WO2012017540A1 - Aromatic polyester and method for producing same - Google Patents

Abstract

Provided is a novel aromatic polyester which has low melt viscosity and good fluidity even if the molecular weight thereof is high. Specifically provided is an aromatic polyester containing a polyvalent phenolic residue and a residue of an aromatic polyvalent carboxylic acid, acid halide thereof or acid anhydride thereof, which is characterized in that the residue of an aromatic polyvalent carboxylic acid, acid halide thereof or acid anhydride thereof is composed of a residue of an aromatic dicarboxylic acid, acid halide thereof or acid anhydride thereof and a residue of an aromatic tricarboxylic acid, acid halide thereof or acid anhydride thereof and that (the mole number of the residue of an aromatic tricarboxylic acid, acid halide thereof or acid anhydride thereof)/[(the mole number of the residue of an aromatic dicarboxylic acid, acid halide thereof or acid anhydride thereof) + (the mole number of the residue of an aromatic tricarboxylic acid, acid halide thereof or acid anhydride thereof)] = 0.001-0.090.

Description

Aromatic polyester and method for producing the same

The present invention relates to an aromatic polyester and a method for producing the same, and more particularly to an aromatic polyester having improved flowability at high temperatures and a method for producing the same.

Conventionally, for example, as disclosed in Patent Document 1, an aromatic polyester has a methylene chloride solution of a mixture of terephthalic acid dichloride and isophthalic acid dichloride in a predetermined molar ratio, and 2,2-di- (4-hydroxyphenyl). ) -Propane [bisphenol A] mixed with an alkaline aqueous solution, and manufactured using, for example, monohydric phenols such as o-phenylphenol and pt-butylphenol as terminal blockers or molecular weight regulators It had been. However, the aromatic polyester produced in this way has low fluidity. Therefore, when processing such as injection molding, it is necessary to heat to 300 ° C. or higher in order to improve fluidity during molding, and as a result, there is a problem that the resin is colored. Fluidity can be improved by mixing heterogeneous components such as olefin copolymers with amorphous aromatic polyester, which is generally known as a means to improve fluidity, but heat resistance during molding There was a problem that decreased. Further, as disclosed in Patent Document 2, a method of adding a melt viscosity reducing agent is also known, but the transparency of the polyester resin is lost due to the mixing of foreign substances, and it is not suitable for optical use.

On the other hand, a method of crosslinking a linear polymer is generally known in order to increase the strength and heat resistance of the resin. For example, Non-Patent Document 1 discloses a method for forming a polymer having a three-dimensional network structure that is insoluble and infusible by eliminating the thermoplasticity of the resin. However, there is no concept of improving liquidity.

Japanese Patent Publication No.55-4771 Japanese Patent Laid-Open No. 5-262966

The present invention provides a novel aromatic polyester having a low melt viscosity even with a high molecular weight and good fluidity.

Conventionally, when the weight average molecular weight (Mw) of the aromatic polyester exceeds 25,000 to 30,000, the melt viscosity is rapidly increased and the fluidity is lowered. . As a result, the polyester was colored and could not be used for optical applications. Therefore, the present inventors tried various studies to solve the problem. As a result, attention was paid to the fact that a rigid skeleton in which aromatic rings such as a benzene ring and an imide ring are linearly connected is generally responsible for increasing the glass transition temperature (Tg) of the polymer. The glass transition temperature is the temperature at which the segmental motion at which several of the basic units of the polymer move starts. Therefore, in order to lower the glass transition temperature, it is necessary to provide a structure that can move easily in a rigid polymer chain to weaken the intermolecular interaction and facilitate the rotational movement of the molecular unit. I thought. Based on this technical idea, in order to suppress the intermolecular interaction, especially the overlap (stacking) caused by the affinity of the aromatic rings, it is effective to give the polymer chain a spherical or nearly spherical structure. As a result, the structure branched in the aromatic polyester molecule was given in a predetermined amount. As a result, even when the weight average molecular weight (Mw) exceeds 25,000 to 30,000, the melt viscosity is relatively low and the fluidity is good, so that molding is possible even at temperatures around 250 to 280 ° C. where coloring does not occur easily. A novel aromatic polyester could be obtained. On the other hand, there is a limit to the amount of branched structure that can be imparted in the aromatic polyester molecule. If the branched structure is increased too much, cross-linking occurs in the molecule during production, and the glass transition temperature is increased. Has been found to be significantly higher and, on the other hand, lower the fluidity. FIG. 1 shows a conventional aromatic polyester composed only of a unit consisting of a dihydric phenol residue and an aromatic dicarboxylic acid residue (BU unit), in addition to these, an aromatic tricarboxylic acid residue ( It is explanatory drawing which represented roughly the difference in frame structure with the aromatic polyester of this invention which has TMTC). As shown in FIG. 1, the aromatic polyester of the present invention has a spherical or nearly spherical structure in the polymer chain as compared with the conventional aromatic polyester.

That is, the present invention
(1) In an aromatic polyester containing a polyhydric phenol residue and an aromatic polyvalent carboxylic acid, its acid halide or acid anhydride residue, an aromatic polyvalent carboxylic acid, its acid halide or acid anhydride A residue of an aromatic dicarboxylic acid, its acid halide or anhydride, and an aromatic tricarboxylic acid, its acid halide or anhydride residue, and (aromatic tricarboxylic acid , Number of moles of acid halide or acid anhydride residue) / [(number of moles of residue of aromatic dicarboxylic acid, acid halide or acid anhydride) + (aromatic tricarboxylic acid, acid halide thereof) Or the number of moles of acid anhydride residues)] = 0.001 to 0.090.

As a preferred embodiment,
(2) (number of moles of residue of aromatic tricarboxylic acid, acid halide or acid anhydride) / [(number of moles of residue of aromatic dicarboxylic acid, acid halide or acid anhydride) + (aromatic Aromatic tricarboxylic acid, the number of moles of acid halide or anhydride thereof)] = 0.001 to 0.070, the aromatic polyester according to (1) above,
(3) (number of moles of residue of aromatic tricarboxylic acid, acid halide or acid anhydride) / [(number of moles of residue of aromatic dicarboxylic acid, acid halide or acid anhydride) + (aromatic Aromatic tricarboxylic acid, the number of moles of acid halide or anhydride thereof)] = 0.001 to 0.050, the aromatic polyester according to (1) above,
(4) (number of moles of residue of aromatic tricarboxylic acid, acid halide or acid anhydride) / [(number of moles of residue of aromatic dicarboxylic acid, acid halide or acid anhydride) + (aromatic Aromatic tricarboxylic acid, the number of moles of acid halide or anhydride thereof)] = 0.001 to 0.030, the aromatic polyester according to (1) above,
(5) The aromatic polyester according to any one of (1) to (4), wherein the weight average molecular weight (Mw) is 2,000 to 200,000,
(6) The aromatic polyester according to any one of (1) to (4) above, wherein the weight average molecular weight (Mw) is 10,000 to 100,000.
(7) The aromatic polyester according to any one of (1) to (4), wherein the weight average molecular weight (Mw) is 15,000 to 60,000,
(8) The fragrance according to any one of (1) to (7) above, wherein the melt flow rate (MFR, unit: g / 10 min, measurement conditions: 280 ° C., 10.0 kg load) is 2 to 60 Tribe polyester,
(9) The melt flow rate (MFR, unit: g / 10 min, measurement conditions: 280 ° C., 10.0 kg load) is 5.0 or more, according to any one of the above (1) to (7) Aromatic polyester,
(10) The fragrance according to any one of (1) to (7) above, wherein the melt flow rate (MFR, unit: g / 10 min, measurement conditions: 280 ° C., 10.0 kg load) is 5 to 40 Tribe polyester,
(11) The fragrance according to any one of (1) to (7) above, wherein the melt flow rate (MFR, unit: g / 10 min, measurement conditions: 280 ° C., 10.0 kg load) is 10 to 30 Tribe polyester,
(12) The aromatic polyester according to any one of (1) to (11) above, wherein the polyhydric phenol residue is a dihydric phenol residue,
(13) The polyhydric phenol residue is represented by the following formula (I)

(In the formula (I), R ¹ to R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an allyl group or a halogen atom, x is 0 or 1, and x is 1; Is substituted by an alkylene group having 1 to 30 carbon atoms, an alkylidene group having 2 to 30 carbon atoms, a cycloalkylene group having 3 to 30 carbon atoms, a cycloalkylidene group having 3 to 30 carbon atoms, or a phenyl group. An alkylene group having 1 to 30 carbon atoms, an alkylidene group having 2 to 30 carbon atoms substituted by a phenyl group, an oxygen atom, a sulfur atom, a sulfoxide group or a sulfone group, and when x is 0, R ¹ and R ^The benzene ring having ³ and the benzene ring having R ² and R ⁴ are covalently bonded)
The aromatic polyester according to any one of (1) to (11) above,
(14) The aromatic polyester according to the above (13), wherein in formula (I), R ¹ to R ⁴ are all hydrogen atoms,
(15) The aromatic polyester according to the above (13) or (14), wherein W is an isopropylidene group [C (CH ₃ ) ₂ ] and x is 1.
(16) The aromatic polyester as described in any one of the above (1) to (15) for optical materials can be mentioned.

The present invention also provides
(17) In a method for producing an aromatic polyester by reacting a polyhydric phenol with an aromatic polycarboxylic acid, an acid halide or an acid anhydride thereof, an aromatic polycarboxylic acid, an acid halide or an acid thereof The anhydride consists of an aromatic dicarboxylic acid, its acid halide or acid anhydride and an aromatic tricarboxylic acid, its acid halide or acid anhydride, and (an aromatic tricarboxylic acid, its acid halide or acid anhydride Number of moles of product) / [(number of moles of aromatic dicarboxylic acid, acid halide or acid anhydride) + (number of moles of aromatic tricarboxylic acid, acid halide or acid anhydride)] = 0.001 The method is characterized by 0.090.

As a preferred embodiment,
(18) (number of moles of aromatic tricarboxylic acid, acid halide or acid anhydride thereof) / [(number of moles of aromatic dicarboxylic acid, acid halide or acid anhydride) + (aromatic tricarboxylic acid, acid thereof The number of moles of halide or acid anhydride)] = 0.001 to 0.070,
(19) (number of moles of aromatic tricarboxylic acid, acid halide or acid anhydride thereof) / [(number of moles of aromatic dicarboxylic acid, acid halide or acid anhydride) + (aromatic tricarboxylic acid, acid thereof The number of moles of halide or acid anhydride)] = 0.001 to 0.050,
(20) (mol number of aromatic tricarboxylic acid, acid halide or acid anhydride thereof) / [(mol number of aromatic dicarboxylic acid, acid halide or acid anhydride) + (aromatic tricarboxylic acid, acid thereof The number of moles of halide or acid anhydride)] = 0.001 to 0.030,
(21) The method according to any one of (17) to (20) above, wherein the aromatic tricarboxylic acid, its acid halide or acid anhydride is trimesoyl trichloride.
(22) The method according to any one of the above (17) to (21), wherein the aromatic dicarboxylic acid, its acid halide or acid anhydride is isophthaloyl dichloride and / or terephthaloyl dichloride,
(23) The method according to any one of (17) to (22) above, wherein the polyphenol is a dihydric phenol,
(24) The method according to any one of (17) to (22) above, wherein the polyphenol is bisphenol A.

Since the aromatic polyester of the present invention has a branched structure in the polymer chain, it is more amorphous, has a low melt viscosity even at a high molecular weight, and has good fluidity, so it can be molded at a relatively low temperature. is there. Therefore, it is possible to provide a polyester material that is hardly colored at the time of molding and remarkably excellent in optical properties.

FIG. 1 is an explanatory view schematically showing the difference in the skeleton structure between a conventional aromatic polyester and the aromatic polyester of the present invention. FIG. 2 is an X-ray diffraction chart of the aromatic polyester of the present invention (Examples 2 and 3) and a conventional aromatic polyester (Comparative Example 1).

The aromatic polyester of the present invention contains a polyhydric phenol residue and a residue of an aromatic polyvalent carboxylic acid, an acid halide or an acid anhydride thereof. In the present invention, an aromatic polycarboxylic acid, its acid halide or acid anhydride residue includes an aromatic dicarboxylic acid, its acid halide or acid anhydride residue, and an aromatic tricarboxylic acid, its acid halogen. Or an acid anhydride residue. Here, (number of moles of residue of aromatic tricarboxylic acid, acid halide or acid anhydride) / [(number of moles of residue of aromatic dicarboxylic acid, acid halide or acid anhydride) + (aromatic Group tricarboxylic acid, the number of moles of acid halide or anhydride thereof)] is 0.090, preferably 0.070, more preferably 0.050, still more preferably 0.040, even more. Preferably it is 0.030, and a minimum is 0.001, Preferably it is 0.005, More preferably, it is 0.010. If the above upper limit is exceeded, cross-linking occurs in the polymer molecules during the production of the polymer, and the glass transition temperature becomes remarkably high. On the contrary, the fluidity is lowered. On the other hand, if it is less than the above lower limit, it becomes a rigid polymer chain, and the glass transition temperature becomes high and the fluidity is lowered.

The lower limit of the weight average molecular weight (Mw) of the aromatic polyester of the present invention is preferably 2,000, more preferably 10,000, still more preferably 15,000, still more preferably 20,000, particularly preferably 25,000. 000. The upper limit is not particularly limited as long as it can be produced, but is preferably 200,000, more preferably 100,000, and still more preferably 60,000. If it is less than the said minimum, it is not suitable for the use as an optical material.

The lower limit of the melt flow rate (MFR, unit: g / 10 min, measurement conditions: 280 ° C., 10.0 kg load) of the aromatic polyester of the present invention is preferably 2, more preferably 5, and still more preferably 10. If the amount is less than the above lower limit, the aromatic polyester cannot be colored at a low temperature, and it must be molded at a high temperature, and the aromatic polyester is colored. Although there is no restriction | limiting in particular in the upper limit of a melt flow rate, Preferably it is 60, More preferably, it is 40, More preferably, it is 30. When the melt flow rate is too high, the molding temperature can be lowered, so that coloring can be further suppressed, which is preferable.

The polyhydric phenol residue contained in the aromatic polyester of the present invention, as well as the residue of an aromatic polyvalent carboxylic acid, its acid halide or acid anhydride, preferably an aromatic dicarboxylic acid, its acid halide or acid Residues of anhydrides and residues of aromatic tricarboxylic acids, acid halides or acid anhydrides thereof, when producing aromatic polyesters, polyhydric phenols and aromatic dicarboxylic acids, acid halides or acid anhydrides thereof And an aromatic tricarboxylic acid, an acid halide or an acid anhydride thereof. Polyhydric phenols, aromatic dicarboxylic acids, acid halides or acid anhydrides thereof, and aromatic tricarboxylic acids, acid halides or acid anhydrides thereof are all known.

Examples of the aromatic tricarboxylic acid include hemimellitic acid, trimellitic acid, trimesic acid, 1,2,4-naphthalene tricarboxylic acid, 2,5,7-naphthalene tricarboxylic acid, and the like. Moreover, the acid halide or acid anhydride of said aromatic tricarboxylic acid can also be used. Examples of the acid halide of aromatic tricarboxylic acid include trimesic acid chloride (trimesoyl trichloride), 1,2,3-benzenetricarboxylic acid chloride, 1,2,4-benzenetricarboxylic acid chloride, and the like. Of these, trimesic acid chloride is preferably used.

Examples of the aromatic dicarboxylic acid include phthalic acid, dimethyl phthalate, diphenyl phthalate, isophthalic acid, dimethyl isophthalate, di (cyanomethyl) isophthalate, diphenyl isophthalate, di (2,4-dinitrophenyl) isophthalate, 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-methyli Sophthalic acid, dimethyl 5-methylisophthalate, 4,5-dimethylisophthalic acid, 4,6-dimethylisophthalic acid, 4-chloroisophthalic acid, dimethyl 4-chloroisophthalate, 5-chloroisophthalic acid, 5-chloroisophthalic acid Dimethyl, 4,6-dichloroisophthalic acid, dimethyl 4,6-dichloroisophthalate, 4-bromoisophthalic acid, 4,6-dibromoisophthalic acid, dimethyl 4,6-dibromoisophthalate, terephthalic acid, dimethyl terephthalate, terephthalate Di (cyanomethyl) acid, diphenyl terephthalate, di (3-benzoisoxazolyl) terephthalate, di (2-benzothiazolyl) terephthalate, 2-methylterephthalic acid, dimethyl 2-methylterephthalate, 2,5-dimethyl Terephthalic acid, 2,6-dimethylterephthalate Dimethyl 2,6-dimethylterephthalate, 2-chloroterephthalic acid, dimethyl 2-chloroterephthalate, 2,5-dichloroterephthalic acid, dimethyl 2,5-dichloroterephthalate, tetrachloroterephthalic 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-naphthalenedicarboxylic acid, 1,2-naphthalenedicarboxylic acid Dimethyl, 1,3-naphthalenedicarboxylic acid, , 4-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid dimethyl, 1,5-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid dimethyl, 1,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid dimethyl, 1,6-Naphthalenedicarboxylic acid diphenyl, 1,7-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid dimethyl, 1,8-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid dimethyl, 1,8-naphthalenedicarboxylic acid Diphenyl, 2,3-naphthalenedicarboxylic acid, dimethyl 2,3-naphthalenedicarboxylic acid, diphenyl 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, dimethyl 2,6-naphthalenedicarboxylic acid, 2,6-naphthalene Dicarboxylic acid dipheny 2,7-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid diphenyl, 1,2- (9-oxofluorene) dicarboxylic acid, 1,2- (9-oxofluorene) dicarboxylic acid dimethyl, 1,5- (9-oxofluorene) dicarboxylic acid dimethyl, 1,6- (9-oxofluorene) dicarboxylic acid, 1,6- (9-oxofluorene) dicarboxylic acid dimethyl, 1,7- (9-oxofluorene) dicarboxylic acid, Dimethyl 1,7- (9-oxofluorene) dicarboxylate, 2,3- (9-oxofluorene) dicarboxylic acid, dimethyl 2,3- (9-oxofluorene) dicarboxylate, 2,7- (9-oxofluorene) ) Dicarboxylic acid, dimethyl 2,7- (9-oxofluorene) dicarboxylate, 1,4-anthracene dicarboxylic acid, 1,5-ant Sendicarboxylic acid, diethyl 1,5-anthracene dicarboxylate, 1,8-anthracene dicarboxylic acid, 1,9-anthracene dicarboxylic acid, 2,3-anthracene dicarboxylic acid, 9,10-anthracene dicarboxylic acid, 9,10-anthracene Dimethyl 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, 1 1,5-anthraquinone dicarboxylic acid dimethyl, 1,5-anthraquinone dicarboxylic acid diphenyl, 1,6-anthraquinone dicarboxylic acid, 1,7-anthraquinone dicarboxylic acid, 1,8-anthraquinone dicarboxylic acid, 2,3-anthraquinone dicarbohydrate Acid, 2,7-anthraquinone dicarboxylic acid, 2,3-biphenyl dicarboxylic acid, dimethyl 2,3-biphenyl dicarboxylic acid, 2,5-biphenyl dicarboxylic acid, 2,6-biphenyl dicarboxylic acid, 3,4-biphenyl dicarboxylic acid Acid, dimethyl 3,4-biphenyldicarboxylate, 3,4-biphenyldicarboxylic acid, dimethyl 3,4-biphenyldicarboxylate, 3,4-biphenyldicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 2,2'- Dimethyl biphenyl dicarboxylate, diphenyl 2,2′-biphenyl dicarboxylate, 2,4′-biphenyl dicarboxylic acid, dimethyl 2,4′-biphenyl dicarboxylate, 3,3′-biphenyl dicarboxylic acid, 3,3′-biphenyl dicarboxylic acid Dimethyl acid, 3,4'-biphenyldicarboxylic acid, 3,4'-biphenyl Dimethyl dicarboxylate, 4,4′-biphenyl dicarboxylic acid, dimethyl 4,4′-biphenyl dicarboxylate, diphenyl 4,4′-biphenyl dicarboxylate, 1,5-biphenylene dicarboxylic acid, dimethyl 1,5-biphenylene dicarboxylate, 1,8-biphenylene dicarboxylic acid, 1,8-biphenylene dicarboxylic acid dimethyl, 2,6-biphenylene dicarboxylic acid, 2,6-biphenylene dicarboxylic acid dimethyl, 2,7-biphenylene dicarboxylic acid, 2,7-biphenylene dicarboxylic acid dimethyl 2,2′-dimethyl 4,4′-biphenyldicarboxylic acid, diethyl 2,2′-dimethyl4,4′-biphenyldicarboxylate, 4,4 ″ -p-terphenyldicarboxylic acid, 4,4 ′ ″ -Dimethyl p-quaterphenyl dicarboxylate, 4,4 '''-p-quaterfe Rudicarboxylic acid, 2,2′-methylene dibenzoic acid, dimethyl 2,2′-methylene dibenzoate, 2,4′-methylene dibenzoic acid, dimethyl 2,4′-methylene dibenzoate, 3,3 ′ -Methylene dibenzoic acid, 4,4'-methylene dibenzoic acid, 4,4'-methylene dibenzoic acid dimethyl, 4,4'-isopropylidene dibenzoic acid, 2,2'-bibenzyldicarboxylic acid, 2, Dimethyl 2'-benzyldicarboxylate, 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-stilbene dicarboxylic acid Dimethyl, 2,2′-transicarboxylic acid, dimethyl 2,2′-transicarboxylate, 2,4′-transicarboxylic acid, 4,4′-transicarboxylic acid, dimethyl 4,4′-transidicarboxylic acid, pseudo -P-dicarboxy [2,2] paracyclophane, 4,4'-carbonyldibenzoic acid, 3,3'-oxydibenzoic acid, 4,4'-oxydibenzoic acid, 4,4'-oxy Dimethyl dibenzoate, diphenyl 4,4′-oxydibenzoate, 4,4′-thiodibenzoic acid, 4,4′-sulfonyldibenzoic acid, 4,4′-sulfoni Dimethyl dibenzoate, 3,3′-dithiodibenzoic acid, 4,4′-dithiodibenzoic acid, diethyl 4,4′-dithiodibenzoate, 2,2′-3,3′-dithiodibenzoic acid 2,2′-azobenzenedicarboxylic acid, 2,2′-azobenzenedicarboxylic acid dimethyl, 3,3′-azobenzenedicarboxylic acid, 3,3′-azobenzenedicarboxylic acid dimethyl, 4,4′-azobenzenedicarboxylic acid, 4, Dimethyl 4'-azobenzenedicarboxylate, homophthalic acid, dimethyl homophthalate, homoisophthalic acid, dimethyl homoisophthalate, homoterephthalic acid, dimethyl homoterephthalate, o-phenylenediacetic acid, diethyl o-phenylenediacetic acid, m-phenylenediamine Acetic acid, diethyl m-phenylenediacetate, p-phenylenediacetic acid, diethyl p-phenylenediacetate, 3,3′-o -Phenylenedipropionic acid, diethyl 3,3'-o-phenylenedipropionic acid, 3,3'-m-phenylenedipropionic acid, diethyl 3,3'-m-phenylenedipropionic acid, 3,3'-p -Phenylenedipropionic acid, diethyl 3,3'-p-phenylenedipropionate, 2-carboxycinnamic acid, 3-carboxycinnamic acid, 4-carboxycinnamic acid, 4-carboxycinnamic acid diethyl, 3t, 3't- o-phenylene diacrylic acid, 3t, 3't-o-phenylene diacrylic acid dimethyl, 3t, 3't-m-phenylene diacrylic acid, 3t, 3't-m-phenylene diacrylic acid dimethyl, 3t, 3't-p-phenylene diacrylic acid, 3t, 3't-p-phenylene diacrylate dimethyl, m-phenylene propiolic acid, m-phenylene propiol Dimethyl, 1,4-naphthalene diacetic acid, 1,5-naphthalene diacetic acid, 1,5-naphthalene diacetic acid dimethyl, 3,3 ′-(1,4-naphthalene) dipropionic acid, 3,3 ′-(1 , 4-Naphthalene) dipropionate diethyl, 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) ] Butyric acid, diphenylsulfone dicarboxylic acid, 1,4-cyclohexanedica Boronic acid, 2,3-furandicarboxylic acid, dimethyl 2,3-furandicarboxylic acid, 2,4-furandicarboxylic acid, dimethyl 2,4-furandicarboxylic acid, 2,5-furandicarboxylic acid, 2,5-furandi Dimethyl carboxylate, diphenyl 2,5-furandicarboxylate, 3,4-furandicarboxylic acid, dimethyl 3,4-furandicarboxylate, 3,4-diphenyl-2,5-furandicarboxylic acid, 3,4-diphenyl- Dimethyl 2,5-furandicarboxylate, 3,3 ′-(2,5-furan) dipropionic acid, dimethyl 3,3 ′-(2,5-furan) dipropionate, 2,5-cis-tetrahydrofuran dicarboxylic acid Acid, dimethyl 2,5-cis-tetrahydrofurandicarboxylate, 3,3 ′-(2,5-cis-tetrahydrofuran) dipropionic acid, Diethyl 3,3 ′-(2,5-cis-tetrahydrofuran) dipropionate, 2,3-thiophenedicarboxylic acid, dimethyl 2,3-thiophenedicarboxylic acid, 2,4-thiophenedicarboxylic acid, 2,4-thiophenedicarboxylic acid Dimethyl acid, 2,5-thiophene dicarboxylic acid, Dimethyl 2,5-thiophene dicarboxylate, Diphenyl 2,5-thiophene dicarboxylate, 3,4-thiophene dicarboxylic acid, Dimethyl 3,4-thiophene dicarboxylate, 3,4- Diphenyl-2,5-thiophene dicarboxylic acid, dimethyl 3,4-diphenyl-2,5-thiophene dicarboxylate, 2,5-thiophene diacetic acid, 3,3 ′-(2,5-thiophene) dipropionic acid, 3 , 3 '-(2,5-thiophene) dipropionic acid diethyl ester, 2,5-cis-tetrahydride Thiophene dicarboxylic acid, diethyl 2,5-cis-tetrahydrothiophene dicarboxylate, 3,4-cis-tetrahydrothiophene dicarboxylic acid, dimethyl 3,4-cis-tetrahydrothiophene dicarboxylate, 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, 4- Diethyl oxo-2,6-4H-pyrandicarboxylate, 2,6-cis-tetrahydropyrandicarboxylic acid, dimethyl 2,6-cis-tetrahydropyrandicarboxylate, 2,6-cis-tetrahydrothiopyrandicarboxylic acid, 2, 6-cis-tetrahydrothi Dimethyl pyrandicarboxylate, 1,1-dioxo-2,6-cis-tetrahydrothiopyrandicarboxylic acid, dimethyl 1,1-dioxo-2,6-cis-tetrahydrothiopyrandicarboxylate, 2,8-dibenzofurandicarboxylic acid, Dimethyl 2,8-dibenzofurandicarboxylate, 3,7-dibenzofurandicarboxylic acid, dimethyl 3,7-dibenzofurandicarboxylate, 4,6-dibenzofurandicarboxylic acid, dimethyl 4,6-dibenzofurandicarboxylate, 2,8-dibenzothiophene dicarboxylic acid Acid, 5,5-dioxo-2,8-dibenzothiophene dicarboxylic acid, 9-oxo-1,8-xanthene dicarboxylic acid, 9-oxo-2,7-xanthene dicarboxylic acid, 9-oxo-2,7-xanthene Dimethyl dicarboxylate, 1,6-dibe Nzo [1,4] dioxin dicarboxylic acid, dimethyl 1,6-dibenzo [1,4] dioxin dicarboxylate, 2,7-dibenzo [1,4] dioxin dicarboxylic acid, 2,7-dibenzo [1,4] Dimethyl dioxin dicarboxylate, 2,8-dibenzo [1,4] dioxin dicarboxylic acid, dimethyl 2,8-dibenzo [1,4] dioxin dicarboxylate, 1,6-phenoxathiin dicarboxylic acid, 4,6-phenoxati Indicarboxylic acid, dimethyl 4,6-phenoxathiin dicarboxylate, 10,10-dioxo-1,6-phenoxy signicarboxylic acid, dimethyl 10,10-dioxo-1,6-phenoxy sign dicarboxylate, 10,10- Dioxo-1,9-phenoxine dicarboxylic acid, 10,10-dioxo-1,9-phenoxine dicar Dimethyl acid, 10,10-dioxo-2,8-phenoxine dicarboxylic acid, dimethyl 10,10-dioxo-2,8-phenoxy signicarboxylic acid, 10,10-dioxo-4,6-phenoxy signicarboxylic acid, 2,7-thiandienedicarboxylic acid, dimethyl 2,7-thianthenedicarboxylate, 10,10-dioxo-1,9-thianthenedicarboxylic acid, 5,5,10,10-tetraoxo-2,7-thianthrene Dicarboxylic acid, dimethyl 5,5,10,10-tetraoxo-2,7-thiandienedicarboxylate, 10-oxo-10-phenyl-2,8-phenoxaphosphine dicarboxylic acid, 9-oxabicyclo [3,3 1] Dimethyl nonane-2,6-dicarboxylate, 9-oxabicyclo [3,3,1] nonane-2,6-dicarboxylate Diphenyl rubonate, 2,4,6,8-tetraoxaspiro [5,5] undecane-3,9-dicarboxylic acid, 2,4,6,8-tetraoxaspiro [5,5] undecane-3,9 Dimethyl 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, dimethyl 2,5-pyrrole dicarboxylate, 1-methyl-2,5-pyrrole dicarboxylic acid, dimethyl 1-methyl-2,5-pyrrole dicarboxylate, 1- Phenyl-2,5-pyrroldica Rubonic 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, diethyl 1-methyl-3,4-pyrrole dicarboxylate, diethyl 1-phenyl-3,4-pyrrole dicarboxylate, diethyl 1-phenyl-3,4-pyrrole dicarboxylate, 3,5-dimethyl -Diethyl 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 dicarboxylic acid diethyl 1-methyl-2,5-pyrroldiacetic acid, 1-methyl-2,5 -Dimethyl pyrrole diacetate 3,3 ′-(2,5-pyrrole) dipropionic acid, 3,3 ′-(1-methyl-2,5-pyrrole) dipropionic acid, 3,3 ′-(1-methyl-2) , 5-pyrrole) dimethyl dipropionate, diethyl 3,3 ′-(1-phenyl-2,5-pyrrole) dipropionate, diethyl 1-methyl-2,5-cis-pyrrolidinedicarboxylate, 1-phenyl- Diethyl 2,5-cis-pyrrolidinedicarboxylate, diethyl 1-methyl-2,5-pyrrolidinediacetate, 3,3 ′-(1-methyl-2,5-pyrrolidine) dipropionic acid, 3,3 ′-( 1-methyl-2,5-pyrrolidine) diethyl dipropionate, diethyl 2,5-indole dicarboxylate, 2,6-indole dicarboxylic acid, diethyl 2,6-indole dicarboxylate, 9-methyl-1, -Carbazole dicarboxylic acid, 2,6-carbazole dicarboxylic acid, diethyl 2,6-carbazole dicarboxylate, 3,6-carbazole dicarboxylic acid, diethyl 3,6-carbazole dicarboxylate, 9-methyl-3,6-carbazole dicarboxylic acid , Diethyl 9-methyl-3,6-carbazole dicarboxylate, 3,4-pyrazole dicarboxylic acid, dimethyl 3,4-pyrazole dicarboxylate, 2-methyl-3,4-pyrazole dicarboxylic acid, 1-phenyl-3,4 -Pyrazole dicarboxylic acid, dimethyl 1-phenyl-3,4-pyrazole dicarboxylate, 2-phenyl-3,4-pyrazole dicarboxylic acid, dimethyl 2-phenyl-3,4-pyrazole dicarboxylate, 3,5-pyrazole dicarboxylic acid 3,5-pyrazole dicarboxylic acid dimethy 1-methyl-3,5-pyrazole dicarboxylic acid, 1-methyl-3,5-pyrazole dicarboxylic acid dimethyl, 1-phenyl-3,5-pyrazole dicarboxylic acid, 1-phenyl-3,5-pyrazole dicarboxylic acid dimethyl 4,5-imidazole dicarboxylic acid, diphenyl 4,5-imidazole dicarboxylate, 1-methyl-4,5-imidazole dicarboxylic acid, dimethyl 1-methyl-4,5-imidazole dicarboxylate, 1-phenyl-4,5 -Imidazole dicarboxylic acid, diethyl 1-phenyl-4,5-imidazole dicarboxylate, 2,3-pyridinedicarboxylic acid, dimethyl 2,3-pyridinedicarboxylic acid, diphenyl 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid Acid, dimethyl 2,4-pyridinedicarboxylate, 2,4-pyridinedica Diphenyl borate, 2,5-pyridinedicarboxylic acid, dimethyl 2,5-pyridinedicarboxylate, diphenyl 2,5-pyridinedicarboxylate, 2,6-pyridinedicarboxylic acid, dimethyl 2,6-pyridinedicarboxylate, 2,6 -Diphenyl pyridinedicarboxylate, 3,4-pyridinedicarboxylic acid, dimethyl 3,4-pyridinedicarboxylate, 3,5-pyridinedicarboxylic acid, diphenyl 3,5-pyridinedicarboxylate, 2,6-dimethyl-3,5- Pyridinedicarboxylic acid, 2,4,6-trimethyl-3,5-pyridinedicarboxylic acid, dimethyl 2,5-piperidinedicarboxylate, diethyl 2,3-piperidinedicarboxylate, 2,6-cis-piperidinedicarboxylic acid, 2, Dimethyl 6-cis-piperidinedicarboxylate, 1-methyl-2,6-c s-piperidinedicarboxylic acid, dimethyl 1-methyl-2,6-cis-piperidinedicarboxylate, diethyl 3,5-piperidinedicarboxylate, 2,6-cis-piperidinediacetic acid, 1-methyl-2,6-cis- Piperidine diacetic acid, 1-methyl-2,6-cis-piperidinediacetic acid diethyl ester, 2,3-quinoline dicarboxylic acid, dimethyl 2,3-quinoline dicarboxylate, 2,4-quinoline dicarboxylic acid, 2,4-quinoline dicarboxylic acid Dimethyl acid, 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, 5,6-quinoline dicarboxylic acid Dimethyl acid, 5,8-quinoline dicarboxylic acid, 6,7-quinoline dicarboxylic acid, 6,7-quino Dimethyl phosphorus dicarboxylate, 6,8-quinoline dicarboxylic acid, 7,8-quinoline dicarboxylic acid, 2,2'-bipyridine-4,4'-dicarboxylic acid, 2,2'-bipyridine-4,4'-dicarboxylic acid Dimethyl, 2,2′-bipyridine-5,5′-dicarboxylic acid, dimethyl 2,2′-bipyridine-5,5′-dicarboxylic acid, 2,2′-bipyridine-6,6′-dicarboxylic acid, 3, Dimethyl 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- Dimethyl pyrazinedicarboxylate, 2,5-pyrazinedicarboxylic acid, dimethyl 2,5-pyrazinedicarboxylate, diphenyl 2,5-pyrazinedicarboxylate, 2,6-pyrazinedicarbo Acid, dimethyl 2,6-pyrazinedicarboxylate, dimethyl 1,4-piperazinediacetate, dimethyl 3,3 ′-(1,4-piperazine) dipropionate, 1,6-phenazinedicarboxylic acid, 1,6-phenazine And dimethyl dicarboxylate. Among these, wholly aromatic polycarboxylic acids having a rigid molecular structure that does not contain an alkylene chain in the main chain, such as 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, thiophenedicarboxylic acids, pyrandicarboxylic acids, dibenzofurandicarboxylic acids, dibenzothiophenedicarboxylic acids, xanthenedicarboxylic acids Acids, dibenzo [1,4] dioxin dicarboxylic acids, phenoxathiin dicarboxylic acids, thianthylene dicarboxylic acids, phenoxy Examples include phosphine dicarboxylic 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. It is done. Moreover, the acid halide or acid anhydride of said aromatic dicarboxylic acid can also be used. Examples of the acid halide of aromatic dicarboxylic acid include phthaloyl dichloride and naphthoyl dichloride. Of these, preferably phthaloyl dichloride, such as isophthaloyl dichloride or terephthaloyl dichloride, is used.

Polyhydric phenols are known. For example, 2,2′-dihydroxybiphenyl, 3,3′-dihydroxybiphenyl, 3,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether, 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-dihydroxynaphthalene, 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-oxofluorene) diol, 1,7- (9-oxofluorene) diol, 2, 3- (9-oxofluorene) diol, 2,7- (9-oxofluorene) Diol, 2,2-bis- (4-hydroxynaphthyl) 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, bis- (4-hydroxyphenyl) ether, 4,3′-dihydroxydiphenyl ether, 4,2′-dihydroxydiphenyl ether, 2,2′-dihydroxydiphenyl ether, 2,3′-hydroxydiphenyl ether, 4,4′-dihydroxy-2,6-dimethyldiphenyl ether, bis- (hydroxy Naphthyl) ether, 3,4'-dihydroxydiphenyl, bis- (4-hydro Xylphenyl) sulfone, bis- (3-hydroxyphenyl) sulfone, 2,4′-dihydroxydiphenylsulfone, catechol, 3-methylcatechol, 4-methylcatechol, 3-ethylcatechol, 4-ethylcatechol, 3-n-propyl Catechol, 4-n-propylcatechol, 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-dichloro Catechol, 3,4-dibromocatechol, 3,5-dibromocatechol, 4,5-dibromocatechol, 4-chloro-5-nitrocatechol, 3-chloro-6-methoxycatechol, 5-bromo-4-nitrocatechol 4-bromo-5-methylcatechol, 3-bromo-5- (t-butyl) catechol, 3,4,5-trichlorocatechol, 3,4,5-tribromocatechol, 3,4,6-tribromo Catechol, tetrachlorocatechol, tetrabromocatechol, 3-aminocatechol, 4-a Nocatechol, 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- Methoxy catechol, 5-nitro-3-methyl catechol, 4-methoxy catechol, 6-methoxy catechol, 4- (2-hydroxyethyl) catechol, 3-propoxy catechol, 3-butyroxy catechol, 3,4-dimethoxy catechol 3,6-dimethoxycatechol, 5-methoxy-3- (t-butyl) Tecor, 3-ethoxy- (t-butyl) catechol, 3,4,6-trimethoxycatechol, 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 Lucinol, 5-bromoresorcinol, 2,4-dibromoresorcinol, 4,6-dibromoresorcinol, 2,4,6-tribromoresorcinol, 6-bromo-4-butylresorcinol, 2-iodoresorcinol, 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 Nord, resorcinol monoacetate, resorcinol monobenzoate, 2-nitroresorcinol, 4-nitroresorcinol, 5-nitroresorcinol, 2,4-dinitroresorcinol, 4,6-dinitroresorcinol, 2,4,6-trinitroresorcinol, Tetranitroresorcinol, 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-methyl Resorcinol, 5-methoxy-4-methylresorcinol, 5-methoxy-6-methylresorcinol, 5-ethoxyresorcinol, 2-methylresorcinol, 4-methylresorcinol, 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- (2- Methylethenyl) resorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 5-n-butylresorcinol, 2-n-butylresorcinol, 4-tert-butylresorcinol, 2-n-pentyl Solcinol, 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-phenyl Tilresorcinol, 2-octylresorcinol, 4-octylresorcinol, 5-octylresorcinol, 4- (1-methylheptyl) 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- -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-butyl resorsi Nord, 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, iodohydroquinone, 2,6 Diiodohydroquinone, tetraiodohydroquinone, nitrohydroquinone, 2,6-dinitrohydroquinone, methoxyhydroquinone, 2-methoxy-3-methylhydroquinone, 2-methoxy-5-methylhydroquinone, 3-methoxy-2-methylhydroquinone, 5- Methoxy-2-methylhydroquinone, 2-methoxy-6-propylhydroquinone, 2-methoxy-5-propenylhydroquinone, 2,3-dimethoxyhydroquinone, 2,5-dimethoxyhydroquinone, 2,6-dimethoxyhydroquinone, phenoxyhydroquinone, mercapto Hydroquinone, acetylhydroquinone, benzoylhydroquinone, hydroxymethylhydroquinone, methylhydroquinone, 2-methyl-6-ethylhydroquinone, 2-methyl-5-isopropylhydro Non, 2-methyl-5-cyclohexyl hydroquinone, 2,3-dimethyl hydroquinone, 2,5-dimethyl hydroquinone, 2,6-dimethyl hydroquinone, trimethyl hydroquinone, tetramethyl hydro
Quinone, ethylhydroquinone, 2,6-diethylhydroquinone, vinylhydroquinone, 5-ethoxyresorcinol, 2-methylresorcinol, 4-methylresorcinol, 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-butyl resorcinol, 4-n-butyl resorcinol, 5-n-butyl resorcinol, 5-sec-butyl resorcinol, 4-tert-butyl resorcinol, 2-n-pentyl resorcinol 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 Sol 2-octyl resorcinol, 5-octyl resorcinol, 4- (1-methylheptyl) resorcinol, 4- (1,1,3,3-tetramethylbutyl) resorcinol, 4- (2-phenethyl) resorcinol, 5- Nonyl resorcinol, 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-methyl Resorcinol, 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-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-Hido Xylethylresorcinol, 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-propenylhydroquinone, hexylhydroquinone, 4-methylpentylhydroquinone, Cyclohexylhydroquinone, 4-phenylmethylhydroquinone, octylhydroquinone, 2,2'-methylidene bisphenol, 3,3'-methylidene bisphenol, 4,4'-methylidene bisphenol 2,2'-methylidenebis (4-methylphenol), 2,2'-methylidenebis (5-methylphenol), 2,2'-methylidenebis (6-methylphenol), 4,4'-methylidene (2-methyl) Phenol), 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- Propylphenol), 4,4'-methylidenebis (2-methyl-6-ethylphenol), 2,2'-methylidenebis (3,4,5,6-te Tramethylphenol), 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-tetramethylbutyl) phenol ), 2,2′-methylidenebis (4,6-di-tert-butylphenol), 2,2′-methylidenebis (4,6-tert-butylphenol), 4,4′-methylidenebis (2,6-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′- Tylidenebis (2-nitrophenol), 2,2'-methylidenebis (4,6-dinitrophenol), 3,3'-methylidenebis (6-methoxyphenol), 4,4'-methylidenebis (2-methoxyphenol), 2 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-bromide) -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'-isopropylidenebi (2-methylphenol), 4,4′-isopropylidenebis (2-cyclohexylphenol), 4,4′-isopropylidenebis (2,6-dibromophenol), 4,4′-isopropylidenebis (2- Nitrophenol), 4,4′-isopropylidenebis (2,6-dinitrophenol), 4,4′-butanediylbis (2-methylphenol), 4,4′-butylidenebisphenol, 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-methyl) Phenol), 4,4 '-(1,3-cyclohexanediyl) bisphenol, 4,4'-cyclohexylidene bisphenol, 4,4'-cyclohexylidene bis (2-chlorophenol), 4,4'-cyclohexyl Silidenebis (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'- Obis (6-tertbutyl-4-methylphenol), 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-dichloro) Phenol), 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′-sulfini Bis (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-nitro) Phenol), 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′-sulfonylbis And hydroquinone. Among these, 2,2′-bis- (4-hydroxyphenyl) propane [bisphenol A] is particularly preferable, 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.

The aromatic polyester of the present invention preferably has a polyhydric phenol residue represented by the following formula (I):

The thing shown by is mentioned. In formula (I), R ¹ to R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an allyl group or a halogen atom, and preferably each independently represents a hydrogen atom, carbon It represents an alkyl group, an allyl group or a chlorine atom represented by formulas ¹ to 3, and particularly preferably, all of R ¹ to R ⁴ represent hydrogen atoms. x is 0 or 1, and when x is 1, W represents an alkylene group having 1 to 30 carbon atoms, an alkylidene group having 2 to 30 carbon atoms, a cycloalkylene group having 3 to 30 carbon atoms, or 3 to 3 carbon atoms. A cycloalkylidene group having 30 carbon atoms, an alkylene group having 1 to 30 carbon atoms substituted by a phenyl group, an alkylidene group having 2 to 30 carbon atoms substituted by a phenyl group, an oxygen atom, a sulfur atom, a sulfoxide group or a sulfone group; Preferred is an alkylene group having 1 to 3 carbon atoms, an oxygen atom, an alkylidene group having 2 to 3 carbon atoms, a sulfur atom, a sulfoxide group or a sulfone group, and particularly preferred is an isopropylidene group [C (CH ₃ ) ₂ ]. Indicates. When x is 0, the benzene ring having R ¹ and R ³ and the benzene ring having R ² and R ⁴ are covalently bonded. In the most preferred embodiment, all of R ¹ to R ⁴ are hydrogen atoms, x is 1, and W is an isopropylidene group [C (CH ₃ ) ₂ ].

The aromatic polyester of the present invention includes, for example, the following formula (II)

Indicated by In formula (II), R ¹ to R ⁴ and W are the same as above. In particular, it is preferable that R ¹ to R ⁴ are all hydrogen atoms, x is 1, and W is all isopropylidene group [C (CH ₃ ) ₂ ]. n, m, l and o are each independently an integer of 0 to 100, and preferably are each independently an integer of 1 to 50. However, m is an integer of 1 or more. Further, m / (n + m + 1 + o) has a lower limit of 0.001, preferably 0.005, more preferably 0.010, and an upper limit of 0.090, preferably 0.070, more preferably 0.050. More preferably, it is 0.040. Here, in the above formula (II), n, m, l and o represent the total number of each structural unit present in one molecule of the aromatic polyester, and actually, as shown in FIG. Units containing one aromatic tricarboxylic acid (TMTC) residue are present dispersed in the aromatic polyester polymer chain.

When the aromatic polyester of the present invention is produced by reacting a polyhydric phenol with an aromatic polyvalent carboxylic acid, an acid halide or an acid anhydride thereof, an aromatic polyvalent carboxylic acid and an acid halide thereof are produced. Or it can manufacture by making aromatic dicarboxylic acid, its acid halide, or an acid anhydride and aromatic tricarboxylic acid, its acid halide, or an acid anhydride exist as an acid anhydride. Where (number of moles of aromatic tricarboxylic acid, acid halide or acid anhydride) / [(number of moles of aromatic dicarboxylic acid, acid halide or acid anhydride) + (aromatic tricarboxylic acid, acid The upper limit of the number of moles of halide or acid anhydride)] is 0.090, preferably 0.070, more preferably 0.050, still more preferably 0.040, still more preferably 0.030, and the lower limit. Is 0.001, preferably 0.005, more preferably 0.010. Beyond the above upper limit, the aromatic tricarboxylic acid, its acid halide or acid anhydride increases, thereby causing cross-linking within the polymer molecule and significantly increasing the glass transition temperature. On the other hand, below the above lower limit, sufficient branching cannot be obtained in the polymer chain, resulting in a rigid polymer chain, and the glass transition temperature is also increased.

Known conditions can be used as the production conditions for the aromatic polyester in the present invention. For example, temperature -10 ~ 55 ℃
At a pressure of 0.01 to 2 MPa for 0.01 to 24 hours. Manufacture can be either batch or continuous.

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

(Example)
Each property of the polyester was measured as follows.

<Glass transition temperature (Tg, ° C.)>
Measurement was performed using a differential thermal analyzer (DSC-60, manufactured by Shimadzu Corporation). The sample used for the measurement is powder. The measurement was performed under a nitrogen stream.

<Weight average molecular weight (Mw)>
It measured using Shimadzu GPC LC20AT type | mold. A column in which a total of three columns, Shodex KF &8722; 802, KF804 and KF806, were connected in series was used. 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.

<Melt flow rate (MFR, g / 10 min)>
Measurement was performed using a melt indexer F-W01 (trademark) manufactured by Toyo Seiki Seisakusho Co., Ltd. with a load of 10.0 kg as a standard. However, in Example 3, the temperature was 255 ° C. and the load was 5.0 kg. Further, when measuring the melt flow rate by temperature change, the temperature was changed at 240 to 280 ° C. At this time, when the temperature was 240 ° C., the load was 5.0 kg. In the measurement, the charged amounts were all constant.

<Total light transmittance and haze>
Using a Nippon Denshoku Co., Ltd. haze meter NDH5000 (trademark), a film having a thickness of about 0.10 mm was measured according to JIS K7361.

<X-ray diffraction>
Using an X-ray diffractometer RINT2000 (trademark) manufactured by Rigaku Corporation, measurement was performed on a hot melt extruded sample (extrusion conditions: melting temperature 280 ° C., load 10.0 kg).

Example 1
Place 1,000 ml of dichloromethane in a glass Erlenmeyer flask, then 2.98 grams (21.2 mmol) of benzoyl chloride, 0.804 grams (3.03 mmol) of trimesoyl trichloride, 15.37 grams of isophthaloyl dichloride ( 75.7 mmol) and 15.37 grams (75.7 mmol) of terephthaloyl dichloride were added and dissolved.

On the other hand, 1,100 milliliters of water was placed in a glass round bottom flask, and then 13.3 grams (0.33 mole) of sodium hydroxide and 38.0 grams (166.6 millimoles) of bisphenol A were added. Stir for minutes. Thereafter, 12.2 mg (0.038 mmol) of tetra-n-butylammonium bromide was further added, and the mixture was also stirred at room temperature for 30 minutes.

Next, the solution in the Erlenmeyer flask was added to the round bottom flask and stirred and mixed at room temperature for 30 minutes. After completion of the reaction, the aqueous layer was removed and the organic layer was transferred to a separatory funnel. Next, 1,000 ml of water was added to the separatory funnel, washed with stirring, and allowed to stand to separate the organic layer. This washing operation was repeated three times. The obtained organic layer was added with stirring to a mixed solution of methanol and water (9: 1 by volume). The precipitated polymer was collected and dried.

The weight average molecular weight (Mw) of the obtained polymer was 29,000, the glass transition temperature (Tg) was 164 ° C., and the melt flow rate (MFR) was 28 g / 10 min. In the polymer obtained, R ¹ to R ⁴ in formula (II) are all hydrogen atoms, x is 1, W is all isopropylidene group [C (CH ₃ ) ₂ ], and m / (N + m + l + o), ie, (number of moles of residues of aromatic tricarboxylic acid, acid halide or acid anhydride) / [(number of moles of residues of aromatic dicarboxylic acid, acid halide or acid anhydride) ) + (Number of moles of residue of aromatic tricarboxylic acid, acid halide or acid anhydride thereof)] = 0.020.

(Example 2)
The same procedure as in Example 1 was repeated except that the benzoyl chloride added to the Erlenmeyer flask was changed to 2.1 gram (150 mmol) and the trimesoyl trichloride was changed to 199 mg (0.75 mmol). The weight average molecular weight (Mw) of the obtained polymer was 35,000, the glass transition temperature (Tg) was 184 ° C., and the melt flow rate (MFR) was 6 g / 10 min. In the polymer obtained, R ¹ to R ⁴ in formula (II) are all hydrogen atoms, x is 1, W is all isopropylidene group [C (CH ₃ ) ₂ ], and m / (N + m + l + o), ie, (number of moles of residues of aromatic tricarboxylic acid, acid halide or acid anhydride) / [(number of moles of residues of aromatic dicarboxylic acid, acid halide or acid anhydride) ) + (Number of moles of residues of aromatic tricarboxylic acid, acid halide or acid anhydride thereof)] = 0.005.

(Example 3)
Performed as in Example 1, except that the benzoyl chloride added to the Erlenmeyer flask was 1.49 grams (10.6 mmol) and the trimesoyl trichloride was changed to 0.402 grams (1.51 mmol). . The weight average molecular weight (Mw) of the obtained polymer was 43,000, the glass transition temperature (Tg) was 177 ° C., and the melt flow rate (MFR) was 9 g / 10 min. In the polymer obtained, R ¹ to R ⁴ in formula (II) are all hydrogen atoms, x is 1, W is all isopropylidene group [C (CH ₃ ) ₂ ], and m / (N + m + l + o), ie, (number of moles of residues of aromatic tricarboxylic acid, acid halide or acid anhydride) / [(number of moles of residues of aromatic dicarboxylic acid, acid halide or acid anhydride) ) + (Number of moles of residue of aromatic tricarboxylic acid, acid halide or acid anhydride thereof)] = 0.010.

Example 4
Performed as in Example 1, except that the benzoyl chloride added to the Erlenmeyer flask was 1.49 grams (10.6 mmol) and the trimesoyl trichloride was changed to 1.202 grams (4.53 mmol). . The weight average molecular weight (Mw) of the obtained polymer was 16,000, the glass transition temperature (Tg) was 158 ° C., and the melt flow rate (MFR) was 61.1 g / 10 min (however, 255 ° C., 5. 0 kg load). In the polymer obtained, R ¹ to R ⁴ in formula (II) are all hydrogen atoms, x is 1, W is all isopropylidene group [C (CH ₃ ) ₂ ], and m / (N + m + l + o), ie, (number of moles of residues of aromatic tricarboxylic acid, acid halide or acid anhydride) / [(number of moles of residues of aromatic dicarboxylic acid, acid halide or acid anhydride) ) + (Number of moles of aromatic tricarboxylic acid, acid halide or acid anhydride residue)] = 0.030.

(Example 5)
Place 1,000 milliliters of dichloromethane in a glass Erlenmeyer flask, then 2.95 grams (21.0 millimoles) of benzoyl chloride, 0.040 grams (0.150 millimoles) of trimesoyl trichloride, 14.60 grams of isophthaloyl dichloride ( 72.0 mmol) and 14.60 grams (72.0 mmol) of terephthaloyl dichloride were added and dissolved. Thereafter, 12.1 mg (0.037 mmol) of tetra-n-butylammonium bromide was further added and stirred.

On the other hand, 1,100 milliliters of water was placed in a glass round bottom flask, and then 13.2 grams (0.33 mole) of sodium hydroxide and 37.67 rams of bisphenol A (165.0 millimoles) were added. Stir for minutes.

Next, the same treatment as in Example 1 was carried out to obtain a polymer. The weight average molecular weight (Mw) of the obtained polymer was 23,000, the glass transition temperature (Tg) was 184.9 ° C., and the melt flow rate (MFR) was 6.0 g / 10 min. In the polymer obtained, R ¹ to R ⁴ in formula (II) are all hydrogen atoms, x is 1, W is all isopropylidene group [C (CH ₃ ) ₂ ], and m / (N + m + l + o), ie, (number of moles of residues of aromatic tricarboxylic acid, acid halide or acid anhydride) / [(number of moles of residues of aromatic dicarboxylic acid, acid halide or acid anhydride) ) + (Number of moles of aromatic tricarboxylic acid, acid halide or acid anhydride residue)] = 0.001.

(Comparative Example 1)
The same procedure as in Example 1 was conducted except that 2.13 g (15.15 mmol) of benzoyl chloride added to the Erlenmeyer flask was added and that trimesoyl trichloride was not added. The weight average molecular weight (Mw) of the obtained polymer was 33,000, the glass transition temperature (Tg) was 182 ° C., and the melt flow rate (MFR) was 6.4 g / 10 min. In the polymer obtained, R ¹ to R ⁴ in formula (II) are all hydrogen atoms, x is 1, W is all isopropylidene group [C (CH ₃ ) ₂ ], and m / (N + m + l + o), ie, (number of moles of residues of aromatic tricarboxylic acid, acid halide or acid anhydride) / [(number of moles of residues of aromatic dicarboxylic acid, acid halide or acid anhydride) ) + (Number of moles of residue of aromatic tricarboxylic acid, acid halide or acid anhydride thereof)] = 0. The obtained aromatic polyester did not have a residue of aromatic tricarboxylic acid, its acid halide or acid anhydride.

(Comparative Example 2)
132 ml of dichloromethane was placed in a glass Erlenmeyer flask, then 0.281 grams (2.0 mmol) of benzoyl chloride, 0.531 grams (2.0 mmol) of trimesoyl trichloride, 1.725 grams (8. 5 mmol) and 1.725 grams (8.5 mmol) of terephthaloyl dichloride were added and dissolved.

On the other hand, 145 ml of water was placed in a glass round bottom flask, and then 1.76 g (44 mmol) of sodium hydroxide and 5.022 g (22 mmol) of bisphenol A were added and stirred at room temperature for 30 minutes. Thereafter, 19.3 mg (0.06 mmol) of tetra-n-butylammonium bromide was further added, and the mixture was also stirred at room temperature for 30 minutes.

Next, the solution in the Erlenmeyer flask was added to the round bottom flask and stirred and mixed at room temperature for 30 minutes. After completion of the reaction, the water tank was removed, and the organic layer was transferred to a separatory funnel. Subsequently, 500 ml of water was added to the separatory funnel, washed with stirring, and then allowed to stand to separate the organic layer. This washing operation was repeated three times. The obtained organic layer was added to a mixed solution of methanol and water (volume ratio 9: 1) with stirring. The precipitated polymer was collected and dried.

The obtained polymer was insoluble in the solvent (chloroform), and the weight average molecular weight could not be measured. In the measurement of the glass transition temperature (Tg), the polymer was not dissolved even when the temperature reached 300 ° C. or higher. Since the polymer could not be dissolved in this way, the polymer could not be pelletized and the melt flow rate (MFR) could not be measured. In the polymer obtained, R in the formula (I) is all hydrogen atoms, W is all CH ₃ (C), and m / (n + m + 1 + o), that is, (aromatic tricarboxylic acid, Mole number of residue of acid halide or acid anhydride) / [(Mole number of residue of aromatic dicarboxylic acid, acid halide or acid anhydride) + (aromatic tricarboxylic acid, acid halide or acid thereof) The number of moles of anhydride residues)] = 0.100.

(Comparative Example 3)
The benzoyl chloride added to the Erlenmeyer flask is 2.13 grams (15.15 mmol), the trimesoyl trichloride is 14.27 grams (50.0 mmol), and both isophthaloyl dichloride and terephthaloyl dichloride are both 10.15. The procedure was the same as Example 1 except that the amount was changed to grams (50.0 mmol). After completion of the reaction, the water layer and the organic layer were removed to obtain an insoluble gel product. Subsequently, the polymer was obtained by drying by evaporation. The obtained polymer was insoluble in the solvent (chloroform), and the weight average molecular weight could not be measured. In the measurement of the glass transition temperature (Tg), the polymer was not dissolved even when the temperature reached 300 ° C. or higher. Since the polymer could not be dissolved in this way, the polymer could not be pelletized and the melt flow rate (MFR) could not be measured. In the polymer obtained, R ¹ to R ⁴ in formula (II) are all hydrogen atoms, x is 1, W is all isopropylidene group [C (CH ₃ ) ₂ ], and m / (N + m + l + o), ie, (number of moles of residues of aromatic tricarboxylic acid, acid halide or acid anhydride) / [(number of moles of residues of aromatic dicarboxylic acid, acid halide or acid anhydride) ) + (Number of moles of aromatic tricarboxylic acid, acid halide or acid anhydride residue)] = 0.333.

The results of Examples 1 to 5 and Comparative Examples 1 to 3 are shown in Table 1 below.

In Table 1, the molar ratio of * 1 is (number of moles of trimesoyl trichloride residues) / [(number of moles of residues of isophthaloyl dichloride) + (number of moles of residues of terephthaloyl dichloride) + (three The number of moles of trimesoyl chloride residues)]. * 2 indicates a value measured at a temperature of 255 ° C. and a load of 5.0 kg. Moreover, * 3 shows that it did not melt even when the temperature was 300 ° C. during measurement.

Examples 1-5 are within the scope of the present invention (number of moles of trimesoyl trichloride residues) / [(number of moles of residues of isophthaloyl dichloride) + (number of moles of residues of terephthaloyl dichloride) + (Number of moles of trimesoyl trichloride residues)]. The glass transition temperature decreased as the molar ratio increased, and it was found that the obtained aromatic polyester was made amorphous. In addition, it was found that the melt flow rate value also increased. In particular, the aromatic polyesters obtained in Examples 1, 3 and 4 have a large melt flow rate value and can be molded at a low temperature of 280 ° C. or less, and can effectively prevent coloring of the product after molding. I understood that. On the other hand, Comparative Example 1 does not contain a residue of trimesoyl trichloride. The resulting aromatic polyester has a relatively low melt flow rate and tends to be colored when molded. Further, Comparative Examples 2 and 3 and the above molar ratios are beyond the scope of the present invention. The obtained aromatic polyester had a weight average molecular weight that was unmeasurable, and the melt flow rate was remarkably high.

(Example 6)
Using the aromatic polyester obtained in Example 1, the change in melt flow rate (MFR) with temperature change was measured. The results are shown in Table 2 below.

From Table 2, it was confirmed that when the temperature rose from 250 ° C. to 260 ° C., the melt flow rate (MFR) significantly increased. Therefore, it was found that the aromatic polyester of the present invention can be molded even at a considerably low temperature of 260 ° C.

The aromatic polyester of the present invention is useful for optical materials such as lenses, optical elements, display substrates, optical fibers and the like because it can provide a polyester material that is difficult to be colored at the time of molding and has extremely excellent optical properties. In addition, it can be used for materials that particularly require heat resistance, such as automobile parts and electronic precision parts.

1 X-ray diffractogram of Example 2 2 X-ray diffractogram of Example 3 X-ray diffractogram BU of Comparative Example 1 Unit TMTC consisting of dihydric phenol residue and aromatic dicarboxylic acid residue Residue of aromatic tricarboxylic acid Base

Claims (24)

1. In an aromatic polyester containing a polyhydric phenol residue and an aromatic polyvalent carboxylic acid, acid halide or acid anhydride residue thereof, the residue of the aromatic polyvalent carboxylic acid, acid halide or acid anhydride The group consists of the residue of an aromatic dicarboxylic acid, its acid halide or acid anhydride and the residue of an aromatic tricarboxylic acid, its acid halide or acid anhydride, and (aromatic tricarboxylic acid, its acid Number of moles of residues of halide or acid anhydride) / [(number of moles of residues of aromatic dicarboxylic acid, acid halide or acid anhydride) + (aromatic tricarboxylic acid, acid halide or acid anhydride) Aromatic polyester, characterized in that the number of moles of the product residues)] = 0.001 to 0.090.
2. (Number of moles of residue of aromatic tricarboxylic acid, acid halide or acid anhydride) / [(number of moles of residue of aromatic dicarboxylic acid, acid halide or acid anhydride) + (aromatic tricarboxylic acid 2. The aromatic polyester according to claim 1, wherein the number of moles of residues of the acid halide or acid anhydride)] = 0.001 to 0.070.
3. (Number of moles of residue of aromatic tricarboxylic acid, acid halide or acid anhydride) / [(number of moles of residue of aromatic dicarboxylic acid, acid halide or acid anhydride) + (aromatic tricarboxylic acid 2. The aromatic polyester according to claim 1, wherein the number of moles of the residue of the acid halide or acid anhydride)] = 0.001 to 0.050.
4. (Number of moles of residue of aromatic tricarboxylic acid, acid halide or acid anhydride) / [(number of moles of residue of aromatic dicarboxylic acid, acid halide or acid anhydride) + (aromatic tricarboxylic acid 2. The aromatic polyester according to claim 1, wherein the number of moles of residues of the acid halide or acid anhydride)] = 0.001 to 0.030.
5. The aromatic polyester according to any one of claims 1 to 4, having a weight average molecular weight (Mw) of 2,000 to 200,000.
6. The aromatic polyester according to any one of claims 1 to 4, having a weight average molecular weight (Mw) of 10,000 to 100,000.
7. The aromatic polyester according to any one of claims 1 to 4, having a weight average molecular weight (Mw) of 15,000 to 60,000.
8. The aromatic polyester according to any one of claims 1 to 7, wherein a melt flow rate (MFR, unit: g / 10 min, measurement condition: 280 ° C, 10.0 kg load) is 2 to 60.
9. The aromatic polyester according to any one of claims 1 to 7, which has a melt flow rate (MFR, unit: g / 10 min, measurement conditions: 280 ° C, 10.0 kg load) of 5.0 or more.
10. The aromatic polyester according to any one of claims 1 to 7, having a melt flow rate (MFR, unit: g / 10 min, measurement conditions: 280 ° C, 10.0 kg load) of 5 to 40.
11. The aromatic polyester according to any one of claims 1 to 7, having a melt flow rate (MFR, unit: g / 10 min, measurement conditions: 280 ° C, 10.0 kg load) of 10 to 30.
12. The aromatic polyester according to any one of claims 1 to 11, wherein the polyhydric phenol residue is a dihydric phenol residue.
13. The polyhydric phenol residue is represented by the following formula (I)
    

    

    (In the formula (I), R ¹ to R ⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an allyl group or a halogen atom, x is 0 or 1, and x is 1; Is substituted by an alkylene group having 1 to 30 carbon atoms, an alkylidene group having 2 to 30 carbon atoms, a cycloalkylene group having 3 to 30 carbon atoms, a cycloalkylidene group having 3 to 30 carbon atoms, or a phenyl group. An alkylene group having 1 to 30 carbon atoms, an alkylidene group having 2 to 30 carbon atoms substituted by a phenyl group, an oxygen atom, a sulfur atom, a sulfoxide group or a sulfone group, and when x is 0, R ¹ and R ^The benzene ring having ³ and the benzene ring having R ² and R ⁴ are covalently bonded)
    The aromatic polyester according to any one of claims 1 to 11, which is represented by:
14. 14. The aromatic polyester according to claim 13, wherein R ¹ to R ^{4 in} formula (I) are all hydrogen atoms.
15. The aromatic polyester according to claim 13 or 14, wherein W is an isopropylidene group [C (CH ₃ ) ₂ ] and x is 1.
16. The aromatic polyester according to any one of claims 1 to 15, which is used for an optical material.
17. In a method for producing an aromatic polyester by reacting a polyhydric phenol with an aromatic polyvalent carboxylic acid, an acid halide or an acid anhydride thereof, the aromatic polyvalent carboxylic acid, an acid halide or an acid anhydride thereof An aromatic dicarboxylic acid, an acid halide or an acid anhydride thereof, and an aromatic tricarboxylic acid, an acid halide or an acid anhydride thereof, and (a mole of an aromatic tricarboxylic acid, an acid halide or an acid anhydride thereof) Number) / [(mol number of aromatic dicarboxylic acid, acid halide or acid anhydride thereof) + (mol number of aromatic tricarboxylic acid, acid halide or acid anhydride)] = 0.001 to 0.090 A method characterized in that
18. (Mole number of aromatic tricarboxylic acid, acid halide or acid anhydride) / [(Mole number of aromatic dicarboxylic acid, acid halide or acid anhydride) + (Aromatic tricarboxylic acid, acid halide or The process according to claim 17, wherein the number of moles of acid anhydride)] = 0.001 to 0.070.
19. (Mole number of aromatic tricarboxylic acid, acid halide or acid anhydride) / [(Mole number of aromatic dicarboxylic acid, acid halide or acid anhydride) + (Aromatic tricarboxylic acid, acid halide or The process according to claim 17, wherein the number of moles of acid anhydride)] = 0.001 to 0.050.
20. (Mole number of aromatic tricarboxylic acid, acid halide or acid anhydride) / [(Mole number of aromatic dicarboxylic acid, acid halide or acid anhydride) + (Aromatic tricarboxylic acid, acid halide or The method according to claim 17, wherein the number of moles of acid anhydride)] = 0.001 to 0.030.
21. The method according to any one of claims 17 to 20, wherein the aromatic tricarboxylic acid, acid halide or acid anhydride thereof is trimesoyl trichloride.
22. The method according to any one of claims 17 to 21, wherein the aromatic dicarboxylic acid, its acid halide or acid anhydride is isophthaloyl dichloride and / or terephthaloyl dichloride.
23. The method according to any one of claims 17 to 22, wherein the polyhydric phenol is a dihydric phenol.
24. The method according to any one of claims 17 to 22, wherein the polyhydric phenol is bisphenol A.

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