TWI445732B - Liquid crystal polyester and the manufacturing process thereof - Google Patents

Description

Liquid crystalline polyester and method of producing the same

The present invention relates to a technique for controlling an average chain length of a structural unit obtained from an aromatic hydroxycarboxylic acid of a high heat-resistant liquid crystalline polyester to a very short range of 0.1 to 1, and a liquid crystalline polycondensation obtained by the technique. An ester and a composition thereof, and a molded article formed therefrom.

The liquid crystalline polyester is used in the electric and electronic fields because of its excellent heat resistance, fluidity, dimensional stability, and flame retardancy. In recent years, the demand for liquid crystalline polyesters has increased, and in particular, the demand for high heat-resistant liquid crystalline polyesters called I-types having a heat distortion temperature of 300 ° C or higher has been increasing. The liquid crystalline polyester is a liquid crystalline polyester obtained by using a structural unit obtained from p-hydroxybenzoic acid or 2-hydroxy-6-naphthoic acid as a mesogen unit; and in 2-hydroxybenzoic acid Or a structural unit obtained by 2-hydroxy-6-naphthoic acid, a mixture of an aromatic diol/aromatic dicarboxylic acid or a copolymerized para-alkyl decanoate. Among them, a liquid crystalline polyester obtained by using 2-hydroxy-6-naphthoic acid as a liquid crystal original unit is known, and a liquid crystalline polyester obtained by using p-hydroxybenzoic acid as a liquid crystal original unit has poor heat resistance. It is excellent in dielectric properties, dimensional stability, and light resistance (for example, Patent Documents 1 to 6).

Patent Document 1 describes a liquid crystalline polyester obtained by copolymerizing 2-hydroxy-6-naphthoic acid, an aromatic diol, or an aromatic dicarboxylic acid. However, the liquid crystalline polyester obtained by copolymerizing 2-hydroxy-6-naphthoic acid, an aromatic diol, or an aromatic dicarboxylic acid has low melting and insufficient heat resistance. Patent Document 2 describes a liquid crystalline polyester obtained by adding an additive to a specific monomer. However, heat resistance or insulation breakdown resistance is lowered due to the influence of the additive. Patent Documents 3 to 6 describe a liquid crystalline polyester obtained by copolymerizing 2-hydroxy-6-naphthoic acid, an aromatic diol, and an aromatic dicarboxylic acid. However, in Patent Documents 3 to 6, solid phase polymerization is carried out for the purpose of high molecular weight, and the polymer has low randomness, dimensional stability, and fluidity.

Prior technical literature Patent literature

Patent Document 1: JP-A-56-10562

Patent Document 2: JP-A-2002-37869

Patent Document 3: JP-A-2004-196930

Patent Document 4: JP-A-2004-244452

Patent Document 5: JP-A-2005-213418

Patent Document 6: JP-A-2007-100078

The present invention provides a liquid crystalline polyester which is particularly excellent in fluidity, has low heterogeneity, is excellent in toughness, low in gas property, heat resistance, and high in insulation breakdown resistance, and a method for producing the same, and provides a composition thereof and The molded article formed by the method.

In order to solve the problem, the inventors of the present invention have found that by controlling the chain length of the structural unit obtained from 2-hydroxy-6-naphthoic acid, it is possible to obtain a liquid crystalline polyester having particularly improved properties. The invention has been achieved.

That is, the present invention provides a liquid crystalline polyester characterized by having 38 to 74 mol% of a structural unit derived from a hydroxycarboxylic acid and 13 to 31 mol% of a 4,4'-dihydroxyl linkage. a structural unit obtained from benzene and 13 to 31 mol% of a structural unit obtained from 2,6-naphthalenedicarboxylic acid, a total of 100 mol% of a liquid crystalline polyester, a structural unit obtained from a hydroxycarboxylic acid 89 mol% or more is a structural unit obtained from 2-hydroxy-6-naphthoic acid, and the structural unit obtained from 2-hydroxy-6-naphthoic acid has an average chain length of 0.1 to 1.

According to the present invention, it is possible to provide a liquid crystalline polyester which is particularly excellent in fluidity, has low anisotropy, is excellent in toughness, low in gas properties, heat resistance, and high in insulation breakdown resistance, and a method for producing the same, and a composition thereof and A molded article formed by the above.

Hereinafter, the present invention will be described in detail. The liquid crystalline polyester (A) of the present invention has 38 to 74 mol% of a structural unit derived from a hydroxycarboxylic acid, and 13 to 31 mol% of a structure obtained from 4,4'-dihydroxybiphenyl. Unit and 13 to 31 mol% of the structural unit obtained from 2,6-naphthalenedicarboxylic acid, a total of 100 mol% of the liquid crystalline polyester, 89 mol% or more of the structural unit obtained from the hydroxycarboxylic acid It is a structural unit obtained from 2-hydroxy-6-naphthoic acid, and the structural unit obtained from 2-hydroxy-6-naphthoic acid has an average chain length of 0.1 to 1.

In the present invention, the liquid crystalline polyester is a polyester which is called a thermotropic liquid crystal polymer which exhibits optical anisotropy upon melting.

In the present invention, the structural unit obtained from the hydroxycarboxylic acid, the structural unit obtained from 4,4'-dihydroxybiphenyl, and the structural unit derived from 2,6-naphthalenedicarboxylic acid means such The structural unit forms an ester bond to form a polyester.

In the liquid crystalline polyester (A) of the present invention, a hydroxycarboxylic acid having a structural unit obtained from a hydroxycarboxylic acid can be, for example, 2-hydroxy-6-naphthoic acid, 2-hydroxy-3-naphthoic acid or 1-hydroxyl group. -4-naphthoic acid, m-hydroxybenzoic acid, 4'-hydroxy-4-biphenylcarboxylic acid, 4-hydroxy-2-phenylbenzoic acid, 3-tert-butyl-4-hydroxybenzoic acid, 3, 5-di-t-butyl-4-hydroxybenzoic acid, 4-hydroxycinnamic acid, and such methyl ester derivatives are used as starting materials. As the hydroxycarboxylic acid, 2-hydroxy-6-naphthoic acid is preferred.

In the liquid crystalline polyester (A) of the present invention, as a structural unit obtained from 4,4'-dihydroxybiphenyl, for example, 4,4'-dihydroxybiphenyl can be used as a raw material.

In the liquid crystalline polyester (A) of the present invention, as a structural unit obtained from 2,6-naphthalene dicarboxylic acid, for example, 2,6-naphthalene dicarboxylic acid or 2,6-naphthalene dicarboxylic acid can be used. The structural unit obtained by the ester-forming derivative is used as a raw material.

The liquid crystalline polyester (A) of the present invention preferably has a methoxycarbonyl group as a terminal group. In particular, when dimethyl 2,6-naphthalenedicarboxylate is used as a raw material, it becomes a liquid crystalline polyester having a methoxycarbonyl group and/or a hydroxyl group as a terminal group, and it is possible to suppress generation of acetic acid gas or carbonic acid gas and reduce gas. The effect of the amount.

The liquid crystalline polyester (A) of the present invention has a total of 100% by mole based on the total structural unit, in order to obtain excellent fluidity, low heterogeneity, excellent toughness, low gas, and improved insulation breakdown resistance. 38 to 74 mol% of the structural unit derived from the hydroxycarboxylic acid, 31 to 13 mol% of the structural unit derived from 4,4'-dihydroxybiphenyl, and 31 to 13 mol% of 2, The structural unit obtained from 6-naphthalenedicarboxylic acid. The liquid crystalline polyester (A) of the present invention has a structure of 40 to 44 mol% of a structural unit derived from a hydroxycarboxylic acid and 28 to 30 mol% of a structure obtained from 4,4'-dihydroxybiphenyl. The unit and 28 to 30 mol% of the structural unit derived from 2,6-naphthalene dicarboxylic acid are preferred.

The liquid crystalline polyester (A) of the present invention has a hydroxycarboxylic acid of 2-hydroxy-6-naphthoic acid and has 38 to 74 mol% of a structural unit derived from a hydroxycarboxylic acid, and 13 to 31 mol%. The structural unit derived from 4,4'-dihydroxybiphenyl and 13 to 31 mol% of the structural unit derived from 2,6-naphthalene dicarboxylic acid are preferred.

The liquid crystalline polyester (A) of the present invention has a hydroxycarboxylic acid of 2-hydroxy-6-naphthoic acid and has 40 to 44 mol% of a structural unit derived from a hydroxycarboxylic acid, and 28 to 30 mol%. The structural unit derived from 4,4'-dihydroxybiphenyl and 28 to 30 mol% of the structural unit derived from 2,6-naphthalene dicarboxylic acid are more preferable.

Further, in order to reduce the effect of the anisotropy, the liquid crystalline polyester (A) of the present invention is derived from 2-hydroxy-6-naphthoic acid in an amount of 89 to 99.9 mol% of the structural unit obtained from the hydroxycarboxylic acid. The structural unit obtained, and 0.1 to 11 mol% is preferably a structural unit obtained from 3,5-di-t-butyl-4-hydroxybenzoic acid. For the purpose of reducing the effect of the anisotropy, the liquid crystalline polyester (A) of the present invention is obtained from 2-hydroxy-6-naphthoic acid in a 95 to 98.9 mol% of a structural unit obtained from a hydroxycarboxylic acid. The structural unit, and 1.1 to 5 mol% is more preferably a structural unit derived from 3,5-di-t-butyl-4-hydroxybenzoic acid.

When a structural unit derived from 3,5-di-t-butyl-4-hydroxybenzoic acid is used, since 3,5-di-t-butyl-4-hydroxybenzoic acid is interposed therebetween, the 2-hydroxy group is moderated. The difference in the polymerization rate of 6-naphthoic acid and other monomers can suppress the bumping caused by the two-phase system in the polymerization process, and the margin of production conditions becomes broad, and the obtained liquid crystalline polycondensation can be improved. The directionality of the ester is preferred.

Among the structural units of the liquid crystalline polyester (A) of the present invention, the structural unit derived from 4,4'-dihydroxybiphenyl and the molar ratio of the structural unit obtained from 2,6-naphthalenedicarboxylic acid It is preferably 0.8 to 1.2, more preferably 0.9 to 1.1, and even more preferably 1.0. When the molar ratio of the structural unit obtained from 4,4'-dihydroxybiphenyl to the structural unit derived from 2,6-naphthalenedicarboxylic acid is 0.8 to 1.2, a sufficient polycondensation rate can be obtained. In the case of 0.9 to 1.1, it is more preferable because the amount of gas is small, and at 1.0, a liquid crystalline polyester (A) having particularly excellent fluidity and low heterogeneity and high heat resistance can be obtained. optimal.

The liquid crystalline polyester (A) of the present invention has an average chain length of 0.1 to 1 in a structural unit obtained from 2-hydroxy-6-naphthoic acid. When the average chain length of the structural unit obtained from 2-hydroxy-6-naphthoic acid is 0.1 to 1, the molecular chain interaction and the crystallization site bias of the structural unit obtained from 2-hydroxy-6-naphthoic acid It can improve fluidity or heterogeneity and low toughness. The structural unit obtained from 2-hydroxy-6-naphthoic acid has an average chain length of preferably 0.2 to 0.8.

When the average chain length of the structural unit obtained from 2-hydroxy-6-naphthoic acid is less than 0.1, the ratio of the original liquid crystal unit obtained from the structural unit derived from 2-hydroxy-6-naphthoic acid in the molecular chain It is too low to exhibit the characteristics as a liquid crystalline polyester.

Further, when the average chain length of the structural unit obtained from 2-hydroxy-6-naphthoic acid is more than 1, the properties of the liquid crystalline polyester which should be obtained originally cannot be obtained, and in particular, the fluidity is lowered and the anisotropy is increased.

The chain length of the structural unit obtained from 2-hydroxy-6-naphthoic acid of the present invention is illustrated.

The chain length of the structural unit obtained from 2-hydroxy-6-naphthoic acid of the present invention means whether the structural unit obtained from 2-hydroxy-6-naphthoic acid and a plurality of 2-hydroxy-6-naphthoic acid The obtained structural unit does not pass through the structural unit obtained from another monomer to form an ester bond and is an index of bonding.

In Fig. 1, the chain length of the structural unit obtained from 2-hydroxy-6-naphthoic acid is explained. Fig. 1 is a structural unit obtained by, for example, 2-hydroxy-6-naphthoic acid, a structural unit derived from 4,4'-dihydroxybiphenyl, and a product obtained from 2,6-naphthalenedicarboxylic acid. The case of three types of structural units. When the 2-hydroxy-6-naphthoic acid-based ester bond is bonded to 4,4'-dihydroxybiphenyl or 2,6-naphthalene dicarboxylic acid, the chain length is 0 (Fig. 1, i). 2-hydroxy-6-naphthoic acid is bonded to 2-hydroxy-6-naphthoic acid through an ester bond, and each bond is bonded to 2-hydroxy-6-naphthoic acid via a transester bond, and the bond length is 1 (Fig. 1, ii). Similarly, when three 2-hydroxy-6-naphthoic acid groups are bonded via an ester bond, and both ends of the two-permeate ester bond are bonded to 2-hydroxy-6-naphthoic acid, the bond length is 2 (Fig. 1) , iii).

In the present invention, the average chain length of the structural unit obtained from 2-hydroxy-6-naphthoic acid is the average number of chain lengths of structural units derived from 2-hydroxy-6-naphthoic acid in the liquid crystal polyester. value. The average chain length is the average of the chain lengths of the structural units obtained from the total 2-hydroxy-6-naphthoic acid present in the polymer, and can be measured by nuclear magnetic resonance apparatus (NMR) spectrometry. For example, by using ¹³ C-NMR, the polymer is dissolved in a mixed solution of pentafluorophenol/heavy chloroform, and the carbon shift at the second position based on the structural unit obtained from 2-hydroxy-6-naphthoic acid is transmitted through the ester bond. The structure (spike A) bonded to the 6th position of the structural unit obtained from other 2-hydroxy-6-naphthoic acid and the structure bonded to 2,6-naphthalenedicarboxylic acid (spike B) Separated from the respective peak areas (each being the peak A area (a) and the peak B area (b)), according to the average chain length of the structural unit obtained from 2-hydroxy-6-naphthoic acid = a / b The calculation is ok.

In Fig. 2, a schematic diagram of a graph by ¹³ C-NMR used for calculating the average chain length of the structural unit obtained from 2-hydroxy-6-naphthoic acid is used. a represents a carbon atom at the second position of a structural unit derived from 2-hydroxy-6-naphthoic acid which is ester-bonded with a hydroxyl group at the second position and a structural unit derived from a carboxylic acid of another 2-hydroxy-6-naphthoic acid. The peak intensity of the ¹³ C-NMR peak A. b is a carbon atom at the second position of the structural unit derived from 2-hydroxy-6-naphthoic acid which is ester-bonded with a hydroxy group at a second position and a carboxylic acid derived from a structural unit of 2,6-naphthalenedicarboxylic acid. Peak intensity of ¹³ C-NMR spike B.

The method for calculating the average chain length can be exemplified by Polymer Journal, 25 (3), 315 (1993). According to the method of the final sequence length of the method of Du Yong et al., the monomer having a p-hydroxybenzhydryl structural unit of 1 and not ester-bonded with a p-hydroxybenzhydryl structural unit is used as the Average. The sequence length=1, but since the single system does not perform the chain locking operation, it is not preferable to represent the monomer as the chain length when the chain length is 1, so in the present invention, the average chain length of the monomer is taken as 0, and is used. The calculation formula obtained by subtracting 1 from the calculation formula of the end Yong et al.

The liquid crystalline polyester (A) of the present invention has a coefficient average molecular weight of preferably 3,000 to 25,000, more preferably 5,000 to 20,000, still more preferably 8,000 to 18,000 in terms of mechanical strength and moldability.

The number average molecular weight is obtained by dissolving the liquid crystalline polyester (A) in a soluble solvent such as a pentafluorophenol solvent and measuring it according to the GPC-LS (gel permeation chromatography light scattering) method.

The liquid crystalline polyester (A) of the present invention preferably has a melt viscosity of from 1 to 200 Pa s, more preferably from 10 to 200 Pa s, and particularly preferably from 10 to 100 Pa s. The melt viscosity is a value measured by a Koka-type flow tester under the conditions of a melting point of liquid crystal polyester + 20 ° C and a shear rate of 1,000 / s.

Here, the melting point (Tm) is measured by differential heat, and after observing the endothermic peak temperature (Tm1) which can be observed when the polymer after completion of polymerization is measured from a room temperature of 20 ° C / min, After the temperature of Tm1+20°C was maintained for 5 minutes, the endothermic peak temperature (Tm2) which can be observed when the temperature was temporarily cooled to room temperature under a temperature drop condition of 20° C./min.

The liquid crystalline polyester (A) of the present invention has high toughness, low heterogeneity, low gas, and excellent insulation breakdown resistance.

The liquid crystalline polyester (A) of the present invention is preferably produced by melt polymerization in a temperature range of (melting point + 20) to (melting point + 40 ° C) of the obtained liquid crystalline polyester. By performing melt polymerization in a temperature range of (melting point + 20) to (melting point + 40 ° C) of the obtained liquid crystalline polyester resin, it is possible to impart sufficient heat to homogenize the liquid crystalline polyester. There is no deterioration in coloring or physical properties caused by thermal decomposition of the polymer.

The liquid crystalline polyester (A) of the present invention is more preferably produced by melt polymerization in a temperature range of (melting point + 25) to (melting point + 35 ° C) of the obtained liquid crystalline polyester, and is particularly uniform. The liquid crystalline polyester (A) of the present invention has a structural unit of 2-hydroxy-6-naphthoic acid having an average chain length of 0.1 to 1 and a low heterogeneity and excellent fluidity and toughness.

The melting point of the obtained liquid crystalline polyester depends on the composition value, and melt polymerization of the liquid crystalline polyester can be carried out at least at a temperature at which the product is completely melted to a temperature of 390 ° C, and the obtained polymer can be obtained. The differential heat is measured to obtain.

In the method for producing a liquid crystalline polyester (A) of the present invention, the reaction of the derivative of 2,6-naphthalenedicarboxylic acid is sufficiently carried out, and the polymer is not thermally decomposed so as to be in the case of melt polymerization. The maximum reaching temperature is preferably 1 to 3 hours in the reaction system, and more preferably 1.2 to 2.5 hours. By retaining in the reaction system for 1 to 3 hours at the highest temperature at the time of the melt polymerization reaction, the polymer can be promoted to be randomized, and the liquid crystalline polyester (A) having the average chain length of the present invention can be easily obtained.

In the method for producing the liquid crystalline polyester (A) of the present invention, the reaction is preferably carried out at a maximum temperature at the time of the melt polymerization reaction under a normal pressure or a nitrogen gas stream.

The melt polymerization of the liquid crystalline polyester (A) of the present invention can be carried out, for example, according to the method described below.

(1) by melting from ethylene oxide containing 2-ethoxycarbonyl-6-naphthoic acid and 4,4'-diethyloxybiphenyl and 2,6-naphthalenedicarboxylic acid A method of producing a liquid crystalline polyester by a polycondensation reaction of acetic acid.

(2) The phenolic hydroxyl group is deuterated by reacting acetic anhydride with a hydroxycarboxylic acid containing 2-hydroxy-6-naphthoic acid and 4,4'-dihydroxybiphenyl or 2,6-naphthalene dicarboxylic acid. Subsequently, a method of producing a liquid crystalline polyester by melt-deacetation polycondensation reaction.

(3) melting of phenyl ester of hydroxycarboxylic acid containing 2-hydroxy-6-naphthoic acid and diphenyl ester of 4,4'-dihydroxybiphenyl and 2,6-naphthalene dicarboxylic acid by dephenolization polymerization A method of producing a liquid crystalline polyester by a condensation reaction.

(4) A predetermined amount of diphenyl carbonate is reacted with a hydroxycarboxylic acid containing 2-hydroxy-6-naphthoic acid and 2,6-naphthalenedicarboxylic acid to form a diphenyl ester.

Subsequently, a method of producing a liquid crystalline polyester by adding 4,4'-dihydroxybiphenyl and performing a melt dephenolization polycondensation reaction is carried out.

(5) A hydroxycarboxylic acid containing 2-hydroxy-6-naphthoic acid and 4,4'-dihydroxybiphenyl are reacted with acetic anhydride to deuterate a part of the phenolic hydroxyl group.

Subsequently, a method of producing a liquid crystalline polyester by distilling off acetic acid by a melt deacetation polycondensation reaction and adding dimethyl 2,6-naphthalene dicarboxylate to carry out a melt demethylation condensation reaction with a residual hydroxyl group.

(6) The phenolic hydroxyl group is deuterated by reacting acetic anhydride with a hydroxycarboxylic acid containing 2-hydroxy-6-naphthoic acid and 4,4'-dihydroxybiphenyl.

Subsequently, a method of producing a liquid crystalline polyester by adding dimethyl 2,6-naphthalene dicarboxylate while performing a melt deacetation/methyl acetate polycondensation reaction while removing acetic acid generated from the system is carried out.

In the melt polymerization method of the liquid crystalline polyester used in the present invention, polymerization using a combination of the above two processes and above, selected from the above (5), (6), by deacetalization condensation condensation of an ethyl hydrazine group and a carboxylic acid In the process, a liquid crystal polyester is preferably produced by a polymerization process in which a methoxycarbonyl group is condensed with an ethyl acetate-deacetated methyl acetate, and a polymerization process in which a methoxycarbonyl group and a hydroxyl group are de-methanol-condensed.

a polymerization process selected from the group 2 process and above selected from a polycondensation condensation reaction of an ethyl hydrazine group with a carboxylic acid, a polycondensation process of a methoxycarbonyl group and an ethyl acetate deacetated methyl ester, and a methoxycarbonyl group When a liquid crystal polyester is produced by a polymerization process in which a hydroxyl group is subjected to a de-methanol polycondensation, when a hydroxyl group, an etidinyl group, a methoxycarbonyl group, a carboxyl group or the like is used as a terminal structure, and a methoxycarbonyl group and/or a hydroxyl group is used as a terminal structure, Since there is almost no terminal group of the acetamidine group, the amount of acetic acid gas generated is remarkably small, and the gas property is excellent.

Among them, in particular, a liquid crystalline polyester produced by a production method comprising a polymerization process of demethylation of a methoxycarbonyl group and a hydroxyl group can have at least a hydroxyl group and a methoxycarbonyl group at the terminal, and has a low gas effect. A liquid crystalline polyester excellent in heat resistance is more preferable.

As a production method comprising a polymerization process by deco-methanol polycondensation of a methoxycarbonyl group and a hydroxyl group, for example, 2-hydroxy-6-naphthoic acid or 4,4'-dihydroxybiphenyl is directly used for polymerization, and ethylene is used. The reactivity of the group and the hydroxyl group is different, and a liquid crystalline polyester having a hydroxyl group as a polymer terminal group can be obtained.

The liquid crystalline polyester (A) of the present invention has any one of an ethylene group, a hydroxyl group, a methoxycarbonyl group, and a carboxyl group as a terminal group, and which is a terminal group, and is capable of dissolving a polymer in a soluble solvent, for example, A mixed solvent of pentafluorophenol/heavy chloroform = 50/50 was measured by ¹ H-NMR and judged from the obtained spectrum.

Further, a liquid crystalline polyester which is fixed by a sequence obtained by melt polymerization, for example, the obtained pellets are pulverized by using a freeze pulverizer, and under a nitrogen gas stream or under reduced pressure and in liquid crystallinity. The range of the polyester (melting point - 5 ° C) to (melting point - 50 ° C) (for example, 200 to 300 ° C) is heated for 1 to 50 hours to obtain a desired degree of polymerization, and also high viscosity.

The above-described production method is different from the conventional solid phase polymerization method in that the sequence of the liquid crystalline polyester obtained by the melt polymerization method at the stage before the solid phase polymerization is sufficiently randomized, and the sequence is after solid phase polymerization. Also for this reason, the chain lock of the structural unit obtained from 2-hydroxy-6-naphthoic acid does not adversely affect.

In the method for producing the liquid crystalline polyester (A) of the present invention, in order to control the average chain length of the structural unit obtained from 2-hydroxy-6-naphthoic acid, a random catalyst may be used in the polymerization.

Here, the random catalyst means an ester bond of a chain which promotes a structural unit derived from 2-hydroxy-6-naphthoic acid in the latter half of the polymerization, and 2,6-naphthalenedicarboxylic acid or 4,4'- A catalyst for the exchange reaction of a hydroxyl group or a carboxyl group of a dihydroxybiphenyl or such an ester group formed.

The random catalyst system must also function at a high temperature of 300 ° C or higher, under acidic conditions, and the like, and specifically, acetic acid such as sodium acetate, potassium acetate, aluminum acetate, manganese acetate, tin acetate, lead acetate, or calcium acetate. a metal salt of a phosphorus compound such as a metal salt, potassium phosphate, sodium phosphate, sodium phosphite, potassium phosphite, sodium hypophosphite, calcium hypophosphite, sodium metaphosphate or potassium metaphosphate, ruthenium chloride or ruthenium chloride Lewis metal halides with high acidity, etc.

Among them, since the effect of randomization is high, it is preferable to use sodium hypophosphite, sodium acetate, or calcium phosphate because the effect of randomization and the effect of aggregation can be obtained, and the directionality of the obtained liquid crystalline polyester also changes. Low, especially sodium hypophosphite or sodium acetate.

The amount of the random catalyst to be added is preferably 0.001 to 1% by weight, more preferably 0.005 to 0.08% by weight, still more preferably 0.02 to 0.05% by weight.

When the amount of the random catalyst is 0.001 to 1% by weight, the heat resistance is good, and when it is 0.005 to 0.08% by weight, a randomization effect of more sufficient heat resistance can be obtained, and when it is 0.02 to 0.05% by weight, the polymerization promoting effect and The balance of random effects is good, but it is better.

The melt polymerization reaction of the liquid crystalline polyester (A) can be carried out without a catalyst.

Three kinds of polycondensation in the deacetation polycondensation, methyl acetate condensation condensation, and methanol depolymerization condensation can be used as a polymerization catalyst for the catalyst, and use dibutyltin oxide, tetrabutyl titanate, antimony trioxide, magnesium metal, etc. The metal compound is preferred. Since the effects of the three kinds of polycondensation catalysts are equal, it is more preferable to use dibutyltin oxide or tetrabutyl titanate as a catalyst. Because of the high catalytic ability of the de-methanol polycondensation and the deacetinated methyl ester polycondensation, dibutyltin oxide is particularly preferred. a polymerization process of polybutylene oxide above a combination of two processes selected from the group consisting of a condensation condensation reaction of an ethyl hydrazine group with a carboxylic acid, a polycondensation process of a methoxycarbonyl group and an ethyl acetate deacetated methyl ester, and a polymerization process When the liquid crystalline polyester (A) is produced by a polymerization process in which the methoxycarbonyl group and the hydroxy group are de-methanol-condensed and condensed, it is preferred that the polymerization can be carried out in a well-balanced manner and the system is less likely to cause two-phase or partial precipitation.

The amount of the polymerization catalyst added is preferably 0.01 to 1% by weight, more preferably 0.01 to 0.5% by weight, even more preferably 0.02 to 0.05% by weight, based on the liquid crystalline polyester (A) to be obtained.

When the amount of the polymerization catalyst added is 0.01 to 1% by weight based on the obtained liquid crystalline polyester (A), a sufficient catalyst effect can be obtained. When the amount of the polymerization catalyst added is 0.01 to 0.5% by weight based on the obtained liquid crystalline polyester (A), the polymerization process selected from the combination of the two processes and the deacetylation of the carboxylic acid is carried out. A process for obtaining a liquid crystal polyester (A) by a polymerization process in which a methoxycarbonyl group is condensed with an ethyl acetate-demethylated methyl acetate and a polymerization process in which a methoxycarbonyl group and a hydroxyl group are de-methanol-condensed and condensed to obtain a speed balance Is better. When the amount of the polymerization catalyst added is 0.02 to 0.05% by weight based on the obtained liquid crystalline polyester (A), it is particularly preferable to obtain a speed balance of two polycondensation systems and to obtain a high polymerization rate. .

In the liquid crystalline polyester (A) of the present invention, it is preferred to further form a liquid crystalline polyester (B) composed of the following structural unit to prepare a liquid crystalline polyester. By blending the liquid crystalline polyester composed of the following structural unit, the anisotropy can be further reduced and the toughness can be further improved, and the fluidity can be further improved.

The above structural unit (I) is preferably a structural unit derived from p-hydroxybenzoic acid, and the structural unit (II) is preferably a structural unit derived from 4,4'-dihydroxybiphenyl, and the structural unit (III) The structural unit formed by hydroquinone is preferred, the structural unit (IV) is preferably a structural unit derived from citric acid, and the structural unit (V) is preferably a structural unit derived from isononanoic acid.

When the structural unit (I) is 65 to 80 mol% with respect to the total of the structural units (I), (II) and (III), it can be remarkably lowered by blending with the liquid crystalline polyester (A). The effect of the different directionality is preferred. Further, when the structural unit (II) is 65 to 73 mol% based on the total of the structural units (II) and (III), it is preferable because the effect of improving the fluidity can be remarkably obtained. When the structural unit (IV) is 60 to 92 mol% based on the total of the structural units (IV) and (V), it is preferable because the effect of improving the fluidity can be remarkably obtained.

The method for producing the liquid crystalline polyester (B) used in the present invention can be produced by a known polycondensation method of polyester.

In terms of compatibility, the liquid crystalline polyester (B) has a number average molecular weight of 3,000 to 25,000, preferably 5,000 to 20,000, more preferably 8,000 to 18,000.

The number average molecular weight is such that the liquid crystalline polyester (B) is dissolved in a soluble solvent such as a pentafluorophenol solvent and measured in accordance with the GPC-LS (gel permeation chromatography light scattering) method.

The solubility of the liquid crystalline polyester (B) and the liquid crystalline polyester (A) is preferably from 1 to 200 Pa s., preferably from 10 to 200 Pa s. And it is particularly good at 10 to 100 Pa‧s. The melt viscosity is a value measured by a high-flow type flow rate tester under the conditions of a melting point of the liquid crystalline polyester + 10 ° C and a shear rate of 1,000 / s.

When the ratio of the liquid crystalline polyester (A) to the liquid crystalline polyester (B) is 100% by weight in total, the liquid crystalline polyester (A) is 0.1 to 99.9% by weight and liquid crystal The polyester (B) is preferably 99.9 to 0.1% by weight, preferably 50 to 99% by weight of the liquid crystalline polyester (A) and 1 to 50% by weight of the liquid crystalline polyester (B). More preferably, the polyester (A) is 80 to 95% by weight, and the liquid crystalline polyester (B) is 5 to 20% by weight.

The method for producing a composition comprising the liquid crystalline polyester (A) and the liquid crystalline polyester (B) can be melt-kneaded by a solution blending method, melt-kneading or the like.

The melt-kneading can be carried out by a well-known method, for example, a Banbury Mixer, a rubber roll, a kneader, a uniaxial or biaxial extruder, or the like, at the melting point of the liquid crystalline polyester (A). The resin composition is melt-kneaded in a temperature range of 20 ° C to a melting point + 50 ° C or lower to prepare a resin composition. It is preferable to carry out melt kneading in a temperature range of -10 ° C to a melting point + 10 ° C by using a twin-screw extruder, in particular, a composition having high fluidity can be obtained.

A filler can be used for the liquid crystalline polyester of the present invention. It is preferable to use a filler to increase strength, toughness, or to improve heat resistance, and to obtain an effect of lowering gasization and reducing anisotropy.

A filler can be used for the liquid crystalline polyester composition of the present invention. It is preferable to use a filler to increase strength, toughness, or to improve heat resistance, and to obtain an effect of lowering gasization and reducing anisotropy.

As the filler, for example, a filler such as a fiber, a plate, a powder, or a granule can be used. Specific examples thereof include metal fibers such as glass fibers, PAN-based or pitch-based carbon fibers, stainless steel fibers, aluminum fibers, or brass fibers, organic fibers such as aromatic polyamide fibers or liquid crystalline polyester fibers, and gypsum fibers. Ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber, cerium oxide fiber, titanium oxide fiber, cerium carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker , fibrous, whisker-like fillers such as cerium nitride whiskers, mica, talc, kaolin, cerium oxide, glass beads, glass flakes, clay, molybdenum disulfide, wallastonite, titanium oxide, zinc oxide Powdery, granular or plate-like fillers such as calcium polyphosphate and graphite. The filler used in the present invention can be used, for example, by treating a surface thereof with a well-known coupling agent such as a decane coupling agent or a titanate coupling agent or another surface treatment agent.

Among these fillers, glass fiber is particularly preferred in terms of balance between availability and mechanical strength. The glass fiber can be used, for example, from a long fiber type or a short fiber type chopped strand, a ground fiber, or the like. In addition, these may be used in combination of two or more types. As the glass fiber used in the present invention, in terms of excellent mechanical strength, it is preferred to use a weakly alkaline one. In particular, it is preferred to use glass fibers having a cerium oxide content of 50 to 80% by weight, more preferably 65 to 77% by weight of glass fibers. Further, the glass fiber is preferably coated with an epoxy resin, an urethane resin or an acrylic resin or treated with a bunching agent, and is preferably an epoxy resin. Moreover, it is preferable to use a coupling agent such as a decane-based or titanate-based compound or a surface treatment agent, and it is particularly preferable to use a coupling agent of an epoxy decane or an amino decane type.

The glass fiber may be coated or bundled with a thermoplastic resin such as an ethylene/vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.

When the amount of the filler is usually 0.1 to 200 parts by weight based on 100 parts by weight of the liquid crystalline polyester, the effect of improving the load bending temperature by the filler is preferable, and the range is from 1 to 150 parts by weight. It is especially good because it can achieve excellent effects by reducing the omnidirectionality.

When the amount of the filler is usually 0.1 to 200 parts by weight based on 100 parts by weight of the liquid crystalline polyester composition, the effect of improving the load bending temperature by the filler is preferable, and the range is from 1 to 150 parts by weight. When it is used, it is excellent because it can obtain excellent effects by reducing the directionality.

In the liquid crystalline polyester or the liquid crystalline polyester composition of the present invention, an anti-oxidant, a thermal stabilizer, a UV-blocking agent, a phosphite, a hypophosphite, or the like, a coloring agent, a lubricant, and a release agent can be formulated. a dye- or pigment-containing coloring agent, a carbon black as a conductive agent or a coloring agent, a nucleating agent, a plasticizer, a flame retardant, a flame retardant, an antistatic agent, and the like, and a polymer other than a thermoplastic resin. Give the specified characteristics.

In the case of the liquid crystalline polyester or the liquid crystalline polyester composition of the present invention, hindered phenol, hydroquinone, phosphite, and the like may be exemplified as the thermal stabilizer. Resorcin and salic acid esters can be exemplified as the ultraviolet absorber. As the release agent, octadecanoic acid and a metal salt thereof, an ester thereof, a half ester thereof, stearyl alcohol, stearylamine, and a polyethylene wax can be exemplified. Examples of the flame retardant include a bromine-based flame retardant, a phosphorus-based flame retardant, a red phosphorus, and a lanthanum-based flame retardant.

In the liquid crystalline polyester of the present invention, a method of blending a filler or an additive can be carried out by dry blending or solution blending, addition during melt polymerization of a liquid crystalline polyester, melt-kneading, or the like, and melt-kneading is preferred.

Melt kneading can use well-known methods. For example, it can be melt-kneaded in a temperature range of a melting point of a liquid crystalline polyester or a melting point of +50 ° C or less, using a Banbury mixer, a rubber roller, a kneader, a uniaxial or biaxial extruder, or the like. A resin composition in which a twin-screw extruder is preferred.

As the kneading method, for example, the following kneading method can be performed.

1) Batch mixing method of liquid crystalline polyester (A), filler and other additives.

2) First, a liquid crystalline polyester (A) is produced, and a liquid crystalline polyester composition (parent particle) containing an additive at a high concentration is produced, and then a liquid crystalline polyester (A), a filler, and an additive are added so as to have a predetermined concentration. Method (master particle method).

3) The liquid crystalline polyester (A) is kneaded once with a part of the additive, and then the remaining filler and the additive are added.

4) A method of producing a liquid crystalline polyester composition composed of a liquid crystalline polyester (A) and a liquid crystalline polyester (B), and then kneading the liquid crystalline polyester particles, the filler, and the additive in batches.

5) After producing a liquid crystalline polyester composition composed of a liquid crystalline polyester (A) and a liquid crystalline polyester (B), a liquid crystalline polyester composition containing an additive in a liquid crystal polyester composition at a high concentration is produced. (Mother particles), followed by a method of adding a liquid crystalline polyester composition, a filler, and an additive composed of the liquid crystalline polyester (A) and the liquid crystalline polyester (B) to a predetermined concentration (mother particle method) .

6) A liquid crystal polyester composition composed of a liquid crystalline polyester (A) and a liquid crystalline polyester (B), and a liquid crystal composed of a liquid crystalline polyester (A) and a liquid crystalline polyester (B) The polyester composition is kneaded once with a part of the additive, and then, the remaining filler and the additive addition method are added.

7) A method of batch-mixing a liquid crystalline polyester (A), a liquid crystalline polyester (B), a filler, and an additive.

The liquid crystalline polyester composition of the present invention has high toughness, low heterogeneity, low gas, and excellent insulation breakdown resistance.

The liquid crystalline polyester of the present invention can be processed into a molded article having an excellent surface appearance (color tone), mechanical properties, heat resistance, and flame retardancy in accordance with a usual molding method such as injection molding, extrusion molding, or press molding.

Further, the liquid crystalline polyester composition of the present invention can be processed to have an excellent surface appearance (hue), mechanical properties, heat resistance, and flame retardancy in accordance with a usual molding method such as injection molding, extrusion molding, or press molding. Molded product.

Examples of the molded article include an injection-molded article, an extruded article, a press-molded article, a sheet, a tube, a film, a fiber, and the like. In particular, when the molded article is produced, the effect of the present invention such as fluidity can be remarkably obtained. It is better.

The molded article composed of the liquid crystalline polyester or the liquid crystalline polyester composition of the present invention is, for example, various gears, various cases, inductors, LED lamps, connectors, sockets, resistors, relay boxes, switches, and windings. Wire tube, capacitor, variable capacitor case, optical pickup, vibrator, various terminal boards, transformers, plugs, printed wiring boards, adjusters, speakers, microphones, earphones, small motors, head bases, power modules , electrical components such as housings, semiconductors, liquid crystal display parts, FDD frames, FDD chassis, HDD parts, motor brush holders, parabolic antennas, computer-related components, etc.; VTR parts, TV parts, irons, hair drying Household appliances, electrical appliances, electric machine parts, electric furnace parts, audio parts, sound, laser discs, compact discs, sound machine parts, lighting parts, refrigerator parts, air conditioning parts, typewriter parts, word processor parts, etc. Product parts, office computer related parts, telephone related parts, fax machine related parts, photocopying machine related parts, Various types of bearings such as polyester jigs, oil-free bearings, stern bearings, and underwater bearings, optical parts, such as mechanical parts, microscopes, binoculars, cameras, clocks, etc., represented by motor parts, lighters, typewriters, etc. Parts, alternator terminal equipment, alternator connector, IC regulator, photographic potentiometer base, exhaust gas valve, various valves, fuel related, exhaust system, suction system, various fittings, air inlet Nozzle vent pipe, inlet manifold, fuel pump, engine cooling water joint, carburetor body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, throttle position sensor, crankshaft position sensor Air flow meter, brake pad wear sensor, air conditioner thermostat base, air conditioner motor insulator, greenhouse warm air flow control valve, radiator motor brush holder, water pump impeller, turbine blade, wiper motor related parts, distribution , starter switch, starter relay, shifting harness, window washer nozzle, Air conditioner panel switch board, fuel-related solenoid valve bobbin, fuse connector, horn terminal equipment, electric component parts insulation board, stepping motor rotor, lamp screen, lamp socket, lamp reflector, lamp housing, brake piston, Spiral bobbin, engine oil filter, ignition box, etc. Cars, vehicle-related parts, etc. In the case of a film, a film for a magnetic recording medium, a film for photographic film, a film for a capacitor, a film for electrical insulation, a film for packaging, a film for patterning, a film for a ribbon, and a sheet for use in a car interior ceiling, a door trim, and an instrument panel a cushioning material, a cushioning material for a bumper or a side bracket, a sound absorbing pad such as a back cover of a hood, a seat material, a pillow, a fuel tank, a brake hose, a nozzle for a window washing liquid, a tube for an air conditioner refrigerant, and the like Peripheral components are useful.

Example

Hereinafter, the present invention will be further described in detail by way of examples.

Liquid crystalline polyester (A)

Example 1

In a reaction vessel equipped with a stirrer and a distillation tube of 5 liters, 724.5 g (3.85 mol) of 2-hydroxy-6-naphthoic acid and 478.6 g (2.57 mol) of 4,4'-dihydroxybiphenyl were added. 555.6 g (2.57 mol) of 2,6-naphthalenedicarboxylic acid, 0.32 g (0.02% by weight) of sodium acetate and 1010.7 g (1.10 equivalents relative to the total phenolic hydroxyl group of the system) of acetic anhydride and stirring under a nitrogen atmosphere After reacting at 145 ° C for 2 hours, the temperature was raised to 365 ° C over 4 hours (this temperature means the highest temperature reached during melt polymerization. The following A-2 to A-24, B-1, C-1, 2) The same applies to C7~10). Subsequently, it was kept at 365 ° C for 1.5 hours, and the pressure was reduced to 133 Pa for 1.0 hour, and the reaction was continued for 60 minutes. When the torque reached 22 kg ‧ cm, the polycondensation was completed. The reaction vessel was then pressurized to 0.1 MPa, and the polymer was spun into strands via a nozzle having a circular discharge port having a diameter of 10 mm, and granulated using a cutter.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (A-1) was 345 °C.

Using a high-flow flow rate tester (nozzle of 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 365 ° C and a shear rate of 1000 / s was 20 Pa ‧ s. The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,500.

Example 2

The same operation as in the above A-1 was carried out except that the melt polymerization temperature was 370 ° C and the torque reached 20 kg ‧ cm, and the polycondensation was terminated.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (A-2) was 345 °C.

Using a high-flow flow rate tester (nozzle of 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 365 ° C and a shear rate of 1000 / s was 20 Pa ‧ s.

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,600.

Example 3

The same operation as in the above A-1 was carried out, except that the melt polymerization temperature was 375 ° C and the torque reached 18 kg ‧ cm, and the polycondensation was terminated.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (A-3) was 345 °C.

Using a high-flow flow rate tester (nozzle of 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 365 ° C and a shear rate of 1000 / s was 20 Pa ‧ s.

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,600.

Example 4

The same operation as in the above A-1 was carried out, except that the melt polymerization temperature was set to 380 ° C, and when the torque reached 16 kg ‧ cm, the polycondensation was terminated.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (A-4) was 345 °C.

Using a high-flow flow rate tester (nozzle of 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 365 ° C and a shear rate of 1000 / s was 20 Pa ‧ s.

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,400.

Example 5

The same operation as in the above A-1 was carried out, except that the melt polymerization temperature was set to 385 ° C and the torque reached 14 kg ‧ cm, and the polycondensation was terminated.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (A-5) was 345 °C.

Using a high-flow flow rate tester (nozzle of 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 365 ° C and a shear rate of 1000 / s was 20 Pa ‧ s.

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,400.

Example 6

In a 5 liter reaction vessel equipped with a stirrer and a distillation tube, except for the addition of 677.4 g (3.60 mol) of 2-hydroxy-6-naphthoic acid, 502.8 g (2.70 mol) of 4,4'-dihydroxybiphenyl , 583.7 g (2.70 mol) of 2,6-naphthalenedicarboxylic acid, 0.32 g (0.02% by weight) of sodium acetate and 1010.7 g (1.10 equivalents relative to the total phenolic hydroxyl group of the system) of acetic anhydride, and the melt polymerization temperature The same operation as in the above A-1 was carried out except that the temperature was set to 375 °C.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (A-6) was 348 °C.

Using a high-flow flow rate tester (nozzle of 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 368 ° C and a shear rate of 1000 / s was 20 Pa ‧ s.

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,400.

Example 7

In a 5 liter reaction vessel equipped with a stirrer and a distillation tube, except for the addition of 745.2 g (3.92 mol) of 2-hydroxy-6-naphthoic acid, 469.2 g (2.52 mol) of 4,4'-dihydroxybiphenyl , 544.8 g (2.52 mol) of 2,6-naphthalenedicarboxylic acid, 0.32 g (0.02% by weight) of sodium acetate and 1010.7 g (1.10 equivalents relative to the total phenolic hydroxyl group of the system) of acetic anhydride, and the melt polymerization temperature The same operation as in the above A-1 was carried out except that the temperature was set to 370 °C.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (A-7) was 343 °C.

Using a high-flow flow rate tester (nozzle of 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 363 ° C and a shear rate of 1000 / s was 20 Pa ‧ .

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,500.

Example 8

In a 5 liter reaction vessel equipped with a stirrer and a distillation tube, except for adding 643.6 g (3.42 mol) of 2-hydroxy-6-naphthoic acid, 519.5 g (2.79 mol) of 4,4'-dihydroxybiphenyl 603.2 g (2.79 mol) of 2,6-naphthalenedicarboxylic acid, 0.32 g (0.02% by weight) of sodium acetate and 1010.7 g (1.10 equivalents relative to the total phenolic hydroxyl group of the system) of acetic anhydride, and the melt polymerization temperature The same operation as in the above A-1 was carried out except that the temperature was set to 375 °C.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (A-8) was 350 °C.

Using a high-flow flow rate tester (nozzle of 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 370 ° C and a shear rate of 1000 / s was 20 Pa ‧ s.

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,800.

Example 9

In a 5 liter reaction vessel equipped with a stirrer and a distillation tube, except for the addition of 816.7 g (4.34 mol) of 2-hydroxy-6-naphthoic acid, 433.9 g (2.33 mol) of 4,4'-dihydroxybiphenyl 503.7 g (2.33 mol) of 2,6-naphthalenedicarboxylic acid, 0.32 g (0.02% by weight) of sodium acetate and 1010.7 g (1.10 equivalents relative to the total phenolic hydroxyl group of the system) of acetic anhydride, and the melt polymerization temperature The same operation as in the above A-1 was carried out, except that the polycondensation was terminated when the torque reached 18 kg ‧ cm at 365 ° C.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (A-9) was 337 °C.

Using a high-flow flow rate tester (nozzle 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 357 ° C and a shear rate of 1000 / s was 20 Pa ‧ s.

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,800.

Example 10

In a 5 liter reaction vessel equipped with a stirrer and a distillation tube, except for the addition of 816.7 g (4.34 mol) of 2-hydroxy-6-naphthoic acid, 433.9 g (2.33 mol) of 4,4'-dihydroxybiphenyl 503.7 g (2.33 mol) of 2,6-naphthalenedicarboxylic acid and 1010.7 g (1.10 equivalents relative to the total phenolic hydroxyl group of the system) of acetic anhydride, and the melt polymerization temperature was set to 370 ° C and when the torque reached 16 Kg The same operation as in the above A-1 was carried out, except that the polycondensation was completed at ‧ cm.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (A-10) was 337 °C.

Using a high-flow flow rate tester (nozzle 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 357 ° C and a shear rate of 1000 / s was 20 Pa ‧ s.

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,800.

Example 11

In a 5 liter reaction vessel equipped with a stirrer and a distillation tube, except for the addition of 846.8 g (4.50 mol) of 2-hydroxy-6-naphthoic acid, 419.0 g (2.25 mol) of 4,4'-dihydroxybiphenyl 486.4 g (2.25 mol) of 2,6-naphthalenedicarboxylic acid, 0.32 g (0.02% by weight) of sodium acetate and 1010.7 g (1.10 equivalents relative to the total phenolic hydroxyl group of the system) of acetic anhydride, and the melt polymerization temperature The same operation as A-1 above was performed except that it was set to 360 °C.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (A-11) was 334 °C.

Using a high-flow flow rate tester (nozzle of 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 354 ° C and a shear rate of 1000 / s was 20 Pa ‧ s.

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,400.

Example 12

In a 5 liter reaction vessel equipped with a stirrer and a distillation tube, except for the addition of 931.5 g (4.95 mol) of 2-hydroxy-6-naphthoic acid, 378.0 g (2.03 mol) of 4,4'-dihydroxybiphenyl , 438.9 g (2.03 mol) of 2,6-naphthalenedicarboxylic acid, 0.32 g (0.02% by weight) of sodium acetate and 1010.7 g (1.10 equivalents relative to the total phenolic hydroxyl group of the system) of acetic anhydride, and the melt polymerization temperature The same operation as in the above A-1 was carried out, except that the polycondensation was terminated when the torque reached 18 kg ‧ cm.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (A-12) was 326 °C.

Using a high-flow flow rate tester (nozzle of 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 346 ° C and a shear rate of 1000 / s was 20 Pa ‧ .

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,400.

Example 13

In a 5 liter reaction vessel equipped with a stirrer and a distillation tube, except for the addition of 1016.2 g (5.40 mol) of 2-hydroxy-6-naphthoic acid, 335.2 g (1.80 mol) of 4,4'-dihydroxybiphenyl 389.1 g (1.80 mol) of 2,6-naphthalenedicarboxylic acid, 0.32 g (0.02% by weight) of sodium acetate and 1010.7 g (1.10 equivalents relative to the total phenolic hydroxyl group of the system) of acetic anhydride, and the melt polymerization temperature The same operation as in the above A-1 was carried out except that it was set to 345 °C.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (A-13) was 319 °C.

The melt viscosity measured at a temperature of 339 ° C and a shear rate of 1000 / s was 20 Pa ‧ using a high-flow flow rate tester (nozzle of 0.5 Φ × 10 mm).

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,400.

Example 14

In a 5 liter reaction vessel equipped with a stirrer and a distillation tube, except for the addition of 1100.9 g (5.85 mol) of 2-hydroxy-6-naphthoic acid, 294.2 g (1.58 mol) of 4,4'-dihydroxybiphenyl , 341.6 g (1.58 mol) of 2,6-naphthalenedicarboxylic acid, 0.31 g (0.02% by weight) of sodium acetate and 1010.7 g (relative to the total phenolic hydroxyl group of the system: 1.10 equivalents) of acetic anhydride, and the melt polymerization temperature The same operation as in the above A-1 was carried out except that it was set to 345 °C.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (A-14) was 318 °C.

Using a high-flow flow rate tester (nozzle 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 338 ° C and a shear rate of 1000 / s was 20 Pa ‧ .

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,400.

Example 15

The same operation as in the above A-2 was carried out, except that the pressure was started immediately after the temperature reached the melt polymerization temperature.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (A-15) was 345 °C. The weight reduction rate was 0.40% by weight using a thermogravimetric measuring apparatus and maintaining at 355 ° C for 120 minutes in a nitrogen atmosphere.

Using a high-flow flow rate tester (nozzle of 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 365 ° C and a shear rate of 1000 / s was 20 Pa ‧ s.

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,600.

Example 16

The same operation as in the above A-2 was carried out, except that the temperature reached the melt polymerization temperature and the pressure was reduced after the same temperature was maintained for 0.8 hours.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (A-16) was 345 °C.

Using a high-flow flow rate tester (nozzle of 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 365 ° C and a shear rate of 1000 / s was 20 Pa ‧ s.

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,600.

Example 17

The same operation as in the above A-2 was carried out, except that the temperature reached the melt polymerization temperature and the pressure was reduced after maintaining the same temperature for 1.0 hour.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (A-17) was 345 °C.

Using a high-flow flow rate tester (nozzle of 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 365 ° C and a shear rate of 1000 / s was 20 Pa ‧ s.

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,600.

Example 18

The same operation as in the above A-2 was carried out, except that the temperature reached the melt polymerization temperature and the pressure was reduced after maintaining the temperature for 2.8 hours.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (A-18) was 345 °C.

Using a high-flow flow rate tester (nozzle of 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 365 ° C and a shear rate of 1000 / s was 20 Pa ‧ s.

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,600.

Example 19

The same operation as in the above A-2 was carried out, except that the melt polymerization temperature was reached, and the pressure was reduced after maintaining the same temperature for 3.2 hours.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (A-19) was 345 °C.

Using a high-flow flow rate tester (nozzle of 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 365 ° C and a shear rate of 1000 / s was 20 Pa ‧ s.

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,600.

Example 20

In a reaction vessel equipped with a stirrer and a distillation tube of 5 liters, 724.5 g (3.85 mol) of 2-hydroxy-6-naphthoic acid and 478.6 g (2.57 mol) of 4,4'-dihydroxybiphenyl were added. 627.4 g (2.57 mol) of dimethyl 2,6-naphthalenedicarboxylate and 937.2 g (1.02 equivalent of total phenolic hydroxyl group of the system) acetic anhydride, and reacted at 145 ° C while stirring under a nitrogen atmosphere. After 2 hours, the temperature was raised to 370 ° C over 6 hours.

After the acetic acid distillation amount was more than 90% of the theoretical value, 0.27 g (0.02% by weight) of dibutyltin oxide was added, and maintained at the same temperature for 1.5 hours and reduced to 1.0 mmHg (133 Pa) in 1 hour, and the reaction was continued for another 30 minutes. When the torque reaches 20kg‧cm, the polycondensation is completed. The reaction vessel was then pressurized to 1.0 kg/cm ² (0.1 MPa), and the polymer was discharged into strands via a nozzle having a circular discharge port having a diameter of 10 mm, and granulated using a cutter.

The Tm of the liquid crystalline polyester (A-20) (melting point of the liquid crystalline polyester) was 345 °C.

Using a high-flow flow rate tester (nozzle of 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 365 ° C and a shear rate of 1000 / s was 20 Pa ‧ s.

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,600.

Example 21

In a reaction vessel equipped with a stirrer and a distillation tube of 5 liters, 724.5 g (3.85 mol) of 2-hydroxy-6-naphthoic acid and 478.6 g (2.57 mol) of 4,4'-dihydroxybiphenyl were added. 627.4 g (2.57 mol) of dimethyl 2,6-naphthalenedicarboxylate and 0.27 g (0.02% by weight) of dibutyltin oxide, and reacted at 145 ° C for 2 hours while stirring under a nitrogen atmosphere for 6 hours. Warm to 370 °C. Subsequently, it was kept at 370 ° C for 1.5 hours and reduced to 1.0 mmHg (133 Pa) at 1.0 hour, and the reaction was further continued for 30 minutes. When the torque reached 20 kg ‧ cm, the polycondensation was completed.

The reaction vessel was then pressurized to 1.0 kg/cm ² (0.1 MPa), and the polymer was discharged into strands via a nozzle having a circular discharge port having a diameter of 10 mm, and granulated using a cutter.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (A-21) was 345 °C.

Using a high-flow flow rate tester (nozzle of 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 365 ° C and a shear rate of 1000 / s was 20 Pa ‧ s.

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,600.

Example 22

In a 5 liter reaction vessel equipped with a stirrer and a distillation tube, except for the addition of 717.0 g (3.81 mol) of 2-hydroxy-6-naphthoic acid, 478.6 g (2.57 mol) of 4,4'-dihydroxybiphenyl 555.6 g (2.57 mol) of 2,6-naphthalenedicarboxylic acid, 12.4 g (0.05 mol) of 3.5-di-t-butyl-4-hydroxybenzoic acid and 0.32 g (0.02% by weight) of sodium acetate, 1010.7 g The same operation as in the above A-2 was carried out, except for acetic anhydride (1.10 equivalents based on the total phenolic hydroxyl group of the system). The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (A-22) was 344 °C.

The melt viscosity measured at a temperature of 364 ° C and a shear rate of 1000 / s was 20 Pa ‧ using a high-flow flow rate tester (nozzle of 0.5 Φ × 10 mm).

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,600.

Example 23

In a 5 liter reaction vessel equipped with a stirrer and a distillation tube, except for the addition of 696.3 g (3.70 mol) of 2-hydroxy-6-naphthoic acid, 478.6 g (2.57 mol) of 4,4'-dihydroxybiphenyl 555.6 g (2.57 mol) of 2,6-naphthalenedicarboxylic acid, 37.2 g (0.15 mol) of 3.5-di-t-butyl-4-hydroxybenzoic acid and 0.32 g (0.02% by weight) of sodium acetate, 1010.7 g The same operation as in the above A-2 was carried out, except for acetic anhydride (1.10 equivalents based on the total phenolic hydroxyl group of the system). The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (A-23) was 344 °C.

The melt viscosity measured at a temperature of 364 ° C and a shear rate of 1000 / s was 20 Pa ‧ using a high-flow flow rate tester (nozzle of 0.5 Φ × 10 mm).

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,600.

Example 24

In a 5 liter reaction vessel equipped with a stirrer and a distillation tube, except for the addition of 673.7 g (3.58 mol) of 2-hydroxy-6-naphthoic acid, 478.6 g (2.57 mol) of 4,4'-dihydroxybiphenyl 555.6 g (2.57 mol) of 2,6-naphthalenedicarboxylic acid, 67.0 g (0.27 mol) of 3.5-di-t-butyl-4-hydroxybenzoic acid and 0.32 g (0.02% by weight) of sodium acetate, 1010.7 g The same operation as in the above A-2 was carried out, except for acetic anhydride (1.10 equivalents based on the total phenolic hydroxyl group of the system).

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (A-24) was 339 °C.

Using a high-flow flow rate tester (nozzle of 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 359 ° C and a shear rate of 1000 / s was 20 Pa ‧ s.

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,600.

Liquid crystalline polyester (C) Comparative example 1

The same operation as in the above A-1 was carried out, except that the melt polymerization temperature was 360 ° C, and when the torque reached 22 kg ‧ cm, the polycondensation was terminated.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (C-1) was 345 °C. Using a high-flow flow rate tester (nozzle of 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 365 ° C and a shear rate of 1000 / s was 24 Pa ‧ s.

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,600.

Comparative example 2

The same operation as in the above A-1 was carried out, except that the melt polymerization temperature was set to 390 ° C and the torque reached 14 kg ‧ cm, and the polycondensation was terminated.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (C-2) was 345 °C. Using a high-flow flow rate tester (nozzle of 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 365 ° C and a shear rate of 1000 / s was 24 Pa ‧ s.

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,600.

Comparative example 3

In a reaction vessel equipped with a stirrer and a distillation tube of 5 liters, 846.8 g (4.50 mol) of 2-hydroxy-6-naphthoic acid and 419.0 g (2.25 mol) of 4,4'-dihydroxybiphenyl were added. 486.4 g (2.25 mol) of 2,6-naphthalenedicarboxylic acid, 0.32 g (0.02% by weight) of sodium acetate and 1010.7 g (1.10 equivalents relative to the total phenolic hydroxyl group of the system) of acetic anhydride and stirring under a nitrogen atmosphere After reacting at 145 ° C for 1 hour, the temperature was raised to 310 ° C for 3 hours (this temperature means the highest temperature reached during melt polymerization) and held for 2.5 hours, and the obtained polymer was taken out. The extracted polymer was pulverized using a pulverizer, and a powder having a particle diameter of 0.1 to 1 mm was placed in a tray type solid phase polymerization apparatus, and heated at 25 ° C for 1 hour under a nitrogen gas flow (nitrogen flow rate of 12 liter / minute). After the temperature was raised to 250 ° C, the temperature was raised from this temperature to 320 ° C for 8 hours and held for 5 hours to carry out solid phase polymerization.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (C-3) was 334 °C.

The melt viscosity measured at a temperature of 354 ° C and a shear rate of 1000 / s was 21 Pa ‧ using a high-flow flow rate tester (nozzle of 0.5 Φ × 10 mm).

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,600.

Comparative example 4

In a reaction vessel equipped with a stirrer and a distillation tube of 5 liters, 890.1 g (4.73 mol) of 2-hydroxy-6-naphthoic acid and 396.6 g (2.13 mol) of 4,4'-dihydroxybiphenyl were added. 460.5 g (2.13 mol) of 2,6-naphthalenedicarboxylic acid, 0.32 g (0.02% by weight) of sodium acetate and 1010.7 g (1.10 equivalents relative to the total phenolic hydroxyl group of the system) of acetic anhydride and stirring under a nitrogen atmosphere After reacting at 145 ° C for 1 hour, the temperature was raised to 310 ° C for 3.5 hours (this temperature means the highest temperature reached during melt polymerization) and held for 2 hours, and the obtained polymer was taken out. The extracted polymer was pulverized using a pulverizer, and a powder having a particle diameter of 0.1 to 1 mm was placed in a tray type solid phase polymerization apparatus, and heated at 25 ° C for 1 hour under a nitrogen gas flow (nitrogen flow rate of 12 liter / minute). After the temperature was raised to 250 ° C, the temperature was raised from the temperature to 325 ° C for 10 hours and maintained for 12 hours to carry out solid phase polymerization.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (C-4) was 330 °C.

The melt viscosity measured at a temperature of 350 ° C and a shear rate of 1000 / s was 21 Pa ‧ using a high-flow flow rate tester (nozzle of 0.5 Φ × 10 mm).

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,600.

Comparative Example 5

In a reaction vessel equipped with a stirrer and a distillation tube of 5 liters, 931.5 g (4.95 mol) of 2-hydroxy-6-naphthoic acid and 378.0 g (2.03 mol) of 4,4'-dihydroxybiphenyl were added. 438.9 g (2.03 mol) of 2,6-naphthalenedicarboxylic acid, 0.32 g (0.02% by weight) of sodium acetate and 1010.7 g (1.10 equivalents relative to the total phenolic hydroxyl group of the system) of acetic anhydride and stirring under a nitrogen atmosphere After reacting at 145 ° C for 1 hour, the temperature was raised to 310 ° C for 3.5 hours (this temperature means the highest temperature reached during melt polymerization) and held for 2 hours, and the obtained polymer was taken out. The extracted polymer was pulverized using a pulverizer, and a powder having a particle diameter of 0.1 to 1 mm was placed in a tray type solid phase polymerization apparatus, and heated at 25 ° C for 1 hour under a nitrogen gas flow (nitrogen flow rate of 12 liter / minute). After the temperature was raised to 250 ° C, the temperature was raised from the temperature to 325 ° C for 10 hours and maintained for 12 hours to carry out solid phase polymerization.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (C-5) was 326 °C.

The melt viscosity measured at a temperature of 346 ° C and a shear rate of 1000 / s was 21 Pa ‧ using a high-speed flow rate tester (nozzle of 0.5 Φ × 10 mm).

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,600.

Comparative Example 6

In a reaction vessel equipped with a stirrer and a distillation tube of 5 liters, 724.5 g (3.85 mol) of 2-hydroxy-6-naphthoic acid and 478.6 g (2.57 mol) of 4,4'-dihydroxybiphenyl were added. 555.6 g (2.57 mol) of 2,6-naphthalenedicarboxylic acid, 0.32 g (0.02% by weight) of sodium acetate and 1010.7 g (1.10 equivalents relative to the total phenolic hydroxyl group of the system) of acetic anhydride and stirring under a nitrogen atmosphere After reacting at 145 ° C for 2 hours, the temperature was raised to 280 ° C for 2 hours and maintained for 1 hour, and then the temperature was further raised to 310 ° C for 0.5 hours (this temperature means the highest temperature reached during melt polymerization) and maintained for 2.5 hours. And the obtained polymer was taken out. The extracted polymer was pulverized using a pulverizer, and a powder having a particle diameter of 0.1 to 1 mm was placed in a tray type solid phase polymerization apparatus, and heated at 25 ° C for 1 hour under a nitrogen gas flow (nitrogen flow rate of 12 liter / minute). After the temperature was raised to 250 ° C, the temperature was raised from this temperature to 320 ° C for 8 hours and held for 5 hours to carry out solid phase polymerization.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (C-6) was 345 °C.

Using a high-flow flow rate tester (nozzle of 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 365 ° C and a shear rate of 1000 / s was 21 Pa ‧ s.

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,600.

Comparative Example 7

In a 5 liter reaction vessel equipped with a stirrer and a distillation tube, except for the addition of 566.4 g (3.01 mol) of 2-hydroxy-6-naphthoic acid, 558 g (3.00 mol) of 4,4'-dihydroxybiphenyl 648.6 g (3.00 mol) of 2,6-naphthalenedicarboxylic acid, 0.32 g (0.02% by weight) of sodium acetate and 1010.7 g (1.10 equivalents relative to the total phenolic hydroxyl group of the system) of acetic anhydride, and the melt polymerization temperature The same operation as in the above A-1 was carried out except that the temperature was set to 380 °C.

The Tm of the liquid crystalline polyester (C-7) (melting point of the liquid crystalline polyester) was 355 °C.

Using a high-flow flow rate tester (nozzle of 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 375 ° C and a shear rate of 1000 / s was 21 Pa ‧ s.

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,600.

Comparative Example 8

The same operation as in the above C-7 was carried out except that the melt polymerization temperature was 370 ° C and the torque reached 24 kg ‧ cm, and the polycondensation was terminated.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (C-8) was 355 °C.

Using a high-flow flow rate tester (nozzle of 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 375 ° C and a shear rate of 1000 / s was 21 Pa ‧ s.

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,600.

Comparative Example 9

In a 5 liter reaction vessel equipped with a stirrer and a distillation tube, except for the addition of 1385.0 g (7.36 mol) of 2-hydroxy-6-naphthoic acid, 152.7 g (0.82 mol) of 4,4'-dihydroxybiphenyl , 177.3 g (0.82 mol) of 2,6-naphthalenedicarboxylic acid, 0.31 g (0.02% by weight) of sodium acetate and 1010.7 g (1.10 equivalents relative to the total phenolic hydroxyl group of the system) of acetic anhydride, and the melt polymerization temperature The same operation as in the above A-1 was carried out except that the temperature was set to 330 °C.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (C-9) was 300 °C.

Using a high-flow flow rate tester (nozzle of 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 320 ° C and a shear rate of 1000 / s was 21 Pa ‧ s.

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,600.

Comparative Example 10

In a 5 liter reaction vessel equipped with a stirrer and a distillation tube, except for the addition of 1385.0 g (7.36 mol) of 2-hydroxy-6-naphthoic acid, 152.7 g (0.82 mol) of 4,4'-dihydroxybiphenyl , 177.3 g (0.82 mol) of 2,6-naphthalenedicarboxylic acid, 0.31 g (0.02% by weight) of sodium acetate and 1010.7 g (1.10 equivalents relative to the total phenolic hydroxyl group of the system) of acetic anhydride, and the melt polymerization temperature When it was set to 310 ° C and the torque reached 26 kg ‧ cm, the same operation as the above C-9 was carried out, except that the polycondensation was completed. The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (C-10) was 300 °C. Using a high-flow flow rate tester (nozzle of 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 320 ° C and a shear rate of 1000 / s was 21 Pa ‧ s. The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,600.

Further, as a comparative example, the liquid crystal polyester (C)-based composition range and/or the average chain length range of the structural unit obtained from 2-hydroxy-6-naphthoic acid are not in the range of the present invention. Liquid crystalline polyester.

The evaluation was carried out in accordance with the methods (1) to (10) below.

(1) The average chain length liquid crystalline polyester of the structural unit obtained from 2-hydroxy-6-naphthoic acid is dissolved in a mixed solution of pentafluorophenol/heavy chloroform=50/50 to become 10 mg/mL, and is manufactured by JEOL. The ¹³ C-NMR was measured by 500 MHz-NMR.

From the obtained spectrum, the shift of carbon at the second position of the structural unit derived from 2-hydroxy-6-naphthoic acid is bonded to the structure obtained from other 2-hydroxy-6-naphthoic acid through an ester bond. Structure of the sixth position of the unit (spike A: 151.0 ppm), separated from the structure bonded to 2,6-naphthalenedicarboxylic acid (spike B: 151.7 ppm), from the respective peak areas (integration The value (peak A area (a) and peak B area (b)) was calculated from the following according to the average chain length of the structural unit obtained from 2-hydroxy-6-naphthoic acid. There is a case where the peak area (integrated value) is called the peak intensity.

(Average chain length of the structural unit obtained from 2-hydroxy-6-naphthoic acid) = a/b.

(2) With or without methoxycarbonyl, hydroxyl end

The liquid crystalline polyester was dissolved in a mixed solution of pentafluorophenol/heavy chloroform=50/50 to obtain 10 mg/mL, and ¹ H nuclear-NMR was measured by 500 MHz-NMR manufactured by JEOL.

In the obtained spectrum, when a peak derived from a methoxycarbonyl group was observed in the vicinity of 4.0 ppm, it was judged that a methoxycarbonyl group was present, and when it was not observed, it was judged to be absent. Similarly, regarding the hydroxyl group, it is based on a peak derived from a proton having a phenolic hydroxyl group having a structural unit derived from 4,4'-dihydroxybiphenyl at 6.8 ppm as a β-position carbon, and from a point at 7.25 ppm. The phenolic hydroxyl group at the vicinity of the structural unit obtained from 2-hydroxy-6-naphthoic acid is the peak of the proton at the second position carbon, and the presence or absence of the determination is made.

(3) Melting point (Tm)

Using a differential scanning calorimeter DSC7 manufactured by PERKIN ELMER, the observed endothermic peak temperature (Tm1) was observed after the polymerization of the polymer was measured at room temperature of 20 ° C / min, at Tm1 + 20 ° C. After the temperature was maintained for 5 minutes, the temperature was temporarily cooled to room temperature under a cooling condition of 20 ° C /min, and then the endothermic peak temperature (Tm2) which can be observed when measured under the temperature rising condition of 20 ° C /min was used as the melting point. However, when the endothermic peak temperature (Tm2) is observed in plural times, the peak on the high temperature side is used as the melting point.

(4) Heterogeneity

A ROBOSHOTα 30C electric injection molding machine manufactured by FANUC Co., Ltd. was used, and the cylinder temperature was set to the melting point Tm + 20 ° C of the liquid crystalline polyester, and the mold temperature was set to 80 ° C to form a width of 70 mm × a length of 70 mm × a thickness of 2 mm. The square plate is measured for the molding shrinkage ratio in the flow direction (MD) of the square plate and the direction perpendicular to the flow direction (TD) to obtain the ratio of the molding shrinkage ratio = the shrinkage ratio of the flow direction (MD) of the crucible ∣ / The forming shrinkage ∣ in the right angle direction (TD) is evaluated, and the directionality is evaluated. The smaller the value obtained from the above, the smaller the out-of-direction property.

(5) Insulation breakdown resistance

The above-mentioned square plate was used and the insulation breakdown resistance was measured in accordance with JIS C 2100 (1994). An aluminum foil electrode having a thickness of 100 μm and 10 cm square was used for the lower electrode, and an 8 mm Φ electrode made of brass was used for the upper electrode, and a square plate was sandwiched therebetween, and a DC high-voltage stabilized power source manufactured by Kasuga Electric Co., Ltd. was used. And the voltage is applied while boosting at a certain speed until the insulation collapses. The voltage at the time of insulation collapse was taken as the insulation breakdown voltage, and the average value measured 10 times was shown. The greater the insulation breakdown voltage, the better the insulation breakdown resistance.

(6) Liquidity

Using the above-mentioned molding machine, the cylinder temperature was set to the melting point Tm + 20 ° C of the liquid crystalline polyester, and the mold temperature was set to 80 ° C, the injection speed was 300 m / s, and the injection pressure was 50, 70, 90 MPa. The length (flow length) of the obtained molded article was measured by forming a test piece by a bar flow length die having a width of 12.7 mm and a thickness of 0.3 mm. From the relationship between the injection pressure and the flow length of the obtained three kinds of molded articles, the flow length at the time when the injection pressure was 100 MPa was calculated and used as an index of fluidity. The longer the flow length, the better the fluidity.

(7) Resilience

Using the above molding machine, a test piece having a thickness of 3.2 mm × a width of 12.7 mm × a length of 127 mm was formed, and the amount of bending was measured in accordance with ASTM D790 to obtain the amount of bending.

(8) Heat resistance

Using the above molding machine, a test piece having a width of 12.7 mm, a length of 50 mm, and a thickness of 0.5 mm was formed, and the test piece was measured in accordance with ASTM D648 at a load of 1.82 MPa. The temperature at which the deformation was constant under a certain load was measured as the load bending temperature. The difference in the bending temperature of the load was used as an index of heat resistance. The smaller the difference, the higher the heat resistance.

(9) amount of gas

Using a PERKIN ELMER thermogravimetric measuring device TGA7, the weight reduction rate at 120 minutes in a nitrogen atmosphere at a melting point of +10 ° C was evaluated. The smaller the weight reduction rate, the lower the gas.

(10) Small bumps in the polymerization system

The liquid crystalline polyester was polymerized using a glass tube, and the small bump of the system was evaluated by observing the reaction. When the foaming due to bumping occurred during the polymerization reaction and the system leaking into the distillation tube was evaluated as ×, it was observed that the liquid level of the system was increased by Δ, and when liquid level foaming or liquid level rising was not observed, ○.

From the comparison of Examples 1 to 5 in Tables 1 and 2 and Comparative Examples 1 and 2 in Tables 3 and 4, it was found that the highest temperature at which the melt polymerization was obtained was obtained in the production of the liquid crystalline polyester of the present invention. In the temperature range of (liquid melting point + 20 ° C) to (melting point + 40 ° C) of the liquid crystalline polyester, the structural unit obtained from 2-hydroxy-6-naphthoic acid can be controlled in the range of 0.1 to 1.

From the comparison of Examples 1 to 5 in Tables 1 and 2 and Comparative Examples 3 to 6 in Tables 3 and 4, it is clear that in order to control the average chain length of the structural unit obtained from 2-hydroxy-6-naphthoic acid 0.1 to 1, it is preferred that the solid phase polymerization is carried out, but the melt polymerization is carried out in the above temperature range.

Further, from Examples 22 to 24 in Tables 1 and 2, it was found that when 3.5-di-tert-butyl-4-hydroxybenzoic acid was contained as a structural unit of the liquid crystalline polyester, it was confirmed that the reaction system was produced at the time of production. The effect of bumping.

From the comparison of Examples 2 and 15 to 19 in Table 5, it was found that the residence time at the highest temperature reached during the polymerization was 1 to 3 hours, and the 2-hydroxy-6-naphthoic acid was easily controlled. The average chain length of the structural unit can be well controlled in the range of 0.2 to 0.8.

From Examples 2, 20, and 21 of Table 6, it is known that when deacetalization polycondensation and methyl acetate decondensation, deacetation polycondensation, and demethylation condensation condensation are selected as the polymerization method, the methoxycarbonyl group is formed at the terminal group. And/or a liquid crystalline polyester of a hydroxyl group.

From the comparison of Examples 1 to 5 in Table 7 and Comparative Examples 1 and 2 in Table 8, it is found that the present invention is controlled when the structural unit obtained from 2-hydroxy-6-naphthoic acid is controlled in the range of 0.1 to 1. The effect is that the directionality, the insulation collapse resistance, the fluidity, the toughness, the heat resistance, and the low gas property are excellent.

Further, from Examples 15 to 19 in Table 7, it is found that when the structural unit obtained from 2-hydroxy-6-naphthoic acid is controlled in the range of 0.2 to 0.8, the above effects can be particularly exhibited.

Further, from the comparison of Comparative Examples 7 to 10 in Examples 2, 6 to 14 and Table 8 in Table 7, the present invention is particularly effective in the composition range of the present invention. It has been found that characteristics such as low heterogeneity, insulation collapse resistance, fluidity, toughness, heat resistance, and low gas properties can be remarkably exhibited.

From the comparison of Examples 2, 21, and 22 in Table 9, it is found that the liquid crystalline polyester having a methoxycarbonyl group at the terminal group is excellent in low gas property, and has a methoxycarbonyl group and/or a hydroxyl group at the terminal group, and a low gas. Better sex.

Further, from Examples 22 to 34 in Table 9, it was found that when 3.5-di-tert-butyl-4-hydroxybenzoic acid was used as the structural unit of the liquid crystalline polyester, the effect of reducing the anisotropy can be obtained.

Further, the liquid crystalline polyester of Reference Example 1 was produced, and the composition was evaluated.

Liquid crystalline polyester (B-1)

In a reaction vessel equipped with a stirrer and a distillation tube of 5 liters, 669.9 g (4.85 mol) of p-hydroxybenzoic acid, 270.0 g (1.45 mol) of 4,4'-dihydroxybiphenyl, 68.3 g (0.62) were added. Mohr) hydroquinone, 224.3 g (1.35 mol) of citric acid, 121.3 g (0.73 mol) of isodecanoic acid and 983.1 g (1.07 equivalent of total phenolic hydroxyl groups relative to the system) acetic anhydride, and in a nitrogen atmosphere The mixture was reacted at 145 ° C for 2 hours while stirring, and then heated to 330 ° C over 4 hours. Subsequently, the polymerization temperature was maintained at 330 ° C for 1 hour, and the pressure was reduced to 133 Pa over 1.0 hour, and further the reaction was continued for 60 minutes, and when the torque reached 20 kg ‧ cm, the polycondensation was completed. The reaction vessel was then pressurized to 0.1 MPa, and the polymer was spun into strands via a nozzle having a circular discharge port having a diameter of 10 mm, and granulated using a cutter.

The Tm (melting point of the liquid crystalline polyester) of the liquid crystalline polyester (B-1) was 314 °C.

Using a high-flow flow rate tester (nozzle of 0.5 Φ x 10 mm), the melt viscosity measured at a temperature of 334 ° C and a shear rate of 1000 / s was 20 Pa ‧ .

The number average molecular weight measured by GPC-LS (pentafluorophenol/chloroform = 50/50 mixed solvent, 80 ° C) was 12,600.

Reference Example 2: Filler GF: Nippon Electric Glass Co., Ltd. E GLASS CHOPPED STRAND (ECS-03T747H) Examples 25 to 41 and Comparative Examples 11 to 15

A side feeder is provided in the C3 section of the cylinder C1 (originally added feeder side heater) to C6 (die side heater) in the TEM35B type twin-shaft extruder manufactured by Toshiba Machine Co., Ltd. (in the same direction as the nip type) And a vacuum vent is provided in the C5 section.

The screw arrangement in which the kneading area is incorporated in the C2 part and the C4 part is used, and the liquid crystalline polyester (A-1, 2, 5, 7, 8, 14, 21 is introduced from the hopper in the amount shown in Tables 10-12). 22, 23) and/or liquid crystalline polyester (B-1) and liquid crystalline polyester (C-1, 3, 4, 6, 8), and 100 weights relative to the liquid crystalline polyester, as the case may be. The amount of the preparation of Tables 10 to 12 was GF (E GLASS CHOPPED STRAND (ECS-03T747H) manufactured by Nippon Electric Glass Co., Ltd.) as a filler, and the cylinder temperature was set to liquid crystalline polyester A-1, 2, and 5. , 7, 8, 14, 21, 22, 23) and (C-1, 3, 4, 6, 8) have a melting point of +10 ° C, and are melt-kneaded to form pellets.

The obtained composition pellets were dried by hot air, and then supplied to a FANUCα 30C injection molding machine (manufactured by FANUC) to obtain a molded article, and the evaluation of the above (4) was carried out in the same manner as in Examples 1 to 24 and Comparative Examples 1 to 10. Directionality, (5) insulation breakdown resistance, (6) fluidity, (7) toughness, (8) heat resistance, and (9) gas amount.

From Examples 25 to 29 in Table 10, it was found that the composition of the liquid crystalline polyesters (A) and (B) of the present invention has an effect of reducing the anisotropy, and in a preferred formulation, It has the effect of improving toughness and fluidity. From the comparison of Examples 30 to 35 in Table 10, 36 to 41 in Table 11, and Comparative Examples 11 to 15 in Table 9, the liquid crystalline polyester of the present invention and the liquid crystalline polyester of the present invention were prepared. When the filler is added to the composition composed of (A) and (B), the effect of increasing the bending temperature of the load and the effect of improving the toughness are high.

Industrial use possibility

It is useful as an SMT connector or an optical head module that is required to be small, thin, and high in heat resistance and high in dimensional stability.

Fig. 1 is a diagram showing the chain length of a structural unit obtained from 2-hydroxy-6-naphthoic acid.

Fig. 2 is a schematic view showing a graph by ¹³ C-NMR used for calculating the average chain length of the structural unit obtained from 2-hydroxy-6-naphthoic acid.

Claims (10)

A liquid crystalline polyester (A) having 38 to 74 mol% of a structural unit derived from a hydroxycarboxylic acid and 13 to 31 mol% of a structure obtained from 4,4'-dihydroxybiphenyl. Unit and 13 to 31 mol% of a structural unit obtained from 2,6-naphthalenedicarboxylic acid, a total of 100 mol% of a liquid crystalline polyester characterized by a structural unit of hydroxycarboxylic acid The above or more % of the ear is a structural unit obtained from 2-hydroxy-6-naphthoic acid, and the structural unit obtained from 2-hydroxy-6-naphthoic acid has an average chain length of 0.2 to 0.8. The liquid crystalline polyester (A) according to claim 1, wherein the hydroxycarboxylic acid is 2-hydroxy-6-naphthoic acid. The liquid crystalline polyester (A) according to the first aspect of the patent application, wherein the hydroxycarboxylic acid is 2-hydroxy-6-naphthoic acid, and 40 to 44 mol% of the structural unit derived from the hydroxycarboxylic acid, 28~ 30 mol% of the structural unit derived from 4,4'-dihydroxybiphenyl and 28 to 30 mol% of the structural unit derived from 2,6-naphthalenedicarboxylic acid. The liquid crystalline polyester (A) of claim 1, wherein 89 to 99.9 mol% of the structural unit derived from the hydroxycarboxylic acid is a structural unit derived from 2-hydroxy-6-naphthoic acid, 0.1 ~11 mol% is a structural unit derived from 3,5-di-t-butyl-4-hydroxybenzoic acid. The liquid crystalline polyester (A) according to any one of claims 1 to 4, which has a methoxycarbonyl group as a terminal group. A method for producing a liquid crystalline polyester (A), which is a method for producing a liquid crystalline polyester (A) according to any one of claims 1 to 5, which is obtained from the obtained liquid crystalline polyester. (melting point +20 ° C) ~ (melting point +40 ° C) temperature The degree range is melt-polymerized, and the highest temperature is reached during the polymerization to be retained in the reaction system for 0.8 to 3 hours. The method for producing a liquid crystalline polyester (A) according to claim 6 which is selected from the group consisting of a polymerization step of polycondensation by deacetation of an ethyl hydrazine group and a carboxylic acid, and a methoxycarbonyl group and an ethyl hydrazide group. The polymerization step of polycondensation of methyl acetate is carried out, and the steps of the polymerization step of demethylation condensation condensation of methoxycarbonyl group and hydroxyl group are combined in two or more steps. A liquid crystalline polyester (A) according to any one of claims 1 to 5, further comprising a liquid crystalline polyester (B) composed of the following structural units , A liquid crystalline polyester composition, which is 100 parts by weight of the liquid crystalline polyester of any one of claims 1 to 5, or 100 parts by weight of the liquid crystalline polyester composition of claim 8 of the patent application. Deploy 0.1~200 weight Part of the filler. A molded article obtained by molding the liquid crystalline polyester of any one of claims 1 to 5 or the liquid crystalline polyester composition of claim 8 of the patent application.