JPH0198618A - Thermosetting polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain the title normally solid, liquid crystal composition which is excellent in storage stability, can form an anisotropic molten phase at a low melting temperature, shows good flow in baking and can give a paint film excellent in appearance, by the esterification of transesterification of a mixture of a specified alcohol with a specified acid. CONSTITUTION:An alcohol or acid mixture (A) comprising 100-50mol.% mesogen group-introducing component of formulas I-IV and 0-50mol.% component other than said mesogen group-introducing component, such as formulas V-VII, and a spacer group-introducing component (B) such as (di)ethylene glycol or adipic acid are esterified or transesterified in an alcohol-excess condition to obtain the title composition comprising repeating units A-X-B [wherein 100-50mol.% of A groups are those composed of at least two benzene rings bonded in para position through an azo, azoxy or the like group or a mesogen group such as 2,6-naphthylene, 0-50mol.% of them are phenylene groups or the like, B is a spacer group such as VIII or IX (wherein n is 2-20 and m is 1-19), and X is an ester group] and terminated with OH, COOH or the like and having a total of an acid number and an OH number of 10-200.

Description

Detailed Description of the Invention Technical Field The present invention relates to a novel polyester resin composition capable of forming an anisotropic melt phase, having a reactive functional group of a hydroxyl group and/or a carboxyl group, and exhibiting thermosetting properties. It is related to.

Prior Art Over the past 20 years, many types of low-molecular liquid crystal materials have been synthesized and have been applied as optical display elements for watches, calculators, televisions, and the like. On the other hand, regarding polymer liquid crystals, research on thermotropic liquid crystals attracted attention, and
As seen in fully aromatic polyester resins such as No. 50594 and No. 55-144024, high-strength and highly heat-resistant resins that are easy to melt and mold due to their reduced viscosity due to liquid crystallinity during melting are in the spotlight. . Furthermore, D. Van Luyen et al. (
Eur, Polym, J.

16, 303.1980) W, R, Kringba
u+s, J, $1atanabe(Polymer
, 24.1299.1983; Polymer processing, note.

[1], 39, 1985), and due to the repeating structure of a rigid mesogenic group and a flexible bent chain (spacer group) in the main chain, it exhibits liquid crystallinity (optical anisotropy) similar to low-molecular liquid crystals. Express. This main-chain polymer liquid crystal generally has a long relaxation time for molecular motion, and is not necessarily suitable for applications in high-responsive displays such as low-molecular liquid crystals. Application research is underway for thermal recording media, wavelength selective transmission, and reflective films.

However, all mono-liquid crystalline polyester resins that have been proposed so far are thermoplastic resins, and if terminal functional groups remain, the resin is likely to thermally decompose at high melting temperatures of 250 to 400°C. It has a blocked ester bond such as an acetyl group or phenyl ester, and its molecular weight is specified to be a high molecular weight of 100,000 to several hundred thousand, which is suitable for melt molding. As such, conventional thermoplastic liquid crystalline polyester resins are not suitable for film molding, fibers, etc. because they do not contain reactive functional groups at the terminals, or even if they remain, the acid value is at most 1O or less. However, it could not be used as a thermosetting resin for paints, etc.

Problems to be Solved by the Invention Therefore, if a polyester resin that can be used as a thermosetting resin and can form an anisotropic melt phase at a lower melting temperature can be obtained, it would be extremely useful in the paint field. It is an object of the present invention to provide such a novel thermosetting polyester resin.

Means for Solving the Problems According to the present invention, the above object is achieved by the formula A group in which the above benzene ring is bonded at the para position with azo, azoxy, ester or transvinylene, and 2.6-
A mesogenic group selected from the group consisting of naphthylene groups, 5
Less than 0 mol% is p-phenylene group, Otori-phenylene group,
It may be a 0-phenylene group or a trans-1,4-cyclohexylene group; B is -(CH2). −
or - (spacer group represented by CH2CH20→rCH2CH2-; n is an integer of 2 to 20, m is an integer of 1 to 19; X is an ester bond), and each adjacent unit is bonded with an ester bond. , the terminal is an OH or C0OH group or a reactive derivative thereof, and the sum of the acid value and OH value is 10.
This is achieved with a thermosetting polyester resin composition that is capable of forming an anisotropic melt phase and has a molecular weight of 200 to 200%.

The polyester resin of the present invention has a mesogenic group (A) and a spacer group (B) as represented by repeating units of A-X-B.
) are alternately bonded by ester bonds, and the main template has a polymer liquid crystal structure in which OH or HO is used as the terminal group.
The polyester of the present invention is clearly distinguishable from conventional main chain type polymeric liquid crystal materials in that it has a crosslinking functional group of OC and contains a thermosetting functional group in a high concentration in the resin. The ingredients incorporated into the resin as 8 are 100
~50 mol% is a group consisting of two or more benzene rings bonded to each other at the para position, such as 4,4'-biphenylene d4
．． 4''-p-tylphenylene () X (such as Less than 50 mol% of 2,6-naphthylene may be P-phenylene, m-phenylene, 0-phenylene or trans-14-cyclohexylene groups.

Since the above component is conveniently incorporated as an acid component of a polyester or as a polyhydric alcohol component, it is preferably derived from a compound whose terminal terminal is a carboxyl group, a carboxylic acid ester, an acid chloride, a hydroxyl group, an acetyl group, or the like. Such representative compounds include the following.

When introduced as a mesogenic group: 1100 C◇X NowC0OH, CH300C■XfuC
00CII 3, U υ U
When introduced as a component other than U mesogenic group: 0 trans 1,4-cyclohekyrine dicarboxylic acid diester These are, of course, only examples of specific compounds used for the purpose of introducing component A of the present invention. However, the present invention is not limited in any way by these compounds.

The component incorporated as B is a spacer group of the formula -(CH2)fi- or =(CH2CH20), -CH2-CH2-, and this spacer group is connected to the aforementioned A component and also to the adjacent A-X-B. The units are each bonded by an ester bond. Therefore, the compounds used to introduce such spacer groups also have terminal ends of OH
Alternatively, COOH or a reactive derivative thereof is preferable, and specifically, the following compounds are used.

Compound having -(CH2)--: ethylene glycol 1,1.3-propanediol, 1
．． 4-butanediol, 1,5-bentanediol, l
.

6-hexanediol, 1,8-octanediol, 1
゜9-nonanediol, 1,10-decanediol, 1
, 12-dodecanediol, aliphatic dicarboxylic acids such as adipic acid, sepatic acid, azelaic acid,
The polyester resin of the present invention, such as compounds having H2・CH20)-CH2-CH2-, diethylene glycol, triethylene glycol, and tetraethylene glycol, is prepared by adding an alcohol or acid raw material compound suitable for introducing the above-mentioned A and B components in a predetermined ratio. can be easily produced using conventional ester formation techniques.

That is, the raw material compound is usually used in excess of alcohol, and 1
The reaction is carried out by esterification or transesterification using a conventional method at a temperature of 30 to 300°C.

The reaction is preferably carried out while passing an inert gas such as nitrogen gas, and if desired, an esterification catalyst or transesterification catalyst is used. Such catalysts include oxides and acetates of metals such as lead, zinc, manganese, barium, calcium, magnesium, lithium, germanium, and antimony, p-)luenesulfonic acid, alkyl titanate, and organotin compounds. etc. are suitable, and are usually used in a proportion of about 0.1 to 0.5% by weight based on the acid component. If the alcohol is excessive, a polyester having a hydroxyl group at the end can be obtained, but if desired, an acid anhydride can be further reacted to form a terminal carboxyl group. Although it is possible to carry out the esterification reaction with excess acid, it is difficult to achieve a homogeneous reaction because the acid is difficult to dissolve or sublimate, and unreacted acid remains. Preferably, a reaction is carried out.

The polyester resin of the present invention contains repeating units in which a relatively rigid mesogenic group (A) having a planar structure and a flexible spacer group (B) are bonded by ester bonds, and are bonded by ester bonds. It constitutes a chain-type polymeric liquid crystal compound, and its terminal end is OH or COOH or a reactive derivative thereof, and the sum of the resin acid value and OH value is 10 to 200.
The molecular weight is preferably controlled between 20 and 100, and exhibits sufficient thermosetting properties.The molecular weight depends on the type of each component selected, but it is generally compatible with a number and average molecular weight of 500 to 20,000 in terms of polystyrene by GPC. The transition temperature is about 80
It is within the range of ~230°C. In addition, in the present invention, less than 50 mol% of the mesogenic group represented by A is replaced with a specific aromatic ring or an organic group having a cyclohexane ring structure, that is, p-phenylene, m-phenylene, 0-phenylene, or 1.
It has been found that even when substituted with 4-cyclohexene, a polyester resin composition suitable for the purpose of the present invention can be obtained without impairing the desired liquid crystallinity.

The thus obtained polyester resin composition according to the present invention is solid at room temperature and has excellent storage stability, and has a large number of hydroxyl groups or carboxyl groups as crosslinkable functional groups.
By selecting aminoplast, etc., or a compound having a glycidyl group for carboxyl as a curing agent, it can be used in thermosetting paints, and since it is liquid crystalline, it has extremely good flowability during baking. It is extremely useful industrially as it can provide a coating film with excellent appearance.

The present invention will be explained below with reference to Examples.

(Left below) Example 1 10 moles of 4,4'-diphenylcarboxylic acid dimethyl ester, 11 moles of 1,9-nonanediol, and 2 moles of dibutyltin oxide were placed in a reactor equipped with a heating device, a stirrer, a nitrogen inlet tube, and a fractionating column. .2g was charged and heating was started under dry nitrogen to melt the raw materials at 0 and then 130-230°C.
Methanol was distilled off by transesterification at a temperature of . After keeping the temperature at 230° C. and collecting methanol 7601, the mixture was reacted for 1 hour under a reduced pressure of 10 mmHH to complete the transesterification reaction to obtain polyester (①).

The obtained polyester had a curable functional group with a hydroxyl value of 25, and as a result of GPC measurement using trichlorobenzene as a solvent and a column temperature of 135° C., the number average molecular weight (in terms of polystyrene) was 6,800.

Furthermore, when this polyester was heated at a rate of 10°C per minute using a differential scanning calorimeter (DSC), it showed a large sharp endothermic peak at about 148°C, and when cooled at a rate of 10°C per minute, it showed a large sharp endothermic peak at about 116°C. A large sharp exothermic peak was also observed.

Furthermore, the texture based on optical anisotropy was confirmed by observation under orthogonal polarized light using a microscope equipped with a heat stage.

The thermosetting polyester resin (■) which can form an anisotropic melt phase obtained here and the blocked isocyanate compound Fulleran 01 (epsilon-cal 10 lactam block of IP opening (■), Ba
Manufactured by Yer, NCO equivalent = 365) as OH7/NCO
They were blended at an equivalent ratio of 1/1, and 1.0% by weight/'total solids of dibutyltin dilaurate was added as a curing catalyst, and then ground to a particle size of 10μ or less. This powder sample was applied onto a tin plate and baked at 230°C for 20 minutes.

It was confirmed that the obtained cured film was transparent and smooth and could be applied as a thermosetting polyester resin. The results are shown in Table 1.

Example 2 The polyester rIOQg obtained in Example 1 was charged into a reaction vessel, and while kept in a molten state at 150°C under dry nitrogen, 6.65 g of phthalic anhydride was added and reacted for 1 hour to obtain polyester ■. .

The obtained polyester had a hydroxyl value of 1.0 and an acid value of 22.
As a result of GPC measurement using trichlorobenzene as a solvent and a column temperature of 135° C., the number average molecular JL (in terms of polystyrene) was 7100.

Furthermore, when this polyester was heated at a rate of 10°C per minute using a differential scanning calorimeter (DSC), it exhibited a large sharp endothermic peak at approximately 148°C, and when cooled at a rate of 10°C per minute, it exhibited a large sharp endothermic peak at approximately 108°C. A large sharp exothermic peak was also observed.

Furthermore, the texture based on optical anisotropy was confirmed by observation under orthogonal polarization using a heat stage 1-m microscope.

The thermosetting polyester resin ■ which can form an anisotropic melt phase obtained here and the epoxy resin Evototo YD~01
1 (manufactured by Tobu Kasei Co., Ltd., epoxy equivalent = 475) was blended at an OH/epoxy equivalent ratio of 1/1, and then ground to a particle size of 10μ or less. Apply this powder sample on a tin plate and
Baked at 30°C for 20 minutes. The obtained cured film was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 3 3 moles of 4.4″-diphenylcarboxylic acid dimethyl ester, 4 moles of 1,9-nonanediol, and 0.8 g of dibutyltin oxide were charged, and heating under dry nitrogen was started to melt the raw materials. Methanol was distilled out by transesterification at a temperature of 230°C.
After keeping the mixture warm and collecting methanol 2301, the mixture was reacted for 1 hour under a reduced pressure of 10 mmHg to complete the transesterification reaction to obtain polyester (2).

The obtained polyester had a curable functional group with a hydroxyl value of 82, and as a result of GPC measurement using trichlorobenzene as a solvent and a column temperature of 135° C., the number average molecular weight (in terms of polystyrene) was 1,550.

Furthermore, when this polyester was heated at a rate of 10°C per minute using a differential scanning calorimeter (DSC), it showed a large endothermic peak at about 138°C, and when it was cooled at a rate of 10°C per minute, it showed a similarly large endothermic peak at about 95°C. An exothermic peak was observed.

Furthermore, the texture based on optical anisotropy was confirmed by observation under orthogonal light leakage using a microscope with a heat stage.

The thermosetting polyester resin ① which can form an anisotropic melt phase obtained here was subjected to a curability test in the same manner as in Example 1. The results are shown in Table 1.

Example 4 100 g of polyester I [I obtained in Example 3 was charged into a reaction vessel, 21.7 parts of phthalic anhydride was added while keeping it in a molten state at 150°C under dry nitrogen, and the mixture was reacted for 1 hour to form polyester I got it.

The obtained polyester had a hydroxyl value of 1.5 and an acid value of 68.
As a result of GPC measurement using trichlorobenzene as a solvent and a column temperature of 135° C., the number average molecular weight (in terms of polystyrene) was 1830.

In addition, when this polyester was heated at a rate of 10°C per minute using a differential scanning calorimeter (DSC), it showed a large endothermic peak at about 135°C, and when it was cooled at a rate of 10°C per minute, it showed a similarly sharp peak at about 96°C. An exothermic peak was observed.

Furthermore, the texture based on optical anisotropy was confirmed by observation under orthogonal conditions using a microscope with a heat stage.

The thermosetting polyester resin 4 capable of forming an anisotropic melt phase obtained here was subjected to a curability test in the same manner as in Example 2. The results are shown in Table 1.

Example 5 7 moles of 4.4'-diphenylcarboxylic acid dimethyl ester, 8 moles of 1,9-nonanediol, and 1.5 g of dibutyltin oxide were charged, and heating under dry nitrogen was started to melt the raw materials. Then, a transesterification reaction was carried out at a temperature of 130 to 230°C to distill methanol. 230℃
After keeping warm and collecting methanol 5301, polyester V was obtained by reacting for 1 hour under a reduced pressure of 10 Hg to complete the transesterification reaction.

The obtained polyester had a hard arsenic functional group with a hydroxyl value of 37, and as a result of GPC measurement using trichlorobenzene as a solvent and a column temperature of 135° C., the number average molecular weight (in terms of polystyrene) was 4,000.

In addition, when this polyester was heated at 10°C per minute using a differential scanning calorimeter (DSC), it showed a large sharp endothermic peak at about 180°C, and when cooled at 10°C per minute, it showed the same temperature at about 173°C. A large sharp exothermic peak was observed.

Furthermore, the texture based on optical anisotropy was confirmed by observation under orthogonal polarized light using a microscope equipped with a heat stage.

The thermosetting polyester resin V capable of forming an anisotropic melt phase obtained here was subjected to a curability test in the same manner as in Example 1. The results are shown in Table 1.

Example 6 7 moles of 4.4'-diphenylcarboxylic acid dimethyl ester, 8 moles of 1,6-hexanediol, and 1.5 g of dibutyltin oxide were charged, and heating under dry nitrogen was started.
The raw materials were melted. Then, a transesterification reaction was carried out at a temperature of 130 to 230°C to distill methanol. 230
After keeping the temperature at ℃ and collecting 530 ml of methanol, the mixture was reacted for 1 hour under a reduced pressure of 10 m+aHH to complete the transesterification reaction to obtain polyester ①.

The obtained polyester had a curable functional group with a hydroxyl value of 40, and as a result of GPC measurement using I-lychlorobenzene as a solvent and a column temperature of 135° C., the number average molecular weight (in terms of polystyrene) was 4,250.

Furthermore, when this polyester was heated at a rate of 10°C per minute using a differential scanning calorimeter (DSC), it exhibited a large sharp endothermic peak at about 215°C, and when cooled at a rate of 10°C per minute, it showed a similar peak at about 180°C. A large sharp exothermic peak was observed.

Furthermore, the texture based on optical anisotropy was confirmed by observation under orthogonal polarization using a heat-stage converging microscope.

The thermosetting polyester resin ① which can form an anisotropic melt phase obtained here was subjected to a curability test in the same manner as in Example 1. The results are shown in Table 1.

Example 7 8 mol of 4.4'-diphenylcarboxylic acid dimethyl ester, 2 mol of terephthalic acid dimethyl ester, 11 mol of 1.9-nonanediol, 2.2 g of dibutyltin oxide
was charged, heating was started under dry nitrogen, the raw materials were melted, and then a transesterification reaction was carried out at a temperature of 130 to 230°C to distill methanol.

After keeping the temperature at 230° C. and collecting methanol 7451, the mixture was reacted for 1 hour under a reduced pressure of 10 mmHH to complete the transesterification reaction to obtain polyester ①.

The obtained polyester has a curable functional group with a hydroxyl value of 26, and as a result of GPC measurement using trichlorobenzene as a solvent and a column temperature of 135°C, it has a value of several thousand.

The average molecular weight (in terms of polystyrene) was 6,100.

Furthermore, when this polyester was heated at a rate of 10°C per minute using a differential scanning calorimeter (DSC), it showed a large endothermic peak at about 125°C, and when it was cooled at a rate of 10°C per minute, it showed a similarly large endothermic peak at about 83°C. An exothermic peak was observed.

Furthermore, the texture based on optical anisotropy was confirmed by observation under orthogonal polarized light using a microscope equipped with a heat stage.

The thermosetting polyester resin ① which can form an anisotropic melt phase obtained here was subjected to a curability test in the same manner as in Example 1. The results are shown in Table 1.

Example 8 6 moles of 4.4'-diphenylcarboxylic acid dimethyl ester, 4 moles of terephthalic acid dimethyl ester, 11 moles of 1.9-nonanediol, 2.0 g of dibutyltin oxide
was charged and heating under dry nitrogen was started to melt the raw materials. Then, a transesterification reaction was carried out at a temperature of 130 to 230°C to distill methanol.

After keeping the temperature at 230 DEG C. and collecting methanol 7601, the mixture was reacted for 1 hour under a reduced pressure of 10 mm 1-1 g to complete the transesterification reaction, thereby obtaining polyester (2).

The obtained polyester had a curable functional group with a hydroxyl value of 27, and as a result of GPC measurement using trichlorobenzene as a solvent and a column temperature of 135° C., the number average molecular weight (in terms of polystyrene) was 5,900.

In addition, when this polyester was heated at a rate of 10°C per minute using a differential scanning calorimeter (DSC), it showed a broad endothermic peak at about 95°C, and when cooled at a rate of 10°C per minute,
A similarly broad exothermic peak was observed at about 83°C.

Furthermore, the texture based on optical anisotropy was confirmed by observation under orthogonal polarized light using a microscope equipped with a heat stage.

The thermosetting polyester resin ① which can form an anisotropic melt phase obtained here was subjected to a curability test in the same manner as in Example 1. The results are shown in Table 1.

Example 9 1000g of toluene and 100g of pyridine as reaction solvents
0.5 mol of 2,6-naphthalene dicarboxylic acid chloride and 55 mol of tetraethylene glycol were added to the reaction vessel containing g, and the reaction was started under dry nitrogen.
The reaction was carried out at a temperature of 100°C. 1780cm by IR
The reaction was carried out until the absorption peak based on the carboxylic acid chloride disappeared, to obtain polyester (2).

The obtained polyester had a curable functional group with a hydroxyl value of 30, and as a result of GPC measurement using trichlorobenzene as a solvent and a column temperature of 135° C., the number average molecule j1 (in terms of polystyrene) was 4900.

In addition, when this polyester was heated at a rate of 10°C per minute using a differential scanning calorimeter (DSC), it showed a large sharp endothermic peak at about 195°C, and when cooled at a rate of 10°C per minute,
An exothermic peak was also observed at about 183°C.

Furthermore, the texture based on optical anisotropy was confirmed by observation under direct polarized light using a microscope equipped with a heat stage.

The thermosetting polyester resin (1) capable of forming an anisotropic melt phase obtained here was subjected to a curability test in the same manner as in Example 1. The results are shown in Table 1.

Example 10 Toluene 1000g, pyridine 100g as reaction solvent
4-[4'-(carbonyl chloride)benzoyloxy 1benzoic acid chloride was added to a reaction vessel containing 0.
5 mol, 0.55 mol of 1,9-nonanediol were subsequently charged, preheating under dry nitrogen was started and the reaction was carried out at a temperature of 100°C. Polyester

The obtained polyester had a curable functional group with a hydroxyl value of 27, and as a result of GPC measurement using trichlorobenzene as a solvent and a column temperature of 135° C., the number average molecular weight (in terms of polystyrene) was 5,300.

Furthermore, when this polyester was heated at a rate of 10°C per minute using a differential scanning calorimeter (DSC), it showed a large sharp endothermic peak at approximately 165°C, and when cooled at a rate of 10°C per minute,
An exothermic peak was also observed at about 134°C.

Furthermore, the texture based on optical anisotropy was confirmed by observation under direct polarized light using a heat-staged microscope.

The thermosetting polyester resin X that can form an anisotropic melt phase obtained here was subjected to a curability test in the same manner as in Example 1. The results are shown in Table 1.

Comparative example 1 4.4'-diphenylcarboxylic acid dimethyl ester 20
21 moles of 1.6-hexanediol and 5.0 g of dibutyltin oxide were charged, and preheating under dry nitrogen was started to melt the raw materials. Then, a transesterification reaction was carried out at a temperature of 130 to 230°C to distill methanol. 23
After keeping the temperature at 0° C. and collecting 1500 ml of methanol, polyester A was obtained by reacting for 5 hours under a reduced pressure of 1 mmHg to complete the transesterification reaction.

The obtained polyester has a curable functional group with a hydroxyl value of 5, trichlorobenzene as a solvent, and a column temperature of 135
As a result of GPC measurement at ℃, the number average molecular weight (polystyrene equivalent) was 28.000.

Furthermore, when this polyester was heated at a rate of 10°C per minute using a differential scanning calorimeter (DSC), it showed a large endothermic peak at about 215°C, and when cooled at a rate of 10°C per minute, it showed the same temperature at about 180°C. A large exothermic peak was observed.

Furthermore, the texture based on optical anisotropy was confirmed by observation under orthogonal polarization using a heat stage 1-inch microscope.

A curability test was conducted on the thermosetting polyester resin A capable of forming an anisotropic melt phase obtained here in the same manner as in Example 1, but the cured film was a cloudy brittle film with a particle shape. However, it cannot be used as a thermosetting polyester resin. The results are shown in Table 1.

Comparative Example 2 4.4°-diphenylcarboxylic acid dimethyl ester 10
mol, 11 mol of 1.4-butanediol, and 2.0 g of dibutyltin oxide were charged, and heating over dry nitrogen was started.
The raw materials were melted and then transesterified at a temperature of 130 to 270°C to distill methanol. 270
After keeping the temperature at ℃ and collecting methanol 7451, polyester B was obtained by reacting for 1 hour under a reduced pressure of 10 emHg to complete the transesterification reaction.

The obtained polyester has a curable functional group with a hydroxyl value of 34, trichlorobenzene as a solvent, and a column temperature of 13
As a result of GPC measurement at 5° C., the number average molecular weight (in terms of polystyrene) was 4,400.

In addition, when this polyester was heated at a rate of 10°C per minute using a differential scanning calorimeter (DSC), it showed a large sharp endothermic peak at about 255°C, and when cooled at a rate of 10°C per minute, it showed a similar peak at about 245°C. A large sharp exothermic peak was observed.

Furthermore, the texture based on optical anisotropy was confirmed by observation under orthogonal polarized light using a microscope equipped with a heat stage.

The thermosetting polyester resin B capable of forming an anisotropic melt phase obtained here was subjected to a curability test in the same manner as in Example 1, but it did not melt and the particle shape remained.
Cannot be used as a thermosetting polyester resin. The results are shown in Table 1.

Comparative Example 3 2 mol of 4.4'-diphenylcarboxylic acid dimethyl ester, 8 mol of terephthalic acid dimethyl ester, 11 mol of 1.9-nonanediol, 2.0 g of dibutyltin oxide
was charged and heating over dry nitrogen was started to melt the raw materials. Then, a transesterification reaction was carried out at a temperature of 130 to 230°C to distill methanol.

After keeping the temperature at 230°C and collecting methanol 7451, polyester C was obtained by reacting for 1 hour under a reduced pressure of 10 mmHH to complete the transesterification reaction.

The obtained polyester has a curable functional group with a hydroxyl value of 8, trichlorobenzene is used as a solvent, and the column temperature is 135.
As a result of GPC measurement at ℃, the number average molecular weight (polystyrene equivalent) was 3940.

Further, when this polyester was heated at 10° C. per minute using a differential scanning calorimeter (DSC), no clear endothermic peak was observed. Similarly, no exothermic peak was observed when cooling was performed at 10° C. per minute.

Furthermore, observation under orthogonal polarization using a microscope with a heat stage did not reveal any texture based on optical anisotropy.

The polyester resin C obtained here was an amorphous resin and did not have a phase transition point.

Example 11 7 moles of 1.10-decanedicarboxylic acid dimethyl ester, 8 moles of 4.4'-biphenol, and 1.5 g of dibutyltin oxide were charged, and heating over dry nitrogen was started to melt the raw materials. Then, a transesterification reaction was carried out at a temperature of 130 to 250°C to distill methanol. After keeping the temperature at 250° C. and collecting 500 ml of methanol, the mixture was reacted for 2 hours under a reduced pressure of 10 degrees Hg to complete the transesterification reaction. After cooling to 200°C, gradually add 00g of N-methylpyrrolidone, then add 150g of N-methylpyrrolidone.
While maintaining the temperature at 0°C, 295 g of phthalic anhydride was added and reacted for 1 hour, and then added dropwise to a mixing tank containing 5000 ml of toluene with stirring.

The resin precipitated in this mixing tank is filtered and polyester
I got I.

The obtained polyester has a curable functional group with a hydroxyl value of 0.1 and an acid value of 35, and as a result of GPC measurement using trichlorobenzene as a solvent and a column temperature of 135°C, the number average molecular weight (in terms of polystyrene) was 4680. Ta.

Furthermore, when this polyester was heated at a rate of 10°C per minute using a differential scanning calorimeter (DSC), it showed a large sharp endothermic peak at about 205°C, and when cooled at a rate of 10°C per minute, it showed a large sharp endothermic peak at about 183°C. A large sharp exothermic peak was also observed.

Furthermore, the texture based on optical anisotropy was confirmed by observation under orthogonal light leakage using a microscope with a heat stage.

The thermosetting polyester resin XI which can form an anisotropic melt phase obtained here was subjected to a curability test in the same manner as in Example 2. The results are shown in Table 1.

(Margin below)

Claims (4)

[Claims] (1) Formula A-X-B (In the formula, 100 to 50 mol% of A is a group formed by two or more benzene rings bonded to each other at the para position, , azoxy, ester or transvinylene, and 2,6-
A mesogenic group selected from the group consisting of naphthylene groups, 5
Less than 0 mol% is p-phenylene group, m-phenylene group,
It may be an o-phenylene group or a trans-1,4-cyclohexylene group; B is -(CH_2)_
A spacer group represented by n- or ▲ (there are mathematical formulas, chemical formulas, tables, etc.); n is an integer of 2 to 20, m is an integer of 1 to 19; X is an ester bond), and each adjacent unit is connected by an ester bond, and the terminal is an OH or COOH group or a reactive derivative thereof, and the sum of the acid value and OH value is 10.
200, a thermosetting polyester resin composition capable of forming an anisotropic melt phase. (2) The composition according to claim 1, which has a phase transition melting temperature of 80 to 230°C. (3) The composition according to claim 1, which has a hydroxyl value of 20 to 100. (4) The composition according to claim 1, which has a number average molecular weight of 500 to 20,000.