TW202100610A - Wholly aromatic polyester and polyester resin composition - Google Patents

Abstract

[Problem] Provided are a wholly aromatic polyester with an extremely small amount of side reactions during polymerization and with excellent color phase and a polyester resin composition containing said wholly aromatic polyester. [Solution] The abovementioned problem is solved with a wholly aromatic polyester characterized by comprising the following structural units (I), (II), (III), and (IV) as essential components, wherein: the content of structural unit (I) with respect to all structural units is 40-75 mol%; the content of structural unit (II) with respect to all structural units is 0.5-7.5 mol%; the content of structural unit (III) with respect to all structural units is 8.5-30 mol%; the content of structural unit (IV) with respect to all structural units is 8.5-30 mol%; the total content of structural units (I), (II), (III), and (IV) with respect to all structural units is 100 mol%; the wholly aromatic polyester comprises ester bonds or a combination of ester bonds and ketone bonds in molecules thereof; and the amount of ketone bonds with respect to the total of ester bonds and ketone bonds is 0.0000-0.0010 mol%.

Description

Fully aromatic polyester and polyester resin composition

The present invention relates to a wholly aromatic polyester that has very few side reactions during the polymerization reaction and is excellent in hue and toughness, and a polyester resin composition thereof.

Liquid crystal resins such as wholly aromatic polyesters have excellent fluidity, mechanical strength, heat resistance, chemical resistance, electrical properties, etc., in a well-balanced manner, so they are widely used as high-performance engineering plastics.

As a fully aromatic polyester, most of the currently marketed products are based on 4-hydroxybenzoic acid as the main component. However, since the melting point of the homopolymer of 4-hydroxybenzoic acid becomes higher than the decomposition point, it is necessary to lower the melting point by copolymerizing various components.

A wholly aromatic polyester using 1,4-phenylene dicarboxylic acid, 1,4-dihydroxybenzene, 4,4'-dihydroxybiphenyl, etc. as the copolymerization component has a high melting point of 350°C or higher. It is too high for melt processing using general-purpose equipment. In addition, various methods have been tried to lower the melting point of such a high melting point to a temperature that can be processed with general-purpose melt processing equipment. However, when the so-called low melting point is achieved to some extent, on the other hand, it cannot be maintained. The problem of mechanical strength at high temperature (near the melting point).

In order to solve this problem, a wholly aromatic polyester has been proposed, which is composed of a specific structure containing 6-hydroxy-2-naphthoic acid as a main component (Patent Document 1). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2002-179776

[The problem to be solved by the invention]

However, the wholly aromatic polyester of Patent Document 1 has the following problems: a ketone bond is formed due to a side reaction during the polymerization reaction, the hue of the polymer is deteriorated by the product produced by the ketone bond, and the toughness of the polymer Will decrease.

The subject of the present invention is to provide a wholly aromatic polyester that has very few side reactions during the polymerization reaction and is excellent in hue and toughness, and a polyester resin composition thereof. [Means used to solve the problem]

The inventors of the present invention have found that the above-mentioned problems can be solved by a wholly aromatic polyester, and then completed the present invention. The wholly aromatic polyester is characterized in that the following structural units (I), (II), ( III) and (IV) the wholly aromatic polyester constituted as essential constituents, the content of the constituent unit (I) is 40 to 75 mol% relative to all constituent units, and the constituent unit ( The content of II) is 0.5 to 7.5 mol%, and the content of structural unit (III) is 8.5 to 30 mol% relative to all structural units, and the content of structural unit (IV) is 8.5 to 30 relative to all structural units. Mole%, the total content of the structural units (I), (II), (III) and (IV) is 100 mole% relative to all the structural units, and has an ester bond or an ester bond and a ketone bond in the molecule The amount of the ketone bond is 0.0000 to 0.0010 mole% relative to the total of the ester bond and the ketone bond. More specifically, the present invention provides the following. [化1]

（2）一種聚酯樹脂組合物，其含有如（1）所記載之全芳香族聚酯。 （3）一種聚酯成形品，其係將如（1）或（2）所記載之全芳香族聚酯或聚酯樹脂組合物成形而得。 （4）一種全芳香族聚酯的製造方法，其係全芳香族聚酯的製造方法，其特徵在於，包含： 利用脂肪酸酐將6－羥基－2－萘甲酸、4－羥苯甲酸、及4,4’－二羥基聯苯進行醯化(acylation)，並與1,4－伸苯基二羧酸進行酯交換的步驟， 相對於由6－羥基－2－萘甲酸、4－羥苯甲酸、1,4－伸苯基二羧酸、及4,4’－二羥基聯苯所構成之全部單體， 6－羥基－2－萘甲酸的使用量為40～75莫耳%， 4－羥苯甲酸的使用量為0.5～7.5莫耳%， 1,4－伸苯基二羧酸的使用量為8.5～30莫耳%， 4,4’－二羥基聯苯的使用量為8.5～30莫耳%， 6－羥基－2－萘甲酸、4－羥苯甲酸、1,4－伸苯基二羧酸、及4,4’－二羥基聯苯的合計使用量為100莫耳%， 最終聚合溫度為340℃以下。 （5）如（4）所記載之全芳香族聚酯的製造方法，其特徵在於，使用含氮雜環化合物作為觸媒。 （6）如（5）所記載之全芳香族聚酯的製造方法，其中，含氮雜環化合物為1－甲咪唑。 （7）如（4）所記載之全芳香族聚酯的製造方法，其特徵在於，使用鉀化合物及／或三價的鈷化合物作為觸媒。 （8）如（7）所記載之全芳香族聚酯的製造方法，其中，鉀化合物為乙酸鉀。 （9）如（7）或（8）所記載之全芳香族聚酯的製造方法，其中，三價的鈷化合物為參（2,4－戊二酮酸）鈷（III）。 [發明效果](1) A wholly aromatic polyester characterized in that it is a wholly aromatic polyester composed of the following structural units (I), (II), (III) and (IV) as essential constituents. The content of structural unit (I) is 40 to 75 mol% in all structural units, and the content of structural unit (II) is 0.5 to 7.5 mol% relative to all structural units. The content of structural unit (II) is 0.5 to 7.5 mol% relative to all structural units. The content of III) is 8.5-30 mol%, and the content of the structural unit (IV) is 8.5-30 mol% relative to all the structural units. The content of the structural units (I), (II), ( The total content of III) and (IV) is 100 mol%, and has an ester bond or a combination of an ester bond and a ketone bond in the molecule. The amount of the ketone bond relative to the total of the ester bond and the ketone bond is 0.0000～0.0010 mole%. [化2]

(2) A polyester resin composition containing the wholly aromatic polyester as described in (1). (3) A polyester molded product obtained by molding the wholly aromatic polyester or polyester resin composition as described in (1) or (2). (4) A method for producing a wholly aromatic polyester, which is a method for producing a wholly aromatic polyester, characterized in that it comprises: using fatty acid anhydride to prepare 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, and The step of acylation of 4,4'-dihydroxybiphenyl and transesterification with 1,4-phenylene dicarboxylic acid is different from 6-hydroxy-2-naphthoic acid and 4-hydroxybenzene All monomers composed of formic acid, 1,4-phenylene dicarboxylic acid, and 4,4'-dihydroxybiphenyl, the usage amount of 6-hydroxy-2-naphthoic acid is 40～75 mol%, 4 －The usage amount of hydroxybenzoic acid is 0.5～7.5 mol%, the usage amount of 1,4-phenylene dicarboxylic acid is 8.5～30 mol%, and the usage amount of 4,4'-dihydroxybiphenyl is 8.5 ～30 mol%, the total usage amount of 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 1,4-phenylene dicarboxylic acid, and 4,4'-dihydroxybiphenyl is 100 mol %, the final polymerization temperature is 340°C or less. (5) The method for producing a wholly aromatic polyester as described in (4), characterized in that a nitrogen-containing heterocyclic compound is used as a catalyst. (6) The method for producing a wholly aromatic polyester as described in (5), wherein the nitrogen-containing heterocyclic compound is 1-methimidazole. (7) The method for producing a wholly aromatic polyester as described in (4), characterized by using a potassium compound and/or a trivalent cobalt compound as a catalyst. (8) The method for producing a wholly aromatic polyester as described in (7), wherein the potassium compound is potassium acetate. (9) The method for producing a wholly aromatic polyester as described in (7) or (8), wherein the trivalent cobalt compound is ginseng (2,4-pentanedionate) cobalt (III). [Invention Effect]

According to the present invention, it is possible to provide a wholly aromatic polyester and a polyester resin composition thereof that have very few side reactions during the polymerization reaction and are excellent in hue and toughness.

[Form for implementing the invention]

Hereinafter, an embodiment of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented with appropriate changes within a range that does not impair the effects of the present invention. In addition, in the present invention, "A-B" means "A or more and B or less".

[Wholly Aromatic Polyester] The wholly aromatic polyester of the present invention is a wholly aromatic polyester characterized in that the following structural units (I), (II), (III) and (IV) are essential The content of structural unit (I) is 40 to 75 mol% relative to all structural units, and the content of structural unit (II) is 0.5 to 7.5 relative to all structural units. Mole%, the content of structural unit (III) is 8.5-30 mol% relative to all structural units, and the content of structural unit (IV) is 8.5-30 mol% relative to all structural units The unit, the total content of the constituent units (I), (II), (III), and (IV) is 100 mol%, and has an ester bond or a combination of an ester bond and a ketone bond in the molecule, relative to the aforementioned ester bond The amount of the ketone bond in total with the ketone bond is 0.0000 to 0.0010 mole%. [化3]

The structural unit (I) is derived from 6-hydroxy-2-naphthoic acid (hereinafter also referred to as "HNA"). The wholly aromatic polyester of the present invention contains 40 to 75 mol% of the structural unit (I) relative to all the structural units. If the content of the structural unit (I) is less than 40 mol%, the melting point is lowered and the heat resistance is insufficient. If the content of the structural unit (I) is more than 75 mol%, curing occurs during polymerization, and a polymer cannot be obtained. From the viewpoint of heat resistance and polymerizability, the content of the constituent unit (I) is preferably 40-70 mol%, more preferably 40-65 mol%, still more preferably 40-63 mol%, and still more It is preferably 40 to 62 mol%, particularly preferably 40 to 60 mol%.

The structural unit (II) is derived from 4-hydroxybenzoic acid (hereinafter also referred to as "HBA"). The wholly aromatic polyester of the present invention contains 0.5 to 7.5 mol% of the structural unit (II) relative to all structural units. If the content of the structural unit (II) is less than 0.5 mol%, curing occurs during polymerization, and a polymer cannot be obtained. If the content of the structural unit (II) exceeds 7.5 mol%, the melting point is lowered and the heat resistance is insufficient. From the viewpoint of heat resistance and polymerizability, the content of the constituent unit (II) is preferably 0.5 to 7.0 mol%, more preferably 1.0 to 7.0 mol%, still more preferably 1.2 to 7.0 mol%, and still more Preferably it is 1.5-6.5 mol%, particularly preferably 2.0-6.0 mol%.

The structural unit (III) is derived from 1,4-phenylene dicarboxylic acid (hereinafter, also referred to as "TA"). The wholly aromatic polyester of the present invention contains 8.5 to 30 mol% of the structural unit (III) with respect to all structural units. If the content of the structural unit (III) is less than 8.5 mol% or more than 30 mol%, at least one of lower melting point and heat resistance tends to become insufficient. From the viewpoint of low melting point and heat resistance, the content of the constituent unit (III) is preferably 10-30 mol%, more preferably 12-28 mol%, and still more preferably 14-28 mol% , And further preferably 15-28 mol%, particularly preferably 17-27 mol%.

The constituent unit (IV) is derived from 4,4'-dihydroxybiphenyl (hereinafter, also referred to as "BP"). The wholly aromatic polyester of the present invention contains 8.5 to 30 mol% of the structural unit (IV) with respect to all structural units. If the content of the structural unit (IV) is less than 8.5 mol% or more than 30 mol%, at least one of lower melting point and heat resistance tends to become insufficient. From the viewpoint of low melting point and heat resistance, the content of the constituent unit (IV) is preferably 10-30 mol%, more preferably 12-28 mol%, and still more preferably 14-28 mol% , And further preferably 15-28 mol%, particularly preferably 17-27 mol%.

As described above, the wholly aromatic polyester of the present invention contains a specific amount of specific structural units (I) to (IV) relative to all structural units, because it has an ester bond or an ester bond and a ketone bond in the molecule. The amount of the ketone bond is 0.0000 to 0.0010 mol% relative to the total of the ester bond and the ketone bond, so there are very few side reactions during the polymerization reaction and the hue is excellent. In addition, in the wholly aromatic polyester of the present invention, the amount of the ketone bond relative to the total of the ester bond and the ketone bond is preferably 0.0000 to 0.0008 mol%, more preferably 0.0000 to 0.0006 mol%, More preferably, it is 0.0000 to 0.0005 mol%, still more preferably 0.0000 to 0.0004 mol%, and particularly preferably 0.0000 to 0.0002 mol%. In addition, the wholly aromatic polyester of the present invention contains a total of 100 mol% of the structural units (I) to (IV) with respect to all the structural units.

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

In the present invention, the term "wholly aromatic polyester is a liquid crystalline polymer" means an indispensable element for the wholly aromatic polyester to have both thermal stability and ease of processing. The wholly aromatic polyester composed of the above-mentioned structural units (I) to (IV) may not form an anisotropic melt phase depending on the composition and sequence distribution in the polymer, but the polymer of the present invention is limited to A wholly aromatic polyester that exhibits optical anisotropy when melted.

The properties of the fusion anisotropy can be confirmed by a conventional polarization inspection method using a crossed polarizer. More specifically, the confirmation of melting anisotropy can be achieved by using a polarizing microscope manufactured by Olympus, melting a sample placed on a thermal stage manufactured by Linkam, and observing it in a nitrogen atmosphere at a magnification of 150 times. Implement. The liquid crystalline polymer is optically anisotropic and allows light to penetrate when inserted between crossed polarizers. If the sample is optically anisotropic, for example, even if it is in a molten static liquid state, polarized light will penetrate.

The nematic liquid crystalline polymer exhibits a significant decrease in viscosity above the melting point, so in general, the fact that it exhibits liquid crystallinity at the melting point or above becomes an index of processability. The melting point is preferably as high as possible from the viewpoint of heat resistance. However, considering the thermal degradation of the polymer during melt processing and the heating capacity of the molding machine, the preferred standard is 380°C or less. In addition, it is more preferably 260 to 370°C, still more preferably 270 to 370°C, particularly preferably 280 to 360°C.

The melt viscosity of the aforementioned wholly aromatic polyester at a temperature 10-40°C higher than the melting point of the wholly aromatic polyester of the present invention and a shear rate of 1000 per second is preferably 1000 Pa･s or less, more preferably 4 ～500Pa･s, more preferably 4～250Pa･s, particularly preferably 5～100Pa･s. If the melt viscosity is within the above range, the wholly aromatic polyester itself or the composition containing the wholly aromatic polyester will easily ensure fluidity during molding, and the filling pressure will not easily become excessive. In addition, in this specification, the so-called melt viscosity refers to the melt viscosity measured in compliance with ISO11443.

Next, the manufacturing method of the wholly aromatic polyester of this embodiment is demonstrated. The wholly aromatic polyester of this embodiment is polymerized using a direct polymerization method, a transesterification method, or the like. In the polymerization, melt polymerization method, solution polymerization method, slurry polymerization method, solid phase polymerization method, etc., or a combination of two or more of these are used, preferably melt polymerization method, or melt polymerization method and solid phase polymerization Combination of law.

In this embodiment, during polymerization, monomers with activated ends can be used as acylating agents and chlorinated derivatives for polymerized monomers. Examples of the acylating agent include fatty acid anhydrides such as acetic anhydride.

In the production method of the wholly aromatic polyester of this embodiment, from the viewpoint of hue, the amount of fatty acid anhydride used is preferably 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, and 4,4'-di The total hydroxyl equivalent of hydroxybiphenyl is less than 1.08 times, more preferably 1.00 to 1.07 times, still more preferably 1.01 to 1.07 times, still more preferably 1.01 to 1.06 times, particularly preferably 1.02 to 1.06 times.

Various catalysts can be used in these polymerizations. Representative examples include potassium acetate, magnesium acetate, tin(II) acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, and ginseng ( Metal salt catalysts such as 2,4-pentanedionate) cobalt (III), and organic compound catalysts such as 1-methimidazole and 4-dimethylaminopyridine.

The reaction system can combine all raw material monomers (6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 1,4-phenylene dicarboxylic acid, and 4,4'-dihydroxybiphenyl), acylating agent , And the catalyst is filled into the same reaction vessel to start the reaction (one-stage method), and 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, and 4,4'-dihydroxy After the hydroxyl group of biphenyl is acylated, it reacts with the carboxyl group of 1,4-phenylene dicarboxylic acid (two-stage method).

The melt polymerization system starts to reduce pressure after reaching a specified temperature in the reaction system, and proceeds to a specified degree of reduced pressure. After the torque of the stirrer reaches the specified value, an inert gas is introduced, and the fully aromatic polyester is discharged from the reaction system through normal pressure from the reduced pressure state to the specified pressurized state.

The wholly aromatic polyester produced by the above-mentioned polymerization method can further increase the molecular weight by solid-phase polymerization by heating under normal pressure or reduced pressure in an inert gas.

The method for producing the wholly aromatic polyester of the present embodiment preferably includes acylating 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, and 4,4'-dihydroxybiphenyl using fatty acid anhydride, and The step of transesterification with 1,4-phenylene dicarboxylic acid, Compared to all monomers composed of 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 1,4-phenylene dicarboxylic acid, and 4,4'-dihydroxybiphenyl, The usage amount of 6-hydroxy-2-naphthoic acid is 40-75 mol%. From the viewpoint of heat resistance and polymerizability, it is preferably 40-70 mol%, more preferably 40-65 mol%, More preferably, it is 40～63 mol%, still more preferably is 40～62 mol%, particularly preferably is 40～60 mol%, The amount of 4-hydroxybenzoic acid used is 0.5 to 7.5 mol%, and from the viewpoint of heat resistance and polymerizability, it is preferably 0.5 to 7.0 mol%, more preferably 1.0 to 7.0 mol%, and still more preferably 1.2～7.0 mol%, more preferably 1.5～6.5 mol%, particularly preferably 2.0～6.0 mol%, The amount of 1,4-phenylene dicarboxylic acid used is 8.5-30 mol%, and from the viewpoint of low melting point and heat resistance, it is preferably 10-30 mol%, more preferably 12- 28 mol%, more preferably 14-28 mol%, still more preferably 15-28 mol%, particularly preferably 17-27 mol%, The amount of 4,4'-dihydroxybiphenyl used is 8.5-30 mol%. From the viewpoint of low melting point and heat resistance, it is preferably 10-30 mol%, more preferably 12-28 Mole%, more preferably 14-28 mol%, still more preferably 15-28 mol%, particularly preferably 17-27 mol%, The total usage amount of 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 1,4-phenylene dicarboxylic acid, and 4,4'-dihydroxybiphenyl is preferably 100 mol%, The final polymerization temperature is preferably 340°C or lower, more preferably 330°C or lower, still more preferably 320°C or lower, still more preferably 310°C or lower, and particularly preferably 300°C or lower.

The method for producing the wholly aromatic polyester of this embodiment preferably uses a nitrogen-containing heterocyclic compound as a catalyst.

In the method for producing the wholly aromatic polyester of the present embodiment, it is preferable that the nitrogen-containing heterocyclic compound used as the catalyst is 1-methimidazole.

The method for producing the wholly aromatic polyester of this embodiment preferably uses a potassium compound and/or a trivalent cobalt compound as a catalyst.

In the method for producing the wholly aromatic polyester of the present embodiment, it is preferable that the potassium compound used as the catalyst is potassium acetate.

In the method for producing the wholly aromatic polyester of the present embodiment, it is preferable that the trivalent cobalt compound used as the catalyst is ginseng (2,4-pentanedionate) cobalt (III).

In the method of producing the wholly aromatic polyester of this embodiment, from the viewpoint of high molecular weight, the amount of 1,4-phenylene dicarboxylic acid used (mol%) and 4,4'-2 The difference between the amount of hydroxybiphenyl used (mole%) is 1.00 mol% or less, more preferably 0.75 mol% or less, still more preferably 0.50 mol% or less, and still more preferably 0.25 mol% or less, especially preferred The usage amount of 1,4-phenylene dicarboxylic acid (mol%) is equal to the usage amount of 4,4'-dihydroxybiphenyl (mol%).

[Polyester resin composition] In the above-mentioned wholly aromatic polyester of the present invention, various fibrous, powdery, and plate-shaped inorganic and organic fillers can be blended according to the purpose of use.

As the inorganic filler blended in the polyester resin composition of the present invention, there are those in the form of fibers, particles, and plates.

Examples of fibrous inorganic fillers include glass fiber, ground glass fiber, asbestos fiber, silica fiber, silica/alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron Fiber, potassium titanate fiber, silicate fiber such as wollastonite, magnesium sulfate fiber, aluminum borate fiber, even stainless steel, aluminum, titanium, copper, brass and other metal fibrous materials such as inorganic fibrous substances. A particularly representative fibrous filler is glass fiber.

In addition, as the powdery inorganic filler, carbon black, graphite, silica, quartz powder, glass beads, glass hollow spheres, glass powder, calcium silicate, aluminum silicate, kaolin, clay, diatomaceous earth, Silicates such as wollastonite, iron oxide, titanium oxide, zinc oxide, antimony trioxide, aluminum oxide and other metal oxides, calcium carbonate, magnesium carbonate and other metal carbonates, calcium sulfate, barium sulfate and other metal sulfuric acid Salt, other ferrous iron, silicon carbide, silicon nitride, boron nitride, various metal powders, etc.

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

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

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

The polyester resin composition of the present invention, as described above, contains the wholly aromatic polyester of the present invention as an essential component, and contains inorganic or organic fillers as needed, but it may be in a range that does not impair the effects of the present invention. Contains other ingredients. Here, the other components may be arbitrary components, and examples thereof include additives such as other resins, antioxidants, stabilizers, pigments, and crystal nucleating agents.

In addition, the production method of the polyester resin composition of the present invention is not particularly limited, and the polyester resin composition can be produced by a conventionally known method.

[Polyester molded product] The polyester molded product of the present invention can be obtained by molding the wholly aromatic polyester or polyester resin composition of the present invention. The molding method is not particularly limited, and general molding methods can be adopted. As general molding methods, methods such as injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, rotational molding, gas injection molding, and inflation molding can be exemplified.

The polyester molded product obtained by molding the wholly aromatic polyester or the like of the present invention has excellent heat resistance. In addition, the polyester molded article obtained by molding the polyester resin composition of the present invention has excellent heat resistance and at the same time contains inorganic or organic fillers as needed, so that mechanical strength and the like are further improved.

In addition, the wholly aromatic polyester and polyester resin composition of the present invention can be processed into various three-dimensional molded products, fibers, films, etc., because of excellent moldability.

Preferred uses of the polyester molded product of the present invention having the above properties include connectors, CPU sockets, relay switch parts, bobbins, actuators, noise reduction filter boxes, electronic circuit boards, or OA equipment The heating fixed roller and so on. [Example]

Examples are disclosed below to explain the present invention more specifically, but the present invention is not limited to these examples.

<Example 1> A polymerization vessel equipped with a mixer, a reflux column, a monomer input port, a nitrogen introduction port, and a pressure reduction/outflow line is filled with the following raw material monomers, fatty acid metal salt catalysts, and acylating agents, and nitrogen substitution is started. (I) 6-hydroxy-2-naphthoic acid 0.883 mol (48 mol%) (HNA) (II) 4-hydroxybenzoic acid 0.037 mol (2 mol%) (HBA) (III) 1,4-phenylene dicarboxylic acid 0.46 mol (25 mol%) (TA) (IV) 4,4’-Dihydroxybiphenyl 0.46 mol (25 mol%) (BP) 1-Memidazole catalyst 1100ppm Acetic anhydride 1.91 mol (1.04 times the total hydroxyl equivalent of HNA, HBA, and BP) After the raw material was charged, the temperature of the reaction system was increased to 140°C and reacted at 140°C for 1 hour. Thereafter, the temperature was further increased at the rate conditions shown in Table 1, and the final polymerization temperature was set as shown in Table 1, and melt polymerization was performed while distilling out acetic acid, excess acetic anhydride, and other low-boiling components. After the stirring torque reaches a specified value, nitrogen is introduced to be in a pressurized state, and the product is discharged from the lower part of the polymerization vessel and pulverized to obtain a powdery prepolymer. The obtained prepolymer was subjected to heat treatment (solid phase polymerization) at 230° C. for 10 hours, 320° C. for 30 hours, and 330° C. for 30 hours under a nitrogen stream to obtain the target polymer.

＜Evaluation＞ For the wholly aromatic polyester of Example 1, the melting point, melt viscosity, ketone bond amount, and hue (L value) were evaluated by the following methods. The evaluation results are shown in Table 1.

[Melting point] Using a differential scanning calorimetry (DSC, manufactured by Perkin Elmer), after measuring the endothermic peak temperature (Tm1) observed when the wholly aromatic polyester is heated from room temperature at 20°C/min. (Tm1+40) After maintaining the temperature of °C for 2 minutes, after cooling it to room temperature temporarily under the cooling conditions of 20 °C/min, the temperature of the endothermic peak observed during heating under the heating conditions of 20 °C/min was measured again.

[Melting viscosity] Using capillography manufactured by Toyo Seiki Seisakusho Co., Ltd., at a temperature 10-30°C higher than the melting point of the wholly aromatic polyester, an orifice with an inner diameter of 0.5 mm and a length of 30 mm is used, and the shear rate is 1000 per second and conforms to ISO11443, Determine the melt viscosity of the wholly aromatic polyester.

[Amount of ketone bond] Calculate the amount of ketone bond by thermal decomposition gas chromatography described in Polymer Degradation and Stability 76 (2002) 85-94. Specifically, using a thermal decomposition device (Frontier Laboratories "PY2020iD"), the wholly aromatic polyester is heated in the coexistence of tetramethylammonium hydroxide (TMAH), and thermal decomposition/methylation Make gas. The gas was analyzed by gas chromatography (“GC-6890N” manufactured by Agilent Technologies Co., Ltd.), and the amount of ketone bond was calculated from the ratio of the peak area derived from the ketone bond to the peak area derived from the ester bond.

[Hue (L value)] Using a spectrophotometer ("SE6000" manufactured by Nippon Denshoku Industries Co., Ltd.), the L value of the polymer was measured.

<Examples 2, 3> Except that the type of raw material monomer, usage amount (mol%), catalyst, heating rate, and final polymerization temperature are set as shown in Table 1, and the prepolymer is placed in a nitrogen stream at 290°C for 10 hours, 300°C Except for performing heat treatment (solid phase polymerization) for 10 hours, 310° C. and 10 hours, 320° C. and 10 hours, the same procedure as in Example 1 was performed to obtain a polymer. In addition, the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 1.

<Example 4, 5> Except that the kind of raw material monomer, the amount of use (mol %), the catalyst, the heating rate, and the final polymerization temperature were as shown in Table 1, the same procedure was performed as in Example 1 to obtain a polymer. In addition, the same evaluation as in Example 1 was performed (the melt viscosity of Example 5 was measured at a temperature of 350°C). The evaluation results are shown in Table 1.

<Comparative example 1> A polymerization vessel equipped with a stirrer, a reflux column, a monomer input port, a nitrogen introduction port, and a pressure reduction/outflow line is filled with the following raw material monomers, fatty acid metal salt catalysts, and acylating agents, and nitrogen substitution begins. (I) 6-hydroxy-2-naphthoic acid 0.883 mol (48 mol%) (HNA) (II) 4-hydroxybenzoic acid 0.037 mol (2 mol%) (HBA) (III) 1,4-phenylene dicarboxylic acid 0.46 mol (25 mol%) (TA) (IV) 4,4’-Dihydroxybiphenyl 0.46 mol (25 mol%) (BP) Potassium acetate catalyst 150ppm Ginseng (2,4-pentanedionate) cobalt (III) catalyst 150ppm Acetic anhydride 1.91 mol (1.04 times the total hydroxyl equivalent of HNA, HBA, and BP) After the raw material was charged, the temperature of the reaction system was increased to 140°C and reacted at 140°C for 1 hour. Thereafter, the temperature was further increased under the speed conditions shown in Table 1, and the final polymerization temperature was set as shown in Table 1, respectively. As a result, it took 20 minutes to reduce pressure to 10 Torr (that is, 1330 Pa), and melt polymerization was performed while distilling acetic acid, excess acetic anhydride, and other low-boiling components. After the stirring torque reaches a specified value, nitrogen is introduced, the reduced pressure is passed through normal pressure to a pressurized state, the product is discharged from the lower part of the polymerization vessel, and granulated to obtain a granular prepolymer. The obtained prepolymer was subjected to heat treatment (solid phase polymerization) at 300°C for 5 hours under a nitrogen stream to obtain the target polymer.

＜Comparative Examples 2, 3＞ Except that the type of raw material monomer, the amount of use (mol %), the catalyst, the heating rate, and the final polymerization temperature were as shown in Table 1, the same procedure was performed as in Comparative Example 1 to obtain a polymer. In addition, the same evaluation as in Example 1 was performed (the melt viscosity of Comparative Example 3 was measured at a temperature of 350°C). The evaluation results are shown in Table 1.

<Example 6> Using a biaxial extruder, the wholly aromatic polyester obtained in Example 1 and the following components were mixed to obtain a resin composition. The extrusion conditions are as described below. The blending amount of each component is as shown in Table 2. Fibrous filler Grinding fiber: EPH-80M made by Nippon Electric Glass (strand), fiber diameter 10.5μm, average fiber length 80μm (manufacturing brand name) Plate filler Mica: AB-25S manufactured by Yamaguchi Mica Industry (Stock), with an average particle size of 25μm

(Extrusion conditions) The temperature of the cylinder (cylinder) installed at the main feed port was set to 250°C, and the temperature of all other cylinders was set to 360°C. The wholly aromatic polyester system is all supplied from the main feed port. In addition, the filler is supplied from the side feed port.

<Comparative Example 4> Except for using the wholly aromatic polyester obtained in Comparative Example 1, the same procedure as in Example 1 was carried out to obtain a resin composition.

(Bending test) Under the following molding conditions, the resin composition was injection molded to obtain a molded product having a thickness of 130 mm×13 mm×0.8 mm. The bending strength, the bending elastic modulus, and the bending strain were measured in compliance with ASTM D790. The evaluation results are shown in Table 2. <Forming conditions> Forming machine: Sumitomo Heavy Industries, SE100DU Cylinder temperature: 370℃ Mold temperature: 80℃ Injection speed: 33mm/sec Holding pressure: 50MPa

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example 1 Comparative example 2 Comparative example 3 Monomer composition (amount used) HNA Mole% 48 48 48 40 60 48 40 60 HBA Mole% 2 2 2 6 6 2 6 6 TA Mole% 25 25 25 27 17 25 27 17 BP Mole% 25 25 25 27 17 25 27 17 total Mole% 100 100 100 100 100 100 100 100 catalyst 1-Memidazole ppm 1100 1100 0 1100 1100 0 0 0 Potassium acetate ppm 0 0 150 0 0 150 150 150 Ginseng (2,4-pentanedionate) cobalt (III) ppm 0 0 150 0 0 150 150 150 Heating rate °C/min 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Final polymerization temperature °C 300 315 320 300 300 360 360 360 Melting point °C 348 356 355 348 318 348 347 317 Melt viscosity Pa･s twenty three 51 54 29 26 26 25 twenty one Ketone bond amount Mole% 0.0001 0.0001 0.0002 0.0001 0.0001 0.12 0.1 0.13 L value - 68 68 67 65 67 57 59 60

[Table 2] Example 6 Comparative example 4 Fully aromatic polyester Monomer composition (amount used) HNA Mole% 48 48 HBA Mole% 2 2 TA Mole% 25 25 BP Mole% 25 25 total Mole% 100 100 catalyst 1-Memidazole ppm 1100 0 Potassium acetate ppm 0 150 Ginseng (2,4-pentanedionate) cobalt (III) ppm 0 150 Heating rate °C/min 0.5 0.5 Final polymerization temperature °C 300 360 Melting point °C 348 348 Melt viscosity Pa･s twenty three 26 Ketone bond amount Mole% 0.0001 0.12 L value - 68 57 Resin composition Fully aromatic polyester quality% 68 68 Filler Milled fiber quality% 10 10 Mica quality% twenty two twenty two total quality% 100 100 Bending strength MPa 196 199 Bending elasticity MPa 14230 14490 Bending strain % 2.70 2.48

In addition, as shown in Table 2, compared to Comparative Example 4 in which the ketone bond amount is 0.12 mol%, the bending strain of Example 6 in which the ketone bond amount is 0.0001 mol% is larger. It is judged that the greater the bending strain, the better the toughness, and therefore it is meant to solve the problem of the present invention.

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Claims (9)

A wholly aromatic polyester characterized in that it is a wholly aromatic polyester composed of the following structural units (I), (II), (III), and (IV) as essential constituents. It is relatively Unit, the content of structural unit (I) is 40 to 75 mol%, relative to all structural units, the content of structural unit (II) is 0.5 to 7.5 mol%, relative to all structural units, the content of structural unit (III) The content is 8.5-30 mol%, the content of the structural unit (IV) is 8.5-30 mol% relative to all the structural units, and the structural units (I), (II), (III) and The total content of (IV) is 100 mol%, which has an ester bond or a combination of an ester bond and a ketone bond in the molecule, and the amount of the ketone bond is 0.0000 to 0.0010 mol relative to the total of the ester bond and the ketone bond %, [化1]

. A polyester resin composition containing the wholly aromatic polyester as claimed in claim 1. A polyester molded product obtained by molding the wholly aromatic polyester or polyester resin composition of claim 1 or 2. A manufacturing method of fully aromatic polyester, which is a manufacturing method of fully aromatic polyester, characterized in that it comprises: A step of acylating 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, and 4,4'-dihydroxybiphenyl using fatty acid anhydride and transesterifying with 1,4-phenylene dicarboxylic acid , Compared to all monomers composed of 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 1,4-phenylene dicarboxylic acid, and 4,4'-dihydroxybiphenyl, The usage amount of 6-hydroxy-2-naphthoic acid is 40～75 mole%, The usage amount of 4-hydroxybenzoic acid is 0.5～7.5 mol%, The usage amount of 1,4-phenylene dicarboxylic acid is 8.5-30 mol%, The usage amount of 4,4’-dihydroxybiphenyl is 8.5-30 mole%, The total usage amount of 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 1,4-phenylene dicarboxylic acid, and 4,4’-dihydroxybiphenyl is 100 mol%, The final polymerization temperature is 340°C or less. The method for producing a wholly aromatic polyester according to claim 4, wherein a nitrogen-containing heterocyclic compound is used as a catalyst. The method for producing a wholly aromatic polyester according to claim 5, wherein the nitrogen-containing heterocyclic compound is 1-methimidazole. The method for producing a wholly aromatic polyester according to claim 4, wherein a potassium compound and/or a trivalent cobalt compound is used as a catalyst. According to claim 7, the method for producing a wholly aromatic polyester, wherein the potassium compound is potassium acetate. For example, the method for producing a wholly aromatic polyester according to claim 7 or 8, wherein the trivalent cobalt compound is ginseng (2,4-pentanedionate) cobalt (III).