TWI733952B - Fully aromatic polyester amide and its production method - Google Patents

Abstract

Provided is a fully aromatic polyester amide that has sufficient low melting point and heat resistance, and a method for producing the same. The wholly aromatic polyester amide of the present invention is composed of the following structural units (I) to (V) as essential constituents; relative to the total structural units, it contains 61 to 75 mol% of the structural units (I) ), 1-4.5 mol% structural unit (II), 10.25-19 mol% structural unit (III), 3.25-18 mol% structural unit (IV), and 1-7 mol% structural unit The unit (V) contains 100 mol% of the structural units (I) to (V) in total, and exhibits optical anisotropy when melted.

Description

Fully aromatic polyester amide and its production method

The present invention relates to a wholly aromatic polyester amide and its manufacturing method.

Since the liquid crystal polymer system has excellent fluidity, mechanical strength, heat resistance, chemical resistance, electrical properties, etc., in a well-balanced manner, it can be suitably and widely used in high-functional engineering plastics. As the liquid crystal polymer, a wholly aromatic polyester amide can be used together with a wholly aromatic polyester. For example, Patent Document 1 discloses an aromatic polyester amide obtained by reacting p-aminophenol, 4-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, terephthalic acid, and isophthalic acid . In addition, Patent Document 2 discloses an aromatic compound obtained by reacting p-aminophenol, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4,4'-dihydroxybiphenyl, and terephthalic acid. Polyesteramide.

Prior art literature

Patent literature

[Patent Document 1] Japanese Patent Application Laid-Open No. 02-086623

[Patent Document 2] Japanese Patent Laid-Open No. 05-170902

However, the wholly aromatic polyesteramide described in Patent Document 1 has insufficient heat resistance, and the wholly aromatic polyesteramide described in Patent Document 2 has insufficient coexistence of low melting point and heat resistance.

In view of the above-mentioned problems, the object of the present invention is to provide a wholly aromatic polyesteramide that has a low melting point and a sufficient heat resistance, and a method for producing the same.

In order to solve the above-mentioned problems, the inventors of the present invention have repeatedly intensively studied. As a result, a wholly aromatic polyester amide was found, which is composed of the following structural units: structural units derived from 4-hydroxybenzoic acid, structural units derived from 6-hydroxy-2-naphthoic acid, Structural units derived from 1,4-benzenedicarboxylic acid, structural units derived from 4,4'-dihydroxybiphenyl, and structural units derived from N-acetyl-p-aminophenol, and each The content of the structural unit is within a specific range, the above-mentioned problems can be solved, and the present invention has been completed. More specifically, the present invention provides the following items.

(1) A wholly aromatic polyester amide, which is composed of the following structural units (I) to (V) as essential constituents: relative to the total structural units, the content of structural unit (I) is 61 to 75 Mole%, relative to the total structural unit, the content of structural unit (II) is 1 to 4.5 mol%, relative to the total structural unit, the content of structural unit (III) is 10.25 to 19 mol%, relative to the total structure Unit, the content of structural unit (IV) is 3.25-18 mol%, and relative to the total structural unit, the content of structural unit (V) is 1-7 mol%, relative to the total structural unit, structural unit (I) The total content of ~(V) is 100 mol% and shows optical anisotropy when melting:

(2) The wholly aromatic polyester amide as described in (1), which has a melting point of 350°C or less.

(3) A wholly aromatic polyester amide, which is a wholly aromatic polyester amide as described in (1) or (2) with a deflection temperature under load of 270°C or higher, wherein the deflection temperature under load is the same as the aforementioned total deflection temperature. 60% by mass of aromatic polyesteramide, and 40% by mass of ground fibers with an average fiber diameter of 11μm and average fiber length of 75μm. Measured in the state of the amide resin composition.

(4) The wholly aromatic polyester amide according to any one of (1) to (3), wherein it is cut at a temperature 10 to 30°C higher than the melting point of the aforementioned wholly aromatic polyester amide The melt viscosity at a cutting speed of 1000/sec is below 500Pa‧s.

(5) The wholly aromatic polyester amide according to any one of items (1) to (4), wherein the molar number of the structural unit (III) is the ratio of the structural unit (IV) and the structural unit (V) The total number of moles is 1 to 1.2 times, or the total number of moles of structural unit (IV) and structural unit (V) is 1 to 1.2 times of the number of moles of structural unit (III).

(6) A method for producing a wholly aromatic polyester amide that exhibits optical anisotropy when melted. The aforementioned method involves the use of fatty acid anhydride in the presence of a fatty acid metal salt to convert 4-hydroxybenzoic acid, 6 -Hydroxy-2-naphthoic acid, 4,4'-dihydroxybiphenyl, and N-acetyl-p-aminophenol are acylated and transesterified with 1,4-benzenedicarboxylic acid; and Compared with 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 1,4-benzenedicarboxylic acid, 4,4'-dihydroxybiphenyl, and N-acetyl-p-aminophenol And the total monomer used in the aforementioned method, the usage amount of 4-hydroxybenzoic acid is 61~75 mol%, the usage amount of 6-hydroxy-2-naphthoic acid is 1~4.5 mol%, 1,4-benzene The usage amount of dicarboxylic acid is 10.25~19 mol%, the usage amount of 4,4'-dihydroxybiphenyl is 3.25~18 mol%, and the usage amount of N-acetyl-p-aminophenol is 1~ 7 mol%, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 1,4-benzenedicarboxylic acid, 4,4'-dihydroxybiphenyl, and N-acetyl-p-aminophenol The total usage amount of the above-mentioned fatty acid anhydride is 100 mol%, and the usage amount of the aforementioned fatty acid anhydride is 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4,4'-dihydroxybiphenyl, and N-acetyl-p- The total hydroxyl equivalent of aminophenol is 1.02~1.05 times.

(7) The method according to (6), wherein the fatty acid metal salt is a metal acetate, and the fatty acid anhydride is acetic anhydride.

(8) The method according to (6) or (7), wherein the molar number of 1,4-benzenedicarboxylic acid is 4,4'-dihydroxybiphenyl and N-acetyl-p-aminophenol 1 to 1.2 times the total number of moles, or the total number of moles of 4,4'-dihydroxybiphenyl and N-acetyl-p-aminophenol is the number of moles of 1,4-benzenedicarboxylic acid 1 to 1.2 times the number.

According to the present invention, the wholly aromatic polyesteramide of the present invention, which is composed of a specific structural unit and exhibits optical anisotropy when melted, is sufficiently compatible with low melting point and heat resistance.

In addition, since the molding processing temperature of the wholly aromatic polyester amide of the present invention is not too high, injection molding, extrusion molding, compression molding, etc. can be performed even without using a molding machine with a special structure.

The wholly aromatic polyester amide system of the present invention has excellent moldability as described above and can be molded using various molding machines. As a result, it can be easily processed into various three-dimensional molded products, fibers, films, and the like. Therefore, connectors, CPU sockets, relay switch parts, bobbins, actuators, noise reduction filter boxes, or heating fixation of OA equipment suitable for the use of the wholly aromatic polyesteramide of the present invention can also be easily obtained Molded products such as rolls.

Hereinafter, embodiments of the present invention will be described. In addition, the present invention is not limited by the following embodiments.

<Wholly aromatic polyester amide>

The wholly aromatic polyester amide of the present invention is composed of the following structural unit (I), the following structural unit (II), the following structural unit (III), the following structural unit (IV), and the following structural unit (V) constituted.

The structural unit (I) is derived from 4-hydroxybenzoic acid (hereinafter, also referred to as "HBA"). The wholly aromatic polyesteramide of the present invention contains 61 to 75 mol% of the structural unit (I) relative to the total structural unit. When the content of the structural unit (I) is less than 61 mol%, or when it is more than 75 mol%, at least one of lower melting point and heat resistance tends to become insufficient. From the viewpoint of coexistence of low melting point and heat resistance, the content of the structural unit (I) is preferably 61.5-73.5 mol%, preferably 62-72 mol%.

The structural unit (II) is derived from 6-hydroxy-2-naphthoic acid (hereinafter also referred to as "HNA"). The wholly aromatic polyesteramide of the present invention contains 1 to 4.5 mol% of the structural unit (II) relative to the total structural unit. When the content of the structural unit (II) is less than 1 mol%, or when it is more than 4.5 mol%, at least one of low melting point and heat resistance tends to become insufficient. From the viewpoint of coexistence of low melting point and heat resistance, the content of the structural unit (II) is preferably 2 to 4 mol%, preferably 3 to 3.6 mol%.

The structural unit (III) is derived from 1,4-benzenedicarboxylic acid (hereinafter, also referred to as "TA"). The wholly aromatic polyesteramide of the present invention contains 10.25 to 19 mol% of the structural unit (III) relative to the total structural unit. When the content of the structural unit (III) is less than 10.25 mol%, or when it is more than 19 mol%, at least one of low melting point and heat resistance tends to become insufficient. From the viewpoint of coexistence of low melting point and heat resistance, the content of structural unit (III) is preferably 11.5-18.25 mol%, preferably 12.5-17.45 mol%.

The structural unit (IV) is derived from 4,4'-dihydroxybiphenyl (hereinafter, also referred to as "BP"). With respect to the total structural units, the wholly aromatic polyesteramide of the present invention contains 3.25 to 18 mol% of structural units (IV). When the content of the structural unit (IV) is less than 3.25 mol% or more than 18 mol%, at least one of lower melting point and heat resistance tends to become insufficient. From the viewpoint of coexistence of low melting point and heat resistance, the content of the structural unit (IV) is preferably 6.5-16 mol%, preferably 10-14.25 mol%.

The structural unit (V) is derived from N-acetyl-p-aminophenol (hereinafter, also referred to as "APAP"). The wholly aromatic polyester amide system of the present invention contains 1 to 7 mol% of the structural unit (V) relative to the total structural unit. When the content of the structural unit (V) is less than 1 mol% or more than 7 mol%, at least one of lower melting point and heat resistance tends to become insufficient. From the viewpoint of coexistence of low melting point and heat resistance, the content of the structural unit (V) is preferably 1.5-6 mol%, preferably 2-5 mol%.

From the viewpoint of coexistence of low melting point and heat resistance, the molar number of structural unit (III) (hereinafter also referred to as "molar number 1A") is the sum of structural unit (IV) and structural unit (V) The number of moles (hereinafter, also referred to as "number of moles 2A") is 1 to 1.2 times, or the total number of moles of structural unit (IV) and structural unit (V), the number of moles of structural unit (III) 1~1.2 times is better. Preferably, the molar number 1A is 1.01 to 1.06 times the molar number 2A, or the molar number 2A is 1.01 to 1.06 times the molar number 1A. The molar number 1A is 1.02~1.03 times the molar number 2A, or the molar number 2A is 1.02~1.03 times the molar number 1A. The molar number 1A is 1.024~1.030 times the molar number 2A, or the molar number 2A is 1.024~1.030 times the molar number 1A.

As described above, since the wholly aromatic polyesteramide of the present invention contains specific structural units (I) to (V) in a specific amount relative to the total structural units, the coexistence of low melting point and heat resistance is sufficient. In addition, the wholly aromatic polyester amide system of the present invention contains 100 mol% of the structural units (I) to (V) in total with respect to the total structural units.

As an index of the above-mentioned heat resistance, a deflection temperature under load (hereinafter, also referred to as "DTUL") can be cited. When the DTUL is 270C or higher, the heat resistance tends to increase, which is preferable. DTUL is based on 60% by mass of the aforementioned wholly aromatic polyesteramide, and 40% by mass of ground fibers with an average fiber diameter of 11μm and an average fiber length of 75μm. The value measured in the state of the polyester amide resin composition obtained by refining, and can be measured in accordance with ISO75-1,2. From the viewpoint of coexistence of low melting point and heat resistance, DTUL is preferably 271°C or more and less than 320°C, preferably 272 to 288°C.

Next, the method for producing the wholly aromatic polyester amide of the present invention will be explained. The wholly aromatic polyester amide system of the present invention can be polymerized using a direct polymerization method, a transesterification method, or the like. For polymerization, melt polymerization method, solution polymerization method, slurry polymerization method, solid phase polymerization method, etc., or a combination of two or more of these can be used, and melt polymerization method, or melt polymerization method and solid phase polymerization method can be suitably used.的组合。 The combination.

In the present invention, it is possible to use an acylating agent for polymerized monomers and a monomer that activates the terminal as an acetyl chloride derivative during polymerization. Examples of the acylating agent include fatty acid anhydrides such as acetic anhydride.

Various catalysts can be used in these polymerizations. Representative examples include dialkyl tin oxides, diaryl tin oxides, titanium dioxide, alkoxide titanium silicates, titanium alcoholates, and fatty acid metals. The salt, such as the Lewis acid salt of BF3, is preferably a fatty acid metal salt. The amount of the catalyst used is usually about 0.001 to 1% by mass based on the total mass of the monomers, preferably about 0.003 to 0.2% by mass.

In addition, when performing solution polymerization or slurry polymerization, fluidized paraffin, highly heat-resistant synthetic oil, inert mineral oil, etc. can be used as the solvent.

As the reaction conditions, for example, the reaction temperature is 200 to 380°C, and the final pressure is 0.1 to 760 Torr (that is, 13 to 101,080 Pa). Especially for melting reaction, for example, the reaction temperature is 260~380C, preferably 300~360℃, and the final pressure is 1~100 Torr (that is, 133~13,300Pa), preferably 1~50 Torr (that is, 133~6,670Pa) .

The reaction system can add all the raw material monomers (HBA, HNA, TA, BP, and APAP), acylating agent, and catalyst to the same reaction vessel to start the reaction (one-stage method), or acylation The agent acylated the hydroxyl groups of the raw material monomers HBA, HNA, BP, and APAP, and then reacted with the carboxyl group of TA (two-stage method).

After the temperature in the melt polymerization system reaches a predetermined temperature, the pressure is reduced to a predetermined degree of pressure reduction. After the torque of the stirrer reaches a predetermined value, an inert gas is introduced and the pressure is passed from the reduced pressure state to a predetermined pressurized state, and the wholly aromatic polyesteramide is discharged from the reaction system.

The wholly aromatic polyester amide produced according to the above-mentioned polymerization method can achieve an increase in molecular weight by further solid-phase polymerization by heating under normal pressure or reduced pressure under an inert gas. The preferred conditions for the solid-phase polymerization reaction are the reaction temperature of 230-350°C, preferably 260-330°C, and the final pressure is 10 to 760 Torr (that is, 1,330 to 101,080 Pa).

The manufacturing method of the wholly aromatic polyester amide of the present invention is to include 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4,4'-di The step of hydroxybiphenyl and N-acetyl-p-aminophenol acylation and transesterification with 1,4-benzenedicarboxylic acid is better, and is better than 4-hydroxybenzoic acid, 6-hydroxy- The total monomer composed of 2-naphthoic acid, 1,4-benzenedicarboxylic acid, 4,4'-dihydroxybiphenyl, and N-acetyl-p-aminophenol and used in the aforementioned method, 4-hydroxyl The amount of benzoic acid used is 61~75 mol%. From the viewpoint of coexistence of low melting point and heat resistance, 61.5-73.5 mol% is preferred, and 62-72 mol% is more preferred. 6-hydroxyl The usage amount of -2-naphthoic acid is 1 to 4.5 mol%. From the viewpoint of coexistence of low melting point and heat resistance, it is preferably 2 to 4 mol%, preferably 3 to 3.6 mol%, The amount of 1,4-benzenedicarboxylic acid used is 10.25-19 mol%. From the viewpoint of coexistence of low melting point and heat resistance, 11.5-18.25 mol% is preferred, and 12.5-17.45 mol% is more preferred. Ear%, the usage amount of 4,4'-dihydroxybiphenyl is 3.25-18 mol%. From the viewpoint of coexistence of low melting point and heat resistance, 6.5-16 mol% is preferred, and more preferably 10~14.25 mol%, the use amount of N-acetyl-p-aminophenol is 1-7 mol%, from the viewpoint of coexistence of low melting point and heat resistance, 1.5-6 mol% Better, preferably 2~5 mol%, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 1,4-benzenedicarboxylic acid, 4,4'-dihydroxybiphenyl, and N-ethyl The total usage amount of acyl-p-aminophenol is preferably 100 mol%. The usage amount of the aforementioned fatty acid anhydride is 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4,4'- The total hydroxyl equivalent of dihydroxybiphenyl and N-acetyl-p-aminophenol is preferably 1.02~1.05 times. The fatty acid metal salt is an acetic acid metal salt, and the fatty acid anhydride is preferably acetic anhydride. In addition, the molar number of 1,4-benzenedicarboxylic acid (hereinafter also referred to as "molar number 1B") is the total of 4,4'-dihydroxybiphenyl and N-acetyl-p-aminophenol The molar number (hereinafter, also referred to as "molar number 2B") is 1 to 1.2 times, or the total molar number system of 4,4'-dihydroxybiphenyl and N-acetyl-p-aminophenol The molar number of 1,4-benzenedicarboxylic acid is preferably 1 to 1.2 times. The molar number 1B is 1.01~1.06 times the molar number 2B, or the molar number 2B is 1.01~1.06 times the molar number 1B. The molar number 1B is 1.02 to 1.03 times the molar number 2B, or the molar number 2B is 1.02 to 1.03 times the molar number 1B. The molar number 1B is 1.024~1.030 times the molar number 2B, or the molar number 2B is 1.024~1.030 times the molar number 1B.

Next, the properties of the wholly aromatic polyester amide will be explained. The wholly aromatic polyesteramide of the present invention exhibits optical anisotropy when melted. The expression of optical anisotropy during melting means that the wholly aromatic polyesteramide of the present invention is a liquid crystal polymer.

In the present invention, the wholly aromatic polyesteramide is a liquid crystal polymer, which is an indispensable element for the wholly aromatic polyesteramide to have both thermal stability and ease of processing. Although the wholly aromatic polyester amides composed of the above structural units (I) to (V) are distributed according to the order of the constituent components and the polymer, there are also substances that do not form an anisotropic melt phase, but the present invention The polymer is limited to a wholly aromatic polyesteramide that exhibits optical anisotropy when melted.

The nature of melting anisotropy can be confirmed by the usual polarization inspection method using crossed polarizers. More specifically, the melting anisotropy can be confirmed by using a polarizing microscope manufactured by Olympus Corporation and melting a sample placed on a hot stage manufactured by Linkam Corporation, and at a magnification of 150 times in a nitrogen environment. Observe to implement. Liquid crystalline polymers are optically anisotropic and transmit light when inserted between crossed polarizers. When the sample is optically anisotropic, for example, even if it is in a molten static liquid state, polarized light is transmitted.

Since nematic liquid crystal polymers have a significant decrease in viscosity above the melting point, the liquid crystallinity is usually shown at a temperature above the melting point and becomes an index of processability. From the viewpoint of heat resistance, the melting point is preferably as high as possible. However, considering the thermal degradation during the melt processing of the polymer, the heating capacity of the molding machine, etc., 350° C. or less is a suitable target. Furthermore, it is preferably 320 to 350°C, more preferably 344 to 349°C.

The melt viscosity of the aforementioned wholly aromatic polyester amide at a temperature 10~30°C higher than the melting point of the wholly aromatic polyester amide of the present invention and a cutting speed of 1000/sec is preferably 500Pa‧s or less , Preferably 0.5~300Pa‧s, more preferably 1~100Pa‧s. When the melt viscosity is within the above range, the wholly aromatic polyesteramide itself or the composition containing the wholly aromatic polyesteramide can easily ensure fluidity during molding and the filling pressure is not likely to be too high. In this specification, the melt viscosity refers to the melt viscosity measured in accordance with ISO11443.

As an index showing the above-mentioned heat resistance, the difference between the melting point and DTUL can also be cited. When the difference is 85°C or less, the heat resistance tends to increase, which is preferable. From the viewpoint of coexistence of low melting point and heat resistance, the above difference is preferably greater than 0°C and 79°C or less (for example, 50°C or more and 79°C or less), and preferably 61 to 75°C.

<Polyesteramide resin composition>

The above-mentioned wholly aromatic polyesteramide of the present invention can be formulated with various fibrous, powdery, and plate-shaped inorganic and organic fillers according to the purpose of use.

As the inorganic filler blended in the polyester amide resin composition of the present invention, there are fibrous, granular, and plate-like materials.

Examples of fibrous inorganic fillers include glass fiber, asbestos fiber, silica fiber, silica and alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, titanic acid Potassium fibers, silicate fibers such as wollastonite, magnesium sulfate fibers, aluminum borate fibers, and inorganic fibrous substances such as fibrous materials of metals such as stainless steel, aluminum, titanium, copper, and brass. A particularly representative fibrous filler is glass fiber.

In addition, as the powdery inorganic filler, carbon black, graphite, silica, quartz powder, glass beads, milled glass fibers, glass balls, glass powder, such as calcium silicate, aluminum silicate, kaolin, and clay can be mentioned. , Diatomaceous earth, silicates of wollastonite, metal oxides such as iron oxide, titanium oxide, zinc oxide, antimony trioxide, aluminum oxide, metal carbonates such as calcium carbonate, magnesium carbonate, such as calcium sulfate, sulfuric acid Metal sulfate of barium, as well as ferrous iron, silicon carbide, silicon nitride, boron nitride, various metal powders, etc.

Moreover, as a plate-shaped inorganic filler, mica, glass fragments, talc, various metal foils, etc. are mentioned.

When revealing examples of organic fillers, there are heat-resistant high-strength synthetic fibers such as aromatic polyester fibers, liquid crystalline polymer fibers, aromatic polyamides, and polyimide fibers.

These inorganic and organic fillers can be used singly or in combination of two or more. The combined use of fibrous inorganic fillers and granular or plate-shaped inorganic fillers is a preferred combination in terms of having both mechanical strength, dimensional accuracy, and electrical properties. Particularly preferred are glass fiber as a fibrous filler, mica and talc as a plate-like filler, and the blending amount is 120 parts by mass or less relative to 100 parts by mass of the wholly aromatic polyester amide, preferably 20 to 80 Mass parts. By combining glass fiber with mica or talc, the heat distortion temperature and mechanical properties of the polyester amide resin composition are particularly improved.

When using these fillers, astringents or surface treatment agents can also be used when necessary.

The polyester amide resin composition of the present invention, as described above, contains the wholly aromatic polyester amide of the present invention, inorganic or organic fillers as essential components, but as long as it is within a range that does not impair the effects of the present invention, May contain other ingredients. Here, the other components may be any components, and for example, additives such as other resins, antioxidants, stabilizers, pigments, and crystal nucleating agents can be cited.

In addition, the production method of the polyester amide resin composition of the present invention is not particularly limited, and a conventionally known method can be used to prepare the polyester amide resin composition.

<Polyester Amide Molded Products>

The polyester amide molded product of the present invention is formed by molding the wholly aromatic polyester amide or the polyester amide resin composition of the present invention. The forming method is not particularly limited, and ordinary forming methods can be adopted. As a general molding method, methods such as injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, rotary molding, and gas injection molding can be exemplified.

The polyester amide molded product formed by molding the wholly aromatic polyester amide etc. of the present invention has excellent heat resistance and toughness. In addition, the polyester amide molded article formed by molding the polyester amide resin composition of the present invention has excellent heat resistance and toughness, and also contains inorganic or organic fillers, so it can further improve the mechanical strength, etc. .

In addition, the wholly aromatic polyester amide and polyester amide resin composition of the present invention has excellent moldability, and therefore, a polyester amide molded product of a desired shape can be easily obtained.

Suitable applications of the polyester amide molded product of the present invention having the above-mentioned properties include connectors, CPU sockets, relay switch parts, bobbins, actuators, noise reduction filter boxes, or OA equipment. Heating fixed rollers, etc.

[Example]

The following examples illustrate the present invention in more detail, but the present invention is not limited by the following examples.

<Example 1>

In a polymerization vessel equipped with a stirrer, a reflux column, a monomer input port, a nitrogen inlet, and a pressure reduction/outflow line, the following raw material monomers, fatty acid metal salt catalysts, and acylating agents are added, and nitrogen substitution is started.

(I) 4-Hydroxybenzoic acid 10.41 mol% (62 mol%) (HBA)

(II) 6-hydroxy-2-naphthoic acid 0.61 mol% (3.6 mol%) (HNA)

(III) Terephthalic acid 2.93 mol% (17.45 mol%) (TA)

(IV) 4,4’-Dihydroxybiphenyl 2.01 mol% (11.95 mol%) (BP)

(V) N-acetyl-p-aminophenol 0.84 mol% (5 mol%) (APAP)

Potassium acetate catalyst 50ppm

Acetic anhydride 1669g (1.03 times the total hydroxyl equivalent of HBA, HNA, BP and APAP)

After adding the raw materials, the temperature of the reaction system was increased to 140°C and reacted at 140°C for 1 hour. Subsequently, the temperature was further increased to 360° C. in 5.5 hours, and then the pressure was reduced to 10 Torr (that is, 1330 Pa) in 20 minutes, and acetic acid, excess acetic anhydride, and other low-boiling components were further melt-polymerized while distilling out. After the stirring torque reaches a predetermined value, nitrogen is introduced to pass through normal pressure from a reduced pressure state to become a pressurized state, and the polymer is discharged from the lower part of the polymerization vessel.

<evaluation>

With respect to the wholly aromatic polyesteramide of Example 1, the following methods were used to evaluate the melting point, DTUL, melt viscosity, and manufacturability. The evaluation results are shown in Table 1.

[Melting point]

After observing the endothermic peak temperature (Tm1) that can be observed when measuring the polymer under a temperature rising condition of 20°C/min from room temperature by DSC (manufactured by TA Instruments), the temperature is maintained at (Tm1+40)°C for 2 Minutes later, after cooling to room temperature once at a temperature decrease of 20°C/min, the endothermic peak temperature that can be observed during the measurement under a temperature increase condition of 20°C/min is measured again.

[DTUL]

60% by mass of polymer and 40% by mass of glass fiber (EFH75-01 manufactured by Central Glass Co., Ltd., ground fiber, flat fiber diameter 11μm, average fiber length 75μm) using a biaxial extruder ((stock) Nippon Steel The prepared TEX30α type) and melt-kneaded at the melting point of the polymer + the cylinder temperature of 20°C to obtain the polyester amide resin composition pellets.

The above-mentioned polyester amide resin composition pellets were molded under the following molding conditions using a molding machine ("SE100DU" manufactured by Sumitomo Heavy Industries Co., Ltd.) to obtain test pieces for measurement (4 mm × 10 mm × 80 mm). Use this test piece and measure the deflection temperature under load by the method according to ISO75-1,2. In addition, 1.8 MPa was adopted as the bending stress. The results are shown in Table 1.

[Forming conditions]

Cylinder temperature: melting point of polymer +15℃

Mold temperature: 80℃

Back pressure: 2MPa

Injection speed: 33mm/sec

[Melting viscosity]

Use CAPIROGRAPH 1B model manufactured by Toyo Seiki Seisakusho Co., Ltd., and use an orifice with an inner diameter of 1 mm and a length of 20 mm at a temperature 10 to 30°C higher than the melting point of the liquid crystalline polymer, at a cutting speed 1000/sec. The melt viscosity of the liquid crystalline polymer was measured in accordance with ISO11443. In addition, the measurement temperature was 360°C for Examples 1 to 6, and Comparative Examples 1, 2, and 4, 370°C for Comparative Example 3, and 380°C for Comparative Examples 5 and 6.

[Manufacturability]

The behavior when the polymer was discharged from the lower part of the polymerization vessel was observed, and the manufacturability was evaluated in accordance with the following criteria. The results are shown in Table 1.

○: When the polymer can be formed into strands and discharged without problems, and the strands can be cut into pellets, the manufacturability is evaluated as good.

×: When solidification or the like occurs in the container during polymerization and the polymer cannot be discharged, or even if the polymer can be discharged as a strand, the strand cannot be cut, it is evaluated as poor manufacturability.

<Examples 2-6, Comparative Examples 1-10>

Except having made the kind of raw material monomer and the addition ratio (mol %) as Tables 1 and 2, it carried out similarly to Example 1, and obtained the polymer. In addition, the same evaluation as in Example 1 was performed. The evaluation results are shown in Tables 1 and 2.

Claims (10)

A wholly aromatic polyester amide, which is composed of the following structural units (I) ~ (V) as essential constituents: relative to the total structural units, the content of structural unit (I) is 62~75 mol% , Relative to the total structural unit, the content of structural unit (II) is 1~4.5 mol%, relative to the total structural unit, the content of structural unit (III) is 10.25-19 mol%, relative to the total structural unit, the structure The content of the unit (IV) is 3.25-18 mol%, and relative to the total structural unit, the content of the structural unit (V) is 1-7 mol%, relative to the total structural unit, the structural unit (I)~(V The total content of) is 100 mol%, and the mol number of structural unit (III) is 1.01~1.06 times the total mol number of structural unit (IV) and structural unit (V), or structural unit (IV) and The total molar number of structural unit (V) is 1.01~1.06 times the molar number of structural unit (III) and shows optical anisotropy when melting:

For the wholly aromatic polyester amide described in the first item of the scope of patent application, the content of structural unit (III) relative to the total structural unit is 10.25-17.45 mol%. The wholly aromatic polyester amide described in item 1 or 2 of the scope of patent application has a melting point of 350°C or less. A wholly aromatic polyester amide, which is a wholly aromatic polyester amide with a deflection temperature under load of 270°C or higher as described in item 1 or 2 of the scope of the patent application. Polyesteramide 60% by mass, and 40% by mass of ground fibers with an average fiber diameter of 11μm and average fiber length of 75μm are melt-kneaded at the melting point of the aforementioned wholly aromatic polyesteramide +20°C. Measured in the state of the resin composition. The wholly aromatic polyester amide as described in item 1 or 2 of the scope of patent application, which melts at a temperature 10~30℃ higher than the melting point of the aforementioned wholly aromatic polyester amide and a shear rate of 1000/sec. The viscosity is below 500Pa‧s. The wholly aromatic polyester amide as described in the first or second scope of the patent application, wherein The molar number of structural unit (III) is 1.02~1.06 times the total molar number of structural unit (IV) and structural unit (V), or the total molar number of structural unit (IV) and structural unit (V) It is 1.02~1.06 times the molar number of structural unit (III). A method for producing a wholly aromatic polyester amide that exhibits optical anisotropy when melted. The aforementioned method involves the use of fatty acid anhydride in the presence of a fatty acid metal salt to combine 4-hydroxybenzoic acid and 6-hydroxy-2-naphthalene Formic acid, 4,4'-dihydroxybiphenyl, and N-acetyl-p-aminophenol are acylated and transesterified with 1,4-benzenedicarboxylic acid; It is composed of benzoic acid, 6-hydroxy-2-naphthoic acid, 1,4-benzenedicarboxylic acid, 4,4'-dihydroxybiphenyl, and N-acetyl-p-aminophenol and used in the aforementioned methods The total monomer, the usage amount of 4-hydroxybenzoic acid is 62~75 mol%, the usage amount of 6-hydroxy-2-naphthoic acid is 1~4.5 mol%, and the usage amount of 1,4-benzenedicarboxylic acid 10.25~19mol%, the usage amount of 4,4'-dihydroxybiphenyl is 3.25~18mol%, the usage amount of N-acetyl-p-aminophenol is 1~7mol%, 4 -Hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 1,4-benzenedicarboxylic acid, 4,4'-dihydroxybiphenyl, and N-acetyl-p-aminophenol in total usage amount is 100 Mole%, the mole number of 1,4-benzenedicarboxylic acid is 1.01~1.06 times the total mole number of 4,4'-dihydroxybiphenyl and N-acetyl-p-aminophenol, or The total number of moles of 4,4'-dihydroxybiphenyl and N-acetyl-p-aminophenol is 1.01~1.06 times the number of moles of 1,4-benzenedicarboxylic acid, and the usage amount of the aforementioned fatty acid anhydride It is 4-hydroxybenzoic acid, 6-hydroxy-2-naphthyl The total hydroxyl equivalent of acid, 4,4'-dihydroxybiphenyl, and N-acetyl-p-aminophenol is 1.02~1.05 times. According to the manufacturing method described in item 7 of the scope of patent application, the amount of 1,4-benzenedicarboxylic acid used is 10.25~17.45 mol% relative to the total monomer. The manufacturing method according to item 7 or 8 of the scope of patent application, wherein the aforementioned fatty acid metal salt is an acetic acid metal salt, and the aforementioned fatty acid anhydride is acetic anhydride. The manufacturing method described in item 7 or 8 of the scope of patent application, wherein the molar number of 1,4-benzenedicarboxylic acid is 4,4'-dihydroxybiphenyl and N-acetyl-p-aminophenol 1.02~1.06 times the total number of moles, or the total number of moles of 4,4'-dihydroxybiphenyl and N-acetyl-p-aminophenol is the number of moles of 1,4-benzenedicarboxylic acid 1.02~1.06 times.