JPH09151255A - Polyarylate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyarylate excellent in abrasion resistance and clarity and sol. in an org. solvent by selecting a polyarylate comprising specific arom. ester units and specific siloxane unit and having specified physical properties. SOLUTION: A polyarylate is selected which comprises 50-99mol% arom. ester units comprising dihydric phenol residues and arom. dicarboxylic acid residues and represented by formula I [R1 to R8 are each H, a (halo)alkyl, or a halogen; X is a (cyclo)alkylidene, alkylene, arom.- or halogen-substd. alkylidene, sulfone, (thio)ether, or ketone group; and Z is a divalent arom. group] and 50-1mol% siloxane unit represented by formula II (R9 and R10 are each an alkyl or aryl) and has a solubility in methylene chloride of 10wt.% or higher and a haze at a thickness of 500μm (measured according to JIS K 7105) of 1 or lower.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to polyarylate. More specifically, it relates to a polyarylate having excellent abrasion resistance and transparency and soluble in an organic solvent.

[0002]

2. Description of the Prior Art Polyallylates composed of dihydric phenols, especially 2,2-bis (4-hydroxyphenyl) propane residues and terephthalic acid and / or isophthalic acid residues are already well known as engineering plastics. ing. Since such polyarylate has high heat resistance, excellent mechanical strength represented by impact strength and dimensional stability, and is transparent, the molded product is widely applied to fields such as electric / electronic, automobile, and machine. It is well known that In addition, polyarylate resin made from bisphenol A is used for optical materials such as various optical parts, liquid crystal display film, and binder resin for electrophotographic photoreceptors by utilizing its excellent mechanical strength and transparency. Is being done.

On the other hand, an amorphous polymer such as polyarylate is generally inferior in abrasion resistance, and polyarylate prepared from bisphenol A has been used for insufficient abrasion resistance. In order to solve such a problem, attempts have been made to alloy a fluororesin having excellent lubricity. However, there is a problem that transparency is greatly reduced by alloying the fluororesin. Also,
After being dissolved in a solvent such as the binder resin or casting film described above, it should be amorphous and have good solubility in a solvent in addition to abrasion resistance and optical properties in the intended use. Is also necessary.

Polymers composed of polyarylate and polysiloxane units are potential solutions to these problems. This polymer is well known in the art. For example, Japanese Patent Application Laid-Open No. 50-96650 describes a resin composition comprising polyarylate and polyorganosiloxane with improved moldability. However, this composition has a problem of transparency because it is merely a mixture,
It could not be applied to applications requiring transparency such as optical parts. Further, JP-A-60-141723 discloses a copolymer for the purpose of improving thermoplastic processability by copolymerizing a polyarylate and a siloxane unit. However, this copolymer also has a problem in terms of optical properties because the siloxane block unit is long and the compatibility is poor. As described above, a polyarylate having optical characteristics and abrasion resistance and excellent in solubility in a solvent has not been known.

[0005]

In view of the above situation, the object of the present invention is to provide optical properties equivalent to those of conventional polyarylate using bisphenol A as a raw material.
Further, the present invention provides a polyarylate having excellent abrasion resistance and good solubility in a solvent.

[0006]

The inventors of the present invention have made earnest studies to develop a polyarylate which solves the above problems, and as a result, the introduction of siloxane units is effective for improving the wear resistance. It was found that shortening the siloxane block is effective for maintaining optical properties and solubility in solvents. That is, the present inventors have found that a polyarylate containing a siloxane unit having a block length of a specified number or less has good optical properties, abrasion resistance, and solubility in a solvent, and reached the present invention.

That is, the gist of the present invention is the following formula (1) consisting of a dihydric phenol residue and an aromatic dicarboxylic acid residue.
An aromatic ester unit (A) represented by

[0008]

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[Wherein R _{1 to} R ₈ represent a hydrogen atom, an alkyl group, a halogen group or a haloalkyl group and may be the same or different, and X is an alkylidene group, a cycloalkylidene group, an alkylene group or an aromatic substituent. It represents an alkylidene group, a halogen-substituted alkylidene group, a sulfone group, an ether group, a thioether group, and a ketone group, and Z represents a divalent aromatic group. ] And a siloxane unit (B) represented by the following formula (2)

[0010]

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[In the formula, R ₉ and R ₁₀ represent an alkyl group or an aryl group. ], The molar ratio of (A) and (B) is
(A) :( B) = 50: 50 to 99: 1 and 10
Dissolves in methylene chloride at a concentration of more than 50% by weight and
A polyarylate having a thickness of 0 μm and a haze of 1 or less as measured by JIS K-7105.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
Preferred as the residue of the dihydric phenol compound constituting the aromatic ester unit (A) constituting the polyarylate resin of the present invention are bis (4-hydroxyphenyl) methane and 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-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-secbutyl-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, 2,2
-Bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (2-hydroxy-3-tertbutyl-5-methylphenyl) methane, bis (4-hydroxy) Phenyl) 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-ditertbutyl-
4-hydroxyphenyl) methane, bis (3,5-dis)
ec-butyl-4-hydroxyphenyl) methane, 1,1
-Bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (2-hydroxy-)
3,5-ditertbutylphenyl) ethane, 1,1-
Bis (3-nonyl-4-hydroxyphenyl) methane,
2,2-bis (3,5-ditertbutyl-4-hydroxyphenyl) propane, 1,1-bis (2-hydroxy-3,5-ditertbutyl-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-tertbutyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3,5-ditertbutyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (2-Methyl-4-hydroxy-5-cyclohexylphenyl) -2-methylpropane, 1,1-bis (2-hydroxy-3,5-diter
t-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-tertbutylphenyl)
Ethane, bis (2-hydroxy-5-phenylphenyl) methane, 1,1-bis (2-methyl-4-hydroxy-5-tertbutylphenyl) 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-ditertbutyl-4-hydroxyphenyl) ethane, bis (2-hydroxy-3,5
-Ditertbutylphenyl) 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-hydroxy) Phenyl) 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 (3,3
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-
Terpene diphenols such as menthane, 4,4'-dihydroxybiphenyl [4,4'-biphenol], 3,
3'-dimethyl-4,4'-dihydroxybiphenyl,
3,3′-dichloro-4,4′-dihydroxybiphenyl, 3,3′-di-tert-butyl-4,4′-dihydroxybiphenyl, 3,3,5,5 ″ -tetramethyl-4,4 '-Dihydroxybiphenyl, 3,3,5
5 ''-tetrachloro-4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 3,3'-
Difluoro-4,4'-biphenol, 3,3 ', 5
5'-tetrafluoro-4,4'-biphenol, 4,
4'-dihydroxydiphenyl ether, 3,3'-dimethyl-4,4'-dihydroxydiphenyl ether,
3,3'-dichloro-4,4'-dihydroxydiphenyl ether, 3,3'-di-tert-butyl-4,
4'-dihydroxydiphenyl ether, 3,3,5
5 ''-tetramethyl-4,4'-dihydroxydiphenyl ether, 3,3,5,5 ''-tetrachloro-
4,4'-dihydroxydiphenyl ether, 2,2 '
-Dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl thioether, 3,3'-dimethyl-
4,4'-dihydroxydiphenyl thioether, 3,
3'-dichloro-4,4'-dihydroxydiphenyl thioether, 3,3'-di-tert-butyl-4,
4'-dihydroxydiphenyl thioether, 3,3
5,5 ″ -tetramethyl-4,4′-dihydroxydiphenylthioether,

3,3,5,5 ''-tetrachloro-4,
4'-dihydroxydiphenyl thioether, 2,2 '
-Dihydroxy diphenyl thioether, 4,4'-dihydroxy diphenyl sulfone, 3,3'-dimethyl-4,4'-dihydroxy diphenyl sulfone, 3,
3'-dichloro-4,4'-dihydroxydiphenyl sulfone, 3,3'-di-tert-butyl-4,4 '
-Dihydroxydiphenyl sulfone, 3,3,5
5 ''-tetramethyl-4,4'-dihydroxydiphenyl sulfone, 3,3,5,5 ''-tetrachloro-
4,4'-dihydroxydiphenyl sulfone, 2,
2'-dihydroxydiphenyl sulfone, 4,4'-
(Diphenylmethylene) bisphenol, 3,3'-dimethyl-4,4 '-(diphenylmethylene) bisphenol, 3,3', 5,5'-tetramethyl-4,4'-
(Diphenylmethylene) bisphenol, 3,3′-dichloro-4,4 ′-(diphenylmethylene) bisphenol, 3,3′-difluoro-4,4 ′-(diphenylmethylene) bisphenol, bisphenolfluorene,

Di (4-hydroxyphenyl) phenylamine, di (3-methyl-4-hydroxyphenyl) phenylamine, di (3,5-dimethyl-4-hydroxyphenyl) phenylamine, di (3-chloro-4) -Hydroxyphenyl) phenylamine, di (3,5-dichloro-4-hydroxyphenyl) phenylamine, 2,2-
Bis (4-hydroxyphenyl) -1,1,1,3
3,3-hexafluoropropane, 2,2-bis (3-
Methyl-4-hydroxyphenyl) -1,1,1,3
3,3-hexafluoropropane, 2,2-bis (3,3
5-dimethyl-4-hydroxyphenyl) -1,1,
1,3,3,3-hexafluoropropane, 2,2-bis (3-chloro-4-hydroxyphenyl) -1,1,
1,3,3,3-hexafluoropropane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl)-
1,1,1,3,3,3-hexafluoropropane,
2,2-bis (3-fluoro-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3,5-difluoro-4-hydroxyphenyl)- 1,1,1,3,3,3-hexafluoropropane, 4,4'-dihydroxydiphenyl ketone, 3,3'-dimethyl-4,4'-dihydroxydiphenyl ketone, 3,3'-dichloro-4, 4'-dihydroxydiphenyl ketone, 3,3'-di-tert-butyl-4,4'-dihydroxydiphenyl ketone, 3,
3,5,5 ″ -tetramethyl-4,4′-dihydroxydiphenyl ketone,

3,3,5,5 ''-tetrachloro-4,
4'-dihydroxydiphenyl ketone, 2,2'-dihydroxydiphenyl ketone, isatin bisphenol,
Isatin biscresol, 9,9'-bis (4-hydroxyphenyl) fluorene, 9,9'-bis (3-methyl-4-hydroxyphenyl) fluorene, 9,9'-
Examples thereof include residues such as bis (3,5-dimethyl-4-hydroxyphenyl) fluorene, and these may be composed of one kind or two or more kinds.

The aromatic dicarboxylic acid residue constituting the aromatic ester unit of the present invention is terephthalic acid,
Isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 5-tert-butylisophthalic acid, diphenic acid, 4,4′-dicarboxydiphenyl ether,
Bis (p-carboxyphenyl) alkane, 4,4'-
Residues of aromatic dicarboxylic acids such as dicarboxyphenyl sulfone are mentioned. These divalent carboxylic acid residues may be composed of one kind or two or more kinds, and a particularly preferable one is an equal mixture of terephthalic acid residue and isophthalic acid residue.

The end-capping material for obtaining polyarylate is phenol, cresol, p-ter.
Monovalent phenols such as t-butylphenol, benzoic acid chloride, methanesulfonyl chloride, monovalent acid chlorides such as phenyl chloroformate, methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, Monohydric alcohols such as pentanol, hexanol, dodecyl alcohol, stearyl alcohol, benzyl alcohol, phenethyl alcohol, acetic acid, propionic acid, octanoic acid, cyclohexanecarboxylic acid, benzoic acid, toluic acid, phenylacetic acid, p-tert-butylbenzoic acid acid,
Examples thereof include monovalent carboxylic acids such as p-methoxyphenylacetic acid.

Preferred examples of the siloxane unit (B) of the polyarylate of the present invention include structures represented by the following formulas (5) to (9).

[0023]

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[In the formulas (5) to (9), n represents an integer of 1 or more] In the formulas (5) to (9), the repeating number n of the siloxane unit is n.
Is preferably in the range of 1-9. When the number of repeating units is 10 or more, transparency tends to decrease and haze tends to increase.

The reactive siloxanes that can be used to form the siloxane unit are exemplified by the compounds of the following formulas (10) to (29).

[0026]

[Chemical 6]

[0027]

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[0028]

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[In the formula, the repeating unit number m represents an integer including 0. ] Considering the optical characteristics of the generated polyarylate, m is
It is preferably 0 to 8.

The molar ratio of the aromatic ester unit (A) to the siloxane unit (B) in the polymer is (A):
(B) = 50: 50 to 99: 1. When the content of (A) is less than 50 mol%, the heat resistance and strength of the polymer are remarkably reduced, while when it exceeds 99 mol%, the effect of improving wear resistance is lost. Considering maintenance of heat resistance and strength of the polymer and improvement of abrasion resistance, (A) :( B) = 70:
It is preferably in the range of 30 to 95: 5. The aromatic ester unit and the siloxane unit may take various forms such as random copolymerization, graft copolymerization and block copolymerization, but as described above, the number of siloxane block units is less than 10. Preferably. If the number of siloxane units exceeds 10, the cloudiness described below tends to increase, which is not preferable.

Further, the polyarylate of the present invention comprises 1,
1,2,2-tetrachloroethane, 25 ° C, 0.1 g
It is preferable that the inherent viscosity measured at a concentration of / dl is 0.4 or more. 0.45-1.4 are more preferable, and 0.5-1.2 are particularly preferable. When the inherent viscosity is less than 0.4, the mechanical strength tends to be low, while when it exceeds 1.2, the melt viscosity tends to be high and the moldability tends to be lowered. Further, the polyarylate of the present invention is substantially amorphous, and is dissolved in a solvent, especially methylene chloride, at a concentration of 10% by weight or more. It is preferably dissolved at a concentration of 15% by weight or more. Concentration is 10% by weight
If it is less than 1, the viscosity is low and it becomes difficult to obtain a thick cast film or coating layer.

The solubility of polyarylate in methylene chloride can be confirmed by various methods, but the simplest method is to carry out interfacial polymerization using methylene chloride as a solvent. When the solubility is good, the methylene chloride solution of the polyarylate after the interfacial polymerization is a homogeneous solution, but when the solubility is bad, the polymer precipitates after the start of the polymerization, and the polymer precipitates after the polymerization.

Whether it is amorphous or not can be confirmed by a known method such as differential scanning calorimetry (DSC) or dynamic viscoelasticity measurement, and the presence of a melting point. Furthermore, the polyarylate of the present invention has good transparency and has a haze of 1 or less at a thickness of 500 μm measured by JISK-7105. In particular, not only in optical applications but also in fields requiring light transmission, the haze needs to be 1 or less. Further, the polyarylate of the present invention does not necessarily have to be a linear resin, and a trifunctional or higher functional substance may be added during polymerization to introduce a branched structure.

The method for producing the polyarylate of the present invention will be described in more detail. For example, in the interfacial polymerization method, in the coexistence of a polymerization catalyst, an aqueous alkaline solution containing a dihydric phenol compound or a monohydric phenol compound is dissolved in a solvent which is inert to the reaction and which dissolves the resulting polymer. An acid halide of an aromatic dicarboxylic acid and a reactive siloxane described below are mixed and reacted at 2 to 50 ° C for 0.5 to 5 hours to obtain the polyarylate of the present invention.

In the solution polymerization method, the dihydric phenol compound is dissolved in a solvent which is inactive in the reaction and dissolves the resulting polymer in the presence of an acid scavenger such as an organic base or an inorganic base to give an aromatic compound. The dicarboxylic acid halide and the reactive siloxane are added and reacted at a temperature of 5 ° C. to the boiling point of the solvent for at least 0.5 to 5 hours to obtain a polyarylate. In addition, examples of the halide in the aromatic dicarboxylic acid dihalide used for producing the polyarylate include chlorine, bromine, and iodine, and chlorine is particularly preferable.

As the polymerization solvent which can be used for the interfacial polymerization, any solvent which is inert to the reaction, is incompatible with water and can dissolve the polymer formed can be used. If preferred ones are listed, chlorinated carbonization of dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chloroform, 1,1,1-trichloroethane, carbon tetrachloride, monochlorobenzene, dichlorobenzene, etc. Hydrogen: benzene, toluene,
Aromatic hydrocarbons such as xylene and ethylbenzene: ether compounds such as diethyl ether can be mentioned,
These organic solvents can be used as a mixture of two or more kinds. In addition, solvents other than the above, such as ethers, ketones, esters, and nitriles, which have an affinity for water may be used within the limit that the mixed solvent system is not completely compatible with water. In the interfacial polymerization, examples of the alkali used during the reaction include sodium hydroxide and potassium hydroxide.

Further, as the polymerization catalyst used in the interfacial polymerization, trimethylamine, triethylamine, tri-n
-Tertiary amines such as -butylamine, tri-n-propylamine, tri-isopropylamine, trihexylamine, tridecylamine, N, N-dimethylcyclohexylamine, pyridine, quinoline, dimethylaniline,
Quaternary ammonium salts such as trimethylbenzylammonium halide, tetramethylbenzylammonium halide, triethylbenzylammonium halide, tri-n-butylbenzylammonium halide, tetra-n-butylammonium halide, trimethylbenzylphosphonium halide, tetramethylbenzylphosphonium Quaternary phosphonium salts such as halides, triethylbenzylphosphonium halides, tri-n-butylbenzylphosphonium halides, tetra-n-butylphosphonium halides, triphenylbenzylphosphonium halides and tetraphenylphosphonium halides, 1
8-crown-6,18-benzocrown-6,18-
Examples include crown ethers such as dibenzocrown-6 and 15-crown-5.

As the base used for solution polymerization, there are inorganic basic compounds such as sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide, as well as tertiary amines such as triethylamine, tributylamine and pyridine. Amines, 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) and 1,8-diazabicyclo [5.
4.0] Organic strongly basic compounds such as undeca-7-ene (DBU) are preferably used, and as a solvent, an aromatic dihydroxyl compound, a polymer which is dissolved without reacting with an aromatic dicarboxylic acid dihalide, is formed. Any material that melts can be used. Examples of these are aromatic hydrocarbon compounds such as benzene, toluene and xylene, dichloromethane, 1,2-dichloroethane, chloroform, chlorobenzene, o, m, p-
Examples thereof include halogenated hydrocarbons such as dichlorobenzene, dioxane, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, hexamethylphosphoryltriamide, N-methylpyrrolidone, pyridine and the like or a mixture thereof as appropriate.

The polyarylate resin of the present invention contains
Hindered phenolic compounds, depending on the purpose of use
Antioxidants such as phosphorous acid compounds, hindered amine compounds or thioether compounds, colorants, inorganic and organic fillers, reinforcing agents such as carbon fibers and glass fibers, lubricants,
You may use together an antistatic agent etc. suitably. Further, the polyarylate of the present invention can be used as various molding materials or in the field of being dissolved in a solvent and used. As an example of being dissolved in a solvent, it can be widely used as a cast film, a binder resin for an electrophotographic photoreceptor, or the like.

[0040]

EXAMPLES The present invention will be specifically described below with reference to examples.
The method used for the characteristic evaluation of the resin of the present invention is as follows. (1) Viscosity measurement The polymer was dissolved in 1,1,2,2-tetrachloroethane as a solvent at a concentration of 0.1 g / dl and the temperature was 25 ° C.
Was measured. (2) The glass transition temperature was measured using a Perkin Elmer DSC-7 system. The temperature of the temperature rising rate of 20 ° C./min and the value of 2nd scan were taken as the glass transition temperature. (3) Methylene chloride solubility The obtained polyarylate was dissolved in methylene chloride at a concentration of 10% by weight, and the state of the solution was visually observed.

(4) Haze Using the solution obtained in (3), a solvent cast film having a thickness of about 500 μm was prepared. J using this film
The haze was measured according to IS K-7105. (5) Abrasion resistance Using the film obtained in (3), Suga Test Instruments Co., Ltd.
The amount of wear was measured after the sample was reciprocated 1200 times on a worn paper loaded with a load of 200 g using a Suga abrasion tester manufactured by Kanamoto. (6) Tensile strength Using the film obtained in (4), JIS C-231
Tensile strength was measured based on 8.

Example 1 0.985 mol of bisphenol A, 0.03 mol of p-tert-butylphenol, 0.007 mol of tetrabutylbenzylammonium chloride and 2.1 mol of sodium hydroxide were dissolved in 5.1 l of water. To this was added 0.95 mol of a 1: 1 mixture of terephthaloyl chloride and isophthalic acid chloride and 0.05 mol of dimethyldichlorosilane dissolved in 3 l of methylene chloride. After continuing stirring for 3 hours, acetic acid was added to stop the reaction, and the methylene chloride phase was washed with water. Then, the methylene chloride phase was poured into a large amount of methanol to precipitate the polymer. The precipitated polymer was filtered and dried to obtain polyarylate.

Example 2 Example 1 was repeated except that diphenyldichlorosilane was used instead of dimethyldichlorosilane in Example 1.
The same was done.

Example 3 In Example 1, the amount of dimethyldichlorosilane was adjusted to 0.1.
The same procedure as in Example 1 was repeated, except that the mole ratio was 0.9 mole and the 1: 1 mixture of terephthaloyl chloride and isophthaloyl chloride was 0.9 mole.

Example 4 0.885 mol of bisphenol A, 0.03 mol of p-tert-butylphenol, 0.007 mol of tetrabutylbenzylammonium chloride and 2.1 mol of sodium hydroxide were dissolved in 5.1 l of water. Here, 1.0 mol of a 1: 1 mixture of terephthalic acid chloride and isophthalic acid chloride and the following formula (30)

[0046]

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0.1 mol of the compound of 3 methylene chloride
Was added. Except for this, the same procedure as in Example 1 was performed.

Example 5 In Example 4, the following formula (31)

[0049]

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The procedure of Example 4 was repeated except that the amount of the compound (1) was 0.1 mol.

Example 6 The same procedure as in Example 1 was carried out except that bisphenol C was used instead of bisphenol A in Example 1.

Example 7 The same procedure as in Example 1 was carried out except that bisphenol Z was used instead of bisphenol A in Example 1.

Comparative Example 1 0.985 mol of bisphenol A, 0.03 mol of p-tert-butylphenol, 0.007 mol of tetrabutylbenzylammonium chloride and 2.1 mol of sodium hydroxide were dissolved together with 5.1 l of water. To this was added 1.0 mol of a 1: 1 mixture of terephthaloyl chloride and isophthalic acid chloride dissolved in 3 l of methylene chloride. Except for this, the same procedure as in Example 1 was performed.

Comparative Example 2 In Example 4, 0.6 mol of a 1: 1 mixture of terephthalic acid chloride and isophthalic acid chloride was added to the compound of formula (2).
The same procedure as in Example 4 was carried out except that 0.4 mol of the compound of 5) and 3 l of methylene chloride were added.

Comparative Example 3 0.955 mol of bisphenol A, 0.03 mol of p-tert-butylphenol, 0.007 mol of tetrabutylbenzylammonium chloride and 2.1 mol of sodium hydroxide were dissolved together with 5.1 l of water. Here, 0.95 mol of a 1: 1 mixture of terephthalic acid chloride and isophthalic acid chloride and the following formula (32)

[0056]

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0.03 mol of the compound of
What was melt | dissolved in 1 was added. Except for this, the same procedure as in Example 1 was performed. The above-mentioned evaluations were performed on the polyarylate obtained in each of the examples and the comparative examples. Table 1 shows the results.

[0058]

[Table 1]

From the results of the above Examples and Comparative Examples, the following matters were found. (1) From the comparison between Examples 1 to 7 and Comparative Example 1, it was found that the polyarylate of the present invention has excellent wear resistance. (2) From the comparison between Examples 1 to 7 and Comparative Example 2, it was found that the polyarylate of the present invention has excellent wear resistance as well as excellent heat resistance and mechanical strength. (3) From the comparison between Examples 1 to 7 and Comparative Example 3, it was found that the polyarylate of the present invention has a low haze and excellent optical characteristics.

[0060]

INDUSTRIAL APPLICABILITY The polyarylate of the present invention has the same optical characteristics, heat resistance and mechanical strength as those of the conventional polyarylate and is excellent in abrasion resistance, and therefore can be used as various molding materials. Also, since it has excellent solubility in a solvent, it can be widely used in the field of being dissolved in a solvent, for example, as a solvent cast film, as a binder resin for electrophotographic photoreceptors and the like.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C08G 77/445 NUK C08G 77/445 NUK (72) Inventor Hashimoto Yashiro 23, Uji Kozakura, Uji City, Kyoto Prefecture Unitika Ltd. Central Research Laboratory

Claims (1)

[Claims] 1. An aromatic ester unit (A) represented by the following formula (1) consisting of a dihydric phenol residue and an aromatic dicarboxylic acid residue: [Wherein R _{1 to} R ₈ represent a hydrogen atom, an alkyl group, a halogen group, or a haloalkyl group and may be the same or different, and X is an alkylidene group, a cycloalkylidene group, an alkylene group, an aromatic substituted alkylidene group, It represents a halogen-substituted alkylidene group, a sulfone group, an ether group, a thioether group and a ketone group, and Z represents a divalent aromatic group. ] And a siloxane unit (B) represented by the following formula (2): [In the formula, R ₉ and R ₁₀ represent an alkyl group or an aryl group. ] And the molar ratio of (A) and (B) is (A):
(B) = 50: 50 to 99: 1, is dissolved in methylene chloride at a concentration of 10% by weight or more, and has a haze of 1 or less at a thickness of 500 μm measured by JIS K-7105. And polyarylate.