JP2000119593A - Resin for forming coat - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin comprising a specific polyarylate obtained from a specific dicarboxylic acid component and a specific diphenol component having high molecular weight and excellent in optical characteristics, wear resistance, lubricating properties, electrical characteristics and storage stability in a coating solution obtained therefrom. SOLUTION: This resin comprises a polyarylate obtained from (A) a dicarboxylic acid component comprising 10-90 mol% terephthalic acid and 90-10 mol% isophthalic acid and (B) a diphenol component containing a siloxane bisphenol of the formula [R1 is an alkylene; R2 and R3 are each a 1-3C alkyl, phenyl or the like; R4 is an alkyl, phenyl or the like; (m) is 1-4; (n) is 1-9] and 2,2-bis(3-methyl-4-hydroxyphenyl)propane at a weight ratio of (3:97) to (50:50) and having >=0.50 inherent viscosity in 1 g/dl concentration measured in 1,1,2,2,- tetrachloroethane at 25 deg.C and has <=30 mol/ton carboxyl value.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyarylate containing a specific diphenol unit, having a high molecular weight and having excellent optical properties, abrasion resistance, lubricity, electrical properties and storage stability when formed into a coating solution. The present invention relates to a film-forming resin comprising:

[0002]

2. Description of the Related Art Polyarylates obtained from 2,2-bis (4-hydroxyphenyl) propane [bisphenol A] and terephthalic acid and isophthalic acid are already well known as engineering plastics. Such polyarylate has high heat resistance, excellent mechanical strength and dimensional stability typified by impact strength, and is amorphous and transparent. Widely applied to

In addition, polyarylate resin made from bisphenol A has solubility in various solvents, excellent electrical properties (insulation properties, dielectric properties, etc.), and abrasion resistance properties. Utilizing it, it is used for forming a film such as a coating resin on a film for an electronic component such as a capacitor or a film for a liquid crystal display device.

However, in fields where surface gloss is required, such as films, and in applications where coatings are formed, such as coating materials, the requirements for friction and abrasion resistance of resins are becoming increasingly stringent. Thus, bisphenol A polyarylate has been used for applications with insufficient properties. For example, there is a problem that a surface coat or a film surface of a sliding portion is scratched by friction sliding with a metal or other plastic material, and a material having lubricity and being hard to wear is required. I have.

On the other hand, it is well known that polysiloxane polymers such as polydimethylsiloxane can impart lubricity by being mixed with various polymers. It is considered that if a polysiloxane-based polymer can be compounded with polyarylate, self-lubricating properties can be imparted while maintaining the properties of polyarylate.

[0006] As a plastic material having such a possibility, a composition comprising polyallylate and polysiloxane is disclosed in Japanese Patent Application Laid-Open No. 50-96650. This publication describes that the meltability of polyarylate with polysiloxane improves the formability and impact resistance of polyarylate. However, this composition is simply blended, and is opaque because polyarylate and polysiloxane are originally incompatible, and has good optical properties in fields where transparency is required such as a film. Had no problem.

As a plastic material for solving such a problem, Japanese Patent Application Laid-Open No. 60-141723 discloses a block copolymer composed of polyarylate and polysiloxane. However, since the object of the present invention was to improve the processability of polyarylate, the siloxane block length was long, and there was still a problem in terms of transparency. In addition, since this block copolymer contained a Si-OC bond in the main chain, it had a problem in terms of hydrolysis resistance. In addition, if the siloxane block is long, so-called surface segregation occurs in which the siloxane block is concentrated on the surface when solvent casting or solvent coating is performed, and the siloxane concentration decreases as the surface of the film is scraped, resulting in reduced lubricity. Had the problem of going down.

Further, JP-A-63-165432 and JP-A-2-138336 also disclose a block copolymer composed of polyarylate and polysiloxane. In each case, the siloxane block is long, There remains a problem of optical characteristics and a problem that the siloxane block concentration becomes non-uniform during casting.

For copolymers having a short block length, JP-A-2-272022 discloses a reaction between tetramethyldisiloxane having acid chloride groups at both ends and bisphenol and an imidophenol group having both ends. Block copolymer of polyarylate and polysiloxane produced by polymerizing a polymer having a polysiloxane bond by the reaction of tetramethyldisiloxane and acid chloride, and then performing an equilibration reaction between this polymer and cyclopolysiloxane Is disclosed. According to the present invention, it is thought that the optical characteristics can be solved by shortening the block length, but conversely, the randomization reduces the wear resistance itself of polyarylate. there were.

As a solution to the problem of further lowering the transparency, Japanese Patent Application Laid-Open No. 9-151255 discloses
Polyarylates containing siloxane units are disclosed. This polyarylate is short in block length and excellent in transparency, but has problems in hydrolysis resistance and color tone because it contains Si-OC bonds and amide bonds in the main chain. I was

As described above, in the prior art, the main purpose is basically to improve the workability by mixing a polysiloxane, and the technique relating to the improvement of the wear resistance and lubricity of a polymer is completely disclosed. Had not been. In particular, in the prior art, polyarylate composed of a siloxane compound and bisphenol A was a basic constituent unit of the resin, so that the abrasion resistance was essentially low, and specific techniques for increasing the abrasion resistance were used. And the structure of polyarylate were not disclosed.

Further, these publications do not mention the effect of the carboxyl number of the terminal of polyarylate on the electrical properties of the resin and the storage stability when formed into a coating solution. No effect was disclosed. In addition, the demands from the electrical and electronic fields, where technological innovations are remarkable, have become increasingly severe, and the above-mentioned polyarylate resins based on bisphenol A have insufficient applications due to the electrical characteristics.

[0013] From such a background, there is a demand for a resin for forming a film which does not impair the optical properties and abrasion resistance of polyarylate, and further has excellent lubricating properties, electrical properties and storage stability when formed into a coating liquid. I was

[0014]

SUMMARY OF THE INVENTION In view of the above situation, an object of the present invention is to provide lubricating properties, electrical properties, and coating liquids having the same optical properties and abrasion resistance as conventional polyarylates. Another object of the present invention is to provide a resin for forming a film which is excellent in storage stability when the film is formed.

[0015]

Means for Solving the Problems The present inventors have made intensive studies to solve such problems, and as a result, obtained from dicarboxylic acid component and diphenol component, and dicarboxylic acid component is obtained from terephthalic acid and isophthalic acid. Wherein the diphenol component comprises bisphenol having a siloxane block having a specific chain length and 2,2-bis (3-methyl-4-hydroxyphenyl) propane (bisphenol C), and has a molecular weight not less than a specific value and a specific molecular weight. The polyarylate having a carboxyl number of not more than the value has excellent abrasion resistance, lubricity, electrical properties and storage stability when formed into a coating liquid while having optical properties equivalent to conventional bisphenol A polyarylate. The present inventors have found that the composition is suitable for a resin for forming a film, and have reached the present invention.

That is, by using bisphenol C having a siloxane block having a specific chain length and bisphenol C at a specific ratio as a bisphenol component, bisphenol having a siloxane block and dicarboxylic acid are bonded by an ester bond, and the siloxane block is randomized. The reduction in abrasion resistance due to this is suppressed by using bisphenol C, and this polyarylate has good color tone and improved hydrolysis resistance, and the electrical properties of polyarylate are polyarylate. The bond between the two benzene rings of the diphenols constituting the diphenol and the carboxyl number of the polymer terminals are affected by the bond between the two benzene rings, and the bond between the two benzene rings between the diphenols is a hydrogen atom at the α or β position such as an alkylene group or an alkylidene group. Di Compared with phenol, the diphenol comprising a siloxane block bond having a specific chain length as in the present invention is electrically stable, and furthermore, it comprises such a diphenol and has a carboxyl number not more than a specific amount. Polyarylate which does not have excellent electrical properties and excellent storage stability of the coating liquid have been found, and have reached the present invention.

The gist of the present invention is obtained from a dicarboxylic acid component and a diphenol component, wherein the dicarboxylic acid component is 10 to 90 mol% terephthalic acid and 90 to 10 isophthalic acid.
Mol%, wherein the diphenol component comprises siloxane bisphenol represented by the following general formula (1) and 2,2-bis (3-methyl-4-hydroxyphenyl) propane, and the siloxane represented by the general formula (1) The weight ratio of bisphenol to 2,2-bis (3-methyl-4-hydroxyphenyl) propane is 3:97 to 50:50 and measured in 1,1,2,2-tetrachloroethane at 25 ° C. Inherent viscosity at a concentration of 1 g / dl is 0.50 or more, and carboxyl value is 30 mol /
It is a resin for forming a film, comprising a polyarylate having a weight of not more than 1 ton.

[0018]

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[In the general formula (1), R ₁ is an alkylene group;
₂ , R ₃ are each independently selected from a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a phenyl group, and a trimethylsilyl ether group; R ₄ is selected from an alkyl group, an alkoxyl group, a phenyl group, and a halogen group; m is 1
And n represents an integer of 1 to 9. ]

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The resin for forming a film according to the present invention comprises a specific polyarylate containing a specific diphenol unit, and the polyarylate will be described in detail below. The diphenol component constituting the polyarylate is composed of siloxane bisphenol represented by the general formula (1) and 2,2-bis (3-methyl-
4-hydroxyphenyl) propane.

In the general formula (1), R ₁ is an alkylene group,
R ₂ and R ₃ each independently represent a methyl group, an ethyl group, n-
R ₄ is selected from an alkyl group, an alkoxyl group, a phenyl group, and a halogen group, m is an integer of 1 to 4, and n is an integer of 1 to 9 Represents Where n
Must be 1 to 9. When n exceeds 9,
Transparency decreases, and when used for coating, surface segregation of siloxane blocks occurs. When n is 0, the lubricity of the polymer based on siloxane bonds is not sufficiently exhibited. Specific examples of the diphenol compound represented by the general formula (1) include the following structural formulas (3) to (2)
The compound shown in 1) can be exemplified.

[0022]

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[0023]

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[0024]

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These compounds may be used alone or in combination of two or more. Further, these compounds can be easily obtained by a known method such as a reaction of bis (hydrogen) polysiloxane with a compound having an unsaturated double bond such as allylphenol in the presence of a platinum catalyst.

Further, as a diphenol component constituting the polyarylate of the present invention, 2,2-bis (3-
Methyl-4-hydroxyphenyl) propane (bisphenol C) is used, but bisphenol C is an essential component for obtaining abrasion resistance.

In the diphenol component constituting the polyarylate, the weight ratio of the siloxane bisphenol represented by the general formula (1) to the bisphenol C is 3:97 to 50:
50, preferably 10:90 to 35:65. If the weight ratio of the siloxane bisphenol represented by the general formula (1) is less than 3, lubricity and electrical properties may be reduced. If the weight ratio of the siloxane bisphenol represented by the general formula (1) exceeds 50, wear resistance and Other mechanical strength decreases. Taking the balance of lubricity, abrasion resistance, mechanical strength and electrical properties into account, their weight ratio is 10:90 to 3
5:65, preferably 15:85 to 30: 7
More preferably, it is 0.

Further, the polyarylate in the present invention can copolymerize the siloxane bisphenol represented by the above general formula (1) with a diphenol other than bisphenol C in an amount of less than 20 mol% based on the total number of moles of the diphenol component. It is. The ratio of other diphenols to be copolymerized is 20
If it exceeds mol%, the abrasion resistance of the resin of the present invention tends to decrease, which is not preferable.

Examples of other copolymerizable diphenols include 4,4'-dihydroxybiphenyl and 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-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 (3,5
-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
-Bis (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-sec-butyl-4-hydroxyphenyl) propane, 1,1-bis (2-methyl-4-hydroxy-
5-tert-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-bis (4-
(Hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (2-hydroxy-3-tert-butyl-5-methylphenyl) 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-tert-) 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, 1,1-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,
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-tert-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-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) -p-
And terpene diphenols such as menthane. Among these, preferred diphenols include 2,2.
2-bis (4-hydroxyphenyl) propane (bisphenol A), 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z), 1,1-bis (4-hydroxyphenyl) -1-phenylethane (bisphenol AP), 4,4'-dihydroxybiphenyl, 3,3'-dimethyl-4,4'-dihydroxybiphenyl and the like.

The dicarboxylic acid component constituting the polyarylate is a mixture composed of 10 to 90 mol% of terephthalic acid and 90 to 10 mol% of isophthalic acid, and particularly preferably a mixture of equal amounts of terephthalic acid and isophthalic acid. is there. When terephthalic acid is less than 10 mol% or more than 90 mol%, the mechanical strength such as abrasion resistance of polyarylate decreases.

The terminal of the polyarylate is phenol, cresol, p-tert-butylphenol, o
-Monovalent phenols such as phenylphenol, benzoic acid chloride, methanesulfonyl chloride, monovalent acid chlorides such as phenyl chloroformate, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, Pentanol, hexanol, dodecyl alcohol, stearyl alcohol, benzyl alcohol, monohydric alcohols such as phenethyl alcohol, acetic acid, propionic acid, octanoic acid, cyclohexanecarboxylic acid, benzoic acid, toluic acid, phenylacetic acid, p-tert-butyl benzoic acid,
It may be sealed with a monovalent carboxylic acid such as p-methoxyphenylacetic acid.

The polyarylate in the present invention can be produced by a known method.
M. EARCKSON J. Poly. Sci. XL
399 1959, Japanese Patent Publication No. 40-1959), the reaction is faster than other methods such as a solution polymerization method, so that the hydrolysis of acid halide can be minimized. It is advantageous to obtain a high molecular weight polymer as in the present invention by selecting a polymerization catalyst to be used.

That is, in the interfacial polymerization method, a polyallylate is obtained by dissolving a polymer and mixing a dicarboxylic acid halide dissolved in an organic solvent incompatible with water and diphenol dissolved in an aqueous alkali solution. However, since siloxane bisphenol is so hydrophobic that it cannot be dissolved in an aqueous alkaline solution, the normal interfacial polymerization method cannot be directly employed in the present invention.

Therefore, first, an alkaline aqueous solution containing 2,2-bis (3-methyl-4-hydroxyphenyl) propane and a catalyst is prepared, and a siloxane bisphenol represented by the general formula (1) is dissolved in a solvent for dissolving a dicarboxylic acid halide. And added to the aqueous alkali solution and mixed. Furthermore, dicarboxylic acid halides are not compatible with water,
And dissolved in a solvent that dissolves polyarylate,
A solution in which a dicarboxylic acid halide is dissolved is prepared, added to the above-mentioned aqueous alkali solution, mixed, and a polymerization reaction is performed. The polymerization reaction is carried out at a temperature of 25 ° C. or lower while stirring for 1 hour to 5 hours.

The catalyst used in the polymerization reaction is not particularly limited as long as a polymer having a high molecular weight and a low carboxyl value can be obtained. Examples of the catalyst include tributylbenzylammonium halide, tetrabutylammonium halide, and the like.
Tetrabutylphosphonium halide, tributylbenzylphosphonium halide and the like are preferable in that they give a polymer having a high molecular weight and a low carboxyl value. Trimethylbenzylammonium halide, triethylbenzylammonium halide or the like having a short alkyl chain of a quaternary ammonium salt is not preferable because a polymer having a high molecular weight and a low carboxyl value cannot be obtained.

Further, as a solvent for dissolving siloxane bisphenol and dicarboxylic acid halide, a solvent for dissolving polyarylate, for example, methylene chloride, 1,
2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, 1,1,2,2-tetrachloroethane,
Chlorinated solvents such as 1,1,1-trichloroethane, o-, m-, p-dichlorobenzene, toluene, benzene,
A solution in which a dicarboxylic acid halide is dissolved in an aromatic hydrocarbon such as xylene is exemplified. In addition, examples of the alkali that can be used here include sodium hydroxide and potassium hydroxide.

The molecular weight of the polyarylate in the present invention can be controlled by the addition amount of the above-mentioned terminal blocking material. The inherent viscosity of a 1 g / dl solution at 25 ° C. used as a solvent for measuring the viscosity of tetrachloroethane is 0.5. It is 50 or more. Preferably 0.7 to 2.5
It is. If the inherent viscosity is less than 0.50, the abrasion resistance may be insufficient. On the other hand, if it exceeds 2.5, spinnability may occur or the viscosity of the solution adjusted during coating may increase when used for coating. It is not preferable because handling tends to be difficult.

Further, the polyarylate carboxyl number in the present invention also affects the storage stability of a polymer solution prepared by dissolving the resin in a solvent such as toluene, methylene chloride or tetrahydrofuran. It is essential that the content be 30 mol / ton or less. When the carboxyl number exceeds 30 mol / ton, the storage stability of the polymer solution deteriorates, and the solution becomes cloudy with the lapse of time, and solids precipitate, or the solution thickens and gels. Further, since the carboxyl number affects electric properties such as arc resistance and dielectric constant, it is more preferable to set the carboxyl number to 20 mol / ton or less in consideration of these properties.
The carboxyl number of the resin can be measured by a known method such as neutralization titration using a potentiometric titrator.

The polyarylate in the present invention is substantially amorphous and transparent. Whether it is amorphous or not may be confirmed by a known method such as differential scanning calorimetry (DSC) or dynamic viscoelasticity measurement to determine whether a melting point exists. In addition, the polyarylate in the present invention has high solubility in general-purpose solvents such as methylene chloride, tetrahydrofuran, and toluene, and can be dissolved in these solvents to form a coating solution. The concentration of the coating solution is preferably at least 10% by weight, preferably 15 to 20% by weight, and the solution is preferably used after being completely dissolved.
If the concentration is less than 10% by weight, the coatability of the coating liquid may be reduced, or the film thickness may become non-uniform when coated.

Further, various antioxidants such as a hindered phenol type, a hindered amine type, a thioether type and a phosphorus type can be added to the polyarylate as long as its properties are not impaired.

The polyarylate as described above is used as a resin for a binder or a resin for a solvent cast film as a resin for forming a film, and can be suitably applied particularly to the field of electronic materials.

[0049]

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, 90 parts by weight of 2,2-bis (3-methyl-4-hydroxyphenyl) propane, p
-Tert-butylphenol (abbreviated as PTBP)
82 parts by weight, 33.9 parts by weight of sodium hydroxide, and 0.82 parts by weight of tri-n-butylbenzylammonium chloride as a polymerization catalyst were charged and dissolved in 2720 parts by weight of water (aqueous phase). 10 parts by weight of the siloxane bisphenol represented by the above formula (18) was dissolved in 500 parts by weight of methylene chloride (organic phase 1). Methylene chloride 15
74.8 parts by weight of a terephthalic acid chloride / isophthalic acid chloride = 1/1 mixture (abbreviated as MPC) was dissolved in 00 parts by weight (organic phase 2). First, the organic phase 1 was added to the previously prepared aqueous phase with vigorous stirring, then the organic phase 2 was added, and a polymerization reaction was performed at 20 ° C. for 3 hours. After that, the reaction was stopped by adding 15 parts by weight of acetic acid, the aqueous phase and the organic phase were separated, and water washing was repeated until the organic phase became neutral. The organic phase was added to methanol to precipitate the polymer. Was. The polymer was separated and dried to obtain a resin.

Examples 2 to 12, Comparative Examples 1 to 3, 2,2-bis (3-methyl-4-hydroxyphenyl)
A resin was produced in the same manner as in Example 1 except that the amounts of propane, p-tert-butylphenol, MPC and the type and amount of siloxane bisphenol were changed. Table 1 shows the types of siloxane bisphenol and the charging conditions. The structural formulas of the siloxane compounds used in Comparative Examples 2 and 3 are shown in Formulas (22) and (23).

[0052]

Embedded image

Comparative Example 4 Example 1 was repeated except that bisphenol A was used instead of 2,2-bis (3-methyl-4-hydroxyphenyl) propane. Table 1 shows the charging conditions.

Comparative Example 5 The procedure of Example 1 was repeated, except that trimethylbenzylammonium chloride was used instead of tri-n-butylbenzylammonium chloride as the polymerization catalyst. Table 1 shows the charging conditions.

Evaluation of Resin The resin synthesized as described above was evaluated for physical properties as described below. Table 2 shows the results. (A) Inherent viscosity The reaction was carried out using 1,1,2,2-tetrachloroethane as a solvent at a temperature of 25 ° C. and a concentration of 1 g / dl. (B) Carboxyl number 0.15 g of 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 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 The resin was dissolved in methylene chloride at 15% by weight to prepare a coating solution. Then, it was left at 25 ° C. for one week, and the state of the solution was visually evaluated. (D) Coefficient of dynamic friction After dissolving the resin in chloroform at a concentration of 15%, a cast film having a thickness of 100 µm was prepared. Using this film as a test piece, the dynamic friction coefficient was measured in accordance with ASTM D-1894-72. Mild steel was used as the mating material. (E) Abrasion resistance Using the film obtained in (d), using a Taber abrasion tester (wear wheel CS-10F) and applying a load of 250 g to 50
The weight loss after the 00 cycle and 10000 cycle tests was measured and used as an index of wear resistance.

(F) Optical properties For the same film having a thickness of 100 μm as in (d), Nippon Denshoku Industries Co., Ltd., Z-Ｚ90, Color Measurin
The haze and yellow index (YI) were measured using g System. (G) Dielectric constant A cast film having a thickness of 50 μm was prepared from a methylene chloride solution of the resin. Using this film as a test piece, AS
The dielectric constant was measured at 1 MHz according to TM D-150. (H) Dielectric breakdown voltage Using the film obtained in (g), ASTM D-1
The dielectric breakdown voltage was measured according to 49.

[0058]

[Table 1]

[0059]

[Table 2]

From the above results, the following became clear. 1) Comparison between Examples 1 to 12 and Comparative Example 1 revealed that the resin of the present invention had a low coefficient of friction and excellent lubricity and electrical properties. 2) From the comparison between Examples 1 to 12 and Comparative Example 2, the resin of the present invention has a low polysiloxane block, has a low haze, is excellent in transparency, and is excellent in initial wear resistance. it is obvious. 3) From a comparison between Examples 1 to 12 and Comparative Example 3, it is clear that the resin of the present invention has an excellent color tone because the siloxane unit and the aromatic polyester unit are ester-bonded. 4) From the comparison between Examples 1 to 12 and Comparative Example 4, it is clear that the resin of the present invention has excellent abrasion resistance because it contains bisphenol C. 5) From a comparison between Examples 1 to 12 and Comparative Example 5, it is clear that the resin of the present invention has excellent electric properties and solution storage stability because of its low carboxyl value.

[0061]

The film-forming resin of the present invention is soluble in a solvent, has good storage stability of a coating solution, has excellent optical properties and wear resistance, and has excellent lubricity and electrical properties. I have. 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.

 ──────────────────────────────────────────────────の Continuing from the front page (72) Inventor Akihiko Hasegawa 23 Uji Kozakura, Uji-city, Kyoto, Japan Unitika R & D Center (72) Inventor Tomohiro Hamada 23 Uji Kozakura, Uji-city, Kyoto, Japan Unitika Central Research In-house F term (reference) 4J029 AA04 AB01 AC02 AD01 AD02 AE01 AE03 AE11 AE18 BB13B BH04 CB05A CB06A KB02 4J038 DD061 DD101 GA15 KA06 NA11 NA19 NA21 NA26 PB08 PB09 PC02 PC08

Claims (1)

[Claims] 1. A dicarboxylic acid component and a diphenol component, wherein the dicarboxylic acid component is terephthalic acid.
-90 mol% and isophthalic acid 90-10 mol%, wherein the diphenol component is a siloxane bisphenol represented by the following general formula (1) and 2,2-bis (3-methyl-
4-hydroxyphenyl) propane, and the weight ratio of the siloxane bisphenol represented by the general formula (1) to 2,2-bis (3-methyl-4-hydroxyphenyl) propane is 3:97 to 50:50. At 25 ° C.
1 g / d measured in 1,2,2-tetrachloroethane
A film-forming resin comprising a polyarylate having an inherent viscosity of 0.50 or more at a concentration of 1 and a carboxyl number of 30 mol / ton or less. Embedded image [In the general formula (1), R ₁ is an alkylene group, R ₂ and R ₃ are each independently selected from a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a phenyl group and a trimethylsilyl ether group, and R ₄ is an alkyl group. Selected from a group, an alkoxyl group, a phenyl group, and a halogen group, m represents an integer of 1 to 4, and n represents an integer of 1 to 9. ]