WO2018097011A1

WO2018097011A1 - Fully aromatic polyesteramide and method for producing same

Info

Publication number: WO2018097011A1
Application number: PCT/JP2017/041152
Authority: WO
Inventors: 俊紀川原; 俊明横田
Original assignee: ポリプラスチックス株式会社
Priority date: 2016-11-24
Filing date: 2017-11-15
Publication date: 2018-05-31
Also published as: CN109843978A; JP6388749B1; JPWO2018097011A1; TWI733952B; TW201833178A

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

Totally aromatic polyester amide and method for producing the same

The present invention relates to a wholly aromatic polyester amide and a method for producing the same.

Since liquid crystalline polymers have excellent fluidity, mechanical strength, heat resistance, chemical resistance, electrical properties and the like in a well-balanced manner, they are widely used as high-performance engineering plastics. As the liquid crystalline polymer, a wholly aromatic polyester amide is 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. Patent Document 2 discloses an aromatic polyester amide obtained by reacting p-aminophenol, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4,4′-dihydroxybiphenyl, and terephthalic acid. It is disclosed.

Japanese Patent Laid-Open No. 02-086623 JP 05-170902 A

However, the wholly aromatic polyester amide described in Patent Document 1 has insufficient heat resistance, and the wholly aromatic polyester amide described in Patent Document 2 has insufficient compatibility between 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 amide having both a low melting point and heat resistance and a method for producing the same.

The inventors of the present invention have made extensive studies to solve the above problems. As a result, structural units derived from 4-hydroxybenzoic acid, structural units derived from 6-hydroxy-2-naphthoic acid, structural units derived from 1,4-phenylenedicarboxylic acid, 4,4′-dihydroxy The above-mentioned problems can be solved by a wholly aromatic polyester amide comprising a structural unit derived from biphenyl and a structural unit derived from N-acetyl-p-aminophenol, and the content of each structural unit is in a specific range. As a result, the present invention has been completed. More specifically, the present invention provides the following.

(1) Consists 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 all the structural units,
The content of the structural unit (II) is 1 to 4.5 mol% with respect to all the structural units,
The content of the structural unit (III) is 10.25 to 19 mol% with respect to all the structural units,
The content of the structural unit (IV) is 3.25 to 18 mol% with respect to all the structural units,
The content of the structural unit (V) is 1 to 7 mol% with respect to all the structural units,
A wholly aromatic polyester amide exhibiting optical anisotropy upon melting, wherein the total content of the structural units (I) to (V) is 100 mol% with respect to the total structural units.

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

(3) The wholly aromatic polyester amide according to (1) or (2), wherein the deflection temperature under load is 270 ° C. or higher,
The deflection temperature under load is 60% by mass of the wholly aromatic polyester amide and 40% by mass of milled fiber having an average fiber diameter of 11 μm and an average fiber length of 75 μm at the melting point of the wholly aromatic polyester amide + 20 ° C. Wholly aromatic polyester amide measured in the state of the polyester amide resin composition obtained in the above.

(4) The total viscosity according to any one of (1) to (3), wherein the melt viscosity at a temperature 10 to 30 ° C. higher than the melting point of the wholly aromatic polyester amide and a shear rate of 1000 / sec is 500 Pa · s or less. Aromatic polyesteramide.

(5) The number of moles of the structural unit (III) is 1 to 1.2 times the total number of moles of the structural unit (IV) and the structural unit (V), or the structural unit (IV) and the structural unit ( The wholly aromatic polyester amide according to any one of (1) to (4), wherein the total number of moles of 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 amide exhibiting optical anisotropy when melted,
The method comprises acylating 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4,4′-dihydroxybiphenyl, and N-acetyl-p-aminophenol with a fatty acid anhydride in the presence of a fatty acid metal salt. And transesterifying with 1,4-phenylenedicarboxylic acid,
4-Hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 1,4-phenylenedicarboxylic acid, 4,4′-dihydroxybiphenyl, and N-acetyl-p-aminophenol. In contrast,
The amount of 4-hydroxybenzoic acid used is 61 to 75 mol%,
The amount of 6-hydroxy-2-naphthoic acid used is 1 to 4.5 mol%,
The amount of 1,4-phenylenedicarboxylic acid used is 10.25 to 19 mol%,
The amount of 4,4′-dihydroxybiphenyl used is 3.25 to 18 mol%,
The amount of N-acetyl-p-aminophenol used is 1-7 mol%,
The total amount of 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 1,4-phenylenedicarboxylic acid, 4,4′-dihydroxybiphenyl, and N-acetyl-p-aminophenol used is 100 mol%.
And
The amount of the fatty acid anhydride used is 1.02 of the total hydroxyl equivalent of 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4,4′-dihydroxybiphenyl, and N-acetyl-p-aminophenol. A method that is ˜1.05 times.

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

(8) The number of moles of 1,4-phenylenedicarboxylic acid is 1 to 1.2 times the total number of moles of 4,4′-dihydroxybiphenyl and N-acetyl-p-aminophenol, (6) or (7), wherein the total number of moles of 4′-dihydroxybiphenyl and N-acetyl-p-aminophenol is 1 to 1.2 times the number of moles of 1,4-phenylenedicarboxylic acid. Method.

According to the present invention, the wholly aromatic polyester amide of the present invention, which consists of a specific structural unit and exhibits optical anisotropy when melted, is sufficient to achieve both low melting point and heat resistance.

Also, the wholly aromatic polyester amide of the present invention is not so high in molding processing temperature that it can be injection-molded, extruded, compression-molded, etc. without using a molding machine having a special structure.

As described above, the wholly aromatic polyester amide of the present invention is excellent in moldability 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. For this reason, molded products such as connectors, CPU sockets, relay switch parts, bobbins, actuators, noise reduction filter cases or heat fixing rolls for OA equipment, which are suitable uses of the wholly aromatic polyester amide of the present invention, can be easily obtained. It is done.

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

<Totally aromatic polyester amide>
The wholly aromatic polyester amide of the present invention comprises 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).

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 all the structural units. When the content of the structural unit (I) is less than 61 mol% or exceeds 75 mol%, at least one of lowering the melting point and heat resistance tends to be insufficient. From the viewpoint of achieving both low melting point and heat resistance, the content of the structural unit (I) is preferably 61.5 to 73.5 mol%, more preferably 62 to 72 mol%.

The structural unit (II) is derived from 6-hydroxy-2-naphthoic acid (hereinafter also referred to as “HNA”). The wholly aromatic polyester amide of the present invention contains 1 to 4.5 mol% of the structural unit (II) with respect to the total structural units. If the content of the structural unit (II) is less than 1 mol% or exceeds 4.5 mol%, at least one of lowering the melting point and heat resistance tends to be insufficient. From the viewpoint of achieving both low melting point and heat resistance, the content of the structural unit (II) is preferably 2 to 4 mol%, more preferably 3 to 3.6 mol%.

The structural unit (III) is derived from 1,4-phenylenedicarboxylic acid (hereinafter also referred to as “TA”). The wholly aromatic polyester amide of the present invention contains 10.25 to 19 mol% of the structural unit (III) with respect to the total structural units. If the content of the structural unit (III) is less than 10.25 mol% or exceeds 19 mol%, at least one of lowering the melting point and heat resistance tends to be insufficient. From the viewpoint of achieving both low melting point and heat resistance, the content of the structural unit (III) is preferably 11.5 to 18.25 mol%, more preferably 12.5 to 17.45 mol%.

The structural unit (IV) is derived from 4,4′-dihydroxybiphenyl (hereinafter also referred to as “BP”). The wholly aromatic polyester amide of the present invention contains 3.25 to 18 mol% of the structural unit (IV) with respect to all the structural units. When the content of the structural unit (IV) is less than 3.25 mol% or more than 18 mol%, at least one of lowering the melting point and heat resistance tends to be insufficient. From the viewpoint of achieving both low melting point and heat resistance, the content of the structural unit (IV) is preferably 6.5 to 16 mol%, more preferably 10 to 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 of the present invention contains 1 to 7 mol% of the structural unit (V) with respect to all the structural units. If the content of the structural unit (V) is less than 1 mol% or exceeds 7 mol%, at least one of lowering the melting point and heat resistance tends to be insufficient. From the viewpoint of achieving both low melting point and heat resistance, the content of the structural unit (V) is preferably 1.5 to 6 mol%, more preferably 2 to 5 mol%.

From the viewpoint of achieving both low melting point and heat resistance, the number of moles of the structural unit (III) (hereinafter also referred to as “number of moles 1A”) is the sum of the structural unit (IV) and the structural unit (V). 1 to 1.2 times the number of moles (hereinafter also referred to as “number of moles 2A”), or the total number of moles of the structural unit (IV) and the structural unit (V) is the structural unit (III) It is preferably 1 to 1.2 times the number of moles. The mole number 1A is 1.01-1.06 times the mole number 2A, or the mole number 2A is more preferably 1.01-1.06 times the mole number 1A. More preferably, the mole number 1A is 1.02 to 1.03 times the mole number 2A, or the mole number 2A is 1.02 to 1.03 times the mole number 1A. The mole number 1A is 1.024 to 1.030 times the mole number 2A, or the mole number 2A is particularly preferably 1.024 to 1.030 times the mole number 1A.

As described above, the wholly aromatic polyester amide of the present invention contains the specific structural units (I) to (V) in a specific amount with respect to the total structural units. Coexistence is enough. Incidentally, the wholly aromatic polyester amide 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 representing the heat resistance, there is a deflection temperature under load (hereinafter also referred to as “DTUL”). When DTUL is 270 ° C. or higher, heat resistance tends to be high, which is preferable. DTUL is obtained by melt-kneading 60% by mass of the wholly aromatic polyester amide and 40% by mass of milled fiber having an average fiber diameter of 11 μm and an average fiber length of 75 μm at the melting point of the wholly aromatic polyester amide + 20 ° C. It is a value measured in the state of the polyesteramide resin composition, and can be measured according to ISO75-1,2. From the viewpoint of achieving both low melting point and heat resistance, DTUL is preferably 271 ° C. or higher and lower than 320 ° C., more preferably 272 to 288 ° C.

Next, a method for producing the wholly aromatic polyester amide of the present invention will be described. The wholly aromatic polyester amide of the present invention is polymerized using a direct polymerization method or a transesterification method. In the polymerization, a melt polymerization method, a solution polymerization method, a slurry polymerization method, a solid phase polymerization method, etc., or a combination of two or more of these are used, and a melt polymerization method or a combination of a melt polymerization method and a solid phase polymerization method is used. Is preferably used.

In the present invention, at the time of polymerization, an acylating agent for the polymerization monomer or a monomer having an activated terminal as an acid chloride derivative can be used. Examples of the acylating agent include fatty acid anhydrides such as acetic anhydride.

In the polymerization, various catalysts can be used. Typical examples include dialkyl tin oxide, diaryl tin oxide, titanium dioxide, alkoxy titanium silicates, titanium alcoholates, fatty acid metal salts, BF ₃ Lewis acid salts such as are mentioned, and fatty acid metal salts are preferred. The amount of the catalyst used is generally about 0.001 to 1% by weight, particularly about 0.003 to 0.2% by weight, based on the total weight of the monomers.

Also, when performing solution polymerization or slurry polymerization, liquid paraffin, high heat resistant synthetic oil, inert mineral oil, or the like is used as a solvent.

The reaction conditions are, for example, a reaction temperature of 200 to 380 ° C. and a final ultimate pressure of 0.1 to 760 Torr (that is, 13 to 101,080 Pa). Particularly in a melt reaction, for example, a reaction temperature of 260 to 380 ° C., preferably 300 to 360 ° C., a final ultimate pressure of 1 to 100 Torr (ie, 133 to 13,300 Pa), preferably 1 to 50 Torr (ie, 133 to 6,670 Pa). ).

In the reaction, all the raw material monomers (HBA, HNA, TA, BP, and APAP), the acylating agent, and the catalyst can be charged into the same reaction vessel to start the reaction (one-stage system), or the raw material monomers HBA, HNA , BP, and APAP can be acylated with an acylating agent and then reacted with a TA carboxyl group (two-stage system).

The melt polymerization is performed after the inside of the reaction system has reached a predetermined temperature, and the pressure reduction is started to a predetermined degree of pressure reduction. After the torque of the stirrer reaches a predetermined value, an inert gas is introduced, and the total aromatic polyester amide is discharged from the reaction system through a normal pressure from a reduced pressure state to a predetermined pressure state.

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

The process for producing a wholly aromatic polyester amide of the present invention comprises 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4,4′-dihydroxybiphenyl, and N-acetyl-p- in the presence of a fatty acid metal salt. Preferably, the method comprises acylating aminophenol with a fatty acid anhydride and transesterifying with 1,4-phenylenedicarboxylic acid,
4-Hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 1,4-phenylenedicarboxylic acid, 4,4′-dihydroxybiphenyl, and N-acetyl-p-aminophenol. In contrast,
4-hydroxybenzoic acid is used in an amount of 61 to 75 mol%, preferably 61.5 to 73.5 mol%, more preferably 62 to 72 mol%, from the viewpoint of achieving both low melting point and heat resistance.
The amount of 6-hydroxy-2-naphthoic acid used is 1 to 4.5 mol%, and preferably 2 to 4 mol%, more preferably 3 to 3.6 mol, from the viewpoint of achieving both low melting point and heat resistance. %,
The amount of 1,4-phenylenedicarboxylic acid used is from 10.25 to 19 mol%, and preferably from 11.5 to 18.25 mol%, more preferably from 12.5 mol%, from the viewpoint of achieving both low melting point and heat resistance. ˜17.45 mol%,
The amount of 4,4′-dihydroxybiphenyl used is 3.25 to 18 mol%, and preferably 6.5 to 16 mol%, more preferably 10 to 14.25 from the viewpoint of achieving both low melting point and heat resistance. Mol%,
N-acetyl-p-aminophenol is used in an amount of 1 to 7 mol%, preferably 1.5 to 6 mol%, more preferably 2 to 5 mol%, from the viewpoint of achieving both low melting point and heat resistance.
The total amount of 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 1,4-phenylenedicarboxylic acid, 4,4′-dihydroxybiphenyl, and N-acetyl-p-aminophenol used is 100 mol%.
It is preferable that
The amount of the fatty acid anhydride used is 1.02 of the total hydroxyl equivalent of 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4,4′-dihydroxybiphenyl, and N-acetyl-p-aminophenol. It is preferably ˜1.05 times. More preferably, the fatty acid metal salt is an acetic acid metal salt and the fatty acid anhydride is acetic anhydride. The number of moles of 1,4-phenylenedicarboxylic acid (hereinafter also referred to as “number of moles 1B”) is the total number of moles of 4,4′-dihydroxybiphenyl and N-acetyl-p-aminophenol (hereinafter referred to as “number of moles 1B”). 1 to 1.2 times the number of moles), or the total number of moles of 4,4′-dihydroxybiphenyl and N-acetyl-p-aminophenol is 1,4- More preferably, it is 1 to 1.2 times the number of moles of phenylenedicarboxylic acid. More preferably, the mole number 1B is 1.01 to 1.06 times the mole number 2B, or the mole number 2B is 1.01 to 1.06 times the mole number 1B. More preferably, the mole number 1B is 1.02 to 1.03 times the mole number 2B, or the mole number 2B is 1.02 to 1.03 times the mole number 1B. The number of moles 1B is 1.024 to 1.030 times the number of moles 2B, or the number of moles 2B is particularly preferably 1.024 to 1.030 times the number of moles 1B.

Next, the properties of wholly aromatic polyester amide will be described. The wholly aromatic polyester amide of the present invention exhibits optical anisotropy when melted. An optical anisotropy when melted means that the wholly aromatic polyester amide of the present invention is a liquid crystalline polymer.

In the present invention, the fact that the wholly aromatic polyester amide is a liquid crystalline polymer is an essential element for the wholly aromatic polyester amide to have both heat stability and easy processability. The wholly aromatic polyester amides composed of the structural units (I) to (V) may not form an anisotropic melt phase depending on the constituent components and the sequence distribution in the polymer. Is limited to wholly aromatic polyester amides exhibiting optical anisotropy when melted.

The property of melt anisotropy can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the melting anisotropy can be confirmed by melting a sample placed on a hot stage manufactured by Linkham Co., Ltd. using a polarizing microscope manufactured by Olympus and observing it at a magnification of 150 times in a nitrogen atmosphere. The liquid crystalline polymer is optically anisotropic and transmits light when inserted between crossed polarizers. If the sample is optically anisotropic, for example, polarized light is transmitted even in a molten stationary liquid state.

Since a nematic liquid crystalline polymer causes a significant decrease in viscosity at a melting point or higher, generally exhibiting liquid crystallinity at a melting point or higher is an index of workability. The melting point is preferably as high as possible from the viewpoint of heat resistance, but considering the thermal deterioration during the melt processing of the polymer, the heating ability of the molding machine, etc., it is preferably 350 ° C. or lower. The temperature is more preferably 320 to 350 ° C, and still more preferably 344 to 349 ° C.

The melt viscosity of the wholly aromatic polyester amide at a temperature 10 to 30 ° C. higher than the melting point of the wholly aromatic polyester amide of the present invention and a shear rate of 1000 / sec is preferably 500 Pa · s or less, more preferably 0. 5 to 300 Pa · s, and even more preferably 1 to 100 Pa · s. When the melt viscosity is within the above range, the wholly aromatic polyester amide itself or the composition containing the wholly aromatic polyester amide is easy to ensure fluidity at the time of molding, and the filling pressure is excessive. It is hard to become. In addition, in this specification, melt viscosity means the melt viscosity measured based on ISO11443.

The difference between the melting point and DTUL can also be cited as an index representing the above heat resistance. If this difference is 85 ° C. or less, the heat resistance tends to increase, which is preferable. From the viewpoint of achieving both low melting point and heat resistance, the difference is preferably more than 0 ° C. and 79 ° C. or less (eg, 50 ° C. or more and 79 ° C. or less), more preferably 61 to 75 ° C.

<Polyesteramide resin composition>
Various fibrous, granular, and plate-like inorganic and organic fillers can be blended with the wholly aromatic polyester amide of the present invention according to the purpose of use.

As the inorganic filler to be blended in the polyesteramide resin composition of the present invention, there are fibrous, granular and plate-like ones.

Silica such as glass fiber, asbestos fiber, silica fiber, silica / alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, wollastonite as fibrous inorganic filler Inorganic fibrous materials such as fibers, magnesium sulfate fibers, aluminum borate fibers, and metal fibrous materials such as stainless steel, aluminum, titanium, copper, and brass. A particularly typical fibrous filler is glass fiber.

In addition, as the granular inorganic filler, carbon black, graphite, silica, quartz powder, glass beads, milled glass fiber, glass balloon, glass powder, calcium oxalate, aluminum oxalate, kaolin, clay, diatomaceous earth, wollast Silicates such as knight, iron oxide, titanium oxide, zinc oxide, antimony trioxide, metal oxides such as alumina, metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate Examples thereof include salts, other ferrites, silicon carbide, silicon nitride, boron nitride, and various metal powders.

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

Examples of organic fillers include 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 alone or in combination of two or more. The combined use of the fibrous inorganic filler and the granular or plate-like inorganic filler is a preferable combination in order to combine mechanical strength, dimensional accuracy, electrical properties, and the like. Particularly preferably, the fibrous filler is glass fiber, and the platy filler is mica and talc. The blending amount is 120 parts by mass or less, preferably 20 to 80 parts by mass with respect to 100 parts by mass of the wholly aromatic polyester amide. Part. By combining the glass fiber with mica or talc, the polyesteramide resin composition is particularly prominent in improving the heat distortion temperature and mechanical properties.

When using these fillers, a sizing agent or a surface treatment agent can be used if necessary.

As described above, the polyesteramide resin composition of the present invention contains the wholly aromatic polyesteramide of the present invention and an inorganic or organic filler as essential components. Ingredients may be included. Here, the other component may be any component, and examples thereof include other resins, antioxidants, stabilizers, pigments, crystal nucleating agents and the like.

The production method of the polyesteramide resin composition of the present invention is not particularly limited, and the polyesteramide resin composition can be prepared by a conventionally known method.

<Polyesteramide molded product>
The polyesteramide molded article of the present invention is formed by molding the wholly aromatic polyesteramide or the polyesteramide resin composition of the present invention. The molding method is not particularly limited, and a general molding method can be employed. Examples of general molding methods include injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, rotational molding, gas injection molding, and the like.

A polyesteramide molded product obtained by molding the wholly aromatic polyesteramide of the present invention is excellent in heat resistance and toughness. Moreover, since the polyesteramide molded article formed by molding the polyesteramide resin composition of the present invention is excellent in heat resistance and toughness and contains an inorganic or organic filler, mechanical strength and the like are further improved.

Also, since the wholly aromatic polyester amide and the polyester amide resin composition of the present invention are excellent in moldability, a polyester amide molded product having a desired shape can be easily obtained.

Preferred uses of the polyesteramide molded product of the present invention having the above properties include connectors, CPU sockets, relay switch parts, bobbins, actuators, noise reduction filter cases, heat fixing rolls for OA equipment, and the like.

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

<Example 1>
A polymerization vessel equipped with a stirrer, a reflux column, a monomer inlet, a nitrogen inlet, and a decompression / outflow line was charged with the following raw material monomers, fatty acid metal salt catalyst, and acylating agent, 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) 2.93 mol (17.45 mol%) terephthalic acid (TA)
(IV) 2.01 mol (11.95 mol%) of 4,4′-dihydroxybiphenyl (BP)
(V) N-acetyl-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 charging the raw materials, the temperature of the reaction system was raised to 140 ° C. and reacted at 140 ° C. for 1 hour. Thereafter, the temperature is further increased to 360 ° C. over 5.5 hours, and then the pressure is reduced to 10 Torr (ie, 1330 Pa) over 20 minutes to melt while distilling acetic acid, excess acetic anhydride, and other low-boiling components. Polymerization was performed. After the stirring torque reached a predetermined value, nitrogen was introduced and the pressure was changed from a reduced pressure state to a normal pressure, and the polymer was discharged from the lower part of the polymerization vessel.

<Evaluation>
About the wholly aromatic polyester amide of Example 1, evaluation of melting | fusing point, DTUL, melt viscosity, and manufacturability was performed with the following method. The evaluation results are shown in Table 1.

[Melting point]
After observing the endothermic peak temperature (Tm1) observed by DSC (manufactured by TA Instruments) at a temperature rising condition of 20 ° C./min from room temperature, the temperature is 2 at (Tm1 + 40) ° C. After being held for a minute, the sample was once cooled to room temperature under a temperature drop condition of 20 ° C./min, and then the temperature of the endothermic peak observed when measured under a temperature rise condition of 20 ° C./min was measured again.

[DTUL]
60% by mass of polymer and 40% by mass of glass fiber (EFH75-01 manufactured by Central Glass Co., Ltd., milled fiber, average fiber diameter 11 μm, average fiber length 75 μm), twin screw extruder (TEX30α type manufactured by Nippon Steel Co., Ltd.) Was melt-kneaded at a cylinder temperature of the melting point of the polymer + 20 ° C. to obtain polyesteramide resin composition pellets.
The polyesteramide resin composition pellets were molded under the following molding conditions using a molding machine (“SE100DU” manufactured by Sumitomo Heavy Industries, Ltd.) to obtain test specimens (4 mm × 10 mm × 80 mm). . Using this test piece, the deflection temperature under load was measured by a method based on ISO75-1,2. Note that 1.8 MPa was used as the bending stress. The results are shown in Table 1.
〔Molding condition〕
Cylinder temperature: Polymer melting point + 15 ° C
Mold temperature: 80 ℃
Back pressure: 2MPa
Injection speed: 33mm / sec

[Melt viscosity]
Using a Capillograph Type 1B manufactured by Toyo Seiki Seisakusho Co., Ltd., using an orifice having 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, and a shear rate of 1000 / sec. In conformity, the melt viscosity of the liquid crystalline polymer was measured. 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 part of the polymerization vessel was observed, and the manufacturability was evaluated according to the following criteria. The results are shown in Table 1.
○: The polymer was discharged as a strand without any problem, and when this strand could be cut into a pellet, it was evaluated that the manufacturability was good.
X: Manufacturability was evaluated to be poor when solidification or the like was caused in the container during polymerization and the polymer could not be discharged, or when the polymer could be discharged as a strand but the strand could not be cut.

<Examples 2 to 6, Comparative Examples 1 to 10>
A polymer was obtained in the same manner as in Example 1 except that the type of raw material monomer and the charging ratio (mol%) were as shown in Tables 1 and 2. Moreover, the same evaluation as Example 1 was performed. The evaluation results are shown in Tables 1 and 2.

Claims

It consists of the following structural units (I) to (V) as essential components:
The content of the structural unit (I) is 61 to 75 mol% with respect to all the structural units,
The content of the structural unit (II) is 1 to 4.5 mol% with respect to all the structural units,
The content of the structural unit (III) is 10.25 to 19 mol% with respect to all the structural units,
The content of the structural unit (IV) is 3.25 to 18 mol% with respect to all the structural units,
The content of the structural unit (V) is 1 to 7 mol% with respect to all the structural units,
A wholly aromatic polyester amide exhibiting optical anisotropy upon melting, wherein the total content of the structural units (I) to (V) is 100 mol% with respect to the total structural units.
The wholly aromatic polyester amide according to claim 1, having a melting point of 350 ° C or lower.
The wholly aromatic polyester amide according to claim 1 or 2, wherein the deflection temperature under load is 270 ° C or higher,
The deflection temperature under load is 60% by mass of the wholly aromatic polyester amide and 40% by mass of milled fiber having an average fiber diameter of 11 μm and an average fiber length of 75 μm at the melting point of the wholly aromatic polyester amide + 20 ° C. Wholly aromatic polyester amide measured in the state of the polyester amide resin composition obtained in the above.
The wholly aromatic polyester amide according to any one of claims 1 to 3, which has a melt viscosity of 500 Pa · s or less at a temperature 10 to 30 ° C higher than the melting point of the wholly aromatic polyester amide and at a shear rate of 1000 / sec.
The number of moles of the structural unit (III) is 1 to 1.2 times the total number of moles of the structural unit (IV) and the structural unit (V), or the structural unit (IV) and the structural unit (V) The wholly aromatic polyester amide according to any one of claims 1 to 4, wherein the total number of moles of is 1 to 1.2 times the number of moles of the structural unit (III).
A process for producing a wholly aromatic polyester amide exhibiting optical anisotropy when melted,
The method comprises acylating 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4,4′-dihydroxybiphenyl, and N-acetyl-p-aminophenol with a fatty acid anhydride in the presence of a fatty acid metal salt. And transesterifying with 1,4-phenylenedicarboxylic acid,
4-Hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 1,4-phenylenedicarboxylic acid, 4,4′-dihydroxybiphenyl, and N-acetyl-p-aminophenol. In contrast,
The amount of 4-hydroxybenzoic acid used is 61 to 75 mol%,
The amount of 6-hydroxy-2-naphthoic acid used is 1 to 4.5 mol%,
The amount of 1,4-phenylenedicarboxylic acid used is 10.25 to 19 mol%,
The amount of 4,4′-dihydroxybiphenyl used is 3.25 to 18 mol%,
The amount of N-acetyl-p-aminophenol used is 1-7 mol%,
The total amount of 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 1,4-phenylenedicarboxylic acid, 4,4′-dihydroxybiphenyl, and N-acetyl-p-aminophenol used is 100 mol%.
And
The amount of the fatty acid anhydride used is 1.02 of the total hydroxyl equivalent of 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4,4′-dihydroxybiphenyl, and N-acetyl-p-aminophenol. A method that is ˜1.05 times.
The method according to claim 6, wherein the fatty acid metal salt is an acetic acid metal salt and the fatty acid anhydride is acetic anhydride.
The number of moles of 1,4-phenylenedicarboxylic acid is 1 to 1.2 times the total number of moles of 4,4′-dihydroxybiphenyl and N-acetyl-p-aminophenol, or 4,4′- The method according to claim 6 or 7, wherein the total number of moles of dihydroxybiphenyl and N-acetyl-p-aminophenol is 1 to 1.2 times the number of moles of 1,4-phenylenedicarboxylic acid.