JPH06345863A - Liquid crystal polyester amide - Google Patents

Abstract

PURPOSE:To obtain the subject polymer composed of a p-aminophenol unit, an aromatic diol unit, a naphthalenedicarboxylic acid unit and a p-oxybenzoic acid unit at specific ratios, having high elastic modulus and high strength and useful for film, etc. CONSTITUTION:This liquid crystal polyester amide consists of (A) 5-22mol% of p-aminophenol unit of formula I, (B) 5-22mol% of an aromatic diol unit of formula II [Ar1 is group of formula III (R is 1-6C alkyl, 1-6C alkoxy, etc.; (m) is 1 or 2; (n) is 1-4 when m=1 and is 1-3 when m=2) and/or formula IV], (C) 16-35mol% of 2,6-naphthalenedicarboxylic acid unit of formula V and (D) 30-65mol% of p-oxybenzoic acid unit of formula VI at molar numbers of A to B satisfying the formula VII. The polyester amide has a melt viscosity of 10-50,000 poise at a shearing rate of 1,000/sec at 280-350 deg.C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel liquid crystalline polyesteramide. The liquid crystalline polyesteramide of the present invention is not only added to the flow direction (MD) of the resin itself but also to the direction (TD) perpendicular to the flow direction without adding fillers such as glass fiber and carbon fiber. It has the characteristics of exhibiting a high elastic modulus and high strength, a small linear expansion coefficient in the MD direction and the TD direction, and a small anisotropy of those values.

Therefore, it can be suitably used as an injection-molded product, particularly as a material for automobiles such as outer panels for automobiles and automobile parts, and as a film material for tapes for next-generation high-definition television. Furthermore, the liquid crystalline polyesteramide of the present invention has solder heat resistance, and extremely little gas generation,
Due to its excellent hydrolysis resistance and excellent electrical characteristics, surface mount technology (SMT) compatible electronic component materials, especially relay components, connector components or withstand voltage bobbins, encapsulating materials for semiconductors, hybrid ICs, etc. It is also suitably used as a component for electric / electronic materials such as.

[0003]

2. Description of the Related Art Liquid crystalline polymers have been expanding their market by taking advantage of their characteristics such as high fluidity, high elastic modulus, high strength and good dimensional accuracy. However, although these liquid crystalline polymers give fibers having a high elastic modulus, in a three-dimensional molded article such as an injection-molded article, the molecular chains are highly oriented in the flow direction of the polymer, so that the elasticity in the flow direction is high. Although the modulus becomes higher, the elastic modulus in the direction perpendicular to the flow direction becomes a value as low as that of other polymers that do not show liquid crystallinity, and therefore fillers such as glass fiber and carbon fiber must be added. Had to be reinforced by.

[0004]

However, the addition of fillers lowers the impact strength, deteriorates the surface roughness, and causes a problem in sorting at the time of recycling because it is an inorganic compound. Therefore, attempts have been made to develop a liquid crystal polymer having a high elastic modulus in both the flow direction (MD direction) and the direction perpendicular to the flow direction (TD direction) of the polymer.

For example, as the wholly aromatic polyester,
JP-A-59-124925, JP-A-61-19627
JP-A-1-261418, JP-A-2-64123
And JP-A-3-188124. Also,
MD · by copolymerizing polyfunctional components with wholly aromatic polyester
As an attempt to improve the physical properties in both directions of TD, Japanese Patent Laid-Open No. 2-22
7428, JP-A-2-238052, JP-A3-1.
No. 52123, JP-A-3-152124, JP-A-3-152124
168213 and so on. In addition, JP-A-2-53819
Japanese Patent Application Laid-Open No. 3-47829 attempts to alleviate anisotropy by introducing an optically active group.

However, these are conventional vertical polymerizations for producing polyesters, which have a low strength in both MD and TD directions, a low impact strength, a low fluidity, and a very high melting point so that they cannot be molded at a considerably high temperature. When using the device, there were major problems such as solidification and being unable to get out of the bottom of the pot. On the other hand, an attempt to increase the elastic modulus and strength by using polyesteramide is disclosed in JP-A-2-294329.
No. 57-177021, etc., but in this case as well, the elastic modulus in the TD direction is lowered, the fluidity is lowered, the molding temperature is increased, and the solidification in a conventional vertical polymerization apparatus is performed. Remained the problem.

Further, since wholly aromatic polyester has heat resistance, it is used in the field of electronic materials compatible with SMT and in the field of semiconductors such as IC. However, when it is used in relay parts, many gases are generated, There is a problem of causing abnormality in the electric system and corrosion, and when used in the sealing field, there are problems of deterioration of hydrolysis resistance and deterioration of adhesion with metal. Furthermore, when used as a bobbin, the high withstand voltage required could not be sufficiently obtained.

[0008]

Therefore, it has a high elastic modulus not only in the MD direction but also in the TD direction, generates little gas, is excellent in hydrolysis resistance, and has a high dielectric breakdown voltage. As a result of intensive studies to obtain a liquid crystalline polymer, it was found that the use of a liquid crystalline polyesteramide having a specific structure solves all of the above problems, and the present invention has been achieved. That is, the gist of the present invention is represented by (a) p-aminophenol unit represented by the above formula (A), (b) aromatic diol unit represented by the above formula (B), and (c) the above formula (C). 2,6-naphthalenedicarboxylic acid unit (d) a structural unit represented by the p-oxybenzoic acid unit represented by the above formula (D), wherein the molar numbers of (A) to (D) are [A] and [D], respectively. B], [C], and [D],

[0009]

[Equation 3]

And a shear rate of 1000 / se
The liquid crystalline polyesteramide is characterized in that the melt viscosity in c is in the range of 10 to 50,000 poise at any temperature of 280 to 350 ° C. Hereinafter, the present invention will be described in more detail.

The liquid crystalline polyesteramide of the present invention comprises constitutional units represented by the following formulas (A) to (D).
First, the p-aminophenol unit represented by the formula (A) is contained in an amount of 5 to 22 mol%, preferably 7 to 22 mol%, and more preferably 12 to 18 mol%. When the ratio of the formula (A) is less than 5 mol%, the elastic modulus in the TD direction does not improve,
When it exceeds 22 mol%, the fluidity is deteriorated, which is not preferable.

Next, the aromatic diol unit is represented by the formula (B), and specific examples of the monomer giving the formula (B) include:
Methylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, t-butylhydroquinone, chlorohydroquinone, phenylhydroquinone, 3,
3'-dimethyl-4,4'-dihydroxybiphenyl,
2,2'-dimethyl-4,4'-dihydroxybiphenyl, 2,2 ', 3,3', 5,5'-bistrimethyl-
4,4'-dihydroxybiphenyl, 1,4-naphthalene diol and the like can be mentioned.

Specifically, methyl hydroquinone and trimethyl hydroquinone are preferable in order to improve the elastic modulus in both MD and TD directions and improve the strength balance. Further, in order to improve heat resistance and strength in the MD direction, methylhydroquinone, 3,3′-dimethyl-4,
4'-dihydroxybiphenyl is preferred and the terminal -CO
Methylhydroquinone is the most preferable because it is easy to introduce many OH groups.

These may be used alone or in combination of two or more. Further, the substituent R in the formula (B) is preferably an alkyl group, particularly a methyl group or a phenyl group, from the viewpoint of improving heat resistance. The ratio of the aromatic diol unit represented by the formula (B) is 5 to 22 mol%, preferably 7
-22 mol%, particularly preferably 12-18 mol%. If this ratio is less than 5 mol%, the elastic modulus in the TD direction decreases, and it becomes impossible to escape from the kettle. Even if it exceeds 22 mol%, the elastic modulus in the TD direction and heat resistance decrease, which is not preferable.

The content ratio of the 2,6-naphthalenedicarboxylic acid unit represented by the formula (C) is 16 to 35 mol%, preferably 20 to 30 mol%, and more preferably 25 to 30 mol%. When this ratio is less than 16 mol%, the elastic modulus in the TD direction becomes low, the strength in both MD and TD decreases, and the hydrolysis resistance decreases, and when it exceeds 35 mol%, the hydrolysis resistance increases. And the heat resistance are reduced.

The content ratio of the p-oxybenzoic acid unit represented by the formula (D) is 30 to 65 mol%, preferably 30 to 5
It is 5 mol%, most preferably 40 to 50 mol%. Three
When it is less than 0 mol%, the hydrolysis resistance and heat resistance are deteriorated, and when it exceeds 65 mol%, the elastic modulus in the TD direction, the strength in both MD and TD, and the fluidity are deteriorated, which is preferable. Absent. And the ratio of each structural unit is
When the number of moles of (A) to (D) is represented by [A] to [D], respectively.

[0017]

[Equation 4]

Although satisfying the condition, the value of the equation (1) is
It is preferably in the range of 0.85 to 1.15, and more preferably in the range of 0.85 to 0.98. If this value is less than 0.8 or more than 1.2, the degree of polymerization is not improved, so that the strength and elongation are lowered, and the impact strength is also lowered, which is not preferable. Furthermore

[0019]

[Equation 5] It is preferable that it is in the range of 0.20 to 0.35, and most preferably in the range of 0.23 to 0.34.

The liquid crystalline polyesteramide of the present invention contains hydroquinone, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4 '"-dihydroxy-p-quater in addition to the above constitutional units. Phenyl, 2,6-dihydroxynaphthalene, 2,
Dihydroxy compounds such as 7-dihydroxynaphthalene, terephthalic acid, isophthalic acid, 1,2-bis (2-
Chlorphenoxy) ethane-4,4'-dicarboxylic acid,
1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 4,4'-dicarboxydiphenyl ether,
Dicarboxylic acids such as 2,2′-diphenyldicarboxylic acid, 3,3′-diphenyldicarboxylic acid, 4,4′-biphenyldicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, m-hydroxybenzoic acid, 2,6-hydroxy The naphthoic acid, oxycarboxylic acids such as 3-chloro-4-hydroxybenzoic acid, p-aminobenzoic acid, p-phenylenediamine and the structural units introduced by these acyl compounds and the like within a range that does not impair the effects of the present invention. It may be contained as a small amount as a copolymerization component.

Next, the manufacturing method will be described in more detail. The liquid crystalline polyesteramide of the present invention can be produced according to the conventional polyester polycondensation method. For example, there are an interfacial polymerization method, a solution polymerization method, a melt polymerization method, and the like, but the melt polymerization method is preferable because the degree of polymerization is easily improved and the manufacturing cost is the lowest.

As the melt polymerization method, 1) a method in which acetic anhydride is added to a phenolic compound and an acid compound to cause a reaction, and then a deacetic acid polycondensation reaction is carried out to produce 2) after the phenolic compound is acetated with acetic anhydride, A method of producing from the obtained acetate compound and an acid compound by a deacetic acid polycondensation reaction 3) A method of producing from a phenolic compound and a phenyl ester compound of an acid by a dephenolic polycondensation reaction and the like are conceivable. 1) and 2)
It is preferable to polymerize by the method.

First, p-aminophenol (corresponding to (A) unit) as a raw material, aromatic diol compound ((B) unit), 2,6-naphthalenedicarboxylic acid ((C) unit), p-hydroxybenzoic acid ( (D) unit) is charged and acetylation reaction is carried out with acetic anhydride. These may be charged all at once and then acetylated, or only the dihydroxy compound may be charged first for acetylation.

In order to adjust the ratio of each constitutional unit so as to satisfy the formula (1), (I) a method of preparing each raw material in advance to a predetermined amount satisfying the formula (1) and then charging II) After charging an appropriate amount of raw materials, a part of the p-aminophenol and / or aromatic diol compound is intentionally distilled during temperature increase and / or polymerization, and adjusted so as to satisfy the formula (1). Method is used.

In this case, both (I) and (II) may be adopted, or either one may be adopted, but the method (II) is advantageous in terms of polymerization rate and cost. In the method (II), the p-aminophenol and / or the aromatic diol compound is positively distilled by shortening the time of the temperature raising step after acetylation or by flowing nitrogen gas at the time of temperature raising. be able to. It is also effective to increase the initial depressurization rate of the reduced pressure polymerization.

In this case, since the aromatic diol compound is generally a diacetate compound, when methylhydroquinone is used as a raw material, it has a low boiling point and is easily distilled. Further, since sublimation does not occur and the melting point is low, It is suitable because it can be distilled out of the system as a liquid.

The acetylation reaction is carried out by adding acetic anhydride to a raw material compound corresponding to the constitutional units of the formulas (A) to (D) to obtain 100
~ 170 ° C for 5 minutes to 3 hours, preferably 20 minutes to 1.5
Do on time. The amount of acetic anhydride is preferably about the same as or about 1.5 times the amount of the starting hydroxy groups. It is preferable to ripen the mixture at 270 to 325 ° C. for 10 minutes to 2 hours at normal pressure after the temperature rise and before starting the depressurization in order to match the charging ratio with the polymer ratio.

Thereafter, the temperature is raised to carry out the polymerization, but it is preferable to carry out the polymerization at 200 to 325 ° C., especially 27
It is preferably carried out at 5 to 325 ° C, most preferably 30
It is 0-320 degreeC. The polymerization is carried out under reduced pressure,
The pressure is gradually reduced from 0 mmHg to 1 mmHg, and the time required for the pressure reduction is 30 minutes or longer, preferably 60 minutes or longer, and it is particularly important to gradually reduce the pressure from 30 mmHg to 1 mmHg.

The reaction can be carried out without a catalyst, but may be carried out in the presence of a catalyst, if necessary. In the case of using no catalyst, the obtained polymer has good electric characteristics and the like, which is preferable. On the other hand, when a catalyst is used, the polymerization rate can be improved. As a catalyst to be used, an ester exchange catalyst, a polycondensation catalyst, an acylation catalyst, a decarboxylic acid catalyst and the like are used, but these may be mixed and used. Preferred catalysts are Ti (OBu) ₄ , BuSnOOH, S
n (OAc) ₂ , Sb ₂ O ₃ , Fe (acac) ₃ , Z
n (OAc) ₂ , Co (OAc) ₂ , NaOAc, KO
Examples include Ac and Mn (OAc) ₂ . The amount used is 5 to 5000 ppm, preferably 50, based on the polymer.
~ 500 ppm. The polymerization time is preferably within 10 hours, preferably within 7 hours, and most preferably within 4 hours.

This polymerization not only can be carried out at a low temperature, but also has a great advantage that even if it is carried out at a lower temperature, it can be easily withdrawn from the polymerization apparatus and no trouble occurs during withdrawal. Therefore, a conventional vertical polymerization apparatus can be used, and the final polymer can be produced only by the melt polymerization method. Examples of the conventional vertical polymerization apparatus for producing a polyester include those described in FIGS. 7 and 11 of p808 (Handbook of Textiles). In the present invention, of course, a horizontal kneader type reactor may be used, or it is possible to carry out solid phase polymerization after melt polymerization to further increase the degree of polymerization.

By adopting such a manufacturing method,
A polyesteramide having a CH ₃ COO-group and / or a -COOH group terminal, particularly a polyesteramide having a large number of terminal carboxy groups and a small number of terminal acetoxy groups is produced. Specifically, CH ₃ COO- group, -COOH
The concentration of each group (equivalent / ton) is [CH ₃ COO
-], [-COOH],

[0032]

[Equation 6] [CH ₃ COO-] ≤ 30 (2) and [-COOH] ≥ 120 (3) are preferable, and more preferable.

[0033]

## EQU7 ## [CH ₃ COO-] ≤ 20 Most preferably

[0034]

## EQU8 ## [CH ₃ COO−] ≦ 10.

In the conventional method known in the art, the terminal carboxyl group and the terminal acetoxy group are substantially equal in amount, but even in this case, in the polyesteramide having the constitutional unit of the present invention, elasticity in both MD and TD directions is obtained. Both rates increase. However, according to the production method of the present invention, the formulas (2) and (3) are simultaneously satisfied, and [-COOH] >>
By using [CH ₃ COO-], the hydrolysis resistance can be further improved and the generated gas can be significantly reduced.

The liquid crystalline polyesteramide of the present invention exhibits optical anisotropy in the melt phase. In particular, when melting is started, the solid part is almost eliminated by raising the temperature a little from the melting start temperature, and almost all of them can be in a liquid crystal state, so that the fluidity is much better than that of conventional polyester. Therefore, it has good moldability, and general melt molding such as extrusion molding, injection molding, and compression molding can be performed, and it can be processed into molded products, films, fibers, and the like.

Regarding the melt viscosity, the melt viscosity of the polyesteramide of the present invention at a shear rate of 1000 / sec is 1 at any temperature of 280 to 350.degree.
It is 0 to 50,000 poise. Such a liquid crystalline polyesteramide can be molded by heating and melting at 280 to 350 ° C. Moreover, since the molding temperature is as low as 350 ° C., the molding can be sufficiently performed using the conventional molding apparatus.

The obtained molded product has a large elastic modulus and strength in both MD and TD directions, good impact strength, and high fluidity, so that an extremely thin molded product can be manufactured. Above all, the elastic modulus is high not only in the molding direction (MD direction) but also in the direction perpendicular to the molding direction (TD direction).
It is generally required as a structural material.

That is, in the polyesteramide of the present invention, T of an injection molded plate having a square or circular projection surface is used.
The flexural modulus in the D direction is 5 GPa or more, preferably 5.5.
It is GPa or more. Also, the bending elastic modulus in the MD direction [1]
And the flexural modulus [2] in the TD direction ([1] / [2])
Is preferably 2 or less, more preferably 1.5
It is the following.

As a molded piece for measuring the elastic modulus,
It is preferable to use a flat plate having a square or circular projection surface. With commonly used dumbbells, strips, etc.,
Since the flow lengths in the MD and TD directions are significantly different, the original physical properties in both directions cannot be accurately measured, and the anisotropy between the two directions is likely to be large even in the measurement of the elastic modulus. Therefore, when measuring the elastic modulus of a polymer having essentially no anisotropy, such as the polyesteramide of the present invention, it is preferable to use a molded plate having the same size in the MD direction and the TD direction.

The size and thickness of the molded plate are not particularly limited, but the length (d) of a square piece is
₁ ) or the diameter (d ₂ ) of the circle is preferably 1 to 500 cm, particularly preferably 5 to 100 cm. The thickness (t) of the plate is preferably 0.1 to 100 mm, and particularly preferably 0.5 to 40 mm, but in any case,

[0042]

[Equation 9] Is good.

In the case of producing a product having a high elastic modulus in a specific direction, it is not necessary to pay particular attention to the shape of the measuring molded plate because the polymer is easily oriented in the direction of long flow length. Since the polyesteramide of the present invention has high fluidity, it has good moldability and can be subjected to general melt molding such as extrusion molding, injection molding, compression molding and the like. Therefore, it can be easily processed into molded articles, films, fibers and the like.

In particular, in the case of injection-molded products, hydrolysis resistance is excellent, almost no gas is generated when kept at high temperature or remelted, few burrs are generated, and dimensional accuracy is also excellent, so thin-wall molding is possible. Also suitable for products and precision molded products. Furthermore, it has excellent adhesiveness and paintability, and is 150-300 ℃.
It is also possible to satisfy the heat resistance of and the solder heat resistance of 260 ° C. or higher.

Accordingly, automotive coatings having excellent coatability, automotive materials such as automotive parts, and electronic component materials compatible with SMT,
It is particularly suitable for use in relay parts, connector parts, coil bobbins, semiconductor encapsulation materials, hybrid IC parts, and the like. Further, at the time of molding, with respect to the polyesteramide of the present invention, fibers such as glass fiber, carbon fiber, talc,
Fillers such as mica and calcium carbonate, nucleating agents, pigments,
It is also possible to add fillers and additives such as antioxidants, lubricants, other stabilizers, flame retardants and the like, thermoplastic resins and the like to give desired properties to the molded article. It is also possible to create a composition that combines the characteristics of other polymers and the advantages of both the polyesteramides of the present invention by blending or alloying with other polymers.

[0046]

EXAMPLES The present invention will be described in more detail below, but the present invention is not limited to the following examples unless it exceeds the gist. In addition, in each of the following examples, each measurement was performed by the following method. (1) Melt viscosity Using a Shimadzu flow tester, a shear rate of 100
0 sec ⁻¹ , cylinder nozzle length / diameter = 20 was used. (2) Preparation of test piece Molding is performed by heating and melting the polymer at any temperature of 280 to 350 ° C., and then using a 0.1 oz injection molding machine manufactured by Nippon Steel Co., Ltd. and a Tokyo Kikai 2.5 oz injection molding machine. Molded pieces were created.

The following two kinds of test pieces were molded as molded products. (1) To measure the anisotropy of the mechanical properties of the polymer,
40 mm (length) x 6 mm (width) for bending test
A test piece of × 0.6 mm (thickness) was molded in both the injection direction (MD) and the direction perpendicular to it (TD) (molded pieces 1 and 2). (2) A flat plate of 80 mm × 80 mm × 1 mm was formed.
One of these injection molded products is parallel to the flow direction (MD) 40
mm × 6 mm × 1 mm was cut out, and one was cut out to 40 mm × 6 mm × 1 mm perpendicular to this flow direction (TD) (molded piece 3). (3) Flexural characteristics (flexural modulus (FM), flexural rigidity (F
S)) The molded piece obtained by the above molding machine was measured using TENSILON / UTM (III) L manufactured by Toyo Baldwin. (4) Terminal group quantification method First, the liquid crystalline polyesteramide of the present invention is ground, a large excess of n-propylamine is added to the ground sample, and the mixture is treated at room temperature for one day. From the main chain,

[0048]

[Chemical 6]

Etc., n-propylacetamide from the acetate terminal and from the carboxylic acid terminal,

[0050]

[Chemical 7]

Etc. are generated. Therefore, the liquid crystalline polyesteramide is decomposed using n-propylamine, and the decomposition product generated from the end is separated from the main chain-derived decomposition product by the GC method and the HPLC method, and the end group is determined from the peak intensity. It is possible to quantify.

The GC method is used to quantify the end of the acetate. The decomposition product, n-propylacetamide, at the end of the acetate is detected by GC separately from other components. Prepare a calibration curve using standard n-propylacetamide,
It quantified by the absolute calibration method. The HPLC method is used to quantify the carboxylic acid terminal. Carboxylic acid terminal decomposition product p-
Hydroxybenzoic acid, terephthalic acid mono-n-propylamide, 2,6-naphthalenedicarboxylic acid n-propylamide and the like are detected by HPLC after being separated from other components. A calibration curve was prepared using a standard such as p-hydroxybenzoic acid, terephthalic acid mono-n-propylamide, and 2,6-naphthalenedicarboxylic acid mono-n-propylamide, and quantified by the absolute calibration method.

(5) Bending strength retention rate (hydrolysis resistance) A sample molded at 0.1 oz was placed in a pressure cooker test apparatus and tested at 121 ° C. under 2 atmospheres of saturated steam for 100 hours. (6) Amount of evolved gas (gas analysis) A polymer that has been made into chips is put into a washed vial bottle, and the vial bottle is capped and heat-treated in an oven at 200 ° C for 1 hour.
A part of this was injected into the GC to quantify the components.

(7) Composition ratio analysis method A methanol solution of tetramethylammonium hydroxide was added to the pulverized polymer, and the polymer was pyrolyzed using pyrolysis GC to quantify the components. (8) Liquid crystallinity (optical anisotropy) It observed using the polarization microscope with a hot stage.

Example 1 A polymerization apparatus equipped with a stirring blade, a nitrogen inlet and a pressure reducing port was charged with p-
Aminophenol 608 g (5.56 mol), methylhydroquinone 695 g (5.56 mol), 2,6-naphthalenedicarboxylic acid 2400 g (11.1 mol), p-
2300 g (16.7 mol) of hydroxybenzoic acid was charged, and after nitrogen substitution, 4370 g (42.8 mol) of acetic anhydride.
Was charged and the temperature was raised to carry out an acetylation reaction at 140 ° C. for 1 hour. Then, the temperature was raised to 320 ° C. over 2 hours, and the temperature was raised to 32
When 0 ° C was reached, depressurization was started. After decompression starts,
The torque was sufficiently increased in 55 minutes, and the pressure was restored to complete the polymerization. The final degree of vacuum was 10 mmHg. After standing for a while, the polymer was extracted from the lower part of the polymerization apparatus. Extractability was good, and sublimation was hardly seen. The polymer obtained by a polarizing microscope equipped with a hot stage showed liquid crystallinity. The solder heat resistance of the injection-molded piece 1 was 260 ° C. or higher.

Examples 2 to 18 Polymerization was carried out in the same manner as in Example 1 except that the monomer composition and the polymerization time were as shown in Tables 1, 2, and 4 to obtain each polymer. Each of the obtained polymers exhibited liquid crystallinity and was excellent in extraction property. The evaluation results are shown in Tables 6 and 7.

Comparative Examples 1 to 5 Polymerization was carried out in the same manner as in Example 1 except that the monomer composition and the polymerization time were as shown in Tables 3 and 5, to obtain each polymer. Each of the obtained polymers showed liquid crystallinity,
Extractability was poor. The evaluation results are shown in Tables 6 and 7.

[0058]

[Table 1] In Table 1, (A) p-aminophenol (B) methylhydroquinone (C) 2,6-naphthalenedicarboxylic acid (D) p-hydroxybenzoic acid

[0059]

[Table 2] In Tables 2 and 3, (A) p-aminophenol (B) (a) methylhydroquinone (b) trimethylhydroquinone (c) t-butylhydroquinone (d) 1,4-naphthalenediol (e) phenylhydroquinone (f) 3 , 3'-Dimethyl-4,4'-dihydroxybiphenyl (g) 4,4'-dihydroxybiphenyl (C) (a) 2,6-naphthalenedicarboxylic acid (b) terephthalic acid (D) p-hydroxybenzoic acid

[0060]

[Table 3]

[0061]

[Table 4] However, in the raw materials [B] and [C] in Tables 4 and 5, no mark indicates that the compound is the compound (a).

[0062]

[Table 5]

[0063]

[Table 6]

[0064]

[Table 7]

[0065]

From the above data, when the composition and composition ratio of the present invention are used, it can be mass-produced because it has a characteristic that it can be manufactured without trouble in a conventional manufacturing apparatus at 325 ° C. or lower. In addition, since the melt viscosity is low, the moldability is excellent, and particularly thin molded products can be molded. In addition, molded products are MD / TD
It is characterized by high elastic modulus and strength in both directions and high Izod impact strength.

Further, it is characterized by excellent fluidity and heat resistance. Therefore, it is very useful for products such as molding materials and films. In particular, molding materials include automobile materials (for example, outer plates), electrical and electronic parts, thin molded products,
Suitable as a precision molded product. It goes without saying that it is also suitable as a uniaxially oriented product such as a fiber. Further, the liquid crystalline polyester of the present invention can be used in a conventional type vertical polymerization device.
Since it can be melt-polymerized at 5 ° C or lower and can be easily withdrawn from the bottom of the kettle, it can be used for general purpose.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] April 25, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0056

[Correction method] Change

[Correction content]

Examples 2 to 17 Polymerization was carried out in the same manner as in Example 1 except that the monomer composition and the polymerization time were as shown in Tables 1, 2, and 4 to obtain each polymer. Each of the obtained polymers exhibited liquid crystallinity and was excellent in extraction property. The evaluation results are shown in Tables 6 and 7.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0063

[Correction method] Change

[Correction content]

[0063]

[Table 6]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Rie Shirahama, 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryoh Kasei Co., Ltd. (72) Hideko Akai, 1000 Kamoshida-cho, Midori-ku, Yokohama, Kanagawa Prefecture Ryokasei Co., Ltd.

Claims (7)

[Claims] 1. (a) 5 to 22 mol% of p-aminophenol unit represented by the formula (A): (B) 5 to 22 mol% of an aromatic diol unit represented by the formula (B): R represents a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ alkoxy group, a halogen group or a C ₆ -C ₁₀ aromatic group, m is 1 or 2, and n is 1 when m = 1. 4, an integer of 1 to 3 when m = 2. ) (C) 16-35 mol% 2,6- of the formula (C)
Naphthalene dicarboxylic acid unit (D) 30 to 65 mol% of p-oxybenzoic acid unit represented by the formula (D) And the number of moles of (A) to (D) is [A],
When represented by [B], [C], and [D], And a melt viscosity at a shear rate of 1000 / sec at a temperature of 280 to 350 ° C. within a range of 10 to 50,000 poises. 2. A flat plate having a square or circular projection surface is molded by heating and melting at 280 to 350 ° C., and the resulting molded plate has a bending elastic modulus in the TD direction of 5 GPa or more, and
The liquid crystalline polyesteramide according to claim 1, wherein the ratio ([1] / [2]) of the bending elastic modulus [1] in the MD direction and the bending elastic modulus [2] in the TD direction is 2 or less. 3. A methylhydroquinone unit whose aromatic diol unit is represented by formula (E): The liquid crystalline polyesteramide according to claim 1, wherein Wherein end groups mainly, CH ₃ COO- consists group and / or a -COOH group, Equation 2] [CH ₃ COO-] ≦ 30 (2) and [-COOH] ≧ 120 (3) ( However, [CH ₃ COO -), (- COOH] each CH ₃ COO- group, the concentration of -COOH groups (eq / to
n) is represented), The liquid crystalline polyesteramide according to claim 1. 5. An injection-molded article obtained by injection-molding the liquid crystalline polyesteramide according to claim 1. 6. A component for electric / electronic materials, which uses the liquid crystalline polyesteramide according to claim 1. 7. A material for automobiles, which uses the liquid crystalline polyesteramide according to claim 1.