JP2000273160A - Film-forming resin and coating fluid obtained therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin which comprises a polyarylate having a specified intrinsic viscosity and having structural units containing a dibasic carboxylic acid component and those containing a dihydric phenol component at a specified ratio, which is excellent in wear resistance and electrical characteristics and which gives a coating fluid excellent in shelf stability. SOLUTION: The polyarylate has repeating units of formula I, or those of formula I and formula II, wherein the mole fraction (1) of the units of formula I and the mole fraction (2) of the units of formula II satisfy the relation of the formula: 0.03<= (1)/[(1)+(2)]}<=1.00. It has an intrinsic viscosity (in 1,1,2,2- tetrachloroethane, at 25 deg.C) of 0.70 dl/g or higher. In the formulas, X is a single bond, O, S, an alkylene, alkylidene, cycloalkylene, cycloalkylidene, or the like; Y is phenylene, biphenylene, naphthylene, a 1-20C aliphatic hydrocarbon group, or a 3-7C cyclic hydrocarbon group; R1 to R4 are each a halogeno, a 1-20C aliphatic, alicyclic or aromatic hydrocarbon group, nitro, or a, halogenated alkyl; (p), (q), (r) and (s) are each 0 to 4; and p+q>=1.

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 having a high molecular weight and excellent abrasion resistance, electrical properties and optical properties, and a storage stability obtained by dissolving the resin in a solvent. It relates to an excellent coating liquid.

[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). Characteristics, etc.), for the electronic parts such as films for capacitors, taking advantage of its excellent abrasion resistance, and for various types of liquid crystal display devices, taking advantage of its excellent abrasion resistance and abrasion resistance. Applications for forming films such as films and coating resins have been made.

However, in fields requiring surface gloss such as films, and in applications where coatings are formed such as coating materials, the requirements for electrical properties and abrasion resistance of resins are becoming increasingly severe. In response to the use of bisphenol A polyarylate, applications in which these properties are insufficient have arisen, and resins having excellent electrical properties and abrasion resistance have been demanded.

[0005] Japanese Patent Application Laid-Open No. Hei 9-22126 discloses a resin capable of solving such a problem.
An electrophotographic photosensitive member using bis (3-methyl-4-hydroxyphenyl) propane (sometimes referred to as bisphenol C) and a polyarylate composed of terephthalic acid and isophthalic acid (described as bisphenol C polyarylate) is described. It is described that an electrophotographic photosensitive member using this polyarylate is excellent in abrasion resistance.

[0006]

The above bisphenol C polyarylate is not always sufficient in electrical characteristics such as a dielectric breakdown voltage. Further, the bisphenol C polyarylate described above is not sufficient in storage stability of a coating liquid, which is required when it is dissolved in a solvent to form a film and used as a coating liquid. . Under these circumstances, there has been a demand for a film-forming resin that is excellent in abrasion resistance and electrical properties and that has excellent storage stability when used as a coating liquid.

[0007] In view of the above situation, an object of the present invention is to provide a film-forming resin made of polyarylate having excellent abrasion resistance and electrical properties, and a coating using this resin having excellent storage stability. In providing the liquid.

[0008]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve such problems, and as a result, have found that a polydiamine having a structural unit containing a specific dihydric carboxylic acid component and a specific dihydric phenol component. Allylate has excellent abrasion resistance and also has better electrical properties than conventionally known bisphenol C polyarylate. Further, if the carboxyl number of this polyarylate is small, the coating liquid and The present inventors have found that the storage stability at the time of carrying out is improved, and completed the present invention.

That is, the gist of the present invention is, first, a film-forming resin made of polyarylate, wherein the polyarylate has a structural unit represented by the following formula (1) or a resin represented by the following formula (1): Having a structural unit represented by the following formula (2) and a structural unit represented by the following formula (2).
Is 0.03 ≦ [(1) /
[(1) + (2)]] ≦ 1.00, 0.70 dl
A resin for forming a film, which is a polyarylate having an intrinsic viscosity of not less than / g (measured in 1,1,2,2-tetrachloroethane at 25 ° C.).

[0010]

Embedded image

[0011]

Embedded image [In the formulas (1) and (2), X represents a single bond, an oxygen atom, a sulfur atom, an alkylene group, an alkylidene group, a cycloalkylene group, a cycloalkylidene group, a halo-substituted alkylene group, a phenylalkylidene group, a substituted phenylalkylidene group. Group, carbonyl group, sulfonyl group, carboxylalkylene group, carboxylalkylidene group, alkoxycarbonylalkylene group, alkoxycarbonylalkylidene group, fluorene group, isatin group, alkylsilane group, selected from the group consisting of dialkylsilane group, Y
Is selected from the group consisting of a phenylene group, a biphenylene group, a naphthylene group, an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a cyclic hydrocarbon group having 3 to 7 carbon atoms, and R1, R2, R3, and R4 are Each independently a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 1 to 20 carbon atoms, a nitro group, a halogenated alkyl group Selected from the group consisting of: p, q,
r and s represent an integer of 0 to 4, and p + q ≧ 1. ]

Secondly, the above resin for forming a film is characterized in that the carboxyl number of the polyarylate is 30 mol / ton or less.

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

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The polyarylate used in the resin for forming a film according to the present invention has structural units as shown in Formulas (1) and (2). These structural units are composed of a dihydric phenol residue and a dihydric carboxylic acid residue.

Formula (1) of the polyarylate in the present invention
As the dihydric phenol giving the structural unit represented by
1,1-bis (3-methyl-4-hydroxyphenyl)
Cyclohexane (sometimes abbreviated as bisphenol OC-Z) and 1,1-bis (3,5-dimethyl-4-
(Hydroxyphenyl) cyclohexane (sometimes abbreviated as tetramethylbisphenol Z) is preferred.

Specific examples of the dihydric phenol which provides the structural unit of the polyarylate represented by the formula (2) include 4,4
4'-dihydroxybiphenyl, 2-methyl-4,4 '
-Dihydroxybiphenyl, 3-methyl-4,4'-dihydroxybiphenyl, 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-ter
t-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. Among them, preferred dihydric phenols that provide the structural unit represented by the formula (2) include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and 1,1-bis (4-hydroxyphenyl) -1-
Phenylethane (sometimes abbreviated as bisphenol AP), 4,4′-dihydroxybiphenyl, 3,3 ′
-Dimethyl-4,4'-dihydroxybiphenyl, 2,
Examples include 2-bis (3-methyl-4-hydroxyphenyl) propane (sometimes abbreviated as bisphenol C), and bisphenol C is particularly preferred.

In the present invention, the divalent carboxylic acid which gives the structural unit represented by the formula (1) or (2) of the polyarylate includes terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, Aliphatic dicarboxylic acids such as diphenic acid, 4,4'-dicarboxydiphenyl ether, bis (p-carboxyphenyl) alkane, 4,4'-dicarboxyphenylsulfone, oxalic acid, malonic acid, succinic acid, and adipic acid; Can be These dicarboxylic acids may be used alone or in combination of two or more. Among these divalent carboxylic acids, terephthalic acid and isophthalic acid are preferable, a mixture of 10 to 90 mol% of terephthalic acid and 90 to 10 mol% of isophthalic acid is more preferable, and an equal mixture of terephthalic acid and isophthalic acid is particularly preferable. preferable

Formula (1) of the polyarylate in the present invention
And the molar fraction of the structural unit represented by the formula (2):
It must be in the range of 0.03 ≦ [(1) / [(1) + (2)]] ≦ 1.00. When the molar fraction of the structural unit represented by the formula (1) is less than 0.03, the abrasion resistance of the resin tends to decrease.

Further, the terminal of the polyarylate in the present invention may be sealed with a monohydric phenol, a monohydric acid chloride, a monohydric alcohol, a monohydric carboxylic acid or the like. Examples of the monohydric phenol used as such a terminal blocking agent include phenol, cresol, p-tert-butylphenol, o-phenylphenol, and the like,
Examples of the monohydric acid chloride include benzoic acid chloride, methanesulfonyl chloride, and phenyl chloroformate.Examples of the monohydric alcohol include methanol,
Ethanol, n-propanol, isopropanol, n
-Butanol, 2-butanol, pentanol, hexanol, dodecyl alcohol, stearyl alcohol,
Benzyl alcohol, phenethyl alcohol and the like, and as the monovalent carboxylic acid, acetic acid, propionic acid,
Octanoic acid, cyclohexanecarboxylic acid, benzoic acid, toluic acid, phenylacetic acid, p-tert-butylbenzoic acid, p-methoxyphenylacetic acid and the like can be mentioned.

The molecular weight of the polyarylate in the present invention is specified by the intrinsic viscosity (measured in 1,1,2,2-tetrachloroethane at 25 ° C.), and the intrinsic viscosity is 0.70 dl / g or more. , Preferably 0.70 to 2.5 dl / g, more preferably 0.85 to 2.0 dl / g. If the intrinsic viscosity is lower than 0.70 dl / g, the abrasion resistance of the resin may be insufficient, or the solution viscosity when used as a coating liquid may be too low to make the coating difficult. The electrical properties of the coating may decrease. On the other hand, when the intrinsic viscosity is higher than 2.5 dl / g, when used as a coating liquid, spinnability tends to occur or the viscosity tends to increase, which is not preferable. The molecular weight of the polyarylate in the present invention can be controlled at the time of production by the amount of the terminal blocking agent described above.

The carboxyl number of the polyarylate in the present invention is preferably 30 mol / ton or less, more preferably 25 mol / ton or less, and particularly preferably 20 mol / ton or less. preferable. If the carboxyl number is too high, electrical properties such as dielectric breakdown voltage, arc resistance and dielectric constant of the resin tend to deteriorate, and furthermore, storage stability when the resin is dissolved in a solvent to form a coating liquid. Tends to decrease. When the storage stability of the coating liquid decreases, over time, cloudiness, precipitation, insoluble matter is generated, or viscosity increases and gelation occurs.As a result, a uniform film cannot be formed, and It is not preferable because mechanical properties and electrical properties may be reduced. The carboxyl value can be measured by a known method such as neutralization titration using a potentiometric titrator.

As a method for producing a polyarylate according to the present invention, an interfacial polymerization method (W) in which a divalent carboxylic acid halide dissolved in an organic solvent incompatible with water and a dihydric phenol dissolved in an aqueous alkali solution are mixed. .M.EARE
CKSON J. Poly. Sci. XL399 19
1959, Japanese Patent Publication No. 40-1959). The interfacial polymerization method is faster in reaction than the solution polymerization method, and therefore, it is possible to minimize the hydrolysis of the acid halide. It is advantageous when obtaining a polymer.

The method of producing by the interfacial polymerization method will be described in more detail. First, an alkaline aqueous solution of dihydric phenol is prepared, and then a polymerization catalyst is added. Examples of the alkali that can be used here include sodium hydroxide and potassium hydroxide. Also, as a polymerization catalyst,
There is no particular limitation as long as a polymer having a high molecular weight and a low carboxyl value can be obtained, but quaternary ammonium salts such as tributylbenzylammonium halide, tetrabutylammonium halide, tributylbenzylphosphonium halide, and tetrabutylphosphonium halide or quaternary ammonium salts can be used. Grade phosphonium salts are preferred in that a polymer having a high molecular weight and a low carboxyl number can be obtained. However, even if the quaternary ammonium salt or the quaternary phosphonium salt has a short alkyl chain, such as trimethylbenzylammonium halide, triethylbenzylammonium halide, trimethylbenzylphosphonium halide, and triethylbenzylphosphonium halide, a polymer having a high molecular weight and a low carboxyl number is obtained. It is not preferable because there is a tendency not to be able to do so.

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,
First, a solution in which a divalent carboxylic acid halide is dissolved in a chlorine-based solvent such as 1-trichloroethane, o-, m-, p-dichlorobenzene, an aromatic hydrocarbon such as toluene, benzene, or xylene, or tetrahydrofuran. After mixing with an alkaline solution of the above, the desired polyarylate can be obtained by performing a polymerization reaction while stirring at a temperature of 25 ° C. or lower for 1 hour to 5 hours. This polyarylate is a film-forming resin having a high molecular weight, excellent electrical properties and abrasion resistance, being substantially amorphous and having excellent optical properties. In addition, whether or not it is amorphous may be confirmed by a known method such as differential scanning calorimetry (DSC) or dynamic viscoelasticity measurement, to determine whether or not a melting point exists.

Further, since the resin for forming a film has high solubility in general-purpose solvents,
The coating liquid of the present invention can be easily obtained. As a solvent used when forming a coating liquid, methylene chloride, 1,2-
Dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, 1,1,2,2-tetrachloroethane, 1,
Examples thereof include chlorinated solvents such as 1,1-trichloroethane, o-, m-, and p-dichlorobenzene, aromatic hydrocarbons such as toluene, benzene, and xylene, and tetrahydrofuran. These solvents may be used alone or in combination. It can be used as a solvent.

When forming a coating liquid, the film-forming resin of the present invention may be completely dissolved in the above-mentioned solvent at a concentration of at least about 10% by weight, preferably about 15 to 20% by weight. preferable. If the concentration of the coating liquid is less than 10% by weight,
The coatability may be reduced, or the thickness of the coating when coated may be non-uniform. In addition, the coating liquid of the present invention may contain various additives as necessary, and coated on a substrate to form a film, and peeled off from the substrate as a coating or as a film Can be used.

In addition, various antioxidants such as hindered phenols, hindered amines, thioethers, and phosphorus may be added to the resin for forming a film of the present invention as long as its properties are not impaired.

The resin for forming a film of the present invention is used as a resin for a binder or a resin for a film, and a coating or a film can be produced by a solvent casting method as the above-mentioned coating liquid. It can be suitably applied to

[0035]

EXAMPLES Next, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these, and various modifications and applications may be made without departing from the spirit of the present invention. It is possible.

Example 1 In a reaction vessel equipped with a stirrer, 1,1'-bis (3-methyl-4-hydroxyphenyl) cyclohexane [bisphenol OC-Z] 100 as a dihydric phenol was added.
Parts by weight, 0.76 parts by weight of p-tert-butylphenol (abbreviated as PTBP), 40.8 parts by weight of sodium hydroxide
Parts by weight, and 0.71 part by weight of tri-n-butylbenzylammonium chloride as a polymerization catalyst were charged.
The aqueous phase was prepared by dissolving in 0 parts by weight. Methylene chloride 19
70 parts by weight of a mixture of terephthalic acid chloride / isophthalic acid chloride = 1/1 as divalent carboxylic acid
One part by weight was dissolved to prepare an 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 the aqueous phase and the organic phase were separated by decantation. Further, washing with water was repeated until the organic phase became neutral. The washed organic phase was added to methanol to precipitate a polymer, and the polymer was separated and dried to obtain a resin. The obtained resin was dissolved in methylene chloride at a resin concentration of 1
The coating solution was dissolved at 5% by weight to prepare a coating solution.

Examples 2 to 11, Comparative Examples 1 and 2 Table 1 shows the results in the same manner as in Example 1 except that the kind and amount of dihydric phenol and the amounts of terephthalic acid chloride and isophthalic acid chloride were changed. This was performed under the charging conditions to produce a resin and prepare a coating liquid.

Comparative Example 3 A resin was prepared and a coating liquid was prepared in the same manner as in Example 1 except that triethylbenzylammonium chloride was used as a polymerization catalyst under the charging conditions shown in Table 1.

Table 1 shows the charging conditions at the time of resin production in Examples and Comparative Examples.

[0040]

[Table 1]

Evaluation of Resin and Coating Liquid Various characteristics were evaluated using the resins and coating liquids obtained in Examples and Comparative Examples by the following methods. Table 2 shows the results.
Shown in A) Intrinsic viscosity The viscosity was measured using 1,1,2,2-tetrachloroethane as a solvent at a concentration of 1 g / dl and a temperature of 25 ° C. B) Carboxyl number 0.15 g of the resin was precisely weighed in a test tube, and dissolved by heating in 5 ml of benzyl alcohol. After mixing 10 ml of chloroform with a benzyl alcohol solution of the above resin, phenol red was added as an indicator, and 0.1N
A neutralization titration was performed with a -KOH benzyl alcohol solution to determine a carboxyl number. C) Storage stability of the coating solution The coating solutions obtained in Examples and Comparative Examples were sealed at 25 ° C. for one week so that the solvent did not evaporate, and whether the solution became cloudy or gelled was determined. It was visually observed and evaluated.

C) Abrasion resistance A cast film having a thickness of 100 μm was prepared from the coating liquids obtained in Examples and Comparative Examples by a solvent casting method. Using a Taber abrasion tester (wear wheel CS-10F) with a load of 250 g and 10,000
The weight loss (amount of wear) after the 0 cycle test was measured and used as an index of wear resistance. D) Dielectric constant From the coating liquids obtained in Examples and Comparative Examples, films having a thickness of 50 μm were produced by a solvent casting method. Using this film, 1M according to ASTM D-150
The measurement was performed at Hz. E) Dielectric breakdown voltage Using the same 50 μm thick cast film as in 2),
Measurements were made according to ASTM D-149.

F) Storage stability of the coating solution The coating solution obtained in each of the Examples and Comparative Examples was sealed at 25 ° C. for one week so that the solvent did not evaporate, and whether the solution became cloudy or gelled. It was visually observed and evaluated.

[0044]

[Table 2]

From the above Examples and Comparative Examples, the resin for forming a film of the present invention is excellent in abrasion resistance and electrical properties.
Further, it was found that the coating liquid was excellent in storage stability due to a low carboxyl value.

[0046]

As described above, the resin for forming a film of the present invention is made of a transparent polyarylate having excellent abrasion resistance and electrical properties, and is easily stored and stable when dissolved in a solvent. A coating liquid having excellent properties can be prepared.
Therefore, it can be suitably used as a resin for various binders and as a resin for a solvent cast film.Electrical equipment, motors, generators, insulating materials such as interphase insulation, transformers, electric wire coatings, dielectric films such as capacitors, liquid crystals It can be applied to various display boards and various substrates. Also,
It can be used in the field of forming a coating such as a surface coating material.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tomohiro Hamada 23 Uji Kozakura, Uji-city, Kyoto, Japan Unitika Central Research Laboratories (72) Inventor Mitsunobu Sato 23 Uji Kozakura, Uji-shi, Kyoto Unitika Central Research, Ltd. In-house (72) Inventor Takamasa Akizuki 23 Uji Kozakura, Uji-shi, Kyoto Unitika Central Research Laboratory F-term (reference) 4J029 AA04 AB01 AC01 AC02 AD01 AD02 AE03 AE11 BB10A BB10B BB12C BB13A BD09A BD09B BF03 BG06CA03 CB04A CB05A CB06A CB10A CC06A CF08 CF15 CH02 DB13 HA05 HB05 KB02 KE11 4J038 DD051 DD052 DD061 DD062 GA06 NA11 NA17 NA19 PB09

Claims (3)

[Claims] 1. A film-forming resin comprising polyarylate, wherein the polyarylate has a structural unit represented by the following formula (1) or a structural unit represented by the following formula (1) and the following formula (2) Wherein the molar fraction of the structural units represented by the formulas (1) and (2) is 0.03 ≦ [(1) / [(1) + (2)]] ≦ 1.00 and an intrinsic viscosity (1,1,1) of 0.70 dl / g or more.
A resin for forming a film, characterized in that the resin is a polyarylate having the following formula: (measured in 2,2-tetrachloroethane at 25C) Embedded image Embedded image [In the formulas (1) and (2), X represents a single bond, an oxygen atom, a sulfur atom, an alkylene group, an alkylidene group, a cycloalkylene group, a cycloalkylidene group, a halo-substituted alkylene group, a phenylalkylidene group, a substituted phenylalkylidene group. Group, carbonyl group, sulfonyl group, carboxylalkylene group, carboxylalkylidene group, alkoxycarbonylalkylene group, alkoxycarbonylalkylidene group, fluorene group, isatin group, alkylsilane group, selected from the group consisting of dialkylsilane group, Y
Is selected from the group consisting of a phenylene group, a biphenylene group, a naphthylene group, an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a cyclic hydrocarbon group having 3 to 7 carbon atoms, and R1, R2, R3, and R4 are Each independently a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 1 to 20 carbon atoms, a nitro group, a halogenated alkyl group Selected from the group consisting of: p, q,
r and s represent an integer of 0 to 4, and p + q ≧ 1. ] 2. The polyarylate having a carboxyl number of 30.
The resin for forming a film according to claim 1, wherein the amount is not more than mol / ton. 3. A coating liquid comprising the resin for forming a film according to claim 1 and a solvent dissolving the resin.