TW201833178A - Fully aromatic polyesteramide and method for producing same - Google Patents

Abstract

Provided are a fully aromatic polyesteramide that is satisfactory in terms of low melting point and heat resistance, and a method for producing same. This fully aromatic polyesteramide: comprises constituent units (I) to (V) as essential constituent components; contains, relative to the total quantity of constituent units, 61-75 mol.% of constituent unit (I), 1-4.5 mol.% of constituent unit (II), 10.25-19 mol.% of constituent unit (III), 3.25-18 mol.% of constituent unit (IV) and 1-7 mol.% of constituent unit (V), with the total quantity of constituent units (I) to (V) being 100 mol.%; and exhibits optical anisotropy when molten.

Description

 Full aromatic polyester decylamine and its production method  

This invention relates to a wholly aromatic polyester decylamine and a process for its manufacture.

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

Prior technical literature

Patent literature

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

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

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

In view of the above problems, an object of the present invention is to provide a wholly aromatic polyester decylamine which is sufficient in both low melting point and heat resistance and a method for producing the same.

In order to solve the above problems, the inventors of the present invention have repeatedly studied intensively. As a result, a wholly aromatic polyester guanamine was found which was composed of the following structural units: a structural unit derived from 4-hydroxybenzoic acid, a structural unit derived from 6-hydroxy-2-naphthoic acid, a structural unit derived from 1,4-benzenedicarboxylic acid, a structural unit derived from 4,4'-dihydroxybiphenyl, and a structural unit derived from N-ethinyl-p-aminophenol, and each The content of the structural unit is within a specific range, and the above 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 decylamine comprising the following structural units (I) to (V) as essential constituent components: the content of the structural unit (I) is 61 to 75 with respect to the total structural unit. Molar%, the content of the structural unit (II) is 1 to 4.5 mol% relative to the total structural unit, and the content of the structural unit (III) is 10.25 to 19 mol% relative to the total structural unit, relative to the total structure The content of the unit and the structural unit (IV) is 3.25 to 18 mol%, and the content of the structural unit (V) is 1 to 7 mol% relative to the total structural unit, and the structural unit (I) is relative to the total structural unit. The total content of ~(V) is 100 mol% and exhibits optical anisotropy upon melting:

(2) The wholly aromatic polyester decylamine according to (1), which has a melting point of 350 ° C or lower.

(3) A wholly aromatic polyester decylamine, which is a wholly aromatic polyester decylamine as described in (1) or (2), having a load deflection temperature of 270 ° C or higher, and the aforementioned load deflection temperature system Polyester obtained by melt-kneading 60% by mass of aromatic polyester decylamine, 40% by mass of ground fiber having an average fiber diameter of 11 μm and an average fiber length of 75 μm at a melting point of the wholly aromatic polyester decylamine + 20 ° C It was measured in the state of a guanamine resin composition.

(4) The wholly aromatic polyester decyl amine according to any one of (1) to (3), wherein the temperature is 10 to 30 ° C higher than the melting point of the aforementioned wholly aromatic polyester decylamine and sheared The melt viscosity at a cutting speed of 1000/sec is 500 Pa‧s or less.

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

(6) A method for producing a wholly aromatic polyester decylamine exhibiting optical anisotropy upon melting, the method comprising the use of a fatty acid anhydride to 4-hydroxybenzoic acid in the presence of a fatty acid metal salt a step of thiolation of -hydroxy-2-naphthoic acid, 4,4'-dihydroxybiphenyl, and N-ethinyl-p-aminophenol and transesterification with 1,4-benzenedicarboxylic acid; It is composed of 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 1,4-benzenedicarboxylic acid, 4,4'-dihydroxybiphenyl, and N-ethinyl-p-aminophenol. And using the total monomer in the foregoing method, the amount of 4-hydroxybenzoic acid used is 61-75 mol%, and the amount of 6-hydroxy-2-naphthoic acid used is 1~4.5 mol%, 1,4-benzene. The amount of dicarboxylic acid used is 10.25-19 mol%, the amount of 4,4'-dihydroxybiphenyl used is 3.25-18 mol%, and the amount of N-ethinyl-p-aminophenol is 1~ 7 mol%, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 1,4-benzenedicarboxylic acid, 4,4'-dihydroxybiphenyl, and N-ethinyl-p-aminophenol The total amount used is 100 mol%, and the amount of the above fatty acid anhydride is 4-hydroxybenzoic acid, 6-hydroxy-2-naphthyl , 4,4'-dihydroxybiphenyl, N- acetyl group and - 1.02 to 1.05 hydroxyl equivalent of the sum of p-aminophenol.

(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-ethinyl-p-aminophenol 1 to 1.2 times the total number of moles, or the total number of 4,4'-dihydroxybiphenyl and N-ethinyl-p-aminophenol in the molar number of 1,4-benzenedicarboxylic acid The number is 1~1.2 times.

According to the present invention, the wholly aromatic polyester decylamine of the present invention which is composed of a specific structural unit and exhibits optical anisotropy upon melting is sufficient in combination of low melting point and heat resistance.

Moreover, since the molding temperature of the wholly aromatic polyester phthalamide of the present invention is not so high, injection molding, extrusion molding, compression molding, and the like can be performed without using a molding machine having a special structure.

The wholly aromatic polyester amide of the present invention has excellent moldability as described above, and can be molded by using various types of molding machines. As a result, it can be easily processed into various three-dimensional molded articles, fibers, films, and the like. Therefore, it is also possible to easily obtain a connector, a CPU socket, a relay switch component, a bobbin, an actuator, a noise reduction filter box, or an OA machine for use in the application of the wholly aromatic polyester phthalamide of the present invention. A molded article such as a roll.

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

<All aromatic polyester decylamine>

The wholly aromatic polyester guanamine 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) constitutes.

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

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

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

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

The structural unit (V) is derived from N-ethinyl-p-aminophenol (hereinafter, also referred to as "APAP"). The wholly aromatic polyester amide of the present invention contains 1 to 7 mol% of the structural unit (V) with respect 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 low melting point and heat resistance is likely to be insufficient. The content of the structural unit (V) is preferably from 1.5 to 6 mol%, more preferably from 2 to 5 mol%, from the viewpoint of coexistence of low melting point and heat resistance.

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

As described above, since the wholly aromatic polyester amide of the present invention contains a specific amount of the specific structural units (I) to (V) with respect to the total structural unit, the combination of the low melting point and the heat resistance is sufficient. Further, the wholly aromatic polyester amide of the present invention is a total of 100 mol% of structural units (I) to (V) based on the total structural unit.

The index of the heat resistance is a load deflection temperature (hereinafter also referred to as "DTUL"). When the DTUL is 270 C or more, the heat resistance tends to be high, which is preferable. DTUL is obtained by melt-mixing 60% by mass of the wholly aromatic polyester decylamine, 40% by mass of the ground fiber diameter of 11 μm, and an average fiber length of 75 μm at a melting point of the wholly aromatic polyester decylamine at 20 ° C. The value measured in the state of the obtained polyester amide resin composition can be measured in accordance with ISO 75-1, 2. From the viewpoint of the combination 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, a method for producing the wholly aromatic polyester decylamine of the present invention will be described. The wholly aromatic polyester guanamine of the present invention can be polymerized by a direct polymerization method, a transesterification method or the like. In the polymerization, a melt polymerization method, a solution polymerization method, a slurry polymerization method, a solid phase polymerization method, or the like, or a combination of two or more thereof can be used, and a melt polymerization method, a melt polymerization method, and a solid phase polymerization method can be suitably used. The combination.

In the present invention, in the polymerization, a thiolating agent for a polymerizable monomer or a monomer which is terminally activated as a mercapto chloro derivative can be used. The thiolating agent may, for example, be a fatty acid anhydride such as acetic anhydride.

Various catalysts can be used for the polymerization, and examples thereof include dialkyl tin oxides, diaryl tin oxides, titanium oxides, titanium alkoxides, titanium alkoxides, and fatty acid metals. A salt such as a Lewis acid salt of BF3 or the like 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, and particularly preferably from about 0.003 to 0.2% by mass.

Further, when solution polymerization or slurry polymerization is carried out, as the solvent, a liquid paraffin, a highly heat-resistant synthetic oil, an inert mineral oil or the like can be used.

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). In particular, the melting reaction is, for example, a reaction temperature of 260 to 380 C, preferably 300 to 360 ° C, and finally a pressure of 1 to 100 Torr (that is, 133 to 13,300 Pa), preferably 1 to 50 Torr (that is, 133 to 6,670 Pa). .

The reaction system can add all the raw material monomers (HBA, HNA, TA, BP, and APAP), thiolating agent, and catalyst to the same reaction vessel to start the reaction (one way), or use thiolation. The hydroxy group of the raw material monomers HBA, HNA, BP, and APAP is thiolated, and then reacted with the carboxyl group of TA (two-stage method).

After the molten polymerization system reaches a predetermined temperature in the reaction system, the pressure reduction is started to be a predetermined degree of pressure reduction. After the torque of the agitator reaches a predetermined value, an inert gas is introduced and a normal pressure is applied from a reduced pressure state to a predetermined pressurized state, and the wholly aromatic polyester decylamine is discharged from the reaction system.

The wholly aromatic polyester decylamine produced by the above polymerization method can be increased in molecular weight by solid phase polymerization which is further heated under normal pressure or reduced pressure in an inert gas. The preferred conditions for the solid phase polymerization are a reaction temperature of 230 to 350 ° C, preferably 260 to 330 ° C, and finally a pressure of 10 to 760 Torr (that is, 1,330 to 101,080 Pa).

The method for producing a wholly aromatic polyester decylamine of the present invention comprises 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4,4'-di using a fatty acid anhydride in the presence of a fatty acid metal salt. Hydroxybiphenyl, and N-ethinyl-p-aminophenol guanidinated and transesterified with 1,4-benzenedicarboxylic acid are preferred, and relative to 4-hydroxybenzoic acid, 6-hydroxy- 2-naphthoic acid, 1,4-benzenedicarboxylic acid, 4,4'-dihydroxybiphenyl, and N-ethinyl-p-aminophenol, and the total monomer used in the foregoing method, 4-hydroxyl The amount of benzoic acid used is 61 to 75 mol%, and from the viewpoint of the coexistence of low melting point and heat resistance, it is preferably 61.5 to 73.5 mol%, preferably 62 to 72 mol%, and 6-hydroxyl group. The amount of use of -2-naphthoic acid is from 1 to 4.5 mol%, and from the viewpoint of the combination of low melting point and heat resistance, it is preferably 2 to 4 mol%, more preferably 3 to 3.6 mol%. The amount of use of 1,4-benzenedicarboxylic acid is from 10.25 to 19 mol%, and from the viewpoint of the coexistence of low melting point and heat resistance, it is preferably from 11.5 to 18.25 mol%, preferably from 12.5 to 17.45 mol. % of ear, 4,4'-dihydroxybiphenyl is used in an amount of 3.25-18 mol%, from low melting point From the viewpoint of coexistence of heat resistance, it is preferably 6.5 to 16 mol%, preferably 10 to 14.25 mol%, and N-acetinyl-p-aminophenol is used in an amount of 1 to 7 mol%. From the viewpoint of the coexistence of low melting point and heat resistance, it is preferably 1.5 to 6 mol%, preferably 2 to 5 mol%, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, The total amount of 1,4-benzenedicarboxylic acid, 4,4'-dihydroxybiphenyl, and N-ethinyl-p-aminophenol is preferably 100 mol%, and the amount of the above fatty acid anhydride is used. It is preferably 1.02 to 1.05 times the total hydroxyl equivalent of 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4,4'-dihydroxybiphenyl, and N-ethinyl-p-aminophenol. . The fatty acid metal salt is a metal acetate salt, and the above fatty acid anhydride is preferably acetic anhydride. Further, 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-ethinyl-p-aminophenol. 1 to 1.2 times the molar number (hereinafter, also referred to as "molar number 2B"), or the total number of moles of 4,4'-dihydroxybiphenyl and N-ethinyl-p-aminophenol It is preferred that the number of moles of 1,4-benzenedicarboxylic acid is from 1 to 1.2 times. The molar number 1B is 1.01 to 1.06 times the molar number 2B, or the molar number 2B is preferably 1.01 to 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 preferably 1.02 to 1.03 times the molar number 1B. The molar number 1B is 1.024 to 1.030 times the molar number 2B, or the molar number 2B is particularly preferably 1.024 to 1.030 times the molar number 1B.

Next, the properties of the wholly aromatic polyester decylamine will be described. The wholly aromatic polyester amide of the present invention exhibits optical anisotropy upon melting. The fact that the optical anisotropy is exhibited during melting means that the wholly aromatic polyester decylamine of the present invention is a liquid crystal polymer.

In the present invention, the wholly aromatic polyester decylamine is a liquid crystal polymer, and the wholly aromatic polyester decylamine is an indispensable element in terms of both thermal stability and ease of processing. Although the wholly aromatic polyester decylamine composed of the above structural units (I) to (V) is distributed in the order of the constituent components and the polymer, there is also a substance in which the anisotropic molten phase is not formed, but the present invention The polymer is limited to a wholly aromatic polyester decylamine which exhibits optical anisotropy upon melting.

The nature of the melting anisotropy can be confirmed by a conventional polarizing inspection method using a crossed polarizer. More specifically, the confirmation of the melting anisotropy can be performed by using a polarizing microscope manufactured by Olympus Co., Ltd., and melting the sample placed on a hot stage of a Linkam company, and at a magnification of 150 times in a nitrogen atmosphere. Observe to implement. The liquid crystalline polymer is optically anisotropic and transmits light when inserted between orthogonal polarizers. When the sample is optically anisotropic, for example, even in the molten stationary state, the polarized light is transmitted.

Since the nematic liquid crystal polymer remarkably exhibits a decrease in viscosity at a melting point or higher, the liquid crystallinity generally indicates an index of workability at a temperature of a melting point or higher. From the viewpoint of heat resistance, the melting point is preferably as high as possible. However, in consideration of thermal deterioration during melt processing of the polymer, heating ability of the molding machine, and the like, 350 ° C or less is an appropriate target. Further, it is preferably 320 to 350 ° C, more preferably 344 to 349 ° C.

The melt viscosity of the wholly aromatic polyester decylamine at a temperature higher than the melting point of the wholly aromatic polyester decylamine of the present invention at a temperature of 10 to 30 ° C and a shear rate of 1000 / sec is preferably 500 Pa ‧ or less Preferably, it is 0.5 to 300 Pa‧s, more preferably 1 to 100 Pa‧s. When the melt viscosity is within the above range, the composition of the wholly aromatic polyester guanamine itself or the wholly aromatic polyester decylamine is easy to ensure fluidity during molding, and the filling pressure is not too high. Further, in the present specification, the term "melt viscosity" means the melt viscosity measured in accordance with ISO11443.

The index indicating the above heat resistance may be the difference between the melting point and DTUL. When the difference is 85 ° C or less, the heat resistance tends to be high, which is preferable. The difference is preferably from more than 0 ° C to 79 ° C (for example, from 50 ° C to 79 ° C), preferably from 61 to 75 ° C, from the viewpoint of coexistence of low melting point and heat resistance.

<Polyester amide resin composition>

The wholly aromatic polyester phthalamide of the present invention described above can be formulated into various fibrous, powdery, and plate-like inorganic and organic fillers depending on the purpose of use.

The inorganic filler to be blended in the polyesteramine resin composition of the present invention has a fibrous, granular or plate-like material.

Examples of the fibrous inorganic filler include glass fibers, asbestos fibers, cerium oxide fibers, cerium oxide ‧ alumina fibers, alumina fibers, zirconia fibers, boron nitride fibers, cerium nitride fibers, boron fibers, and titanic acid. An inorganic fibrous material such as a potassium fiber, a fiber of a strontium salt of wollastonite, a magnesium sulfate fiber, an aluminum borate fiber, or a fibrous material of a metal such as stainless steel, aluminum, titanium, copper or brass. A particularly representative fibrous filler is glass fiber.

Further, examples of the particulate inorganic filler include carbon black, graphite, cerium oxide, quartz powder, glass beads, milled glass fibers, glass spheres, glass powders such as calcium silicate, aluminum silicate, kaolin, and clay. , diatomaceous earth, strontium silicate, such as iron oxide, titanium oxide, zinc oxide, antimony trioxide, metal oxides of aluminum oxide, metal carbonates such as calcium carbonate, magnesium carbonate, such as calcium sulfate, sulfuric acid Sulfate of bismuth metal, ferrite iron, tantalum carbide, tantalum nitride, boron nitride, various metal powders, and the like.

Further, examples of the plate-like inorganic filler include mica, glass cullet, talc, and various metal foils.

When an example of the organic filler is disclosed, there are a heat-resistant high-strength synthetic fiber such as an aromatic polyester fiber, a liquid crystalline polymer fiber, an aromatic polyamine or a polyimide fiber.

These inorganic and organic fillers can be used alone or in combination of two or more. The combination of the fibrous inorganic filler and the granular or plate-shaped inorganic filler is a preferable combination in terms of mechanical strength, dimensional accuracy, electrical properties and the like. The glass fiber which is a fibrous filler, the mica which is a plate-shaped filler, and the talc are preferably 120 parts by mass or less, preferably 20 to 80 parts by mass based on 100 parts by mass of the wholly aromatic polyester phthalamide. Parts by mass. The increase in the heat distortion temperature, mechanical properties, and the like of the polyester guanamine resin composition is particularly remarkable by combining the glass fibers with mica or talc.

When such a filler is used, an astringent or a surface treatment agent can also be used as necessary.

The polyester guanamine resin composition of the present invention contains the wholly aromatic polyester guanamine, an inorganic or organic filler of the present invention as an essential component as described above, but it does not impair the effects of the present invention. May contain other ingredients. Here, the other component may be any component, and examples thereof include additives such as other resins, antioxidants, stabilizers, pigments, and crystal nucleating agents.

Further, the method for producing the polyesteramine resin composition of the present invention is not particularly limited, and a polyesteramine resin composition can be prepared by a conventional method.

<Polyester amide moldings>

The polyester melamine molded article of the present invention is obtained by molding the wholly aromatic polyester decylamine or the polyester guanamine resin composition of the present invention. The molding method is not particularly limited, and a usual molding method can be employed. As a usual molding method, a method of injection molding, extrusion molding, compression molding, air blowing molding, vacuum molding, foam molding, rotational molding, gas injection molding, or the like can be exemplified.

The polyester amide molded article obtained by molding the wholly aromatic polyester phthalamide or the like of the present invention has excellent heat resistance and toughness. In addition, the polyester melamine molded article obtained by molding the polyester phthalamide resin composition of the present invention has excellent heat resistance and toughness, and also contains an inorganic or organic filler, so that mechanical strength and the like can be further improved. .

Moreover, since the wholly aromatic polyester phthalamide and the polyester decylamine resin composition of the present invention have excellent moldability, a polyester melamine molded article having a desired shape can be easily obtained.

Suitable examples of the polyester amide molded article of the present invention having the above properties include a connector, a CPU socket, a relay switch component, a bobbin, an actuator, a noise reduction filter box, or an OA machine. Heat the fixed roller, etc.

[Examples]

Hereinafter, the present invention will be described in more detail with reference to examples but the present invention is not limited by the following examples.

<Example 1>

The following raw material monomers, fatty acid metal salt catalysts, and sulfhydrylating agents were added to a polymerization vessel equipped with a stirrer, a reflux column, a monomer inlet, a nitrogen inlet, and a pressure reduction/outflow line, and nitrogen substitution was 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-Ethyl-p-aminophenol 0.84 mol% (5 mol%) (APAP)

Potassium acetate catalyst 50ppm

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

After the addition of the raw materials, the temperature of the reaction system was raised to 140 ° C and allowed to react at 140 ° C for 1 hour. Subsequently, the temperature was further raised 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 off. After the stirring torque reaches a predetermined value, nitrogen gas is introduced, and the pressure is released from the reduced pressure state through normal pressure, and the polymer is discharged from the lower portion of the polymerization vessel.

<evaluation>

The wholly aromatic polyester decylamine of Example 1 was evaluated for melting point, DTUL, melt viscosity, and manufacturability by the following method. The evaluation results are shown in Table 1.

[melting point]

The observed endothermic peak temperature (Tm1) was observed by DSC (manufactured by TA Instruments Co., Ltd.) at a temperature rise of 20 ° C /min from room temperature, and then maintained at a temperature of (Tm1 + 40) ° C. After the minute, the temperature was once cooled to room temperature under a cooling condition of 20 ° C /min, and the endothermic peak temperature which can be observed when measured under a temperature rising condition of 20 ° C /min was measured again.

[DTUL]

60% by mass of the polymer and 40% by mass of glass fiber (EFH75-01 made of Central Glass Co., Ltd., ground fiber, flat fiber diameter: 11 μm, average fiber length: 75 μm) using a biaxial extruder (Japanese steel) The TEX30α type produced was melt-kneaded at a cylinder temperature of a melting point of the polymer + 20 ° C to obtain a polyester guanamine resin composition pellet.

The test piece (4 mm × 10 mm × 80 mm) for measurement was obtained by molding the above-mentioned polyester phthalamide resin composition pellets using a molding machine ("SE100DU" manufactured by Sumitomo Heavy Industries, Ltd.) under the following molding conditions. The test piece was used and the load deflection temperature was measured by the method according to ISO 75-1, 2. Further, as the bending stress, 1.8 MPa was used. The results are shown in Table 1.

[forming conditions]

Cylinder temperature: melting point of polymer +15 ° C

Mold temperature: 80 ° C

Back pressure: 2MPa

Injection speed: 33mm/sec

[melt viscosity]

CAPIROGRAPH type 1B manufactured by Toyo Seiki Seisakusho Co., Ltd., and using an orifice having an inner diameter of 1 mm and a length of 20 mm at a cutting speed of 10 to 30 ° C higher than the melting point of the liquid crystalline polymer. 1000/sec The melt viscosity of the liquid crystalline polymer was measured in accordance with ISO11443. Further, the measurement temperatures were 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 portion of the above-mentioned polymerization container was observed, and the manufacturability was evaluated in accordance with the following criteria. The results are shown in Table 1.

○: The polymer was made into a strand and discharged without any problem, and when the strand was cut into pellets, it was evaluated that the strandability was good.

X: When the polymer was discharged in the container during the polymerization, and the polymer could not be discharged, or the strand could be discharged as a strand, the strand could not be cut.

<Examples 2 to 6 and Comparative Examples 1 to 10>

A polymer was obtained in the same manner as in Example 1 except that the types and addition ratios (mol%) of the raw material monomers were as shown in Tables 1 and 2. Further, the same evaluation as in Example 1 was carried out. The evaluation results are shown in Tables 1 and 2.

Claims (8)

A wholly aromatic polyester decylamine is composed of the following structural units (I) to (V) as essential constituents: the content of the structural unit (I) is 61 to 75 mol% with respect to the total structural unit. The content of the structural unit (II) is 1 to 4.5 mol% relative to the total structural unit, and the content of the structural unit (III) is 10.25 to 19 mol% relative to the total structural unit, relative to the total structural unit, the structure The content of the unit (IV) is 3.25 to 18 mol%, and the content of the structural unit (V) is 1 to 7 mol% relative to the total structural unit, and the structural unit (I) to (V) is relative to the total structural unit. The total content is 100 mol% and exhibits optical anisotropy upon melting:  The wholly aromatic polyester decylamine described in claim 1 has a melting point of 350 ° C or less.    A wholly aromatic polyester decylamine, which is a wholly aromatic polyester decylamine as described in claim 1 or 2, having a load deflection temperature of 270 ° C or higher, and the above-mentioned load deflection temperature is the above-mentioned wholly aromatic Polyester decylamine obtained by melt-kneading 60% by mass of polyester decylamine and 40% by mass of ground fiber having an average fiber diameter of 11 μm and an average fiber length of 75 μm at a melting point of the wholly aromatic polyester phthalamide + 20 ° C It was measured in the state of a resin composition.    The wholly aromatic polyester decylamine according to claim 1 or 2, wherein the melting is higher than the melting point of the wholly aromatic polyester decylamine by 10 to 30 ° C and the shear rate is 1000 sec. The viscosity is below 500 Pa‧s.    The wholly aromatic polyester decylamine according to claim 1 or 2, wherein the molar number of the structural unit (III) is 1 to 1.2 of the total number of moles of the structural unit (IV) and the structural unit (V). The total number of moles of the structural unit (IV) and the structural unit (V) is 1 to 1.2 times the number of moles of the structural unit (III).    One method is a method for producing an optically anisotropic wholly aromatic polyester decylamine which comprises 4-hydroxybenzoic acid, 6-hydroxy- in the presence of a fatty acid metal salt in the presence of a fatty acid metal salt. 2-naphthoic acid, 4,4'-dihydroxybiphenyl, and N-ethinyl-p-aminophenol are thiolated and transesterified with 1,4-benzenedicarboxylic acid; 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 1,4-benzenedicarboxylic acid, 4,4'-dihydroxybiphenyl, and N-ethinyl-p-aminophenol are used and used in The total monomer of the above method, the amount of 4-hydroxybenzoic acid used is 61-75 mol%, and the amount of 6-hydroxy-2-naphthoic acid used is 1~4.5 mol%, 1,4-benzenedicarboxylic acid The amount of use is 10.25~19 mol%, the amount of 4,4'-dihydroxybiphenyl is 3.25-18 mol%, and the amount of N-ethinyl-p-aminophenol is 1-7 mol. Total use of %, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 1,4-benzenedicarboxylic acid, 4,4'-dihydroxybiphenyl, and N-ethinyl-p-aminophenol The amount is 100 mol%, and the amount of the above fatty acid anhydride is 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid. 4,4'-dihydroxybiphenyl, N- acetyl group and - 1.02 to 1.05 hydroxyl equivalent of the sum of p-aminophenol.    The method of claim 6, wherein the fatty acid metal salt is a metal acetate salt, and the fatty acid anhydride is acetic anhydride.    The method of claim 6 or 7, wherein the molar number of 1,4-benzenedicarboxylic acid is 4,4'-dihydroxybiphenyl and N-ethinyl-p-aminophenol. 1 to 1.2 times the molar number, or the total number of moles of 4,4'-dihydroxybiphenyl and N-ethinyl-p-aminophenol is the molar number of 1,4-benzenedicarboxylic acid 1~1.2 times.