
A resin was produced in the same manner as in Example 1, except that 100 parts by weight of 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane were used instead of propane. A coating solution was prepared.

Comparative Example 6 In the same manner as in Example 1 except that terephthalic acid chloride was used instead of MPC according to the example described in BP901605,
A resin was manufactured and a coating liquid was prepared.

Evaluation of Resin and Coating Liquid Various evaluations were performed as described below using the resin and the coating liquid obtained as described above. Table 2 shows the results. Table 1 shows the resin production conditions.

1) Inherent Viscosity Using 1,1,2,2-tetrachloroethane as a solvent, the reaction was carried out at a temperature of 25 ° C. and a concentration of 1 g / dl. 2) Carboxyl number 0.15 g of the resin is precisely weighed in a test tube, and dissolved by heating in 5 ml of benzyl alcohol. After mixing 10 ml of chloroform and a benzyl alcohol solution of the polymer, phenol red is added as an indicator, and 0.1N-
Neutralization titration was performed with a KOH benzyl alcohol solution to determine the carboxyl number.

3) Molecular weight distribution The number average molecular weight and the weight average molecular weight in terms of polystyrene were measured using a liquid chromatograph (600 series) manufactured by Waters, and using MIX-Gel manufactured by Polymer Laboratory as a column. The measurement was performed at 40 ° C. using chloroform as a solvent. From this value, the molecular weight dispersity was calculated. 4) Phenolic hydroxyl value The polymer was dissolved in heavy chloroform and measured by proton NMR.

5) Residual sodium content Nitric acid was added to the polymer, and a heat treatment was performed by a microwave wet decomposition apparatus. The sample was made into a solution by sequentially adding sulfuric acid and perchloric acid and repeating the same thermal decomposition treatment. The obtained solution was analyzed with an atomic absorption spectrometer to measure the amount of residual sodium in the polymer. 6) Amount of residual catalyst After dissolving the polymer in chloroform, methanol was added to cause reprecipitation, a certain amount of diphenyl was added as an internal standard, and a methanol solution containing the residual catalyst was passed through a gus chromatographic apparatus (HP, manufactured by Hewlett-Packard Company).
The amount of the catalyst remaining in the polymer was quantified by analysis using -5890 series II).

7) Storage stability The coating solutions obtained in Examples and Comparative Examples were allowed to stand at 25 ° C. for one month, and the state of the solutions was visually evaluated. 8) Abrasion resistance A cast film having a thickness of 100 μm was prepared from the coating liquids obtained in Examples and Comparative Examples. About this film,
Using a Taber abrasion tester (wear wheel CS-10F), the weight loss after a 10,000 cycle test under a load of 250 g was measured and used as an index of wear resistance.

9) Dielectric constant A solvent cast film having a thickness of 50 μm was prepared from the coating solutions obtained in Examples and Comparative Examples. Using this film as a test piece, measurement was performed at 1 MHz according to ASTM D-150. 10) Dielectric breakdown voltage The measurement was performed according to ASTM D149 using the same polyarylate film having a thickness of 50 μm as in 9).

[0050]

[Table 1]

[0051]

[Table 2]

From the above results, the following has become clear. 1) Comparison of Comparative Examples 1 to 2 and 6 with the examples showed that the polyarylate of the present invention had a high molecular weight and excellent abrasion resistance. 2) From the comparison of Comparative Examples 2-3, 6 and 6 with the examples, it was found that the polyarylate of the present invention had a low carboxyl number, and thus had excellent electrical properties. 3) From the comparison between Comparative Examples 4 and 5 and Examples, the polyarylate of the present invention is excellent in abrasion resistance because it contains 2,2-bis (3-methyl-4-hydroxyphenyl) propane unit. I understand.

[0053]

The resin for forming a film according to the present invention comprises a polyarylate having a high molecular weight, excellent electrical properties and abrasion resistance, and is a coating liquid which is soluble in a solvent and has excellent storage stability. be able to. Therefore, it is dissolved in a solvent to form a coating liquid, coated on a substrate, and the solvent is removed to form a coating to form a coating, or the coating is peeled off as a film, for various electric and electronic applications. It can be applied as a material. Further, according to the manufacturing method of the present invention, such a resin for forming a film can be easily manufactured.

 ──────────────────────────────────────────────────続 き Continuation of the front page (31) Priority claim number Japanese Patent Application No. 9-139706 (32) Priority date Hei 9 (1997) May 29 (33) Priority claim country Japan (JP) (31) Priority Claim No. 9-187956 (32) Priority date Hei 9 (1997) July 14 (33) Priority claiming country Japan (JP) (31) Priority claim number Patent application No. 9-316819 (32) Priority Japan, Japan (JP) (72) Inventor Akihiko Hasegawa 23 Uji Kozakura, Uji-city, Kyoto Prefecture Unitika Corporation Central Research Laboratory (72) Inventor Kazuhiro Hamada 23 Uji Kozakura, Uji City, Kyoto Unitika Unit Research Laboratory

Claims (9)

[Claims] 1. A dihydric phenol component forming a polyarylate comprises 2,2-bis (3-methyl-4-hydroxyphenyl) propane, and a dihydric carboxylic acid component comprises 10 to 90 mol% of terephthalic acid and isophthalic acid. 90 to 10 mol%, having an inherent viscosity of 0.85 or more at a concentration of 1 g / dl measured in 1,1,2,2-tetrachloroethane at 25 ° C. and a carboxyl number of 2
A resin for forming a film, comprising a polyarylate of 0 mol / ton or less. 2. The polyarylate having a residual sodium content of 1
The resin for forming a film according to claim 1, wherein the amount is less than 0 ppm. 3. The resin for forming a film according to claim 1, wherein the content of the quaternary ammonium salt or quaternary phosphonium salt of the polyarylate measured by gas chromatography is less than 100 ppm. 4. The resin according to claim 3, wherein the amount of the quaternary ammonium salt or the quaternary phosphonium salt of the polyarylate measured by gas chromatography is less than 5 ppm. 5. The resin according to claim 1, wherein the polyarylate has a phenolic hydroxyl value of 30 mol / ton or less. 6. The resin for forming a film according to claim 1, wherein the ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn of the polyarylate in terms of polystyrene is less than 3.0. 7. A catalyst for obtaining a polyarylate by reacting a divalent carboxylic acid halide dissolved in an organic solvent incompatible with water with a divalent phenol dissolved in an aqueous alkali solution by an interfacial polymerization method. A method for producing a resin for forming a film, comprising using a quaternary ammonium salt or a quaternary phosphonium salt having three or more alkyl groups having three or more carbon atoms. 8. A quaternary ammonium salt having a distribution ratio of 2.0 × 10 ⁻² or more and 2.5 or less measured at 20 ° C. in a water-chloroform system as a catalyst. 8. The method for producing a resin for forming a film according to 7 above. 9. A coating liquid comprising the resin for forming a film according to claim 1 and a solvent for dissolving the resin.