JP2000001530A - Film-forming resin and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin having a high molecular weight and being excellent in abrasion resistance, lubricity, and optical properties by reacting a dicarboxylic acid component comprising terephthalic acid and isophthalic acid with a specified diphenol component. SOLUTION: An alkaline aqueous solution containing 97-50 wt.% 2,2-bis(3- methyl-4-hydroxyphenyl)propane and a catalyst is mixed with a solution prepared by dissolving 3-50 wt.% siloxane bisphenol of the formula (wherein R1 is an alkylene; R2 and R3 are each methyl, ethyl, n-propyl, isopropyl, phenyl, or trimethylsilyl ether; R4 is an alkyl, an alkoxyl, phenyl, or a halogen; m is 1-4; and n is 1-9) in a solvent which is inmiscible with water and dissolves a polyarylate. This mixture is mixed with 90-10 mol.% terephthalic acid, 90-10 mol.% isophthalic acid and a solvent immiscible with water, and the resultant mixture is reacted at 25 deg.C or below for 1-5 hr to obtain a polyarylate having an inherent viscosity of 0.50 or above.

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 diphenol unit and having a high molecular weight and excellent optical properties, abrasion resistance and lubricity, and a method for producing the same. .

[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.

[0004] However, the demands for friction and wear of resins in fields such as films that require a surface gloss or in applications where coatings are formed such as coating materials are as follows.
Increasingly stringent, bisphenol A polyarylate has created applications where these properties are inadequate. 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 such a possible plastic material, 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. Furthermore, if the siloxane block is long, so-called surface segregation occurs where the siloxane block is concentrated on the surface when a solvent cast film or solvent coating is performed, and the siloxane concentration decreases as the surface is abraded, resulting in a decrease in lubricity. Had the problem that

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 an acid chloride group at both ends and bisphenol or tetramethyldisiloxane having an imidephenol group at both ends. Disclosed is a block copolymer of polyarylate and polysiloxane produced by polymerizing a polymer having a polysiloxane bond by the reaction of methyldisiloxane and acid chloride, and then performing an equilibration reaction between the polymer and cyclopolysiloxane. Have been. 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, and therefore the abrasion was essentially poor. No effect of the structure of arylate was disclosed. Against this background, without impairing the optical properties and wear resistance of polyarylate,
There has been a demand for a film-forming resin having lubricity.

[0012]

SUMMARY OF THE INVENTION In view of the above circumstances, an object of the present invention is to provide a resin for forming a coating film having the same optical properties and abrasion resistance as conventional polyarylate and excellent lubricity. And a method for producing such a polyarylate easily.

[0013]

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 of a specific value or more. Arylate has the same optical properties as conventional bisphenol A polyarylate, but also has excellent abrasion resistance and lubricity, and has been found to be suitable for a resin for forming a film, and has reached the present invention.

That is, by using bisphenol C having a siloxane block having a specific chain length and bisphenol C as a diphenol component in a specific ratio, the resulting polyarylate allows the bisphenol having a siloxane block and the dicarboxylic acid to be bonded by an ester bond. The present inventors have found that the reduction of abrasion due to randomization of the siloxane block can be suppressed by using bisphenol C, and that the polyarylate has good color tone and improved hydrolysis resistance. Reached. Furthermore, they have found that such a film-forming resin can be easily produced by applying an interfacial polymerization method, and have reached the present invention.

That is, the gist of the present invention is to obtain a dicarboxylic acid component and a diphenol component, wherein the dicarboxylic acid component is 10 to 90 mol% of terephthalic acid and 9% by weight of isophthalic acid.
0 to 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: A coating comprising a polyarylate having an inherent viscosity of 0.50 or more at a concentration of 1 g / dl, measured in 1,1,2,2-tetrachloroethane at 25 ° C., of from 97 to 50:50. It is a forming resin.

Further, the resin for forming a film is composed of 2,2-
An alkaline aqueous solution containing bis (3-methyl-4-hydroxyphenyl) propane and a catalyst is prepared, and an aqueous solution of the general formula (1)
The siloxane bisphenol shown in is not compatible with water, and is dissolved in a solvent that dissolves polyarylate, added to the aqueous alkali solution and mixed, and further, is not compatible with water,
In addition, it can be produced by dissolving terephthalic acid and isophthalic acid in a solvent capable of dissolving polyarylate, adding the resulting mixture to the aqueous alkali solution, and mixing.

[0017]

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[(1) In the formula, R ₁ is an alkylene group, R ₂ ,
R ₃ is 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; 1-4
And n represents an integer of 1 to 9. ]

[0019]

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 in the present invention comprises 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 having 1 to 1 carbon atoms, R ₂ and R ₃ are each independently a methyl group,
R ₄ is selected from an alkyl group having 1 to 1 carbon atoms, an alkoxyl group having 1 to 1 carbon atoms, a phenyl group, and a halogen group; an ethyl group, an n-propyl group, an isopropyl group, a phenyl group and a trimethylsilyl ether group. . m is 1
To 4 and n represents 1 to 9. Here, it is essential that n is 1 to 9. If n exceeds 9, the transparency is reduced, and when used for coating, siloxane block surface segregation 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 compounds represented by the following structural formulas (3) to (21).

[0021]

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[0022]

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[0023]

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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. When the weight ratio of the siloxane bisphenol represented by the general formula (1) is less than 3, lubricity may decrease, and the weight ratio of the siloxane bisphenol represented by the general formula (1) is 5
If it exceeds 0, abrasion resistance and other mechanical strength decrease. Taking the balance of lubricity, wear resistance and mechanical strength into account, the weight ratio thereof is preferably from 10:90 to 35:65, and more preferably from 15:85 to 30:70.

Further, the polyarylate of 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 diphenols which can be copolymerized are 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-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-hydroxy Phenyl) -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 in the present invention is a mixture comprising 10 to 90 mol% of terephthalic acid and 90 to 10 mol% of isophthalic acid, and particularly preferably, an equal amount of terephthalic acid and isophthalic acid. It is a mixture. 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.

[0038] 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 polymer is dissolved, and a dicarboxylic acid halide dissolved in an organic solvent incompatible with water is mixed with a diphenol dissolved in an aqueous alkali solution to obtain a polyarylate. However, since siloxane bisphenol used in the polyarylate of the present invention has high hydrophobicity and cannot be dissolved in an aqueous alkali solution, a normal interfacial polymerization method cannot be employed as it is.

Therefore, first, an aqueous alkaline solution containing 2,2-bis (3-methyl-4-hydroxyphenyl) propane and a catalyst is prepared, and the siloxane bisphenol represented by the general formula (1) is a solvent 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. Ammonium 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 the siloxane bisphenol and the dicarboxylic acid halide, a solvent capable of dissolving the polyarylate, for example, methylene chloride, 1,1
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. 5 or more. Preferably it is 0.7-2.5. If the inherent viscosity is less than 0.5, 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. It is not preferable because handling tends to be difficult.

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 hindered phenol-based, hindered amine-based, thioether-based and phosphorus-based antioxidants can be added to the polyarylate of the present invention as long as its properties are not impaired. The above-mentioned polyarylate 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.

[0046]

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 2-4, Comparative Examples 1-3 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).

[0049]

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Comparative Example 4 The procedure of 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.

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) Dynamic friction coefficient 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.

(C) Abrasion resistance Using the film obtained in (b), using a Taber abrasion tester (wear wheel CS-10F) under a load of 250 g and a load of 50 g.
The weight loss after the 00 cycle and 10000 cycle tests was measured and used as an index of wear resistance. (D) Optical properties For the same film having a thickness of 100 μm as in (b), Nippon Denshoku Industries Co., Ltd., Z-Σ90, Color Measurin
The haze and yellow index (YI) were measured using g System.

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[Table 1]

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[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. 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.

[0056]

The resin for forming a film according to the present invention is soluble in a solvent, has excellent optical properties and abrasion resistance, and has excellent lubricity. 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. Further, such a resin for forming a film can be easily produced by applying an interfacial polymerization method.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kazuhiro Hamada 23 Uji Kozakura, Uji City, Kyoto Prefecture Unitika Central Research Laboratory F-term (reference) 4J029 AA04 AB04 AC02 AC03 AD01 AE03 AE11 BB13B BH04 CB05A CB06A FA02 FA03 FA06 FA06 FA07 FB02 FB03 FB07 FB13 HA01 HB05 JC091 JC381 KA01 KD01 KE11 4J038 DD101 DL151 MA14 NA01 NA10 NA11

Claims (2)

[Claims] 1. A dicarboxylic acid component obtained from a dicarboxylic acid component and a diphenol component, wherein the dicarboxylic acid component is terephthalic acid 10 to 10.
90 mol% and 90 to 10 mol% of isophthalic acid, 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. 1 g, measured in 1,1,2,2-tetrachloroethane at 25 ° C.
A resin for forming a film, comprising a polyarylate having an inherent viscosity of 0.50 or more at a / dl concentration. Embedded image [(1) In the formula, 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. , An alkoxyl group, a phenyl group, or a halogen group, m is an integer of 1-4, n
Represents an integer of 1 to 9. ] 2. An alkaline aqueous solution containing 2,2-bis (3-methyl-4-hydroxyphenyl) propane and a catalyst is prepared, and the siloxane bisphenol represented by the general formula (1) is insoluble in water Dissolved in a solvent that dissolves allylate and added to the aqueous alkali solution and mixed,
Further, a method for producing a resin for forming a film, characterized in that terephthalic acid and isophthalic acid are dissolved in a solvent which is incompatible with water and dissolves polyarylate, and is added to the aqueous alkali solution and mixed. Embedded image [(1) In the formula, 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. , An alkoxyl group, a phenyl group, or a halogen group, m is an integer of 1-4, n
Represents an integer of 1 to 9. ]