JP2008255262A - Method for producing aromatic polyester pellet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing pellets which are little discolored and are excellent in transparency. <P>SOLUTION: This method for producing aromatic polyester pellets comprises mixing an aromatic polyester having a weight-average mol.wt. of 10,000 to 50,000 with one or more solvents (a) selected from the group consisting of dichloromethane, trichloromethane, 1,2-dichloroethane and chlorobenzene and one or more solvents (b) selected from the group consisting of tetrahydrofuran, methyltetrahydrofuran, methylhydrofuran and diethyl ether in a volume ratio of 0.3 to 2.0 times the volume of the solvents (a), evaporating the solvents from the mixture at a temperature of 5 to 40°C, and then cutting and/or crushing the resultant aromatic polyester mass. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a method for producing aromatic polyester pellets.

Conventionally, when producing aromatic polyester pellets, an aromatic polyester powder is supplied to a pelletizer and heated and melted at a high temperature of 300 ° C. or higher, and then the aromatic polyester is extruded and cut (Patent Document 1).

In this method, the aromatic polyester deteriorates due to heat-melting at a high temperature and turns yellow (yellowing), and a pellet having excellent transparency cannot be obtained. Conventionally, aromatic polyester has been exclusively used only as a heat-resistant resin, and thus yellowing of such aromatic polyester has not been a problem.

However, in recent years, various uses relating to aromatic polyesters have been developed. For example, in the use of optical fibers, yellowing of aromatic polyesters has become a major problem.

JP 2003-285320 A

The present invention provides a method for producing pellets with less coloring and excellent transparency.

The inventors of the present invention have made various studies in order to solve the coloring problem of the conventional method for producing aromatic polyester pellets. As a result, the aromatic polyester can be mixed with the solvent (a) and the solvent (b) in a volume ratio of 0.3 to 2.0 times the solvent (a), and these solvents can be evaporated from the mixture at a low temperature. For example, the inventors have found that pellets having a remarkably high density and little coloration and excellent transparency can be easily produced like a film, thereby completing the present invention.

That is, the present invention
(1) One or more solvents (a) selected from the group consisting of dichloromethane, trichloromethane, 1,2-dichloroethane, and chlorobenzene, aromatic polyester having a weight average molecular weight of 10,000 to 50,000, and the solvent (a) Is mixed with one or more solvents (b) selected from the group consisting of tetrahydrofuran, methyltetrahydrofuran, methylhydrofuran and diethyl ether in a volume ratio of 0.3 to 2.0 times, and then from the mixture at a temperature of 5 to 40 ° C. This is a process for producing aromatic polyester pellets in which these solvents are evaporated and the resulting aromatic polyester mass is crushed and / or cut.

As a preferred embodiment,
(2) The method according to (1) above, wherein the aromatic polyester is mixed with the solvent (a), and the solvent (b) is mixed with the resulting solution,
(3) The method according to (1) or (2) above, wherein the temperature at which the solvent is evaporated is 10 to 35 ° C.
(4) The method according to (1) or (2) above, wherein the solvent is evaporated under environmental conditions,
(5) The method according to any one of (2) to (4) above, wherein the concentration of the solution is 0.2 to 1.0 g / ml.
(6) The method according to any one of (2) to (4) above, wherein the concentration of the solution is 0.4 to 0.8 g / ml.
(7) The method according to any one of (1) to (6) above, wherein the solvent (a) is dichloromethane and the solvent (b) is tetrahydrofuran,
(8) The method according to any one of (1) to (7) above, wherein the aromatic polyester obtained by crushing and / or cutting is further heated at 40 to 100 ° C. under reduced pressure,
(9) The method according to any one of (1) to (8) above, wherein the mixture is placed in a container to a depth of 2 cm or less, and the solvent is evaporated.
(10) The method according to any one of (1) to (9) above, wherein the aromatic polyester has a weight average molecular weight of 20,000 to 40,000,
(11) The method according to any one of (1) to (10) above, wherein the mixing amount of the solvent (b) is 0.5 to 1.5 times by volume with respect to the solvent (a),
(12) The method according to any one of (1) to (11) above, wherein the aromatic polyester to be mixed with the solvent is in a powder form.

According to the method of the present invention, aromatic polyester pellets with little coloring, excellent transparency and high density can be obtained. In addition, there is no thermal degradation of the aromatic polyester. In addition, since conventional heat melting is not performed, thermal energy can be saved and the manufacturing process can be simplified.

In the method of the present invention, the aromatic polyester obtained by polymerization, preferably the aromatic polyester powder, is one or more solvents (a) selected from the group consisting of dichloromethane, trichloromethane, 1,2-dichloroethane and chlorobenzene. And one or more solvents (b) selected from the group consisting of tetrahydrofuran, methyltetrahydrofuran, methylhydrofuran and diethyl ether. Preferably, first, the aromatic polyester obtained by polymerization is mixed with the solvent (a) to produce a solution. Of these solvents (a), dichloromethane is preferably used. The upper limit of the concentration of the solution is preferably 1.0 gram / milliliter, more preferably 0.7 gram / milliliter, still more preferably 0.5 gram / milliliter, and the lower limit is preferably 0.2 gram / milliliter, more preferably 0.4 gram / milliliter. is there. Beyond the above upper limit, the thickness of the aromatic polyester lump after evaporation of the solvent is thin and powder tends to be generated when crushed, and below the lower limit, it takes a long time to evaporate the solvent.

The solution is then mixed with one or more solvents (b) selected from the group consisting of tetrahydrofuran, methyltetrahydrofuran, methylhydrofuran and diethyl ether. Of these solvents (b), tetrahydrofuran is preferably used. The upper limit of the mixing amount of the solvent (b) is 2.0 times, preferably 1.7 times, more preferably 1.5 times by volume ratio with respect to the solvent (a), and the lower limit is volume ratio with respect to the solvent (a). And 0.3 times, preferably 0.4 times, more preferably 0.5 times. Most preferably, approximately the same volume of solvent (b) as solvent (a) is mixed. If the mixing amount of the solvent (b) exceeds the above upper limit, the aromatic polyester becomes powdery and pellets cannot be produced, and if it is less than the above lower limit, the aromatic polyester becomes filmy. By mixing the solvent (b) within the above range, an aromatic polyester mass having a remarkably high density and which can be easily crushed and / or cut can be produced.

From the mixture obtained by mixing the aromatic polyester with the solvent (a) and the solvent (b), the temperature at which these solvents are evaporated has an upper limit of 40 ° C, preferably 35 ° C, more preferably 30 ° C, The lower limit is 5 ° C, preferably 10 ° C, more preferably 15 ° C. If the above upper limit is exceeded, the aromatic polyester after evaporation of the solvent may turn yellow and become colored and become powdery. If it is less than the above lower limit, it takes a long time to evaporate the solvent. The pressure at the time of solvent evaporation is not particularly limited as long as the solvent can be evaporated at the above temperature. The upper limit is preferably 103 kPa, more preferably 101 kPa, and the lower limit is preferably 10 kPa, more preferably 50 kPa. The evaporation of the solvent is preferably carried out under environmental conditions.

The upper limit of the weight average molecular weight of the aromatic polyester used in the present invention is 50.000, preferably 45,000, more preferably 40,000, and the lower limit is 10,000, preferably 15,000, more preferably 20,000. Beyond the above upper limit, the hardness of the aromatic polyester mass after evaporation of the solvent (a) and the solvent (b) becomes high, and much energy is required for crushing and / or cutting. If it is less than the said minimum, the obtained aromatic polyester will be sandy (fine powder).

In a preferred embodiment of the present invention, a mixture obtained by mixing the aromatic polyester powder with the solvent (a) and the solvent (b) is put in a container of any shape, and the solvent is evaporated to evaporate. Later, the aromatic polyester is removed from the container, and the resulting aromatic polyester mass of any shape is crushed and / or cut and then classified to produce pellets. The pellet can be heated at 40 to 100 ° C. under reduced pressure to further remove the solvent.

A preferred embodiment of the present invention will be described with reference to FIG. First, the aromatic polyester powder (1) is mixed with the solvent (a) (2) to prepare the solution (3) having the predetermined concentration. Next, the solution (3) is mixed with the above-mentioned predetermined amount of the solvent (b) (4), and the resulting mixture (5) is put into a container (6), for example, a flat container such as a petri dish or bat, The depth is preferably 3 cm or less, more preferably 2 cm or less, and further preferably 0.5 to 1.0 cm. These solvents are then evaporated under predetermined temperature and pressure conditions. Thereafter, the aromatic polyester lump (7) remaining in the container is taken out and crushed with a crusher (8), for example, a hammer, a mill or the like, or cut with a cutter or the like. The aromatic polyester that has been crushed or cut is classified by, for example, a sieve (10) to obtain pellets (9) having a desired size.

In the present invention, the aromatic polyester is obtained by reacting an aromatic polyhydric alcohol with an aromatic polycarboxylic acid, an acid halide or an acid anhydride thereof. Aromatic polyhydric alcohols and aromatic polycarboxylic acids, their acid halides or acid anhydrides are known. The production method thereof is known and is described in detail, for example, in Patent Document 1 described above.

Examples of the aromatic polyhydric alcohol include 2,2′-dihydroxybiphenyl, 3,3′-dihydroxybiphenyl, 3,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether, and 2,2′-bis- ( 4-hydroxyphenyl) propane [bisphenol A], 2,4'-dihydroxydiphenylmethane, bis- (4-hydroxyphenyl) methane, bis- (2-hydroxyphenyl) methane, bis- (4-hydroxy-2,6- Dimethyl-3-methoxyphenyl) methane, 1,1-bis- (4-hydroxyphenyl) ethane, 1,1-bis- (4-hydroxyphenyl) cyclohexane, 1,2-bis- (4-hydroxyphenyl) ethane 1,1-bis- (4-hydroxy-2-chlorophenyl) ethane, 1,1'-binaphthalene-2,2'-diol, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4- Dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6- Hydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 9,9-bis (4-hydroxyphenyl) fluorene 9,9-bis (5-methyl-4-hydroxyphenyl) fluorene, 1,2- (9-oxofluorene) diol, 1,5- (9-oxofluorene) diol, 1,6- (9-oxo Fluorene) diol, 1,7- (9-oxofluorene) diol, 2,3- (9-oxofluorene) diol, 2,7- (9-oxofluorene) diol, 2,2-bis- (4-hydroxy) Naphthyl) propane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxyphenyl) pentane, 3,3-bis- (4-hydroxyphenyl) Phenylmethane, para-α, α'-bis- (4-hydroxyphenyl) -para-diisopropylbenzene, bi Su- (4-hydroxyphenyl) ether, 4,3'-dihydroxydiphenyl ether, 4,2'-dihydroxydiphenyl ether, 2,2'-dihydroxydiphenyl ether, 2,3'-dihydroxydiphenyl ether, 4,4'-dihydroxy-2 , 6-Dimethyldiphenyl ether, bis- (hydroxynaphthyl) ether, 3,4'-dihydroxydiphenyl, bis- (4-hydroxyphenyl) sulfone, bis- (3-hydroxyphenyl) sulfone, 2,4'-dihydroxydiphenylsulfone Catechol, 3-methyl catechol, 4-methyl catechol, 3-ethyl catechol, 4-ethyl catechol, 3-n-propyl catechol, 4-n-propyl catechol, 3- (t-butyl) catechol, 3-n- Pentylcatechol, 4-n-pentylcatechol, 4- (1,1-dimethylpropyl) catechol, 4-hexylcatechol, 4-cyclohexylcatechol 4- (1,1,3,3-tetramethylbutyl) catechol, 4-nonylcatechol, 3,4-dimethylcatechol, 3,5-dimethylcatechol, 3,6-dimethylcatechol, 4,5- Dimethylcatechol, 4-methyl-5-ethylcatechol, 3-chlorocatechol, 4-chlorocatechol, 3-bromocatechol, 4-bromocatechol, 3-fluorocatechol, 4-fluorocatechol, 3,5-dichlorocatechol, 4 , 5-dichlorocatechol, 3,4-dichlorocatechol, 3,4-dibromocatechol, 3,5-dibromocatechol, 4,5-dibromocatechol, 4-chloro-5-nitrocatechol, 3-chloro-6-methoxy Catechol, 5-bromo-4-nitrocatechol, 4-bromo-5-methylcatechol, 3-bromo-5- (t-butyl) catechol, 3,4,5-trichlorocatechol, 3,4,5-tribromo Catechol, 3,4,6-tribromocatechol, tetrac Locatechol, tetrabromocatechol, 3-aminocatechol, 4-aminocatechol, 3- (2-aminoethyl) catechol, 4- (2-methylaminoethyl) catechol, 4- (2-dimethylaminoethyl) catechol, 4- (2-aminoethyl) catechol, 6-amino-4- (2-aminoethyl) catechol, 3-nitrocatechol, 3,4-dinitrocatechol, 3,4-dinitrocatechol, 4,5-dinitrocatechol, 3- Nitro-6-methoxycatechol, 4-nitro-3-methoxycatechol, 5-nitro-3-methylcatechol, 4-methoxycatechol, 6-methoxycatechol, 4- (2-hydroxyethyl) catechol, 3-propioxycatechol , 3-butyroxycatechol, 3,4-dimethoxycatechol, 3,6-dimethoxycatechol, 5-methoxy-3- (t-butyl) catechol, 3-ethoxy- (t-butyl) catechol, 3,4,6 -Trimethoxyca Tecor, resorcinol, 2-chlororesorcinol, 4-chlororesorcinol, 5-chlororesorcinol, 2,4-dichlororesorcinol, 4,6-dichlororesorcinol, 2,4,6-trichlororesorcinol, 2-bromo-4-chlororesorcinol 4-bromo-2-chlororesorcinol, 4-chloro-5-methylresorcinol, 6-chloro-4-ethylresorcinol, 2-chloro-4-butylresorcinol, 6-chloro-4-butylresorcinol, 6-chloro- 4-cyclohexylresorcinol, 2,4-dichloro-5-methylresorcinol, trichlororesorcinol, 2-bromoresorcinol, 4-bromoresorcinol, 5-bromoresorcinol, 2,4-dibromoresorcinol, 4,6-dibromoresorcinol, 2, 4,6-tribromoresorcinol, 6-bromo-4-butylresorcinol, 2-iodoresor Nord, 4-iodoresorcinol, 5-iodoresorcinol, 4,6-diiodoresorcinol, 2,4,6-triiodoresorcinol, 2-aminoresorcinol, 5-aminoresorcinol, 4-amino-2,5-dimethylresorcinol 4-benzaminoresorcinol, 5-mercaptoresorcinol, 5-methylthioresorcinol, 5-ethylthioresorcinol, 5-propylthioresorcinol, 5-propylthioresorcinol, 5-butylthioresorcinol, 2-benzsulfonylresorcinol, resorcinol monoacetate , Resorcinol monobenzoate, 2-nitroresorcinol, 4-nitroresorcinol, 5-nitroresorcinol, 2,4-dinitroresorcinol, 4,6-dinitroresorcinol, 2,4,6-trinitroresorcinol, tetranitroresorcino , 6-nitro-5-methoxyresorcinol, 2-nitro-5-methoxyresorcinol, 4-nitro-5-methoxyresorcinol, 2,4-dinitro-5-methylresorcinol, 2,4,6-trinitro-5 -Methylresorcinol, 2-methoxyresorcinol, 4-methoxyresorcinol, 5-methoxyresorcinol, 2,3-methoxyresorcinol, 2,5-methoxyresorcinol, 2-methoxy-5-methylresorcinol, 5-methoxy-4-methylresorcinol 5-methoxy-6-methylresorcinol, 5-ethoxyresorcinol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 5-ethylresorcinol, 2-n-propyl Resorcinol, 4-n-propyl resorcinol, 5-n-propyl resorcinol, 2- (2-propenyl ) Resorcinol, 4- (2-propenyl) resorcinol, 4- (2-methylethenyl) resorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 5-n-butylresorcinol, 2-n-butylresorcinol, 4 -tert-butylresorcinol, 2-n-pentylresorcinol, 4-n-pentylresorcinol, 5-n-pentylresorcinol, 4- (1-methylbutyl) resorcinol, 5- (2-methyl-1 -Ethylpropyl) resorcinol, 2-n-hexylresorcinol, 4-n-hexylresorcinol, 5-n-hexylresorcinol, 4- (4-methylpentyl) resorcinol, 5- (4-methylpentyl) resorcinol, 5 -(1,1-dimethylbutyl) resorcinol, 5- (1,2-dimethylbutyl) resorcinol, 5- (1-methyl-1-pentenyl) resorcinol, 4-cyclohexylresorcinol, 4-phenylresorcinol 4-heptylresorcinol, 5-heptylresorcinol, 5- (1-methylhexyl) resorcinol, 4-phenylmethylresorcinol, 2-octylresorcinol, 4-octylresorcinol, 5-octylresorcinol, 4- (1-methyl (Heptyl) resorcinol, 4- (1,1,3,3-tetrabutyl) resorcinol, 4- (2-phenylethyl) resorcinol, 5-nonylresorcinol, 5- (1-methyloctyl) resorcinol, 5- (1,1 -Dimethylheptyl) resorcinol, 5- (1,2-dimethylheptyl) resorcinol, 5- (1,2,4-trimethylhexyl) resorcinol, 4-decylresorcinol, 5- (1-methylnonyl) resorcinol, 2,4- Dimethylresorcinol, 2,5-dimethylresorcinol, 4,5-dimethylresorcinol, 4,6-dimethylresorcinol, 4-ethyl-2-methylresorcinol 5-ethyl-2-methylresorcinol, 2-ethyl-4-methylresorcinol, 5-ethyl-4-methylresorcinol, 6-ethyl-4-methylresorcinol, 5-ethenyl-4-methylresorcinol, 2,4- Dimethylresorcinol, 5-methyl-4-propylresorcinol, 2-methyl-5-sec-butylresorcinol, 4,6-di (isopropyl) resorcinol, 4-ethyl-6-pentylresorcinol, 4,6-di- (tert-butyl) resorcinol, 2-methyl-4- (benzyl) resorcinol, 2,4,5-trimethylresorcinol, 2,4,6-trimethylresorcinol, 4,5,6-trimethylresorcinol, 4,6-dimethyl -5-sec-butylresorcinol, tetramethylresorcinol, 2-hydroxyethylresorcinol, 5-trifluoromethylresorcinol, hydroquinone, phenylhydroquinone, chlorohydroquinone , Methylhydroquinone, trifluorohydroquinone, tetrafluorohydroquinone, 2-chloro-3-methoxyhydroquinone, 2-chloro-5-methoxyhydroquinone, 2-chloro-6-methoxyhydroquinone, 2,3-dichlorohydroquinone, 2,5- Dichlorohydroquinone, 2,6-dichlorohydroquinone, trichlorohydroquinone, tetrachlorohydroquinone, bromohydroquinone, 3-bromo-2,6-dimethylhydroquinone, 2,5-dibromohydroquinone, 2,6-dibromohydroquinone, tribromohydroquinone, iodo Hydroquinone, 2,6-diiodohydroquinone, tetraiodohydroquinone, nitrohydroquinone, 2,6-dinitrohydroquinone, methoxyhydroquinone, 2-methoxy-3-methylhydroquinone, 2-methoxy-5-methylhydroquinone, 3-methoxy-2 -Methylhydroquinone, 5-methoxy-2-methyl Luhydroquinone, 2-methoxy-6-propylhydroquinone, 2-methoxy-5-propenylhydroquinone, 2,3-dimethoxyhydroquinone, 2,5-dimethoxyhydroquinone, 2,6-dimethoxyhydroquinone, phenoxyhydroquinone, mercaptohydroquinone, acetylhydroquinone Benzoylhydroquinone, hydroxymethylhydroquinone, methylhydroquinone, 2-methyl-6-ethylhydroquinone, 2-methyl-5-isopropylhydroquinone, 2-methyl-5-cyclohexylhydroquinone, 2,3-dimethylhydroquinone, 2,5-dimethyl Hydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, tetramethylhydroquinone, ethylhydroquinone, 2,6-diethylhydroquinone, vinylhydroquinone, 5-ethoxyresorcinol, 2-methylresorcinol, 4-methylresorcino 5-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 5-ethylresorcinol, 2-n-propylresorcinol, 4-n-propylresorcinol, 5-n-propylresorcinol, 2- (2-propenyl) Resorcinol, 4- (2-propenyl) resorcinol, 4- (1-methylethenyl) resorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 5-n-butylresorcinol, 5-sec-butylresorcinol, 4- tert-butylresorcinol, 2-n-pentylresorcinol, 4-n-pentylresorcinol, 5-n-pentylresorcinol, 4- (1-methylbutyl) resorcinol, 5- (2-methyl-1-ethylpropyl) resorcinol, 2 -n-hexyl resorcinol, 4-n-hexyl resorcinol, 5-n-hexyl resorcinol, 4- (4-methylpentyl) resorcinol, 5- (4-methylpentyl) resorcinol, 5- (1,1-dimethylbutyl) resorcinol, 5- (1,2-dimethylbutyl) resorcinol, 5- (1-methyl-1-pentenyl) resorcinol, 4-cyclohexyl Resorcinol, 4-phenylresorcinol, 4-heptylresorcinol, 5-heptylresorcinol, 5- (1-methylhexyl) resorcinol, 4-phenylmethylresorcinol, 2-octylresorcinol, 5-octylresorcinol, 4- (1-methylheptyl ) Resorcinol, 4- (1
, 1,3,3-tetramethylbutyl) resorcinol, 4- (2-phenethyl) resorcinol, 5-nonylresorcinol, 5- (1-methyloctyl) resorcinol, 5- (1,1-dimethylheptyl) resorcinol, 5 -(1,2-dimethylheptyl) resorcinol, 5- (1,2,4-trimethylhexyl) resorcinol, 4-decylresorcinol, 5- (1-methylnonyl) resorcinol, 2,4-dimethylresorcinol, 2,5- Dimethylresorcinol, 4,5-dimethylresorcinol, 4,6-dimethylresorcinol, 4-ethyl-2-methylresorcinol, 5-ethyl-2-methylresorcinol, 2-ethyl-4-methylresorcinol, 5-ethyl-4- Methyl resorcinol, 6-ethyl-4-methyl resorcinol, 5-ethenyl-4-methyl resorcinol, 2,4-dimethyl resorcinol, 5-methyl-4-propyl resorcinol, 2-methyl-5-sec- Tilresorcinol, 4,6-diisopropylresorcinol, 4-ethyl-6-pentylresorcinol, 4,6-di-tert-butylresorcinol, 2-methyl-4- (benzyl) resorcinol, 2,4,5-trimethylresorcinol, 2,4,6-trimethylresorcinol, 4,5,6-trimethylresorcinol, 4,6-dimethyl-5-sec-butylresorcinol, tetramethylresorcinol, 2-hydroxyethylresorcinol, 5-trifluoromethylresorcinol, n- Propylhydroquinone, isopropylhydroquinone, 1-propenylhydroquinone, 2-propenylhydroquinone, 2,5-diisopropylhydroquinone, 4-butylhydroquinone, 4-butylhydroquinone, 2,3-di (tert-butyl) hydroquinone, 2,5-di (tert-butyl) hydroquinone, 2,6-di (tert-butyl) hydroquinone, 2-methyl-2-propenyl hydroxyl , Hexylhydroquinone, 4-methylpentylhydroquinone, cyclohexylhydroquinone, 4-phenylmethylhydroquinone, octylhydroquinone, 2,2'-methylidenebisphenol, 3,3'-methylidenebisphenol, 4,4'-methylidenebisphenol, 2,2'-methylidenebis (4-methylphenol), 2,2'-methylidenebis (5-methylphenol), 2,2'-methylidenebis (6-methylphenol), 4,4'-methylidene (2-methylphenol) ), 4,4'-methylidene (3-methylphenol), 2,2'-methylidenebis (4,6-dimethylphenol), 2,2'-methylidenebis (3,5-dimethylphenol), 4,4'- Methylidenebis (2,6-dimethylphenol), 3,3'-methylidenebis (2,4,6-trimethylphenol), 2,2'-methylidenebis (4-propylphenol), 4,4'-methylidenebis (2-propyl) Phenol), 4,4'-methylide Bis (2-methyl-6-ethylphenol), 2,2'-methylidenebis (3,4,5,6-tetramethylphenol), 4,4'-methylidenebis (2,3,5,6-tetramethylphenol) ), 2,2'-methylidenebis (4-tert-butylphenol), 4,4'-methylidenebis (2-methyl-5-isopropylphenol), 4,4'-methylidenebis (3-methyl-6-isopropylphenol), 4,4'-methylidenebis (5-methyl-6-isopropylphenol), 2,2'-methylidenebis (4-tert-butyl-6-methylphenol), 2,2'-methylidenebis (6-tert-butyl-4 -Methylphenol), 4,4'-methylidenebis (4-tert-butyl-6-methylphenol), 4,4'-methylidenebis (2-tert-butyl-5-methylphenol), 2,2'-methylidenebis ( 3,4-dimethyl-6-isopropylphenol), 2,2'-methylidenebis (6-tert-butyl-4-methylphenol), 2,2'-methylidenebis (4- (1,1,3,3-tetramethyl) Butyl) phenol), 2,2'-methylidenebis (4,6-di-tert-butylphenol), 2,2'-methylidenebis (4,6-tert-butylphenol), 4,4'-methylidenebis (2,6- Di-tert-butylphenol), 4,4'-methylidenebis (3,5-di-tert-butylphenol), 2,2'-methylidenebis (4-chlorophenol), 4,4'-methylidenebis (2-chlorophenol) 2,2'-methylidenebis (4-bromophenol), 2,2'-methylidenebis (4,6-dichlorophenol), 2,2'-methylidenebis (4,5-dichlorophenol), 3,3'-methylidenebis (4,5-dichlorophenol), 4,4'-methylidenebis (2,5-dichlorophenol), 4,4'-methylidenebis (2,6-dichlorophenol), 2,2'-methylidenebis (4,6- Dibromophenol), 4,4'-methylidenebis (2,6-dibromophenol), 2,2'-methylidenebis (3,4,6-trichlorophenol), 3,3'-methylidenebis (2,4 , 6-trichlorophenol), 2,2'-methylidenebis (6-bromo-4-chlorophenol), 2,2'-methylidenebis (4-bromo-6-nitrophenol), 2,2'-methylidenebis (6- Chloro-4-nitrophenol), 2,2'-methylidenebis (4-nitrophenol), 4,4'-methylidenebis (2-nitrophenol), 2,2'-methylidenebis (4,6-dinitrophenol), 3 , 3'-methylidenebis (6-methoxyphenol), 4,4'-methylidenebis (2-methoxyphenol), 2,2'-methylidenebis (4-chloro-6-methylphenol), 2,2'-methylidenebis (6 -Chloro-4-methylphenol), 4,4'-methylidenebis (2-chloro-6-methylphenol), 2,2'-methylidenebis (6-bromo-4-methylphenol), 4,4'-methylidenebis ( 6-bromo-2-methylphenol), 2,2'-methylidenebis (4-chloro-3,5-dimethylphenol), 2,2'-methylidenebis (3-chloro-4, 6-dimethylphenol), 2,2'-methylidenebis (6-bromo-4,5-dimethylphenol), 4,4'-methylidenebis (2-chloro-3,5,6-trimethylphenol), 2,2 ' -Methylidenebis (4-chloro-6-isopropylphenol), 2,2'-methylidenebis (6-chloro-4-tert-butylphenol), 2,2'-methylidenebis (4-chloro-3-methyl-6-isopropylphenol) ), 2,2'-methylidenebis (4-chloro-6-tert-butyl-3-methylphenol), 2,2'-methylidenebis (4,6-dichloro-3-methylphenol), 2,2'-methylidenebis (6-nitro-4-tert-butylphenol), 4,4'-isopropylidenebisphenol, 2,2'-isopropylidenebis (5-methylphenol), 4,4'-isopropylidenebis (2-methylphenol) 4,4′-isopropylidenebis (2-cyclohexylphenol), 4,4′-isopropylidenebis (2,6-dibromophenol), 4'-isopropylidenebis (2-nitrophenol), 4,4'-isopropylidenebis (2,6-dinitrophenol), 4,4'-butanediylbis (2-methylphenol), 4,4'-butylidene Bisphenol, 2,2'-butylidenebis (6-tert-butyl-4-methylphenol), 4,4'-butylidenebis (6-tert-butyl-2-methylphenol), 4,4'-sec-butylidenebisphenol 4,4'-sec-butylidenebis (3-methylphenol), 2,2'-sec-butylidenebis (3-methyl-6-isopropylphenol), 2,2'-sec-butylidenebis (6-tert-butyl- 4-methylphenol), 4,4'-isobutylidenebisphenol, 4,4'-isobutylidenebis (6-tert-butyl-4-methylphenol), 4,4 '-(1,3-cyclohexanediyl ) Bisphenol, 4,4'-cyclohexylidene bisphenol, 4,4'-cyclohexylidene bis (2-chlorophenol), 4,4'-cyclohexyl Denbis (2,6-dichlorophenol), 2,2'-thiobisphenol, 4,4'-thiobisphenol, 4,4'-thiobis (2-methylphenol), 2,2'-thiobis (4,5- Dimethylphenol), 2,2'-thiobis (4,6-dimethylphenol), 4,4'-thiobis (2,6-dimethylphenol), 2,2'-thiobis (6-tert-butyl-4-methyl) Phenol), 4,4'-thiobis (2-tert-butyl-5-methylphenol), 2,2'-thiobis (4-fluorophenol), 2,2'-thiobis (4-chlorophenol), 4, 4'-thiobis (3-chlorophenol), 2,2'-thiobis (4-chloro-5-methylphenol), 2,2'-thiobis (4,6-dichlorophenol), 4,4'-thiobis ( 2-bromophenol), 2,2'-thiobis (5-nitrophenol), 4,4'-sulfinylbisphenol, 4,4'-sulfinylbis (2-methylphenol), 4,4'-sulfinylbis (2 -tert-butyl-5-methylphenol), 4,4 '-Sulfinylbis (2-chlorophenol), 4,4'-sulfinylbis (4-chlorophenol), 2,2'-sulfinylbis (4,6-dichlorophenol), 4,4'-sulfinylbis (2 -Bromophenol), 2,2'-sulfonylbisphenol, 4,4'-sulfonylbisphenol, 4,4'-sulfonylbis (2-methylphenol), 4,4'-sulfonylbis (2,5-dimethylphenol) 4,4′-sulfonylbis (2-tert-butyl-5-methylphenol), 4,4′-sulfonylbis (2-chlorophenol), 4,4′-sulfonylbis (3-chlorophenol), 4 , 4'-sulfonylbis (2-bromophenol), 4,4'-sulfonylbis (2-nitrophenol), 2,3'-oxybisphenol, 2,2'-ethanediyl dimercaptobisphenol, 4,4 ' -Methylidenebiscatechol, 4,4'-methylidenebisresorcin, 4,4'-ethylidenebisresorcin, 2,2 ' -Propanediylbisresorcin, 2,2'-butanediylbisresorcin, 2,2'-pentanediylbisresorcin, 2,2'-methylidenebis (6-chlororesorcin), 2,2'-methylidenebis (4-chloro- 6-nitroresorcin), 4,4′-sulfinbisresorcin, 2,2′-ethanediylbishydroquinone, 4,4′-sulfonylbishydroquinone and the like. Among these, 2,2′-bis- (4-hydroxyphenyl) propane [bisphenol A] is particularly preferred, and other compounds containing a wholly aromatic hydroxyl group having a rigid molecular structure containing no alkylene chain in the main chain, For example, biphenols, binaphthalenediols, dihydroxynaphthalenes, dihydroxyfluorenes, dihydroxyoxofluorenes, catechols, resorcinols, hydroquinones and the like are preferably used.

Examples of aromatic polycarboxylic acids include phthalic acid, dimethyl phthalate, diphenyl phthalate, isophthalic acid, dimethyisophthalic acid isophthalate, di (cyanomethyl) isophthalate, diphenyl isophthalate, and di (2,4-dinitroisophthalate). Phenyl), isophthalic acid (1,1-dioxobenzothiophen-3-yl), di (3-benzoisoxazolyl) isophthalate, di (2-benzothiazolyl) isophthalate, isophthalic acid (1-benzotriazolyl) Dithioisophthalic acid S, S'-dipropyl, dithioisophthalic acid S, S'-di (p-nitrophenyl), dithioisophthalic acid S, S'-di (2-benzoxazolyl), dithioisophthalic acid S, S'-di (2-benzothiazolyl), 4-methylisophthalic acid, dimethyl isophthalate, 5-methylisophthalic acid, dimethyl 5-methylisophthalate, 4,5-dimethylisophthalic acid, 4,6- Methyl isophthalic acid, 4-chloroisophthalic acid, dimethyl 4-chloroisophthalate, 5-chloroisophthalic acid, dimethyl 5-chloroisophthalate, 4,6-dichloroisophthalic acid, dimethyl 4,6-dichloroisophthalate, 4-bromo Isophthalic acid, 4,6-dibromoisophthalic acid, dimethyl 4,6-dibromoisophthalate, terephthalic acid, dimethyl terephthalate, di (cyanomethyl) terephthalate, diphenyl terephthalate, di (3-benzoisoxazolyl) terephthalate , Di (2-benzothiazolyl) terephthalate, 2-methyl terephthalic acid, dimethyl 2-methyl terephthalate, 2,5 dimethyl terephthalic acid, 2,6-dimethyl terephthalic acid, dimethyl 2,6-dimethyl terephthalate, 2-chloro Terephthalic acid, dimethyl 2-chloroterephthalate, 2,5-dichloroterephthalic acid, dimethyl 2,5-dichloroterephthalate, Lachloroterephthalic acid, dimethyl tetrachloroterephthalate, 2-bromoterephthalic acid, dimethyl 2-bromoterephthalate, 2,5-dibromoterephthalic acid, diethyl 2,5-dibromoterephthalate, 2,2'-diphenyldicarboxylic acid, 3,3'-diphenyldicarboxylic acid, 3,4'-diphenyldicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 3,4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl ether, 1,2-naphthalene Dicarboxylic acid, 1,2-naphthalenedicarboxylic acid dimethyl, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid dimethyl, 1,5-naphthalenedicarboxylic acid, 1,5-naphthalene Dimethyl dicarboxylate, 1,6-naphthalenedicarboxylic acid, dimethyl 1,6-naphthalenedicarboxylate, 1,6-naphthalenedicarboxylic acid diphenyl, 1,7-naphthalene Carboxylic acid, 1,7-naphthalenedicarboxylic acid dimethyl, 1,8-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid dimethyl, 1,8-naphthalenedicarboxylic acid diphenyl, 2,3-naphthalenedicarboxylic acid, 2,3- Dimethyl naphthalenedicarboxylate, 2,3-naphthalenedicarboxylic acid diphenyl, 2,6-naphthalenedicarboxylic acid, dimethyl 2,6-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid diphenyl, 2,7-naphthalenedicarboxylic acid, 2, Diphenyl 7-naphthalenedicarboxylate, 1,2- (9-oxofluorene) dicarboxylic acid, dimethyl 1,2- (9-oxofluorene) dicarboxylate, dimethyl 1,5- (9-oxofluorene) dicarboxylate, 1, 6- (9-oxofluorene) dicarboxylic acid, 1,6- (9-oxofluorene) dicarboxylic acid dimethyl, 1,7- (9-oxofluorene) dicarboxylic acid, 1,7- (9-oxofluorene) dicarboxylic acid Dimethyl rubonate, 2,3- (9-oxofluorene) dicarboxylic acid, dimethyl 2,3- (9-oxofluorene) dicarboxylate, 2,7- (9-oxofluorene) dicarboxylic acid, 2,7- (9 -Oxofluorene) dimethyl dicarboxylate, 1,4-anthracene dicarboxylic acid, 1,5-anthracene dicarboxylic acid, diethyl 1,5-anthracene dicarboxylate, 1,8-anthracene dicarboxylic acid, 1,9-anthracene dicarboxylic acid, 2 1,3-anthracene dicarboxylic acid, 9,10-anthracene dicarboxylic acid, dimethyl 9,10-anthracene dicarboxylate, 1,2-anthraquinone dicarboxylic acid, dimethyl 1,2-anthraquinone dicarboxylate, 1,3-1,2-anthraquinone Dicarboxylic acid, 1,4-anthraquinone dicarboxylic acid, 1,5-anthraquinone dicarboxylic acid, dimethyl 1,5-anthraquinone dicarboxylate, 1,5-anthraquinone dicarboxylate diphenyl, 1, 6-anthraquinone dicarboxylic acid, 1,7-anthraquinone dicarboxylic acid, 1,8-anthraquinone dicarboxylic acid, 2,3-anthraquinone dicarboxylic acid, 2,7-anthraquinone dicarboxylic acid, 2,3-biphenyl dicarboxylic acid, 2,3- Dimethyl biphenyl dicarboxylate, 2,5-biphenyl dicarboxylic acid, 2,6-biphenyl dicarboxylic acid, 3,4-biphenyl dicarboxylic acid, dimethyl 3,4-biphenyl dicarboxylate, 3,4-biphenyl dicarboxylic acid, 3,4- Dimethyl biphenyl dicarboxylate, 3,4-biphenyl dicarboxylic acid, 2,2'-biphenyl dicarboxylic acid, dimethyl 2,2'-biphenyl dicarboxylate, diphenyl 2,2'-biphenyl dicarboxylate, 2,4'-biphenyl dicarboxylic acid 2,4'-biphenyldicarboxylic acid dimethyl, 3,3'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid dimethyl, 3,4'-biphenyldicarboxylic acid Dimethyl 3,4′-biphenyldicarboxylate, 4,4′-biphenyldicarboxylic acid, dimethyl 4,4′-biphenyldicarboxylate, diphenyl 4,4′-biphenyldicarboxylate, 1,5-biphenylenedicarboxylic acid, 1, Dimethyl 5-biphenylene dicarboxylate, 1,8-biphenylene dicarboxylic acid, dimethyl 1,8-biphenylene dicarboxylate, 2,6-biphenylene dicarboxylic acid, dimethyl 2,6-biphenylene dicarboxylate, 2,7-biphenylene dicarboxylic acid, 2 Dimethyl 2,7'-biphenylenedicarboxylate, 2,2'-dimethyl-4,4'-biphenyldicarboxylic acid, diethyl 2,2'-dimethyl4,4'-biphenyldicarboxylate, 4,4 "-p-terphenyldicarboxylic acid Dimethyl 4,4 ′ ″-p-quaterphenyl dicarboxylate, 4,4 ′ ″-p-quaterphenyl dicarboxylic acid, 2,2′-methylene dibenzoic acid, 2,2′-methylene dibenzoic acid Dimethyl acid, 2,4'-me Len dibenzoic acid, dimethyl 2,4'-methylene dibenzoate, 3,3'-methylene dibenzoic acid, 4,4'-methylene dibenzoic acid, dimethyl 4,4'-methylene dibenzoate, 4,4 '-Isopropylidene dibenzoic acid, 2,2'-bibenzyldicarboxylic acid, dimethyl 2,2'-bibenzyldicarboxylate, dimethyl 3,3'-bibenzyldicarboxylate, 4,4'-bibenzyldicarboxylic acid, Dimethyl 4,4'-bibenzyldicarboxylate, 2,2'-trans-stilbene dicarboxylic acid, dimethyl 2,2'-trans-stilbene dicarboxylate, diphenyl 2,2'-trans-stilbene dicarboxylate, 2,4 ' -trans-stilbene dicarboxylic acid, 4,4'-trans-stilbene dicarboxylic acid, 4,4'-trans-stilbene dicarboxylic acid, 2,4'-trans-stilbene dicarboxylic acid, 4,4'-trans-stilbene dicarboxylic acid 4,4'-trans-dimethyl stilbene dicarboxylate, 2,2'-transicarboxylic acid, 2,2'-transicarbo Dimethyl acid, 2,4′-transicarboxylic acid, 4,4′-transicarboxylic acid, dimethyl 4,4′-transicarboxylate, pseudo-p-dicarboxy [2,2] paracyclophane, 4,4 '-Carbonyldibenzoic acid, 3,3'-oxydibenzoic acid, 4,4'-oxydibenzoic acid, dimethyl 4,4'-oxydibenzoate, diphenyl 4,4'-oxydibenzoate, 4 , 4'-thiodibenzoic acid, 4,4'-sulfonyldibenzoic acid, 4,4'-sulfonyldibenzoic acid dimethyl, 3,3'-dithiodibenzoic acid, 4,4'-dithiodibenzoic acid, Diethyl 4,4'-dithiodibenzoate, 2,2'-3,3'-dithiodibenzoic acid, 2,2'-azobenzenedicarboxylic acid, dimethyl 2,2'-azobenzenedicarboxylate, 3,3'- Azobenzene dicarboxylic acid, dimethyl 3,3'-azobenzenedicarboxylate, 4,4'-azobenzenedicarboxylic acid, dimethyl 4,4'-azobenzenedicarboxylate, homophthalic acid, homophthalate Dimethyl acid, homoisophthalic acid, dimethyl homoisophthalate, homoterephthalic acid, dimethyl homoterephthalate, o-phenylene diacetate, diethyl o-phenylene diacetate, m-phenylene diacetate, diethyl m-phenylene diacetate, p-phenylene Diacetic acid, diethyl p-phenylenediacetate, 3,3'-o-phenylenedipropionic acid, diethyl 3,3'-o-phenylenedipropionic acid, 3,3'-m-phenylenedipropionic acid, 3,3 '-M-Phenylenedipropionic acid diethyl, 3,3'-p-phenylenedipropionic acid, 3,3'-p-phenylenedipropionic acid diethyl, 2-carboxycinnamic acid, 3-carboxycinnamic acid, 4-carboxy Cinnamic acid, diethyl 4-carboxycinnamate, 3t, 3't-o-phenylene diacrylic acid, 3t, 3't-o-phenylene diacrylate, 3t, 3't-m-phenylene diacrylic acid, 3t, 3't-m-fe Dimethyl diacrylate, 3t, 3't-p-phenylene diacrylic acid, 3t, 3't-p-phenylene diacrylate, m-phenylene propiolic acid, dimethyl m-phenylene propiolate, 1,4 -Naphthalene diacetic acid, 1,5-naphthalene diacetic acid, 1,5-naphthalene diacetate dimethyl, 3,3 '-(1,4-naphthalene) dipropionic acid, 3,3'-(1,4-naphthalene) Diethyl dipropionate, 4,4'-biphenyldiacetic acid, diethyl 4,4'-biphenyldiacetate, 3,3 '-(4,4'-biphenyl) dipropionic acid, 3,3'-[4,4 '-(Methylenedi-p-phenylene)] dipropionic acid, 4,4'-bibenzyldibutyric acid, 3,3'-(4,4'-bibenzyl) dipropionic acid, 4,4 '-(oxydi-p- Phenylene) dibutyric acid, 3,3 '-"4,4'-(oxydi-p-phenylene)" dipropionic acid, 3,3 '-[4,4'-(oxydi-p-phenylene)] dibutyric acid, Diphenyls Hondicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2,3-furandicarboxylic acid, 2,3-furandicarboxylic acid dimethyl, 2,4-furandicarboxylic acid, 2,4-furandicarboxylic acid dimethyl, 2,5- Flange carboxylic acid, 2,5-furandicarboxylate dimethyl, 2,5-furandicarboxylate diphenyl, 3,4-furandicarboxylate, 3,4-furandicarboxylate dimethyl, 3,4-diphenyl-2,5-flange Carboxylic acid, 3,4-diphenyl-2,5-furandicarboxylic acid dimethyl, 3,3 '-(2,5-furan) dipropionic acid, 3,3'-(2,5-furan) dipropionic acid dimethyl 2,5-cis-tetrahydrofuran dicarboxylic acid, dimethyl 2,5-cis-tetrahydrofuran dicarboxylate, 3,3 '-(2,5-cis-tetrahydrofuran) dipropionic acid, 3,3'-(2,5- cis-tetrahydrofuran) diethyl dipropionate, 2,3- Offendicarboxylic acid, dimethyl 2,3-thiophene dicarboxylate, 2,4-thiophene dicarboxylic acid, dimethyl 2,4-thiophene dicarboxylate, 2,5-thiophene dicarboxylic acid, dimethyl 2,5-thiophene dicarboxylate, 2,5 Diphenyl thiophene dicarboxylate, 3,4-thiophene dicarboxylic acid, dimethyl 3,4-thiophene dicarboxylate, 3,4-diphenyl-2,5-thiophene dicarboxylic acid, 3,4-diphenyl-2,5-thiophene dicarboxylic acid Dimethyl, 2,5-thiophenediacetic acid, 3,3 '-(2,5-thiophene) dipropionic acid, diethyl 3,3'-(2,5-thiophene) dipropionate, 2,5-cis-tetrahydro Thiophene dicarboxylic acid, diethyl 2,5-cis-tetrahydrothiophene dicarboxylate, 3,4-cis-tetrahydrothiophene dicarboxylic acid, 3,4-cis-tetrahydrothiophene dicarboxylic acid Dimethyl acid, 1,1-dioxo-2,5-cis-tetrahydrothiophene dicarboxylic acid, diethyl 1,1-dioxo-2,5-cis-tetrahydrothiophene dicarboxylate, 2,6-4H-pyrandicarboxylic acid, 4-oxo -2,6-4H-pyrandicarboxylic acid, diethyl 4-oxo-2,6-4H-pyrandicarboxylate, 2,6-cis-tetrahydropyrandicarboxylic acid, dimethyl 2,6-cis-tetrahydropyrandicarboxylate, 2 , 6-cis-tetrahydrothiopyrandicarboxylic acid, dimethyl 2,6-cis-tetrahydrothiopyrandicarboxylate, 1,1-dioxo-2,6-cis-tetrahydrothiopyrandicarboxylic acid, 1,1-dioxo-2 Dimethyl 6-cis-tetrahydrothiopyrandicarboxylate, 2,8-dibenzofurandicarboxylic acid, dimethyl 2,8-dibenzofurandicarboxylate, 3,7-dibenzofurandicarboxylic acid, 3,7-diben Dimethyl zofurancarboxylate, 4,6-dibenzofurandicarboxylic acid, dimethyl 4,6-dibenzofurancarboxylate, 2,8-dibenzothiophene dicarboxylic acid, 5,5-dioxo-2,8-dibenzothiophene dicarboxylic acid, 9-oxo- 1,8-xanthene dicarboxylic acid, 9-oxo-2,7-xanthene dicarboxylic acid, dimethyl 9-oxo-2,7-xanthene dicarboxylate, 1,6-dibenzo [1,4] dioxin dicarboxylic acid, 1,6 -Dibenzo [1,4] dioxin dicarboxylate, 2,7-dibenzo [1,4] dioxin dicarboxylic acid, 2,7-dibenzo [1,4] dioxin dicarboxylate, 2,8-dibenzo [1,4 ] Dioxin dicarboxylic acid, 2,8-dibenzo [1,4] dioxin dicarboxylic acid dimethyl, 1,6-phenoxathiin dicarboxylic acid, 4,6-phenoxathiin dicarboxylic acid, dimethyl 4,6-phenoxathiin dicarboxylic acid 10,10-dioxo-1,6- Enoxydine dicarboxylic acid, dimethyl 10,10-dioxo-1,6-phenoxydine dicarboxylate, 10,10-dioxo-1,9-phenoxydine dicarboxylic acid, 10,10-dioxo-1,9-phenoxydine dicarboxylic acid Dimethyl acid, 10,10-dioxo-2,8-phenoxine dicarboxylic acid, Dimethyl 10,10-dioxo-2,8-phenoxine dicarboxylate, 10,10-dioxo-4,6-phenoxine dicarboxylic acid, 2 , 7-thianthenedicarboxylic acid, 2,7-thianthenedicarboxylic acid dimethyl, 10,10-dioxo-1,9-thianthenedicarboxylic acid, 5,5,10,10-tetraoxo-2,7-thiandylene dicarboxylic acid Acid, dimethyl 5,5,10,10-tetraoxo-2,7-thianthylene dicarboxylate, 10-oxo-10-phenyl-2,8-phenoxaphosphine dicarboxylic acid, 9-oxabicyclo [3.3.1] nonane Dimethyl-2,6-dicarboxylate, 9-oxabicyclo [3.3.1] nonane-2,6-dicarbo Diphenyl acid, 2,4,6,8-tetraoxaspiro [5.5] undecane-3,9-dicarboxylic acid, dimethyl 2,4,6,8-tetraoxaspiro [5.5] undecane-3,9-dicarboxylate, 2,4,6,8-tetraoxaspiro [5.5] undecane-3,9-diacetic acid, 2,4,6,8-tetraoxaspiro [5.5] undecane-3,9-diethyl acetate, 2,3 -Pyrrole dicarboxylic acid, dimethyl 2,3-pyrrole dicarboxylate, 2,4-pyrrole dicarboxylic acid, dimethyl 2,4-pyrrole dicarboxylate, 2,5-pyrrole dicarboxylic acid, 2 Dimethyl 1,5-pyrrole dicarboxylate, 1-methyl-2,5-pyrrole dicarboxylic acid, dimethyl 1-methyl-2,5-pyrrole dicarboxylate, 1-phenyl-2,5-pyrrole Dicarboxylic acid, dimethyl 1-phenyl-2,5-pyrrole dicarboxylate, 3,4-pyrrole dicarboxylic acid, dimethyl 3,4-pyrrole dicarboxylate, 1-methyl-3,4-pyrrole Dicarboxylic acid, 1-methyl-3,4-pyrrole Diethyl dicarboxylate, 1-phenyl-3,4-pyrrole dicarboxylic acid, diethyl 1-phenyl-3,4-pyrrole dicarboxylate, diethyl 3,5-dimethyl-2,4-pyrrole dicarboxylate, 2,5-dimethyl-3,4-pyrrole dicarboxylic acid, diethyl 2,5-dimethyl-3,4-pyrrole dicarboxylate, 1,2,5-trimethyl-3,4-pyrrole dicarboxylic acid 1,2,5-trimethyl-3,4-pyrrole dicarboxylate, 1-methyl-2,5-pyrrolediacetic acid, 1-methyl-2,5-pyrrolediacetate, 3,3'- Dimethyl (2,5-pyrrole) dipropionate, 3,3 '-(1-methyl-2,5-pyrrole) dipropionic acid, 3,3'-(1-methyl-2,5-pyrrole) dipropion Dimethyl acid, diethyl 3,3 '-(1-phenyl-2,5-pyrrole) dipropionate, diethyl 1-methyl-2,5-cis-pyrrolidinedicarboxylate, 1-phenyl-2,5-cis-pyrrolidine Diethyl dicarboxylate 1-methyl-2,5-pyrrolidine diacetate, 3,3 '-(1-methyl-2,5-pyrrolidine) dipropionic acid, 3,3'-(1-methyl-2,5-pyrrolidine) di Diethyl propionate, diethyl 2,5-indole dicarboxylate, 2,6-indole dicarboxylic acid, diethyl 2,6-indole dicarboxylate, 9-methyl-1,8-carbazole dicarboxylic acid, 2,6-carbazole dicarboxylic acid, Diethyl 2,6-carbazoledicarboxylate, 3,6-carbazoledicarboxylic acid, diethyl 3,6-carbazoledicarboxylate, 9-methyl-3,6-carbazoledicarboxylic acid, diethyl 9-methyl-3,6-carbazoledicarboxylate 3,4-pyrazole dicarboxylic acid, dimethyl 3,4-pyrazole dicarboxylate, 2-methyl-3,4-pyrazole dicarboxylic acid, 1-phenyl-3,4-pyrazole dicarboxylic acid, 1-phenyl-3,4 -Dimethyl pyrazole dicarboxylate, 2-phenyl-3,4-pyrazole dicarboxylic acid, dimethyl 2-phenyl-3,4-pyrazole dicarboxylate, 3,5-pyrazole dicarboxylic acid, dimethyl 3,5-pyrazole dicarboxylate, 1- Methyl-3,5-pyrazoledicarboxylic acid, dimethyl 1-methyl-3,5-pyrazoledicarboxylate, 1-phenyl-3,5-pyrazoledicarboxylic acid, dimethyl 1-phenyl-3,5-pyrazoledicarboxylate, 4, 5-imidazole dicarboxylic acid, 4,5-imidazole dicarboxylic acid diphenyl, 1-methyl-4,5-imidazole dicarboxylic acid, dimethyl 1-methyl-4,5-imidazole dicarboxylate, 1-phenyl-4,5-imidazole dicarboxylic acid Acid, diethyl 1-phenyl-4,5-imidazole dicarboxylate, 2,3-pyridinedicarboxylic acid, 2,3-pyridinedicarboxylic acid di Methyl, 2,3-pyridinedicarboxylic acid diphenyl, 2,4-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid dimethyl, 2,4-pyridinedicarboxylic acid diphenyl, 2,5-pyridinedicarboxylic acid, 2,5-pyridine Dimethyl dicarboxylate, 2,5-pyridinedicarboxylic acid diphenyl, 2,6-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid dimethyl, 2,6-pyridinedicarboxylic acid diphenyl, 3,4-pyridinedicarboxylic acid, 3,4 Dimethyl pyridine dicarboxylate, 3,5-pyridinedicarboxylic acid, diphenyl 3,5-pyridinedicarboxylate, 2,6-dimethyl-3,5-pyridinedicarboxylic acid, 2,4,6-trimethyl-3,5-pyridine Dicarboxylic acid, dimethyl 2,5-piperidinedicarboxylate, diethyl 2,3-piperidinedicarboxylate, 2,6-cis-piperidinedicarboxylic acid, 2,6-cis-piperidinedicar Dimethyl acid, 1-methyl-2,6-cis-piperidinedicarboxylic acid, 1-methyl-2,6-cis-piperidinedicarboxylate, diethyl 3,5-piperidinedicarboxylate, 2,6-cis-piperidine Acetic acid, 1-methyl-2,6-cis-piperidinediacetic acid, 1-methyl-2,6-cis-piperidinediacetic acid diethyl ester, 2,3-quinolinedicarboxylic acid, dimethyl 2,3-quinolinedicarboxylate, 2, 4-quinoline dicarboxylic acid, dimethyl 2,4-quinoline dicarboxylate, 2,6-quinoline dicarboxylic acid, 3,7-quinoline dicarboxylic acid, 4,8-quinoline dicarboxylic acid, dimethyl 4,8-quinoline dicarboxylate, 5, 6-quinoline dicarboxylic acid, dimethyl 5,6-quinoline dicarboxylate, 5,8-quinoline dicarboxylic acid, 6,7-quinoline dicarboxylic acid, dimethyl 6,7-quinoline dicarboxylate, 6,8-quinoline dicarboxylic acid, 7, 8-kinori Dicarboxylic acid, 2,2'-bipyridine-4,4'-dicarboxylic acid, 2,2'-bipyridine-4,4'-dicarboxylic acid dimethyl, 2,2'-bipyridine-5,5'-dicarboxylic acid, 2 Dimethyl 2,2'-bipyridine-5,5'-dicarboxylate, 2,2'-bipyridine-6,6'-dicarboxylic acid, dimethyl 3,3'-bipyridine-2,2'-dicarboxylate, 4,5- Pyridazine dicarboxylic acid, 4,5-pyrimidine dicarboxylic acid, 4,6-pyrimidine dicarboxylic acid, 2,3-pyrazine dicarboxylic acid, 2,3-pyrazine dicarboxylic acid dimethyl, 2,5-pyrazine dicarboxylic acid, 2,5-pyrazine Dimethyl dicarboxylate, diphenyl 2,5-pyrazine dicarboxylate, 2,6-pyrazine dicarboxylic acid, dimethyl 2,6-pyrazine dicarboxylate, dimethyl 1,4-piperazine diacetate, 3,3 '-(1,4-piperazine ) Dimethyl dipropionate, 1,6-phenazine dicarboxylic acid, 1,6-phenazine And dimethyl dicarboxylate. Among them, wholly aromatic polycarboxylic acids having a rigid molecular structure not containing an alkylene chain in the main chain, for example, phthalic acids, terephthalic acids, isophthalic acids, biphenyldicarboxylic acids, naphthalenedicarboxylic acids, oxofluorenedicarboxylic acids, anthracene Dicarboxylic acids, anthraquinone dicarboxylic acids, biphenylene dicarboxylic acids, terphenyl dicarboxylic acids, quaterphenyl dicarboxylic acids, azobenzene dicarboxylic acids, furandicarboxylic acids, thiophene dicarboxylic acids, pyran dicarboxylic acids, dibenzofurandicarboxylic acids, dibenzothiophene dicarboxylic acids, xanthene dicarboxylic acids , Dibenzo [1,4] dioxin dicarboxylic acids, phenoxathiin dicarboxylic acids, thianthylene dicarboxylic acids, phenoxafo Findicarboxylic acids, pyrrole dicarboxylic acids, indole dicarboxylic acids, carbazole dicarboxylic acids, pyrazole dicarboxylic acids, imidazole dicarboxylic acids, pyridine dicarboxylic acids, quinoline dicarboxylic acids, bipyridine dicarboxylic acids, pyrimidine dicarboxylic acids, pyrazine dicarboxylic acids, phenazine dicarboxylic acids, etc. are preferred . Moreover, the acid halide or acid anhydride of said aromatic polycarboxylic acid can also be used. Examples of the acid halide of the aromatic polycarboxylic acid include phthaloyl dichloride and naphthoyl dichloride. Of these, preferably phthaloyl dichloride, such as isophthaloyl dichloride or terephthaloyl dichloride, is used.

(Example)
In the following examples, the present invention will be described in more detail, but the present invention is not limited to these examples.

The weight average molecular weight of the aromatic polyester powder and the average particle diameter, bulk density and absorbance (coloring degree) of the aromatic polyester pellets were measured as follows.

Weight average molecular weight: Measured using a GPC LC20AT model manufactured by Shimadzu Corporation. A column in which a total of three columns, Shodex KF-802, KF804, and KF806, were connected in series. Chloroform for liquid chromatography was used as an elution solvent. A commercially available polystyrene having a known molecular weight was used as a standard substance.

Average particle diameter: Using a stereomicroscope (SZXILLB2-100 manufactured by OLYNPUS) with a magnification of 16 times, the long diameter of 100 arbitrarily selected pellets was measured, and the average value was taken as the average particle diameter.

Bulk density: measured in accordance with JIS K6911.

Absorbance (ΔI): The obtained pellet was dissolved in chloroform so as to have a concentration of 0.2 g / milliliter, and the absorbance was measured with a UV spectrum of 400 nm using a cell having an optical path length of 20 mm.

(Synthesis Example 1)
Production of aromatic polyester A reactor equipped with a stirrer was charged with 1,100 parts by weight of water, then 38 parts by weight of 2,2-bis (4-hydroxyphenyl) propane, and 0.6 parts by weight of p-tert-butylphenol. Part and 14 parts by weight of sodium hydroxide were dissolved (aqueous phase). Separately, 1,300 parts by mass of dichloromethane was charged into another container, and then 31 parts by mass of an equimolar mixture of terephthalic acid chloride and isophthalic acid chloride and 2.1 parts by mass of benzoyl chloride were dissolved (organic phase). The organic phase was added to the aqueous phase in the reactor with stirring, and then a polycondensation reaction was carried out at room temperature for 1 hour. After the reaction, the aqueous phase and the organic phase were separated, and washing with water was repeated until the organic phase became neutral. The obtained dichloromethane solution of the aromatic polyester is supplied to 4,000 parts by mass of a 9/1 mixture (volume ratio) of methanol and pure water at a rate of 1.3 kg / hour with stirring to precipitate the aromatic polyester powder. I let you. Subsequently, it filtered and 55 mass parts of aromatic polyester powder was obtained. The aromatic polyester powder had a weight average molecular weight of 35,000.

(Synthesis Example 2)
Production of aromatic polyester The same procedure as in Synthesis Example 1 was performed except that 1.05 parts by mass of benzoyl chloride was used instead of 2.1 parts by mass. The weight average molecular weight of the obtained aromatic polyester powder was 55,000.

(Synthesis Example 3)
Production of aromatic polyester The same procedure as in Synthesis Example 1 was performed except that 4.2 parts by mass of benzoyl chloride was used instead of 2.1 parts by mass. The resulting aromatic polyester powder had a weight average molecular weight of 12,000.

(Synthesis Example 4)
Production of aromatic polyester The same procedure as in Synthesis Example 1 was performed except that 1.2 parts by mass of benzoyl chloride was used instead of 2.1 parts by mass. The weight average molecular weight of the obtained aromatic polyester powder was 48,000.

(Synthesis Example 5)
Production of aromatic polyester The same procedure as in Synthesis Example 1 was performed except that 5.0 parts by mass of benzoyl chloride was used instead of 2.1 parts by mass. The weight average molecular weight of the obtained aromatic polyester powder was 8,500.

(Example 1)
The aromatic polyester powder having a weight average molecular weight of 35,000 produced in Synthesis Example 1 was dissolved in dichloromethane (methylene chloride) to prepare a solution having a concentration of 0.4 g / ml. Next, an equal amount of tetrahydrofuran was added in a volume ratio with respect to dichloromethane and stirred to uniformly dissolve the tetrahydrofuran. The obtained solution was poured into a round glass petri dish having a diameter of about 15 cm to a depth of about 1 cm. After allowing the dichloromethane and tetrahydrofuran to evaporate for about 48 hours under environmental conditions, an aromatic polyester lump solidified into 0.5 to 1.5 cm pieces was taken out from the petri dish. The aromatic polyester mass was crushed with a hammer, and then passed through a sieve having a mesh size of 2.8 mm square and 4.0 mm square to remove particles of 2.8 mm under and 4.0 mm over. The obtained aromatic polyester particles were dried under reduced pressure at 60 ° C. for about 80 hours to obtain a product. The product had an average particle size of 3.9 mm and a bulk density of 0.54 grams / cc. The absorbance (ΔI) of the pellet was 0.02, and no discoloration was observed.

(Example 2)
The same operation as in Example 1 was conducted, except that the aromatic polyester powder was dissolved in dichloromethane to prepare a solution having a concentration of 0.2 g / ml. The average particle size of the obtained product was 3.5 mm, and the bulk density was 0.52 g / cc. The absorbance (ΔI) of the pellet was 0.02, and no discoloration was observed.

(Example 3)
The same procedure as in Example 1 was performed except that a metal bat having a length of 40 cm and a width of 60 cm was used instead of the round glass petri dish. The average particle size of the obtained product was 3.8 mm, and the bulk density was 0.54 g / cc. The absorbance (ΔI) of the pellet was 0.02, and no discoloration was observed.

(Example 4)
The same procedure as in Example 1 was performed except that trichloromethane (chloroform) was used instead of dichloromethane. The average particle size of the obtained product was 3.7 mm, and the bulk density was 0.53 g / cc. The absorbance (ΔI) of the pellet was 0.02, and no discoloration was observed.

(Example 5)
The same operation as in Example 1 was carried out except that an aromatic polyester powder having a weight average molecular weight of 12,000 was used. The average particle size of the obtained product was 3.3 mm, and the bulk density was 0.54 g / cc. The absorbance (ΔI) of the pellet was 0.02, and no discoloration was observed.

(Example 6)
The same operation as in Example 1 was carried out except that an aromatic polyester powder having a weight average molecular weight of 48,000 was used. The average particle size of the obtained product was 3.8 mm, and the bulk density was 0.51 gram / cc. The absorbance (ΔI) of the pellet was 0.02, and no discoloration was observed.

(Example 7)
The same procedure as in Example 1 was performed, except that the amount of tetrahydrofuran added was 0.3 times the volume ratio to dichloromethane. The obtained product had an average particle size of 3.8 mm and a bulk density of 0.55 g / cc. The absorbance (ΔI) of the pellet was 0.02, and no discoloration was observed.

(Example 8)
The same procedure as in Example 1 was conducted, except that the amount of tetrahydrofuran added was 2.0 times the volume ratio to dichloromethane. The obtained product had an average particle size of 3.2 mm and a bulk density of 0.53 g / cc. The absorbance (ΔI) of the pellet was 0.02, and no discoloration was observed.

(Comparative Example 1)
The same operation as in Example 1 was carried out except that the aromatic polyester powder having a weight average molecular weight of 55,000 produced in Synthesis Example 2 was used. The aromatic polyester solidified in the petri dish was film-like, excellent in elasticity, and could not be easily crushed.

(Comparative Example 2)
The same operation as in Example 1 was performed except that an aromatic polyester powder having a weight average molecular weight of 8,500 was used. The aromatic polyester solidified in the petri dish became sandy with an average particle size of 0.8 mm, and pellets could not be obtained.

(Comparative Example 3)
The same procedure as in Example 1 was conducted except that the amount of tetrahydrofuran added was 0.2 times the volume ratio to dichloromethane. The aromatic polyester solidified in the petri dish was film-like, excellent in elasticity, and could not be easily crushed.

(Comparative Example 4)
The same procedure as in Example 1 was performed except that the amount of tetrahydrofuran added was 2.5 times the volume ratio to dichloromethane. The aromatic polyester solidified in the petri dish was in a powder form, and pellets could not be obtained.

(Comparative Example 5)
The same procedure as in Example 1 was performed except that the solvent was evaporated at 45 ° C. The aromatic polyester solidified in the petri dish was in a powder form, and pellets could not be obtained.

Since the aromatic polyester pellets produced by the method of the present invention are not colored and are transparent, they are useful in electrical / electronic materials and optical materials such as optical fibers, spectacle lenses, imaging lenses and coatings.

FIG. 1 is a diagram showing an embodiment of the present invention.

Explanation of symbols

1． Aromatic polyester powder
2． One or more solvents selected from the group consisting of dichloromethane, trichloromethane, 1,2-dichloroethane and chlorobenzene (a)
3． solution
Four. One or more solvents (b) selected from the group consisting of tetrahydrofuran, methyltetrahydrofuran, methylhydrofuran and diethyl ether
Five. blend
6． container
7． Aromatic polyester mass
8． Crushing machine
9． pellet
Ten. Sieve

Claims (5)

An aromatic polyester having a weight average molecular weight of 10,000 to 50,000, one or more solvents (a) selected from the group consisting of dichloromethane, trichloromethane, 1,2-dichloroethane and chlorobenzene, and a volume ratio to the solvent (a); Mixed with at least one solvent (b) selected from the group consisting of 0.3 to 2.0 times tetrahydrofuran, methyltetrahydrofuran, methylhydrofuran and diethyl ether at a temperature of 5 to 40 ° C. A process for producing aromatic polyester pellets by evaporating and crushing and / or cutting the resulting aromatic polyester mass. 2. The method according to claim 1, wherein the aromatic polyester is mixed with the solvent (a), and the solvent (b) is mixed with the obtained solution. The process according to claim 1 or 2, wherein the solvent is evaporated under environmental conditions. The method according to claim 2 or 3, wherein the concentration of the solution is 0.2 to 1.0 gram / milliliter. The process according to any one of claims 1 to 4, wherein the solvent (a) is dichloromethane and the solvent (b) is tetrahydrofuran.

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