WO2020204124A1 - Wholly aromatic polyester and polyester resin composition - Google Patents
Wholly aromatic polyester and polyester resin composition Download PDFInfo
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- WO2020204124A1 WO2020204124A1 PCT/JP2020/015149 JP2020015149W WO2020204124A1 WO 2020204124 A1 WO2020204124 A1 WO 2020204124A1 JP 2020015149 W JP2020015149 W JP 2020015149W WO 2020204124 A1 WO2020204124 A1 WO 2020204124A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
Definitions
- the present invention relates to a total aromatic polyester in which sublimation substances are less generated during the polymerization reaction and foreign substances are reduced, and this polyester resin composition.
- Liquid crystal resins such as all-aromatic polyester have excellent fluidity, mechanical strength, heat resistance, chemical resistance, electrical properties, etc. in a well-balanced manner, and are therefore suitably widely used as high-performance engineering plastics.
- Patent Document 1 a totally aromatic polyester having a specific structure containing 6-hydroxy-2-naphthoic acid as a main component has been proposed.
- the sublimated product generated during the polymerization reaction of all aromatic polyesters is a monomer component, which causes a deviation in the terminal balance and hinders the increase in molecular weight.
- the present inventors consist of the following constituent units (I), (II), (III) and (IV) as essential constituents, and the content of the constituent unit (I) is 40 to 40 for all the constituent units. It is 75 mol%, the content of the constituent unit (II) is 0.5 to 7.5 mol% with respect to all the constituent units, and the content of the constituent unit (III) with respect to all the constituent units is 8.
- the content of the constituent unit (IV) is 8.5 to 30 mol% with respect to all the constituent units, and the constituent units (I), (II), ( A total aromatic polyester characterized in that the total content of III) and (IV) is 100 mol%, which is the content of the structural unit (III) and the content of the structural unit (IV).
- the essential constituents consist of the following constituent units (I), (II), (III) and (IV).
- the content of the constituent unit (I) is 40 to 75 mol% with respect to all the constituent units.
- the content of the constituent unit (II) is 0.5 to 7.5 mol% with respect to all the constituent units.
- the content of the constituent unit (III) is 8.5 to 30 mol% with respect to all the constituent units.
- the content of the constituent unit (IV) is 8.5 to 30 mol% with respect to all the constituent units.
- the total content of the constituent units (I), (II), (III) and (IV) with respect to all the constituent units is 100 mol%.
- All aromatic polyester A total aromatic polyester in which the difference between the content of the structural unit (III) and the content of the structural unit (IV) is 0.150 mol% or less.
- a method for producing an all-aromatic polyester comprises the steps of acylating 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, and 4,4'-dihydroxybiphenyl with fatty acid anhydride and transesterifying with 1,4-phenylenedicarboxylic acid.
- acylating 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, and 4,4'-dihydroxybiphenyl with fatty acid anhydride and transesterifying with 1,4-phenylenedicarboxylic acid.
- monomers consisting of 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 1,4-phenylenedicarboxylic acid, and 4,4'-dihydroxybiphenyl.
- the amount of 6-hydroxy-2-naphthoic acid used is 40-75 mol%
- the amount of 4-hydroxybenzoic acid used is 0.5 to 7.5 mol%
- the amount of 1,4-phenylenedicarboxylic acid used is 8.5 to 30 mol%
- the amount of 4,4'-dihydroxybiphenyl used is 8.5 to 30 mol%
- the total amount of 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 1,4-phenylenedicarboxylic acid, and 4,4'-dihydroxybiphenyl used is 100 mol%.
- a method for producing a totally aromatic polyester which comprises gradually raising the temperature from 140 ° C. to 360 ° C. in a stepwise manner.
- the total aromatic polyester according to the present invention comprises the following constituent units (I), (II), (III) and (IV) as essential constituents, and the constituent units (I) are contained in all the constituent units.
- the amount is 40 to 75 mol%
- the content of the constituent unit (II) is 0.5 to 7.5 mol% with respect to all the constituent units
- the content of the constituent unit (III) is contained with respect to all the constituent units.
- the amount is 8.5 to 30 mol%, and the content of the constituent unit (IV) is 8.5 to 30 mol% with respect to all the constituent units, and the constituent units (I), ( A total aromatic polyester characterized in that the total content of II), (III) and (IV) is 100 mol%, and the content of the constituent unit (III) and the constituent unit (IV). It is a total aromatic polyester having a difference from the content of 0.150 mol% or less.
- the structural unit (I) is derived from 6-hydroxy-2-naphthoic acid (hereinafter, also referred to as "HNA").
- the total aromatic polyester of the present invention contains 40 to 75 mol% of the structural unit (I) with respect 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) exceeds 75 mol%, solidification occurs during polymerization and a polymer cannot be obtained. From the viewpoint of heat resistance and polymerizable property, the content of the structural unit (I) is preferably 40 to 70 mol%, more preferably 40 to 65 mol%, and further preferably 40 to 63 mol%. , Even more preferably 40 to 62 mol%, and particularly preferably 40 to 60 mol%.
- the structural unit (II) is derived from 4-hydroxybenzoic acid (hereinafter, also referred to as "HBA").
- the total aromatic polyester of the present invention contains 0.5 to 7.5 mol% of the constituent unit (II) with respect to all the constituent units. If the content of the structural unit (II) is less than 0.5 mol%, solidification 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 polymerizable property, the content of the structural unit (II) is preferably 0.5 to 7.0 mol%, more preferably 1.0 to 7.0 mol%, and even more preferably. Is 1.2 to 7.0 mol%, more preferably 1.5 to 6.5 mol%, and particularly preferably 2.0 to 6.0 mol%.
- the structural unit (III) is derived from 1,4-phenylenedicarboxylic acid (hereinafter, also referred to as "TA").
- the total aromatic polyester of the present invention contains 8.5 to 30 mol% of the constituent unit (III) with respect to all the constituent 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 be insufficient. From the viewpoint of achieving both a low melting point and heat resistance, the content of the structural unit (III) is preferably 10 to 30 mol%, more preferably 12 to 28 mol%, and further preferably 14 to 28. It is mol%, more preferably 15 to 28 mol%, and particularly preferably 17 to 27 mol%.
- the structural unit (IV) is derived from 4,4'-dihydroxybiphenyl (hereinafter, also referred to as "BP").
- the total aromatic polyester of the present invention contains 8.5 to 30 mol% of structural units (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 be insufficient. From the viewpoint of achieving both a low melting point and heat resistance, the content of the structural unit (IV) is preferably 10 to 30 mol%, more preferably 12 to 28 mol%, and further preferably 14 to 28 mol%. It is mol%, more preferably 15 to 28 mol%, and particularly preferably 17 to 27 mol%.
- the total aromatic polyester of the present invention contains specific structural units (I) to (IV) in a specific amount with respect to all the structural units, and the content and composition of the structural unit (III). Since the difference from the content of the unit (IV) is 0.150 mol% or less, the generation of sublimated substances during the polymerization reaction is small, and foreign substances are reduced.
- the difference between the content of the structural unit (III) and the content of the structural unit (IV) is preferably 0.145 mol% or less, preferably 0.140 mol% or less. It is more preferably 0.135 mol% or less, further preferably 0.130 mol% or less, and particularly preferably 0.125 mol% or less.
- the total aromatic polyester of the present invention contains 100 mol% of the constituent units (I) to (IV) in total with respect to all the constituent units.
- the total aromatic polyester of the present invention exhibits optical anisotropy when melted. Exhibiting optical anisotropy when melted means that the all-aromatic polyester of the present invention is a liquid crystal polymer.
- the fact that the total aromatic polyester is a liquid crystal polymer is an indispensable element for the total aromatic polyester to have both thermal stability and easy workability.
- the total aromatic polyester composed of the constituent units (I) to (IV) may not form an anisotropic molten phase depending on the constituent components and the sequence distribution in the polymer, but the polymer of the present invention has. Limited to all aromatic polyesters that exhibit optical anisotropy when melted.
- melt anisotropy can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the confirmation of melt anisotropy can be carried out by melting a sample placed on a hot stage manufactured by Linkham Co., Ltd. using a polarizing microscope manufactured by Olympus Corporation and observing it at a magnification of 150 times in a nitrogen atmosphere. Liquid crystal polymers are optically anisotropic and transmit light when inserted between orthogonal polarizers. If the sample is optically anisotropic, polarized light is transmitted even in a molten static liquid state, for example.
- a nematic liquid crystal polymer causes a significant decrease in viscosity above the melting point, it is generally an index of processability to exhibit liquid crystallinity at a temperature above the melting point.
- the melting point is preferably as high as possible from the viewpoint of heat resistance, but it is preferably 380 ° C. or lower in consideration of thermal deterioration during melt processing of the polymer and the heating capacity of the molding machine. It should be noted that the temperature is more preferably 260 to 370 ° C, even more preferably 270 to 370 ° C, and particularly preferably 280 to 360 ° C.
- the melt viscosity of the total aromatic polyester at a temperature 10 to 40 ° C. higher than the melting point of the total aromatic polyester of the present invention and a shear rate of 1000 / sec is preferably 1000 Pa ⁇ s or less, more preferably 4 to 500 Pa. It is s, more preferably 4 to 250 Pa ⁇ s, and particularly preferably 5 to 100 Pa ⁇ s.
- the melt viscosity means the melt viscosity measured according to ISO11443.
- the total aromatic polyester of the present embodiment is polymerized by using a direct polymerization method, a transesterification method, or the like.
- 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 is used, and a melt polymerization method or a combination of the melt polymerization method and the solid phase polymerization method is used. Is preferably used.
- an acylating agent for the polymerized monomer or a monomer having an activated terminal can be used as an acid chloride derivative.
- the acylating agent include fatty acid anhydrides such as acetic anhydride.
- the total amount of fatty acid anhydride used is 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, and 4,4'-dihydroxybiphenyl from the viewpoint of hue. It is preferably less than 1.08 times the hydroxyl group equivalent of, more preferably 1.00 to 1.07 times, further preferably 1.01 to 1.07 times, and 1.01 to 1 It is more preferably .06 times, and particularly preferably 1.02 to 1.06 times.
- catalysts can be used for these polymerizations, and typical ones are potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, and tris (2).
- 4-Pentandionato) Examples include metal salt-based catalysts such as cobalt (III) and organic compound-based catalysts such as 1-methylimidazole and 4-dimethylaminopyridine.
- melt polymerization is carried out by starting depressurization to a predetermined decompression degree.
- an inert gas is introduced, and the pressure is changed from a reduced pressure state to a normal pressure state to a predetermined pressure state, and the total aromatic polyester is discharged from the reaction system.
- the total aromatic polyester produced by the above polymerization method can be further increased in molecular weight by solid phase polymerization of normal pressure, reduced pressure, or heating in an inert gas.
- 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, and 4,4'-dihydroxybiphenyl are acylated with a fatty acid anhydride to form 1,4-phenylene. It is preferable to include a step of transesterifying with a dicarboxylic acid. For all monomers consisting of 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 1,4-phenylenedicarboxylic acid, and 4,4'-dihydroxybiphenyl.
- the amount of 6-hydroxy-2-naphthoic acid used is 40 to 75 mol%, preferably 40 to 70 mol%, more preferably 40 to 65 mol%, still more preferably 40 to 63, from the viewpoint of heat resistance and polymerizable property. Mol%, even more preferably 40-62 mol%, particularly preferably 40-60 mol%, The amount of 4-hydroxybenzoic acid used is 0.5 to 7.5 mol%, preferably 0.5 to 7.0 mol%, more preferably 1.0 to 7.0 from the viewpoint of heat resistance and polymerizable property.
- the amount of 1,4-phenylenedicarboxylic acid used is 8.5 to 30 mol%, preferably 10 to 30 mol%, more preferably 12 to 28 mol%, and further, from the viewpoint of achieving both a low melting point and heat resistance.
- the amount of 4,4'-dihydroxybiphenyl used is 8.5 to 30 mol%, preferably 10 to 30 mol%, more preferably 12 to 28 mol%, and further, from the viewpoint of achieving both a low melting point and heat resistance.
- 14-28 mol%, even more preferably 15-28 mol%, particularly preferably 17-27 mol% The total amount of 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 1,4-phenylenedicarboxylic acid, and 4,4'-dihydroxybiphenyl is preferably 100 mol%. It is preferable to raise the temperature in steps from 140 ° C. to 360 ° C.
- the temperature rise divided in stages is 140 ° C to 200 ° C, 200 ° C to 270 ° C, 270 ° C to 360 ° C. preferable.
- the rate of temperature rise from 140 ° C. to 200 ° C. is preferably 0.4 ° C./min or more and less than 0.8 ° C./min, and 0.5 ° C./min. More preferably, it is at least 0.7 ° C./min.
- the rate of temperature rise from 200 ° C. to 270 ° C. is preferably 0.8 ° C./min or more and 1.2 ° C./min or less, and 0.9 ° C./min. More preferably, it is at least 1.1 ° C./min.
- the rate of temperature rise from 270 ° C. to 360 ° C. is preferably 0.4 ° C./min or more and 1.2 ° C./min or less, and 0.5 ° C./min. More preferably, it is at least 1.1 ° C./min.
- the amount of 1,4-phenylenedicarboxylic acid used (mol%) and the amount of 4,4'-dihydroxybiphenyl used (mol%) are determined from the viewpoint of increasing the molecular weight. It is preferable that they are equal. It should be noted that the generation of sublimated products during the production of the total aromatic polyester of the present embodiment causes a difference in their contents.
- polyester resin composition Various fibrous, powdery, plate-like inorganic and organic fillers can be blended in the above-mentioned all-aromatic polyester of the present invention depending on the purpose of use.
- the inorganic filler blended in the polyester resin composition of the present invention includes fibrous, powdery, and plate-like fillers.
- fibrous inorganic filler glass fiber, milled 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
- silicate fibers such as magnesium sulfate fibers, aluminum borate fibers
- inorganic fibrous substances such as metal fibrous materials such as stainless steel, aluminum, titanium, copper and brass.
- a particularly typical fibrous filler is glass fiber.
- the powdery granular inorganic filler carbon black, graphite, silica, quartz powder, glass beads, glass balloon, glass powder, calcium silicate, aluminum silicate, kaolin, clay, diatomaceous earth, wollastonite and the like.
- Acid salts iron oxide, titanium oxide, zinc oxide, antimony trioxide, metal oxides such as alumina, carbonates of metals such as calcium carbonate and magnesium carbonate, sulfates of metals such as calcium sulfate and barium sulfate, and other ferrites.
- examples of the plate-shaped inorganic filler include mica, glass flakes, talc, and various metal foils.
- organic fillers examples include aromatic polyester fibers, liquid crystal polymer fibers, aromatic polyamides, and heat-resistant high-strength synthetic fibers such as polyimide fibers.
- 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 terms of combining mechanical strength, dimensional accuracy, electrical properties, and the like.
- glass fiber is used as the fibrous filler
- mica and talc are used as the plate-shaped filler, and the blending amount thereof is 120 parts by mass or less, preferably 20 to 80 parts by mass with respect to 100 parts by mass of the total aromatic polyester. Is.
- the polyester resin composition is particularly remarkable in improving the thermal deformation temperature, mechanical properties and the like.
- a converging agent or a surface treatment agent can be used if necessary.
- the polyester resin composition of the present invention contains the all-aromatic polyester of the present invention as an essential component, and optionally contains an inorganic or organic filler, as long as it does not impair the effects of the present invention.
- other components may be contained.
- the other component may be any component, and examples thereof include additives such as other resins, antioxidants, stabilizers, pigments, and crystal nucleating agents.
- the method for producing the polyester resin composition of the present invention is not particularly limited, and the polyester resin composition can be prepared by a conventionally known method.
- the polyester molded product of the present invention can be obtained by molding the all-aromatic polyester or polyester resin composition of the present invention.
- the molding method is not particularly limited, and a general molding method can be adopted. Examples of general molding methods include injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, rotary molding, gas injection molding, and inflation molding.
- the polyester molded product obtained by molding the all-aromatic polyester or the like of the present invention has excellent heat resistance. Further, the polyester molded product obtained by molding the polyester resin composition of the present invention has excellent heat resistance and contains an inorganic or organic filler as required, so that the mechanical strength and the like are further improved.
- the all-aromatic polyester and polyester resin composition of the present invention are excellent in moldability, they can be processed into various three-dimensional molded products, fibers, films and the like.
- Preferred applications 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 cases, electronic circuit boards, heating fixing rolls for OA equipment, and the like. Be done.
- Example 1 The following raw material monomers, fatty acid metal salt catalysts, and acylating agents were charged into a polymerization vessel equipped with a stirrer, a reflux column, a monomer inlet, a nitrogen inlet, and a depressurization / outflow line, and nitrogen substitution was started.
- the monomer composition was calculated by the pyrolysis gas chromatography method described in Polymer Degradation and Stability 76 (2002) 85-94. Specifically, using a pyrolysis device (“PY2020iD” manufactured by Frontier Lab Co., Ltd.), all aromatic polyester is heated in the presence of tetramethylammonium hydroxide (TMAH), and gas is pyrolyzed / methylated. Was generated. This gas was analyzed using gas chromatography (“GC-6890N” manufactured by Azilent Technology Co., Ltd.), and the peak area derived from 1,4-phenylenedicarboxylic acid and the peak derived from 4,4′-dihydroxybiphenyl were analyzed. From the ratio to the area, the difference between the content of the constituent unit derived from 1,4-phenylenedicarboxylic acid and the content of the constituent unit derived from 4,4'-dihydroxybiphenyl was calculated.
- TMAH tetramethylammonium hydroxide
- Examples 2 to 4 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, the amount used (mol%), and the rate of temperature rise were as shown in Tables 1 and 2. Further, the same evaluation as in Example 1 was performed (the melt viscosities of Example 4 and Comparative Example 4 were measured at a temperature of 350 ° C.). The evaluation results are shown in Tables 1 and 2.
- Comparative Example 8 in which the rate of temperature rise from 140 ° C. to 200 ° C. is 0.30 ° C./min and Comparative Example 9 in which the temperature rise rate is 0.89 ° C./min, foreign matter is generated. It was. Further, as shown in Tables 1 and 2, Comparative Example 2 in which the rate of temperature rise from 200 ° C. to 270 ° C. is 0.60 ° C./min, and Comparative Example 5, 1.30 ° C. in which the temperature rise rate is 0.69 ° C./min. In Comparative Example 6 at / min, foreign matter was generated. Further, as shown in Tables 1 and 2, Comparative Examples 1 to 4 in which the rate of temperature rise from 270 ° C. to 360 ° C. is 1.50 ° C./min, and Comparative Examples 7 and 1 in which 0.30 ° C./min. Foreign matter was also generated in Comparative Example 10 at 29 ° C./min.
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Abstract
[Problem] To provide: a wholly aromatic polyester which produces less sublimates during a polymerization reaction, and includes less foreign substances; and this polyester resin composition.
[Solution] The above-described problem is solved by a wholly aromatic polyester which is characterized by containing, as essential constituents, the constituent units (I), (II), (III) and (IV) described below so that: the content of the constituent unit (I) relative to all constituent units is 40-75% by mole; the content of the constituent unit (II) relative to all constituent units is 0.5-7.5% by mole; the content of the constituent unit (III) relative to all constituent units is 8.5-30% by mole; the content of the constituent unit (IV) relative to all constituent units is 8.5-30% by mole; the total content of the constituent units (I), (II), (III) and (IV) relative to all constituent units is 100% by mole; and the difference between the content of the constituent unit (III) and the content of the constituent unit (IV) is 0.150% by mole or less.
Description
本発明は、重合反応時の昇華物の発生が少なく、異物が低減された全芳香族ポリエステル、及びこのポリエステル樹脂組成物に関する。
The present invention relates to a total aromatic polyester in which sublimation substances are less generated during the polymerization reaction and foreign substances are reduced, and this polyester resin composition.
全芳香族ポリエステルなどの液晶性樹脂は、優れた流動性、機械強度、耐熱性、耐薬品性、電気的性質等をバランス良く有するため、高機能エンジニアリングプラスチックスとして好適に広く利用されている。
Liquid crystal resins such as all-aromatic polyester have excellent fluidity, mechanical strength, heat resistance, chemical resistance, electrical properties, etc. in a well-balanced manner, and are therefore suitably widely used as high-performance engineering plastics.
全芳香族ポリエステルとして現在市販されているものの多くは４－ヒドロキシ安息香酸が主成分である。しかし、４－ヒドロキシ安息香酸のホモポリマーは、融点が分解点よりも高くなってしまう為、種々の成分を共重合する事により、低融点化する必要がある。
Most of the total aromatic polyesters currently on the market are mainly composed of 4-hydroxybenzoic acid. However, since the melting point of 4-hydroxybenzoic acid homopolymers is higher than the decomposition point, it is necessary to lower the melting point by copolymerizing various components.
共重合成分として１，４－フェニレンジカルボン酸、１，４－ジヒドロキシベンゼン、４，４’－ジヒドロキシビフェニル等を用いた全芳香族ポリエステルは、融点が３５０℃以上と高く、汎用の装置にて溶融加工を行うには高すぎる。又、このような高い融点のものを、汎用の溶融加工機器で加工できる温度まで融点を下げるために種々の方法が試みられているが 、低融点化がある程度実現される一方で高温（融点下近傍）での機械的強度を保てないという問題がある。
All aromatic polyesters using 1,4-phenylenedicarboxylic acid, 1,4-dihydroxybenzene, 4,4'-dihydroxybiphenyl, etc. as copolymerization components have a high melting point of 350 ° C. or higher and are melted by a general-purpose device. Too expensive to process. 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 by a general-purpose melting processing device, but while the melting point can be lowered to some extent, the temperature is high (below the melting point). There is a problem that the mechanical strength cannot be maintained in the vicinity).
この問題を解決するために、６－ヒドロキシ－２－ナフトエ酸を主成分とした特定構造からなる全芳香族ポリエステルが提案されている（特許文献１）。
In order to solve this problem, a totally aromatic polyester having a specific structure containing 6-hydroxy-2-naphthoic acid as a main component has been proposed (Patent Document 1).
しかし、特許文献１の全芳香族ポリエステルは、重合反応時に昇華物が発生し、該昇華物が重合容器の内壁等に析出堆積し、そこで重縮合したり、劣化したり、あるいは炭化したりしたものが、異物としてポリマーに混入する問題があった。
However, in the total aromatic polyester of Patent Document 1, a sublimated product is generated during the polymerization reaction, and the sublimated product is deposited and deposited on the inner wall of the polymerization vessel or the like, where it is polycondensed, deteriorated, or carbonized. There was a problem that the substance was mixed into the polymer as a foreign substance.
また、全芳香族ポリエステルの重合反応時に発生する昇華物は、モノマー成分であり、末端バランスの乖離を引き起こし、高分子量化の障害となる。
In addition, the sublimated product generated during the polymerization reaction of all aromatic polyesters is a monomer component, which causes a deviation in the terminal balance and hinders the increase in molecular weight.
そのため本発明は、重合反応時の昇華物の発生が少なく、異物が低減された全芳香族ポリエステル、及びこのポリエステル樹脂組成物を提供することを課題とする。
Therefore, it is an object of the present invention to provide a total aromatic polyester in which sublimation substances are less generated during a polymerization reaction and foreign substances are reduced, and a polyester resin composition thereof.
本発明者らは、必須の構成成分として、下記構成単位（Ｉ）、（ＩＩ）、（ＩＩＩ）及び（ＩＶ）からなり、全構成単位に対して構成単位（Ｉ）の含有量は４０～７５モル％であり、全構成単位に対して構成単位（ＩＩ）の含有量は０．５～７．５モル％であり、全構成単位に対して構成単位（ＩＩＩ）の含有量は８．５～３０モル％であり、全構成単位に対して構成単位（ＩＶ）の含有量は８．５～３０モル％であり、全構成単位に対して構成単位（Ｉ）、（ＩＩ）、（ＩＩＩ）及び（ＩＶ）の合計の含有量は１００モル％であることを特徴とする、全芳香族ポリエステルであって、構成単位（ＩＩＩ）の含有量と構成単位（ＩＶ）の含有量との差を０．１５０モル％以下とすることにより、上記の課題を解決できることを見出し、本発明者らは本発明を完成させるに至った。より具体的には、本発明は以下のものを提供する。
The present inventors consist of the following constituent units (I), (II), (III) and (IV) as essential constituents, and the content of the constituent unit (I) is 40 to 40 for all the constituent units. It is 75 mol%, the content of the constituent unit (II) is 0.5 to 7.5 mol% with respect to all the constituent units, and the content of the constituent unit (III) with respect to all the constituent units is 8. It is 5 to 30 mol%, and the content of the constituent unit (IV) is 8.5 to 30 mol% with respect to all the constituent units, and the constituent units (I), (II), ( A total aromatic polyester characterized in that the total content of III) and (IV) is 100 mol%, which is the content of the structural unit (III) and the content of the structural unit (IV). We have found that the above problems can be solved by setting the difference to 0.150 mol% or less, and the present inventors have completed the present invention. More specifically, the present invention provides the following.
（１）必須の構成成分として、下記構成単位（Ｉ）、（ＩＩ）、（ＩＩＩ）及び（ＩＶ）からなり、
全構成単位に対して構成単位（Ｉ）の含有量は４０～７５モル％であり、
全構成単位に対して構成単位（ＩＩ）の含有量は０．５～７．５モル％であり、
全構成単位に対して構成単位（ＩＩＩ）の含有量は８．５～３０モル％であり、
全構成単位に対して構成単位（ＩＶ）の含有量は８．５～３０モル％であり、
全構成単位に対して構成単位（Ｉ）、（ＩＩ）、（ＩＩＩ）及び（ＩＶ）の合計の含有量は１００モル％であることを特徴とする、
全芳香族ポリエステルであって、
構成単位（ＩＩＩ）の含有量と構成単位（ＩＶ）の含有量との差が０．１５０モル％以下である、全芳香族ポリエステル。
(1) The essential constituents consist of the following constituent units (I), (II), (III) and (IV).
The content of the constituent unit (I) is 40 to 75 mol% with respect to all the constituent units.
The content of the constituent unit (II) is 0.5 to 7.5 mol% with respect to all the constituent units.
The content of the constituent unit (III) is 8.5 to 30 mol% with respect to all the constituent units.
The content of the constituent unit (IV) is 8.5 to 30 mol% with respect to all the constituent units.
The total content of the constituent units (I), (II), (III) and (IV) with respect to all the constituent units is 100 mol%.
All aromatic polyester
A total aromatic polyester in which the difference between the content of the structural unit (III) and the content of the structural unit (IV) is 0.150 mol% or less.
全構成単位に対して構成単位（Ｉ）の含有量は４０～７５モル％であり、
全構成単位に対して構成単位（ＩＩ）の含有量は０．５～７．５モル％であり、
全構成単位に対して構成単位（ＩＩＩ）の含有量は８．５～３０モル％であり、
全構成単位に対して構成単位（ＩＶ）の含有量は８．５～３０モル％であり、
全構成単位に対して構成単位（Ｉ）、（ＩＩ）、（ＩＩＩ）及び（ＩＶ）の合計の含有量は１００モル％であることを特徴とする、
全芳香族ポリエステルであって、
構成単位（ＩＩＩ）の含有量と構成単位（ＩＶ）の含有量との差が０．１５０モル％以下である、全芳香族ポリエステル。
The content of the constituent unit (I) is 40 to 75 mol% with respect to all the constituent units.
The content of the constituent unit (II) is 0.5 to 7.5 mol% with respect to all the constituent units.
The content of the constituent unit (III) is 8.5 to 30 mol% with respect to all the constituent units.
The content of the constituent unit (IV) is 8.5 to 30 mol% with respect to all the constituent units.
The total content of the constituent units (I), (II), (III) and (IV) with respect to all the constituent units is 100 mol%.
All aromatic polyester
A total aromatic polyester in which the difference between the content of the structural unit (III) and the content of the structural unit (IV) is 0.150 mol% or less.
（２）（１）に記載の全芳香族ポリエステルを含有するポリエステル樹脂組成物。
(2) A polyester resin composition containing the total aromatic polyester according to (1).
（３）（１）または（２）に記載の全芳香族ポリエステルまたはポリエステル樹脂組成物を成形して得られるポリエステル成形品。
(3) A polyester molded product obtained by molding the total aromatic polyester or polyester resin composition according to (1) or (2).
（４）全芳香族ポリエステルの製造方法であって、
６－ヒドロキシ－２－ナフトエ酸、４－ヒドロキシ安息香酸、及び４，４’－ジヒドロキシビフェニルを脂肪酸無水物でアシル化して、１，４－フェニレンジカルボン酸とエステル交換する工程を含み、
６－ヒドロキシ－２－ナフトエ酸、４－ヒドロキシ安息香酸、１，４－フェニレンジカルボン酸、及び４，４’－ジヒドロキシビフェニルからなる全モノマーに対し、
６－ヒドロキシ－２－ナフトエ酸の使用量が４０～７５モル％、
４－ヒドロキシ安息香酸の使用量が０．５～７．５モル％、
１，４－フェニレンジカルボン酸の使用量が８．５～３０モル％、
４，４’－ジヒドロキシビフェニルの使用量が８．５～３０モル％、
６－ヒドロキシ－２－ナフトエ酸、４－ヒドロキシ安息香酸、１，４－フェニレンジカルボン酸、及び４，４’－ジヒドロキシビフェニルの合計の使用量が１００モル％であり、
１４０℃から３６０℃まで段階的に分けて昇温することを特徴とする、全芳香族ポリエステルの製造方法。 (4) A method for producing an all-aromatic polyester.
It comprises the steps of acylating 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, and 4,4'-dihydroxybiphenyl with fatty acid anhydride and transesterifying with 1,4-phenylenedicarboxylic acid.
For all monomers consisting of 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 1,4-phenylenedicarboxylic acid, and 4,4'-dihydroxybiphenyl.
The amount of 6-hydroxy-2-naphthoic acid used is 40-75 mol%,
The amount of 4-hydroxybenzoic acid used is 0.5 to 7.5 mol%,
The amount of 1,4-phenylenedicarboxylic acid used is 8.5 to 30 mol%,
The amount of 4,4'-dihydroxybiphenyl used is 8.5 to 30 mol%,
The total amount of 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 1,4-phenylenedicarboxylic acid, and 4,4'-dihydroxybiphenyl used is 100 mol%.
A method for producing a totally aromatic polyester, which comprises gradually raising the temperature from 140 ° C. to 360 ° C. in a stepwise manner.
６－ヒドロキシ－２－ナフトエ酸、４－ヒドロキシ安息香酸、及び４，４’－ジヒドロキシビフェニルを脂肪酸無水物でアシル化して、１，４－フェニレンジカルボン酸とエステル交換する工程を含み、
６－ヒドロキシ－２－ナフトエ酸、４－ヒドロキシ安息香酸、１，４－フェニレンジカルボン酸、及び４，４’－ジヒドロキシビフェニルからなる全モノマーに対し、
６－ヒドロキシ－２－ナフトエ酸の使用量が４０～７５モル％、
４－ヒドロキシ安息香酸の使用量が０．５～７．５モル％、
１，４－フェニレンジカルボン酸の使用量が８．５～３０モル％、
４，４’－ジヒドロキシビフェニルの使用量が８．５～３０モル％、
６－ヒドロキシ－２－ナフトエ酸、４－ヒドロキシ安息香酸、１，４－フェニレンジカルボン酸、及び４，４’－ジヒドロキシビフェニルの合計の使用量が１００モル％であり、
１４０℃から３６０℃まで段階的に分けて昇温することを特徴とする、全芳香族ポリエステルの製造方法。 (4) A method for producing an all-aromatic polyester.
It comprises the steps of acylating 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, and 4,4'-dihydroxybiphenyl with fatty acid anhydride and transesterifying with 1,4-phenylenedicarboxylic acid.
For all monomers consisting of 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 1,4-phenylenedicarboxylic acid, and 4,4'-dihydroxybiphenyl.
The amount of 6-hydroxy-2-naphthoic acid used is 40-75 mol%,
The amount of 4-hydroxybenzoic acid used is 0.5 to 7.5 mol%,
The amount of 1,4-phenylenedicarboxylic acid used is 8.5 to 30 mol%,
The amount of 4,4'-dihydroxybiphenyl used is 8.5 to 30 mol%,
The total amount of 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 1,4-phenylenedicarboxylic acid, and 4,4'-dihydroxybiphenyl used is 100 mol%.
A method for producing a totally aromatic polyester, which comprises gradually raising the temperature from 140 ° C. to 360 ° C. in a stepwise manner.
（５）段階的に分けられた昇温が、１４０℃から２００℃、２００℃から２７０℃、２７０℃から３６０℃に分けられた昇温である、（４）に記載の全芳香族ポリエステルの製造方法。
(5) The all-aromatic polyester according to (4), wherein the temperature rise divided in stages is a temperature rise divided into 140 ° C to 200 ° C, 200 ° C to 270 ° C, and 270 ° C to 360 ° C. Production method.
（６）１４０℃から２００℃への昇温速度が、０．４℃／分以上０．８℃／分未満である、（４）または（５）に記載の全芳香族ポリエステルの製造方法。
(6) The method for producing an all-aromatic polyester according to (4) or (5), wherein the rate of temperature rise from 140 ° C. to 200 ° C. is 0.4 ° C./min or more and less than 0.8 ° C./min.
（７）２００℃から２７０℃への昇温速度が、０．８℃／分以上１．２℃／分以下である、（４）から（６）のいずれか一項に記載の全芳香族ポリエステルの製造方法。
(7) The total aromatic according to any one of (4) to (6), wherein the rate of temperature rise from 200 ° C. to 270 ° C. is 0.8 ° C./min or more and 1.2 ° C./min or less. Method of manufacturing polyester.
（８）２７０℃から３６０℃への昇温速度が、０．４℃／分以上１．２℃／分以下である、（４）から（７）のいずれか一項に記載の全芳香族ポリエステルの製造方法。
(8) The total aromatic according to any one of (4) to (7), wherein the rate of temperature rise from 270 ° C. to 360 ° C. is 0.4 ° C./min or more and 1.2 ° C./min or less. Method of manufacturing polyester.
本発明によれば、重合反応時の昇華物の発生が少なく、異物が低減された全芳香族ポリエステル、及びこのポリエステル樹脂組成物を提供することができる。
According to the present invention, it is possible to provide a total aromatic polyester in which sublimation substances are less generated during the polymerization reaction and foreign substances are reduced, and this polyester resin composition.
以下、本発明の一実施形態について詳細に説明する。本発明は、以下の実施形態に限定されるものではなく、本発明の効果を阻害しない範囲で適宜変更を加えて実施することができる。なお、本発明において「Ａ～Ｂ」とは、「Ａ以上Ｂ以下」であることを意味している。
Hereinafter, one embodiment of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be carried out with appropriate modifications as long as the effects of the present invention are not impaired. In addition, in this invention, "AB" means "A or more and B or less".
［全芳香族ポリエステル］
本発明に係る全芳香族ポリエステルは、必須の構成成分として、下記構成単位（Ｉ）、（ＩＩ）、（ＩＩＩ）及び（ＩＶ）からなり、全構成単位に対して構成単位（Ｉ）の含有量は４０～７５モル％であり、全構成単位に対して構成単位（ＩＩ）の含有量は０．５～７．５モル％であり、全構成単位に対して構成単位（ＩＩＩ）の含有量は８．５～３０モル％であり、全構成単位に対して構成単位（ＩＶ）の含有量は８．５～３０モル％であり、全構成単位に対して構成単位（Ｉ）、（ＩＩ）、（ＩＩＩ）及び（ＩＶ）の合計の含有量は１００モル％であることを特徴とする、全芳香族ポリエステルであって、構成単位（ＩＩＩ）の含有量と構成単位（ＩＶ）の含有量との差が０．１５０モル％以下である、全芳香族ポリエステルである。
[All aromatic polyester]
The total aromatic polyester according to the present invention comprises the following constituent units (I), (II), (III) and (IV) as essential constituents, and the constituent units (I) are contained in all the constituent units. The amount is 40 to 75 mol%, the content of the constituent unit (II) is 0.5 to 7.5 mol% with respect to all the constituent units, and the content of the constituent unit (III) is contained with respect to all the constituent units. The amount is 8.5 to 30 mol%, and the content of the constituent unit (IV) is 8.5 to 30 mol% with respect to all the constituent units, and the constituent units (I), ( A total aromatic polyester characterized in that the total content of II), (III) and (IV) is 100 mol%, and the content of the constituent unit (III) and the constituent unit (IV). It is a total aromatic polyester having a difference from the content of 0.150 mol% or less.
本発明に係る全芳香族ポリエステルは、必須の構成成分として、下記構成単位（Ｉ）、（ＩＩ）、（ＩＩＩ）及び（ＩＶ）からなり、全構成単位に対して構成単位（Ｉ）の含有量は４０～７５モル％であり、全構成単位に対して構成単位（ＩＩ）の含有量は０．５～７．５モル％であり、全構成単位に対して構成単位（ＩＩＩ）の含有量は８．５～３０モル％であり、全構成単位に対して構成単位（ＩＶ）の含有量は８．５～３０モル％であり、全構成単位に対して構成単位（Ｉ）、（ＩＩ）、（ＩＩＩ）及び（ＩＶ）の合計の含有量は１００モル％であることを特徴とする、全芳香族ポリエステルであって、構成単位（ＩＩＩ）の含有量と構成単位（ＩＶ）の含有量との差が０．１５０モル％以下である、全芳香族ポリエステルである。
The total aromatic polyester according to the present invention comprises the following constituent units (I), (II), (III) and (IV) as essential constituents, and the constituent units (I) are contained in all the constituent units. The amount is 40 to 75 mol%, the content of the constituent unit (II) is 0.5 to 7.5 mol% with respect to all the constituent units, and the content of the constituent unit (III) is contained with respect to all the constituent units. The amount is 8.5 to 30 mol%, and the content of the constituent unit (IV) is 8.5 to 30 mol% with respect to all the constituent units, and the constituent units (I), ( A total aromatic polyester characterized in that the total content of II), (III) and (IV) is 100 mol%, and the content of the constituent unit (III) and the constituent unit (IV). It is a total aromatic polyester having a difference from the content of 0.150 mol% or less.
構成単位（Ｉ）は、６－ヒドロキシ－２－ナフトエ酸（以下、「ＨＮＡ」ともいう。）から誘導される。本発明の全芳香族ポリエステルは、全構成単位に対して構成単位（Ｉ）を４０～７５モル％含む。構成単位（Ｉ）の含有量が４０モル％未満であると、融点が低下し、耐熱性が不足する。構成単位（Ｉ）の含有量が７５モル％を超えると、重合時に固化が発生し、ポリマーが得られない。耐熱性と重合性の観点から、構成単位（Ｉ）の含有量は、好ましくは４０～７０モル％であり、より好ましくは４０～６５モル％であり、更に好ましくは４０～６３モル％であり、より更に好ましくは４０～６２モル％であり、特に好ましくは４０～６０モル％である。
The structural unit (I) is derived from 6-hydroxy-2-naphthoic acid (hereinafter, also referred to as "HNA"). The total aromatic polyester of the present invention contains 40 to 75 mol% of the structural unit (I) with respect 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) exceeds 75 mol%, solidification occurs during polymerization and a polymer cannot be obtained. From the viewpoint of heat resistance and polymerizable property, the content of the structural unit (I) is preferably 40 to 70 mol%, more preferably 40 to 65 mol%, and further preferably 40 to 63 mol%. , Even more preferably 40 to 62 mol%, and particularly preferably 40 to 60 mol%.
構成単位（ＩＩ）は、４－ヒドロキシ安息香酸（以下、「ＨＢＡ」ともいう。）から誘導される。本発明の全芳香族ポリエステルは、全構成単位に対して構成単位（ＩＩ）を０．５～７．５モル％含む。構成単位（ＩＩ）の含有量が０．５モル％未満であると、重合時に固化が発生し、ポリマーが得られない。構成単位（ＩＩ）の含有量が７．５モル％を超えると、融点が低下し、耐熱性が不足する。耐熱性と重合性の観点から、構成単位（ＩＩ）の含有量は、好ましくは０．５～７．０モル％であり、より好ましくは１．０～７．０モル％であり、更に好ましくは１．２～７．０モル％であり、より更に好ましくは１．５～６．５モル％であり、特に好ましくは２．０～６．０モル％である。
The structural unit (II) is derived from 4-hydroxybenzoic acid (hereinafter, also referred to as "HBA"). The total aromatic polyester of the present invention contains 0.5 to 7.5 mol% of the constituent unit (II) with respect to all the constituent units. If the content of the structural unit (II) is less than 0.5 mol%, solidification 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 polymerizable property, the content of the structural unit (II) is preferably 0.5 to 7.0 mol%, more preferably 1.0 to 7.0 mol%, and even more preferably. Is 1.2 to 7.0 mol%, more preferably 1.5 to 6.5 mol%, and particularly preferably 2.0 to 6.0 mol%.
構成単位（ＩＩＩ）は、１，４－フェニレンジカルボン酸（以下、「ＴＡ」ともいう。）から誘導される。本発明の全芳香族ポリエステルは、全構成単位に対して構成単位（ＩＩＩ）を８．５～３０モル％含む。構成単位（ＩＩＩ）の含有量が８．５モル％未満、または３０モル％を超えると、低融点化及び耐熱性の少なくとも一方が不十分となりやすい。低融点化と耐熱性との両立の観点から、構成単位（ＩＩＩ）の含有量は、好ましくは１０～３０モル％であり、より好ましくは１２～２８モル％であり、更に好ましくは１４～２８モル％であり、より更に好ましくは１５～２８モル％であり、特に好ましくは１７～２７モル％である。
The structural unit (III) is derived from 1,4-phenylenedicarboxylic acid (hereinafter, also referred to as "TA"). The total aromatic polyester of the present invention contains 8.5 to 30 mol% of the constituent unit (III) with respect to all the constituent 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 be insufficient. From the viewpoint of achieving both a low melting point and heat resistance, the content of the structural unit (III) is preferably 10 to 30 mol%, more preferably 12 to 28 mol%, and further preferably 14 to 28. It is mol%, more preferably 15 to 28 mol%, and particularly preferably 17 to 27 mol%.
構成単位（ＩＶ）は、４，４’－ジヒドロキシビフェニル（以下、「ＢＰ」ともいう。）から誘導される。本発明の全芳香族ポリエステルには、全構成単位に対して構成単位（ＩＶ）を８．５～３０モル％含む。構成単位（ＩＶ）の含有量が８．５モル％未満、または３０モル％を超えると、低融点化及び耐熱性の少なくとも一方が不十分となりやすい。低融点化と耐熱性との両立の観点から、構成単位（ＩＶ）の含有量は、好ましくは１０～３０モル％であり、より好ましくは１２～２８モル％であり、更に好ましくは１４～２８モル％であり、より更に好ましくは１５～２８モル％であり、特に好ましくは１７～２７モル％である。
The structural unit (IV) is derived from 4,4'-dihydroxybiphenyl (hereinafter, also referred to as "BP"). The total aromatic polyester of the present invention contains 8.5 to 30 mol% of structural units (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 be insufficient. From the viewpoint of achieving both a low melting point and heat resistance, the content of the structural unit (IV) is preferably 10 to 30 mol%, more preferably 12 to 28 mol%, and further preferably 14 to 28 mol%. It is mol%, more preferably 15 to 28 mol%, and particularly preferably 17 to 27 mol%.
以上の通り、本発明の全芳香族ポリエステルは、特定の構成単位である（Ｉ）～（ＩＶ）を、全構成単位に対して特定の量含有し、構成単位（ＩＩＩ）の含有量と構成単位（ＩＶ）の含有量との差が０．１５０モル％以下であるため、重合反応時の昇華物の発生が少なく、異物が低減されている。なお、本発明の全芳香族ポリエステルは、構成単位（ＩＩＩ）の含有量と構成単位（ＩＶ）の含有量との差が０．１４５モル％以下であることが好ましく、０．１４０モル％以下であることがより好ましく、０．１３５モル％以下であることが更に好ましく、０．１３０モル％以下であることがより更に好ましく、０．１２５モル％以下であることが特に好ましい。また、本発明の全芳香族ポリエステルは、全構成単位に対して構成単位（Ｉ）～（ＩＶ）を合計で１００モル％含む。
As described above, the total aromatic polyester of the present invention contains specific structural units (I) to (IV) in a specific amount with respect to all the structural units, and the content and composition of the structural unit (III). Since the difference from the content of the unit (IV) is 0.150 mol% or less, the generation of sublimated substances during the polymerization reaction is small, and foreign substances are reduced. In the total aromatic polyester of the present invention, the difference between the content of the structural unit (III) and the content of the structural unit (IV) is preferably 0.145 mol% or less, preferably 0.140 mol% or less. It is more preferably 0.135 mol% or less, further preferably 0.130 mol% or less, and particularly preferably 0.125 mol% or less. In addition, the total aromatic polyester of the present invention contains 100 mol% of the constituent units (I) to (IV) in total with respect to all the constituent units.
次いで、全芳香族ポリエステルの性質について説明する。本発明の全芳香族ポリエステルは、溶融時に光学的異方性を示す。溶融時に光学的異方性を示すことは、本発明の全芳香族ポリエステルが液晶性ポリマーであることを意味する。
Next, the properties of all aromatic polyesters will be described. The total aromatic polyester of the present invention exhibits optical anisotropy when melted. Exhibiting optical anisotropy when melted means that the all-aromatic polyester of the present invention is a liquid crystal polymer.
本発明において、全芳香族ポリエステルが液晶性ポリマーであることは、全芳香族ポリエステルが熱安定性と易加工性を併せ持つ上で不可欠な要素である。上記構成単位（Ｉ）～（ＩＶ）から構成される全芳香族ポリエステルは、構成成分及びポリマー中のシーケンス分布によっては、異方性溶融相を形成しないものも存在するが、本発明のポリマーは溶融時に光学的異方性を示す全芳香族ポリエステルに限られる。
In the present invention, the fact that the total aromatic polyester is a liquid crystal polymer is an indispensable element for the total aromatic polyester to have both thermal stability and easy workability. The total aromatic polyester composed of the constituent units (I) to (IV) may not form an anisotropic molten phase depending on the constituent components and the sequence distribution in the polymer, but the polymer of the present invention has. Limited to all aromatic polyesters that exhibit optical anisotropy when melted.
溶融異方性の性質は直交偏光子を利用した慣用の偏光検査方法により確認することができる。より具体的には溶融異方性の確認は、オリンパス社製偏光顕微鏡を使用しリンカム社製ホットステージにのせた試料を溶融し、窒素雰囲気下で１５０倍の倍率で観察することにより実施できる。液晶性ポリマーは光学的に異方性であり、直交偏光子間に挿入したとき光を透過させる。試料が光学的に異方性であると、例えば溶融静止液状態であっても偏光は透過する。
The nature of melt anisotropy can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the confirmation of melt anisotropy can be carried out by melting a sample placed on a hot stage manufactured by Linkham Co., Ltd. using a polarizing microscope manufactured by Olympus Corporation and observing it at a magnification of 150 times in a nitrogen atmosphere. Liquid crystal polymers are optically anisotropic and transmit light when inserted between orthogonal polarizers. If the sample is optically anisotropic, polarized light is transmitted even in a molten static liquid state, for example.
ネマチックな液晶性ポリマーは融点以上で著しく粘性低下を生じるので、一般的に融点又はそれ以上の温度で液晶性を示すことが加工性の指標となる。融点は、でき得る限り高い方が耐熱性の観点からは好ましいが、ポリマーの溶融加工時の熱劣化や成形機の加熱能力等を考慮すると、３８０℃以下であることが好ましい目安となる。なお、より好ましくは２６０～３７０℃であり、更により好ましくは２７０～３７０℃であり、特に好ましくは２８０～３６０℃である。
Since a nematic liquid crystal polymer causes a significant decrease in viscosity above the melting point, it is generally an index of processability to exhibit liquid crystallinity at a temperature above the melting point. The melting point is preferably as high as possible from the viewpoint of heat resistance, but it is preferably 380 ° C. or lower in consideration of thermal deterioration during melt processing of the polymer and the heating capacity of the molding machine. It should be noted that the temperature is more preferably 260 to 370 ° C, even more preferably 270 to 370 ° C, and particularly preferably 280 to 360 ° C.
本発明の全芳香族ポリエステルの融点より１０～４０℃高い温度、かつ、剪断速度１０００／秒における前記全芳香族ポリエステルの溶融粘度は、好ましくは１０００Ｐａ・ｓ以下であり、より好ましくは４～５００Ｐａ・ｓであり、更により好ましくは４～２５０Ｐａ・ｓであり、特に好ましくは５～１００Ｐａ・ｓである。上記溶融粘度が上記範囲内であると、前記全芳香族ポリエステルそのもの、又は、前記全芳香族ポリエステルを含有する組成物は、その成形時において、流動性が確保されやすく、充填圧力が過度になりにくい。なお、本明細書において、溶融粘度とは、ＩＳＯ１１４４３に準拠して測定した溶融粘度をいう。
The melt viscosity of the total aromatic polyester at a temperature 10 to 40 ° C. higher than the melting point of the total aromatic polyester of the present invention and a shear rate of 1000 / sec is preferably 1000 Pa · s or less, more preferably 4 to 500 Pa. It is s, more preferably 4 to 250 Pa · s, and particularly preferably 5 to 100 Pa · s. When the melt viscosity is within the above range, the total aromatic polyester itself or the composition containing the total aromatic polyester tends to secure fluidity at the time of molding, and the filling pressure becomes excessive. Hateful. In addition, in this specification, the melt viscosity means the melt viscosity measured according to ISO11443.
次いで、本実施形態の全芳香族ポリエステルの製造方法について説明する。本実施形態の全芳香族ポリエステルは、直接重合法やエステル交換法等を用いて重合される。重合に際しては、溶融重合法、溶液重合法、スラリー重合法、固相重合法等、又はこれらの２種以上の組み合わせが用いられ、溶融重合法、又は溶融重合法と固相重合法との組み合わせが好ましく用いられる。
Next, the method for producing the all-aromatic polyester of the present embodiment will be described. The total aromatic polyester of the present embodiment is polymerized by using 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, etc., or a combination of two or more of these is used, and a melt polymerization method or a combination of the melt polymerization method and the solid phase polymerization method is used. Is preferably used.
本実施形態では、重合に際し、重合モノマーに対するアシル化剤や、酸塩化物誘導体として末端を活性化したモノマーを使用できる。アシル化剤としては、無水酢酸等の脂肪酸無水物が挙げられる。
In the present embodiment, during polymerization, an acylating agent for the polymerized monomer or a monomer having an activated terminal can be used as an acid chloride derivative. Examples of the acylating agent include fatty acid anhydrides such as acetic anhydride.
本実施形態の全芳香族ポリエステルの製造方法は、色相の観点から、脂肪酸無水物の使用量が６－ヒドロキシ－２－ナフトエ酸、４－ヒドロキシ安息香酸、及び４，４’－ジヒドロキシビフェニルの合計の水酸基当量の１．０８倍未満であることが好ましく、１．００～１．０７倍であることがより好ましく、１．０１～１．０７倍であることが更に好ましく、１．０１～１．０６倍であることがより更に好ましく、１．０２～１．０６倍であることが特に好ましい。
In the method for producing a total aromatic polyester of the present embodiment, the total amount of fatty acid anhydride used is 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, and 4,4'-dihydroxybiphenyl from the viewpoint of hue. It is preferably less than 1.08 times the hydroxyl group equivalent of, more preferably 1.00 to 1.07 times, further preferably 1.01 to 1.07 times, and 1.01 to 1 It is more preferably .06 times, and particularly preferably 1.02 to 1.06 times.
これらの重合に際しては種々の触媒の使用が可能であり、代表的なものとしては、酢酸カリウム、酢酸マグネシウム、酢酸第一錫、テトラブチルチタネート、酢酸鉛、酢酸ナトリウム、三酸化アンチモン、トリス（２，４－ペンタンジオナト）コバルト(III)等の金属塩系触媒、１－メチルイミダゾール、４－ジメチルアミノピリジン等の有機化合物系触媒を挙げることができる。
Various catalysts can be used for these polymerizations, and typical ones are potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, and tris (2). , 4-Pentandionato) Examples include metal salt-based catalysts such as cobalt (III) and organic compound-based catalysts such as 1-methylimidazole and 4-dimethylaminopyridine.
反応は、全原料モノマー（６－ヒドロキシ－２－ナフトエ酸、４－ヒドロキシ安息香酸、１，４－フェニレンジカルボン酸、及び４，４’－ジヒドロキシビフェニル）、アシル化剤、及び触媒を同一反応容器に仕込んで反応を開始させることもできるし（一段方式）、６－ヒドロキシ－２－ナフトエ酸、４－ヒドロキシ安息香酸、及び４，４’－ジヒドロキシビフェニルの水酸基をアシル化剤によりアシル化させた後、１，４－フェニレンジカルボン酸のカルボキシル基と反応させることもできる（二段方式）。
In the reaction, all raw material monomers (6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 1,4-phenylenedicarboxylic acid, and 4,4'-dihydroxybiphenyl), an acylating agent, and a catalyst are used in the same reaction vessel. The reaction can be started by charging in (one-step method), and the hydroxyl groups of 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, and 4,4'-dihydroxybiphenyl are acylated with an acylating agent. Later, it can be reacted with the carboxyl group of 1,4-phenylenedicarboxylic acid (two-stage method).
溶融重合は、反応系内が所定温度に達した後、減圧を開始して所定の減圧度にして行う。撹拌機のトルクが所定値に達した後、不活性ガスを導入し、減圧状態から常圧を経て、所定の加圧状態にして反応系から全芳香族ポリエステルを排出する。
After the inside of the reaction system reaches a predetermined temperature, melt polymerization is carried out by starting depressurization to a predetermined decompression degree. After the torque of the stirrer reaches a predetermined value, an inert gas is introduced, and the pressure is changed from a reduced pressure state to a normal pressure state to a predetermined pressure state, and the total aromatic polyester is discharged from the reaction system.
上記重合方法により製造された全芳香族ポリエステルは、更に常圧又は減圧、不活性ガス中で加熱する固相重合により分子量の増加を図ることができる。
The total aromatic polyester produced by the above polymerization method can be further increased in molecular weight by solid phase polymerization of normal pressure, reduced pressure, or heating in an inert gas.
本実施形態の全芳香族ポリエステルの製造方法は、６－ヒドロキシ－２－ナフトエ酸、４－ヒドロキシ安息香酸、及び４，４’－ジヒドロキシビフェニルを脂肪酸無水物でアシル化して、１，４－フェニレンジカルボン酸とエステル交換する工程を含むことが好ましく、
６－ヒドロキシ－２－ナフトエ酸、４－ヒドロキシ安息香酸、１，４－フェニレンジカルボン酸、及び４，４’－ジヒドロキシビフェニルからなる全モノマーに対し、
６－ヒドロキシ－２－ナフトエ酸の使用量が４０～７５モル％、耐熱性と重合性の観点から、好ましくは４０～７０モル％、より好ましくは４０～６５モル％、更に好ましくは４０～６３モル％、より更に好ましくは４０～６２モル％、特に好ましくは４０～６０モル％、
４－ヒドロキシ安息香酸の使用量が０．５～７．５モル％、耐熱性と重合性の観点から、好ましくは０．５～７．０モル％、より好ましくは１．０～７．０モル％、更に好ましくは１．２～７．０モル％、より更に好ましくは１．５～６．５モル％、特に好ましくは２．０～６．０モル％、
１，４－フェニレンジカルボン酸の使用量が８．５～３０モル％、低融点化と耐熱性との両立の観点から、好ましくは１０～３０モル％、より好ましくは１２～２８モル％、更に好ましくは１４～２８モル％、より更に好ましくは１５～２８モル％、特に好ましくは１７～２７モル％、
４，４’－ジヒドロキシビフェニルの使用量が８．５～３０モル％、低融点化と耐熱性との両立の観点から、好ましくは１０～３０モル％、より好ましくは１２～２８モル％、更に好ましくは１４～２８モル％、より更に好ましくは１５～２８モル％、特に好ましくは１７～２７モル％、
６－ヒドロキシ－２－ナフトエ酸、４－ヒドロキシ安息香酸、１，４－フェニレンジカルボン酸、及び４，４’－ジヒドロキシビフェニルの合計の使用量が１００モル％であることが好ましく、
１４０℃から３６０℃まで段階的に分けて昇温することが好ましい。 In the method for producing a total aromatic polyester of the present embodiment, 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, and 4,4'-dihydroxybiphenyl are acylated with a fatty acid anhydride to form 1,4-phenylene. It is preferable to include a step of transesterifying with a dicarboxylic acid.
For all monomers consisting of 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 1,4-phenylenedicarboxylic acid, and 4,4'-dihydroxybiphenyl.
The amount of 6-hydroxy-2-naphthoic acid used is 40 to 75 mol%, preferably 40 to 70 mol%, more preferably 40 to 65 mol%, still more preferably 40 to 63, from the viewpoint of heat resistance and polymerizable property. Mol%, even more preferably 40-62 mol%, particularly preferably 40-60 mol%,
The amount of 4-hydroxybenzoic acid used is 0.5 to 7.5 mol%, preferably 0.5 to 7.0 mol%, more preferably 1.0 to 7.0 from the viewpoint of heat resistance and polymerizable property. Mol%, more preferably 1.2 to 7.0 mol%, even more preferably 1.5 to 6.5 mol%, particularly preferably 2.0 to 6.0 mol%,
The amount of 1,4-phenylenedicarboxylic acid used is 8.5 to 30 mol%, preferably 10 to 30 mol%, more preferably 12 to 28 mol%, and further, from the viewpoint of achieving both a low melting point and heat resistance. Preferably 14-28 mol%, even more preferably 15-28 mol%, particularly preferably 17-27 mol%,
The amount of 4,4'-dihydroxybiphenyl used is 8.5 to 30 mol%, preferably 10 to 30 mol%, more preferably 12 to 28 mol%, and further, from the viewpoint of achieving both a low melting point and heat resistance. Preferably 14-28 mol%, even more preferably 15-28 mol%, particularly preferably 17-27 mol%,
The total amount of 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 1,4-phenylenedicarboxylic acid, and 4,4'-dihydroxybiphenyl is preferably 100 mol%.
It is preferable to raise the temperature in steps from 140 ° C. to 360 ° C.
６－ヒドロキシ－２－ナフトエ酸、４－ヒドロキシ安息香酸、１，４－フェニレンジカルボン酸、及び４，４’－ジヒドロキシビフェニルからなる全モノマーに対し、
６－ヒドロキシ－２－ナフトエ酸の使用量が４０～７５モル％、耐熱性と重合性の観点から、好ましくは４０～７０モル％、より好ましくは４０～６５モル％、更に好ましくは４０～６３モル％、より更に好ましくは４０～６２モル％、特に好ましくは４０～６０モル％、
４－ヒドロキシ安息香酸の使用量が０．５～７．５モル％、耐熱性と重合性の観点から、好ましくは０．５～７．０モル％、より好ましくは１．０～７．０モル％、更に好ましくは１．２～７．０モル％、より更に好ましくは１．５～６．５モル％、特に好ましくは２．０～６．０モル％、
１，４－フェニレンジカルボン酸の使用量が８．５～３０モル％、低融点化と耐熱性との両立の観点から、好ましくは１０～３０モル％、より好ましくは１２～２８モル％、更に好ましくは１４～２８モル％、より更に好ましくは１５～２８モル％、特に好ましくは１７～２７モル％、
４，４’－ジヒドロキシビフェニルの使用量が８．５～３０モル％、低融点化と耐熱性との両立の観点から、好ましくは１０～３０モル％、より好ましくは１２～２８モル％、更に好ましくは１４～２８モル％、より更に好ましくは１５～２８モル％、特に好ましくは１７～２７モル％、
６－ヒドロキシ－２－ナフトエ酸、４－ヒドロキシ安息香酸、１，４－フェニレンジカルボン酸、及び４，４’－ジヒドロキシビフェニルの合計の使用量が１００モル％であることが好ましく、
１４０℃から３６０℃まで段階的に分けて昇温することが好ましい。 In the method for producing a total aromatic polyester of the present embodiment, 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, and 4,4'-dihydroxybiphenyl are acylated with a fatty acid anhydride to form 1,4-phenylene. It is preferable to include a step of transesterifying with a dicarboxylic acid.
For all monomers consisting of 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 1,4-phenylenedicarboxylic acid, and 4,4'-dihydroxybiphenyl.
The amount of 6-hydroxy-2-naphthoic acid used is 40 to 75 mol%, preferably 40 to 70 mol%, more preferably 40 to 65 mol%, still more preferably 40 to 63, from the viewpoint of heat resistance and polymerizable property. Mol%, even more preferably 40-62 mol%, particularly preferably 40-60 mol%,
The amount of 4-hydroxybenzoic acid used is 0.5 to 7.5 mol%, preferably 0.5 to 7.0 mol%, more preferably 1.0 to 7.0 from the viewpoint of heat resistance and polymerizable property. Mol%, more preferably 1.2 to 7.0 mol%, even more preferably 1.5 to 6.5 mol%, particularly preferably 2.0 to 6.0 mol%,
The amount of 1,4-phenylenedicarboxylic acid used is 8.5 to 30 mol%, preferably 10 to 30 mol%, more preferably 12 to 28 mol%, and further, from the viewpoint of achieving both a low melting point and heat resistance. Preferably 14-28 mol%, even more preferably 15-28 mol%, particularly preferably 17-27 mol%,
The amount of 4,4'-dihydroxybiphenyl used is 8.5 to 30 mol%, preferably 10 to 30 mol%, more preferably 12 to 28 mol%, and further, from the viewpoint of achieving both a low melting point and heat resistance. Preferably 14-28 mol%, even more preferably 15-28 mol%, particularly preferably 17-27 mol%,
The total amount of 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 1,4-phenylenedicarboxylic acid, and 4,4'-dihydroxybiphenyl is preferably 100 mol%.
It is preferable to raise the temperature in steps from 140 ° C. to 360 ° C.
本実施形態の全芳香族ポリエステルの製造方法は、段階的に分けられた昇温が、１４０℃から２００℃、２００℃から２７０℃、２７０℃から３６０℃に分けられた昇温であることが好ましい。
In the method for producing an all-aromatic polyester of the present embodiment, the temperature rise divided in stages is 140 ° C to 200 ° C, 200 ° C to 270 ° C, 270 ° C to 360 ° C. preferable.
本実施形態の全芳香族ポリエステルの製造方法は、１４０℃から２００℃への昇温速度が、０．４℃／分以上０．８℃／分未満であることが好ましく、０．５℃／分以上０．７℃／分未満であることがより好ましい。
In the method for producing an all-aromatic polyester of the present embodiment, the rate of temperature rise from 140 ° C. to 200 ° C. is preferably 0.4 ° C./min or more and less than 0.8 ° C./min, and 0.5 ° C./min. More preferably, it is at least 0.7 ° C./min.
本実施形態の全芳香族ポリエステルの製造方法は、２００℃から２７０℃への昇温速度が、０．８℃／分以上１．２℃／分以下であることが好ましく、０．９℃／分以上１．１℃／分以下であることがより好ましい。
In the method for producing an all-aromatic polyester of the present embodiment, the rate of temperature rise from 200 ° C. to 270 ° C. is preferably 0.8 ° C./min or more and 1.2 ° C./min or less, and 0.9 ° C./min. More preferably, it is at least 1.1 ° C./min.
本実施形態の全芳香族ポリエステルの製造方法は、２７０℃から３６０℃への昇温速度が、０．４℃／分以上１．２℃／分以下であることが好ましく、０．５℃／分以上１．１℃／分以下であることがより好ましい。
In the method for producing an all-aromatic polyester of the present embodiment, the rate of temperature rise from 270 ° C. to 360 ° C. is preferably 0.4 ° C./min or more and 1.2 ° C./min or less, and 0.5 ° C./min. More preferably, it is at least 1.1 ° C./min.
本実施形態の全芳香族ポリエステルの製造方法は、高分子量化の観点から、１，４－フェニレンジカルボン酸の使用量（モル％）と４，４’－ジヒドロキシビフェニルの使用量（モル％）が等しいことが好ましい。なお、本実施形態の全芳香族ポリエステルの製造中に昇華物が発生することで、これらの含有量に差が生じる。
In the method for producing a total aromatic polyester of the present embodiment, the amount of 1,4-phenylenedicarboxylic acid used (mol%) and the amount of 4,4'-dihydroxybiphenyl used (mol%) are determined from the viewpoint of increasing the molecular weight. It is preferable that they are equal. It should be noted that the generation of sublimated products during the production of the total aromatic polyester of the present embodiment causes a difference in their contents.
［ポリエステル樹脂組成物］
上記の本発明の全芳香族ポリエステルには、使用目的に応じて各種の繊維状、粉粒状、板状の無機及び有機の充填剤を配合することができる。 [Polyester resin composition]
Various fibrous, powdery, plate-like inorganic and organic fillers can be blended in the above-mentioned all-aromatic polyester of the present invention depending on the purpose of use.
上記の本発明の全芳香族ポリエステルには、使用目的に応じて各種の繊維状、粉粒状、板状の無機及び有機の充填剤を配合することができる。 [Polyester resin composition]
Various fibrous, powdery, plate-like inorganic and organic fillers can be blended in the above-mentioned all-aromatic polyester of the present invention depending on the purpose of use.
本発明のポリエステル樹脂組成物に配合される、無機充填剤としては、繊維状、粉粒状、板状のものがある。
The inorganic filler blended in the polyester resin composition of the present invention includes fibrous, powdery, and plate-like fillers.
繊維状無機充填剤としてはガラス繊維、ミルドガラスファイバー、アスベスト繊維、シリカ繊維、シリカ・アルミナ繊維、アルミナ繊維、ジルコニア繊維、窒化硼素繊維、窒化珪素繊維、硼素繊維、チタン酸カリ繊維、ウォラストナイトなどの珪酸塩の繊維、硫酸マグネシウム繊維、ホウ酸アルミニウム繊維、更にステンレス、アルミニウム、チタン、銅、真鍮等の金属の繊維状物等の無機質繊維状物質が挙げられる。特に代表的な繊維状充填剤はガラス繊維である。
As the fibrous inorganic filler, glass fiber, milled 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 Examples thereof include silicate fibers such as magnesium sulfate fibers, aluminum borate fibers, and inorganic fibrous substances such as metal fibrous materials such as stainless steel, aluminum, titanium, copper and brass. A particularly typical fibrous filler is glass fiber.
また、粉粒状無機充填剤としてはカーボンブラック、黒鉛、シリカ、石英粉末、ガラスビーズ、ガラスバルーン、ガラス粉、硅酸カルシウム、硅酸アルミニウム、カオリン、クレー、硅藻土、ウォラストナイトなどの硅酸塩、酸化鉄、酸化チタン、酸化亜鉛、三酸化アンチモン、アルミナなどの金属の酸化物、炭酸カルシウム、炭酸マグネシウムなどの金属の炭酸塩、硫酸カルシウム、硫酸バリウムなどの金属の硫酸塩、その他フェライト、炭化硅素、窒化硅素、窒化硼素、各種金属粉末等が挙げられる。
In addition, as the powdery granular inorganic filler, carbon black, graphite, silica, quartz powder, glass beads, glass balloon, glass powder, calcium silicate, aluminum silicate, kaolin, clay, diatomaceous earth, wollastonite and the like. Acid salts, iron oxide, titanium oxide, zinc oxide, antimony trioxide, metal oxides such as alumina, carbonates of metals such as calcium carbonate and magnesium carbonate, sulfates of metals such as calcium sulfate and barium sulfate, and other ferrites. , Calcium carbonate, nitrous oxide, boron nitride, various metal powders and the like.
また、板状無機充填剤としてはマイカ、ガラスフレーク、タルク、各種の金属箔等が挙げられる。
In addition, examples of the plate-shaped inorganic filler include mica, glass flakes, talc, and various metal foils.
有機充填剤の例を示せば芳香族ポリエステル繊維、液晶性ポリマー繊維、芳香族ポリアミド、ポリイミド繊維等の耐熱性高強度合成繊維等である。
Examples of organic fillers include aromatic polyester fibers, liquid crystal polymer fibers, aromatic polyamides, and heat-resistant high-strength synthetic fibers such as polyimide fibers.
これらの無機及び有機充填剤は一種又は二種以上を併用することができる。繊維状無機充填剤と粒状又は板状無機充填剤との併用は、機械的強度と寸法精度、電気的性質等を兼備する上で好ましい組み合わせである。特に好ましくは、繊維状充填剤としてガラス繊維、板状充填剤としてマイカ及びタルクであり、その配合量は、全芳香族ポリエステル１００質量部に対して１２０質量部以下、好ましくは２０～８０質量部である。ガラス繊維をマイカ又はタルクと組み合わせることで、ポリエステル樹脂組成物は、熱変形温度、機械的物性等の向上が特に顕著である。
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 terms of combining mechanical strength, dimensional accuracy, electrical properties, and the like. Particularly preferably, glass fiber is used as the fibrous filler, and mica and talc are used as the plate-shaped filler, and the blending amount thereof is 120 parts by mass or less, preferably 20 to 80 parts by mass with respect to 100 parts by mass of the total aromatic polyester. Is. By combining the glass fiber with mica or talc, the polyester resin composition is particularly remarkable in improving the thermal deformation temperature, mechanical properties and the like.
これらの充填剤の使用にあたっては必要ならば収束剤又は表面処理剤を使用することができる。
When using these fillers, a converging agent or a surface treatment agent can be used if necessary.
本発明のポリエステル樹脂組成物は、上述の通り、必須成分として、本発明の全芳香族ポリエステルを含み、必要に応じて無機又は有機充填剤を含むが、本発明の効果を害さない範囲であれば、その他の成分が含まれていてもよい。ここで、その他の成分とは、どのような成分であってもよく、例えば、その他の樹脂、酸化防止剤、安定剤、顔料、結晶核剤等の添加剤を挙げることができる。
As described above, the polyester resin composition of the present invention contains the all-aromatic polyester of the present invention as an essential component, and optionally contains an inorganic or organic filler, as long as it does not impair the effects of the present invention. For example, other components may be contained. Here, the other component may be any component, and examples thereof include additives such as other resins, antioxidants, stabilizers, pigments, and crystal nucleating agents.
また、本発明のポリエステル樹脂組成物の製造方法は特に限定されず、従来公知の方法で、ポリエステル樹脂組成物を調製することができる。
Further, the method for producing the polyester resin composition of the present invention is not particularly limited, and the polyester resin composition can be prepared by a conventionally known method.
［ポリエステル成形品］
本発明のポリエステル成形品は、本発明の全芳香族ポリエステル又はポリエステル樹脂組成物を成形して得ることができる。成形方法としては、特に限定されず一般的な成形方法を採用することができる。一般的な成形方法としては、射出成形、押出成形、圧縮成形、ブロー成形、真空成形、発泡成形、回転成形、ガスインジェクション成形、インフレーション成形等の方法を例示することができる。 [Polyester molded product]
The polyester molded product of the present invention can be obtained by molding the all-aromatic polyester or polyester resin composition of the present invention. The molding method is not particularly limited, and a general molding method can be adopted. Examples of general molding methods include injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, rotary molding, gas injection molding, and inflation molding.
本発明のポリエステル成形品は、本発明の全芳香族ポリエステル又はポリエステル樹脂組成物を成形して得ることができる。成形方法としては、特に限定されず一般的な成形方法を採用することができる。一般的な成形方法としては、射出成形、押出成形、圧縮成形、ブロー成形、真空成形、発泡成形、回転成形、ガスインジェクション成形、インフレーション成形等の方法を例示することができる。 [Polyester molded product]
The polyester molded product of the present invention can be obtained by molding the all-aromatic polyester or polyester resin composition of the present invention. The molding method is not particularly limited, and a general molding method can be adopted. Examples of general molding methods include injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, rotary molding, gas injection molding, and inflation molding.
本発明の全芳香族ポリエステル等を成形して得られるポリエステル成形品は、耐熱性に優れる。また、本発明のポリエステル樹脂組成物を成形して得られるポリエステル成形品は、耐熱性に優れるとともに、必要に応じて無機又は有機充填剤を含むため、機械的強度等が更に改善される。
The polyester molded product obtained by molding the all-aromatic polyester or the like of the present invention has excellent heat resistance. Further, the polyester molded product obtained by molding the polyester resin composition of the present invention has excellent heat resistance and contains an inorganic or organic filler as required, so that the mechanical strength and the like are further improved.
また、本発明の全芳香族ポリエステル、ポリエステル樹脂組成物は、成形性に優れるため、種々の立体成形品、繊維、フィルム等に加工できる。
Further, since the all-aromatic polyester and polyester resin composition of the present invention are excellent in moldability, they can be processed into various three-dimensional molded products, fibers, films and the like.
以上のような性質を有する本発明のポリエステル成形品の好ましい用途としては、コネクター、ＣＰＵソケット、リレースイッチ部品、ボビン、アクチュエータ、ノイズ低減フィルターケース、電子回路基板又はＯＡ機器の加熱定着ロール等が挙げられる。
Preferred applications 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 cases, electronic circuit boards, heating fixing rolls for OA equipment, and the like. Be done.
以下に実施例を示して本発明をさらに具体的に説明するが、本発明はこれらの実施例により限定されるものではない。
The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these Examples.
＜実施例１＞
撹拌機、還流カラム、モノマー投入口、窒素導入口、減圧／流出ラインを備えた重合容器に、以下の原料モノマー、脂肪酸金属塩触媒、アシル化剤を仕込み、窒素置換を開始した。
（Ｉ）６－ヒドロキシ－２－ナフトエ酸 ０．８８３モル（４８モル％）（ＨＮＡ）
（ＩＩ）４－ヒドロキシ安息香酸 ０．０３７モル（２モル％）（ＨＢＡ）
（ＩＩＩ）１，４－フェニレンジカルボン酸 ０．４６モル（２５モル％）（ＴＡ）
（ＩＶ）４，４’－ジヒドロキシビフェニル ０．４６モル（２５モル％）（ＢＰ）
酢酸カリウム触媒 １５０ｐｐｍ
トリス（２，４－ペンタンジオナト）コバルト(III)触媒 １５０ｐｐｍ
無水酢酸 １．９１モル（ＨＮＡ、ＨＢＡ、及びＢＰの合計の水酸基当量の１．０４倍）
原料を仕込んだ後、反応系の温度を１４０℃に上げ、１４０℃で１時間反応させた。その後、更に表１に示す速度条件で昇温し、そこから２０分かけて１０Ｔｏｒｒ（すなわち１３３０Ｐａ）まで減圧にして、酢酸、過剰の無水酢酸、その他の低沸分を留出させながら溶融重合を行った。撹拌トルクが所定の値に達した後、窒素を導入して減圧状態から常圧を経て加圧状態にして、重合容器の下部から生成物を排出し、ペレタイズしてペレット状のプレポリマーを得た。得られたプレポリマーを、窒素気流下、３００℃で３時間、加熱処理（固相重合）を行い、目的とするポリマーを得た。 <Example 1>
The following raw material monomers, fatty acid metal salt catalysts, and acylating agents were charged into a polymerization vessel equipped with a stirrer, a reflux column, a monomer inlet, a nitrogen inlet, and a depressurization / outflow line, and nitrogen substitution was started.
(I) 0.883 mol (48 mol%) of 6-hydroxy-2-naphthoic acid (HNA)
(II) 4-Hydroxybenzoic acid 0.037 mol (2 mol%) (HBA)
(III) 1,4-phenylenedicarboxylic acid 0.46 mol (25 mol%) (TA)
(IV) 4,4'-Dihydroxybiphenyl 0.46 mol (25 mol%) (BP)
Potassium acetate catalyst 150ppm
Tris (2,4-pentanedionato) cobalt (III) catalyst 150ppm
1.91 mol of acetic anhydride (1.04 times the total hydroxyl equivalent of HNA, HBA, and BP)
After charging the raw materials, the temperature of the reaction system was raised to 140 ° C., and the reaction was carried out at 140 ° C. for 1 hour. Then, the temperature is further raised under the speed conditions shown in Table 1, and the pressure is reduced to 10 Torr (that is, 1330 Pa) over 20 minutes, and melt polymerization is carried out while distilling acetic acid, excess acetic anhydride, and other low boiling points. went. After the stirring torque reaches a predetermined value, nitrogen is introduced to change the pressure from a reduced pressure state to a pressurized state through normal pressure, and the product is discharged from the lower part of the polymerization vessel and pelletized to obtain a pellet-shaped prepolymer. It was. The obtained prepolymer was heat-treated (solid phase polymerization) at 300 ° C. for 3 hours under a nitrogen stream to obtain the desired polymer.
撹拌機、還流カラム、モノマー投入口、窒素導入口、減圧／流出ラインを備えた重合容器に、以下の原料モノマー、脂肪酸金属塩触媒、アシル化剤を仕込み、窒素置換を開始した。
（Ｉ）６－ヒドロキシ－２－ナフトエ酸 ０．８８３モル（４８モル％）（ＨＮＡ）
（ＩＩ）４－ヒドロキシ安息香酸 ０．０３７モル（２モル％）（ＨＢＡ）
（ＩＩＩ）１，４－フェニレンジカルボン酸 ０．４６モル（２５モル％）（ＴＡ）
（ＩＶ）４，４’－ジヒドロキシビフェニル ０．４６モル（２５モル％）（ＢＰ）
酢酸カリウム触媒 １５０ｐｐｍ
トリス（２，４－ペンタンジオナト）コバルト(III)触媒 １５０ｐｐｍ
無水酢酸 １．９１モル（ＨＮＡ、ＨＢＡ、及びＢＰの合計の水酸基当量の１．０４倍）
原料を仕込んだ後、反応系の温度を１４０℃に上げ、１４０℃で１時間反応させた。その後、更に表１に示す速度条件で昇温し、そこから２０分かけて１０Ｔｏｒｒ（すなわち１３３０Ｐａ）まで減圧にして、酢酸、過剰の無水酢酸、その他の低沸分を留出させながら溶融重合を行った。撹拌トルクが所定の値に達した後、窒素を導入して減圧状態から常圧を経て加圧状態にして、重合容器の下部から生成物を排出し、ペレタイズしてペレット状のプレポリマーを得た。得られたプレポリマーを、窒素気流下、３００℃で３時間、加熱処理（固相重合）を行い、目的とするポリマーを得た。 <Example 1>
The following raw material monomers, fatty acid metal salt catalysts, and acylating agents were charged into a polymerization vessel equipped with a stirrer, a reflux column, a monomer inlet, a nitrogen inlet, and a depressurization / outflow line, and nitrogen substitution was started.
(I) 0.883 mol (48 mol%) of 6-hydroxy-2-naphthoic acid (HNA)
(II) 4-Hydroxybenzoic acid 0.037 mol (2 mol%) (HBA)
(III) 1,4-phenylenedicarboxylic acid 0.46 mol (25 mol%) (TA)
(IV) 4,4'-Dihydroxybiphenyl 0.46 mol (25 mol%) (BP)
Potassium acetate catalyst 150ppm
Tris (2,4-pentanedionato) cobalt (III) catalyst 150ppm
1.91 mol of acetic anhydride (1.04 times the total hydroxyl equivalent of HNA, HBA, and BP)
After charging the raw materials, the temperature of the reaction system was raised to 140 ° C., and the reaction was carried out at 140 ° C. for 1 hour. Then, the temperature is further raised under the speed conditions shown in Table 1, and the pressure is reduced to 10 Torr (that is, 1330 Pa) over 20 minutes, and melt polymerization is carried out while distilling acetic acid, excess acetic anhydride, and other low boiling points. went. After the stirring torque reaches a predetermined value, nitrogen is introduced to change the pressure from a reduced pressure state to a pressurized state through normal pressure, and the product is discharged from the lower part of the polymerization vessel and pelletized to obtain a pellet-shaped prepolymer. It was. The obtained prepolymer was heat-treated (solid phase polymerization) at 300 ° C. for 3 hours under a nitrogen stream to obtain the desired polymer.
［昇華物量］
上述の溶融重合において、還流カラム及びリアクター上部の重量変化から、昇華物量を測定した。評価結果を表１に示す。 [Sublimation quantity]
In the above-mentioned melt polymerization, the amount of sublimated material was measured from the weight change of the reflux column and the upper part of the reactor. The evaluation results are shown in Table 1.
上述の溶融重合において、還流カラム及びリアクター上部の重量変化から、昇華物量を測定した。評価結果を表１に示す。 [Sublimation quantity]
In the above-mentioned melt polymerization, the amount of sublimated material was measured from the weight change of the reflux column and the upper part of the reactor. The evaluation results are shown in Table 1.
＜評価＞
実施例１の全芳香族ポリエステルについて、融点、溶融粘度、末端基量、異物の評価を以下の方法で行った。評価結果を表１に示す。 <Evaluation>
The melting point, melt viscosity, amount of terminal groups, and foreign matter were evaluated for the total aromatic polyester of Example 1 by the following methods. The evaluation results are shown in Table 1.
実施例１の全芳香族ポリエステルについて、融点、溶融粘度、末端基量、異物の評価を以下の方法で行った。評価結果を表１に示す。 <Evaluation>
The melting point, melt viscosity, amount of terminal groups, and foreign matter were evaluated for the total aromatic polyester of Example 1 by the following methods. The evaluation results are shown in Table 1.
［融点］
示差走査熱量計（ＤＳＣ、パーキンエルマー社製）にて、全芳香族ポリエステルを室温から２０℃／分の昇温条件で加熱した際に観測される吸熱ピーク温度（Ｔｍ１）の測定後、（Ｔｍ１＋４０）℃の温度で２分間保持した後、２０℃／分の降温条件で室温まで一旦冷却した後、再度、２０℃／分の昇温条件で加熱した際に観測される吸熱ピークの温度を測定した。 [Melting point]
After measuring the endothermic peak temperature (Tm1) observed when all aromatic polyester is heated from room temperature to 20 ° C./min with a differential scanning calorimeter (DSC, manufactured by Perkin Elmer), (Tm1 + 40). ) Measure the temperature of the endothermic peak observed when the temperature is maintained at a temperature of 20 ° C. for 2 minutes, then cooled to room temperature under a temperature decreasing condition of 20 ° C./min, and then heated again under a heating condition of 20 ° C./min. did.
示差走査熱量計（ＤＳＣ、パーキンエルマー社製）にて、全芳香族ポリエステルを室温から２０℃／分の昇温条件で加熱した際に観測される吸熱ピーク温度（Ｔｍ１）の測定後、（Ｔｍ１＋４０）℃の温度で２分間保持した後、２０℃／分の降温条件で室温まで一旦冷却した後、再度、２０℃／分の昇温条件で加熱した際に観測される吸熱ピークの温度を測定した。 [Melting point]
After measuring the endothermic peak temperature (Tm1) observed when all aromatic polyester is heated from room temperature to 20 ° C./min with a differential scanning calorimeter (DSC, manufactured by Perkin Elmer), (Tm1 + 40). ) Measure the temperature of the endothermic peak observed when the temperature is maintained at a temperature of 20 ° C. for 2 minutes, then cooled to room temperature under a temperature decreasing condition of 20 ° C./min, and then heated again under a heating condition of 20 ° C./min. did.
［溶融粘度］
キャピログラフ（（株）東洋精機製作所製）を使用し、温度３８０℃で、内径０．５ｍｍ、長さ３０ｍｍのオリフィスを用いて、剪断速度１０００／秒で、ＩＳＯ１１４４３に準拠して、全芳香族ポリエステルの溶融粘度を測定した。 [Melting viscosity]
Using a capillograph (manufactured by Toyo Seiki Seisakusho Co., Ltd.), using an orifice with an inner diameter of 0.5 mm and a length of 30 mm at a temperature of 380 ° C. The melt viscosity of was measured.
キャピログラフ（（株）東洋精機製作所製）を使用し、温度３８０℃で、内径０．５ｍｍ、長さ３０ｍｍのオリフィスを用いて、剪断速度１０００／秒で、ＩＳＯ１１４４３に準拠して、全芳香族ポリエステルの溶融粘度を測定した。 [Melting viscosity]
Using a capillograph (manufactured by Toyo Seiki Seisakusho Co., Ltd.), using an orifice with an inner diameter of 0.5 mm and a length of 30 mm at a temperature of 380 ° C. The melt viscosity of was measured.
［モノマー組成（含有量）］
Ｐｏｌｙｍｅｒ Ｄｅｇｒａｄａｔｉｏｎ ａｎｄ Ｓｔａｂｉｌｉｔｙ ７６（２００２）８５－９４に記載される、熱分解ガスクロマトグラフィー法によってモノマー組成を算出した。具体的には、熱分解装置（フロンティア・ラボ（株）製「ＰＹ２０２０ｉＤ」）を用いて、全芳香族ポリエステルを水酸化テトラメチルアンモニウム（ＴＭＡＨ）共存下で加熱し、熱分解／メチル化によりガスを発生させた。このガスをガスクロマトグラフィー（アジレント・テクノロジー（株）製「ＧＣ－６８９０Ｎ」）を用いて分析し、１，４－フェニレンジカルボン酸に由来するピーク面積と４，４’－ジヒドロキシビフェニルに由来するピーク面積との比から、１，４－フェニレンジカルボン酸から誘導される構成単位の含有量と４，４’－ジヒドロキシビフェニルから誘導される構成単位の含有量との差を算出した。 [Monomer composition (content)]
The monomer composition was calculated by the pyrolysis gas chromatography method described in Polymer Degradation and Stability 76 (2002) 85-94. Specifically, using a pyrolysis device (“PY2020iD” manufactured by Frontier Lab Co., Ltd.), all aromatic polyester is heated in the presence of tetramethylammonium hydroxide (TMAH), and gas is pyrolyzed / methylated. Was generated. This gas was analyzed using gas chromatography (“GC-6890N” manufactured by Azilent Technology Co., Ltd.), and the peak area derived from 1,4-phenylenedicarboxylic acid and the peak derived from 4,4′-dihydroxybiphenyl were analyzed. From the ratio to the area, the difference between the content of the constituent unit derived from 1,4-phenylenedicarboxylic acid and the content of the constituent unit derived from 4,4'-dihydroxybiphenyl was calculated.
Ｐｏｌｙｍｅｒ Ｄｅｇｒａｄａｔｉｏｎ ａｎｄ Ｓｔａｂｉｌｉｔｙ ７６（２００２）８５－９４に記載される、熱分解ガスクロマトグラフィー法によってモノマー組成を算出した。具体的には、熱分解装置（フロンティア・ラボ（株）製「ＰＹ２０２０ｉＤ」）を用いて、全芳香族ポリエステルを水酸化テトラメチルアンモニウム（ＴＭＡＨ）共存下で加熱し、熱分解／メチル化によりガスを発生させた。このガスをガスクロマトグラフィー（アジレント・テクノロジー（株）製「ＧＣ－６８９０Ｎ」）を用いて分析し、１，４－フェニレンジカルボン酸に由来するピーク面積と４，４’－ジヒドロキシビフェニルに由来するピーク面積との比から、１，４－フェニレンジカルボン酸から誘導される構成単位の含有量と４，４’－ジヒドロキシビフェニルから誘導される構成単位の含有量との差を算出した。 [Monomer composition (content)]
The monomer composition was calculated by the pyrolysis gas chromatography method described in Polymer Degradation and Stability 76 (2002) 85-94. Specifically, using a pyrolysis device (“PY2020iD” manufactured by Frontier Lab Co., Ltd.), all aromatic polyester is heated in the presence of tetramethylammonium hydroxide (TMAH), and gas is pyrolyzed / methylated. Was generated. This gas was analyzed using gas chromatography (“GC-6890N” manufactured by Azilent Technology Co., Ltd.), and the peak area derived from 1,4-phenylenedicarboxylic acid and the peak derived from 4,4′-dihydroxybiphenyl were analyzed. From the ratio to the area, the difference between the content of the constituent unit derived from 1,4-phenylenedicarboxylic acid and the content of the constituent unit derived from 4,4'-dihydroxybiphenyl was calculated.
［異物］
高温対応ホットプレス機（（株）東洋精機製作所製「ＮＰ－ＳＮＨ」）を用いて全芳香族ポリエステルをフィルム化（０．５ｇ／枚、膜厚１００μｍ）した。フィルムに白色のバックライトを当て、ルーペを用いて、０．３ｍｍ以上の異物の個数を確認した。この異物の個数の確認をフィルム５枚（２．５ｇ）に対して行い、単位重量あたりの異物の個数を求めた。異物の個数が０個／ｇの場合を「〇」、１個／ｇ以上の場合を「×」として示した。 [Foreign matter]
A total aromatic polyester was filmed (0.5 g / sheet, film thickness 100 μm) using a high temperature hot press machine (“NP-SNH” manufactured by Toyo Seiki Seisakusho Co., Ltd.). A white backlight was applied to the film, and a magnifying glass was used to check the number of foreign substances of 0.3 mm or more. The number of foreign substances was confirmed for 5 films (2.5 g), and the number of foreign substances per unit weight was determined. The case where the number of foreign substances is 0 / g is shown as “◯”, and the case where the number of foreign substances is 1 / g or more is shown as “x”.
高温対応ホットプレス機（（株）東洋精機製作所製「ＮＰ－ＳＮＨ」）を用いて全芳香族ポリエステルをフィルム化（０．５ｇ／枚、膜厚１００μｍ）した。フィルムに白色のバックライトを当て、ルーペを用いて、０．３ｍｍ以上の異物の個数を確認した。この異物の個数の確認をフィルム５枚（２．５ｇ）に対して行い、単位重量あたりの異物の個数を求めた。異物の個数が０個／ｇの場合を「〇」、１個／ｇ以上の場合を「×」として示した。 [Foreign matter]
A total aromatic polyester was filmed (0.5 g / sheet, film thickness 100 μm) using a high temperature hot press machine (“NP-SNH” manufactured by Toyo Seiki Seisakusho Co., Ltd.). A white backlight was applied to the film, and a magnifying glass was used to check the number of foreign substances of 0.3 mm or more. The number of foreign substances was confirmed for 5 films (2.5 g), and the number of foreign substances per unit weight was determined. The case where the number of foreign substances is 0 / g is shown as “◯”, and the case where the number of foreign substances is 1 / g or more is shown as “x”.
＜実施例２～４、比較例１～１０＞
原料モノマーの種類、使用量（モル％）、昇温速度を表１及び表２に示す通りとした以外は、実施例１と同様にしてポリマーを得た。また、実施例１と同様の評価を行った（実施例４、比較例４の溶融粘度は温度３５０℃で測定した）。評価結果を表１及び表２に示す。 <Examples 2 to 4, 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, the amount used (mol%), and the rate of temperature rise were as shown in Tables 1 and 2. Further, the same evaluation as in Example 1 was performed (the melt viscosities of Example 4 and Comparative Example 4 were measured at a temperature of 350 ° C.). The evaluation results are shown in Tables 1 and 2.
原料モノマーの種類、使用量（モル％）、昇温速度を表１及び表２に示す通りとした以外は、実施例１と同様にしてポリマーを得た。また、実施例１と同様の評価を行った（実施例４、比較例４の溶融粘度は温度３５０℃で測定した）。評価結果を表１及び表２に示す。 <Examples 2 to 4, 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, the amount used (mol%), and the rate of temperature rise were as shown in Tables 1 and 2. Further, the same evaluation as in Example 1 was performed (the melt viscosities of Example 4 and Comparative Example 4 were measured at a temperature of 350 ° C.). The evaluation results are shown in Tables 1 and 2.
なお、表２に示す通り、１４０℃から２００℃への昇温速度が、０．３０℃／分である比較例８、０．８９℃／分である比較例９では、異物が発生していた。また、表１、２に示す通り、２００℃から２７０℃への昇温速度が、０．６０℃／分である比較例２、０．６９℃／分である比較例５、１．３０℃／分である比較例６では、異物が発生していた。さらに、表１、２に示す通り、２７０℃から３６０℃への昇温速度が、１．５０℃／分である比較例１～４、０．３０℃／分である比較例７、１．２９℃／分である比較例１０においても、異物が発生していた。
As shown in Table 2, in Comparative Example 8 in which the rate of temperature rise from 140 ° C. to 200 ° C. is 0.30 ° C./min and Comparative Example 9 in which the temperature rise rate is 0.89 ° C./min, foreign matter is generated. It was. Further, as shown in Tables 1 and 2, Comparative Example 2 in which the rate of temperature rise from 200 ° C. to 270 ° C. is 0.60 ° C./min, and Comparative Example 5, 1.30 ° C. in which the temperature rise rate is 0.69 ° C./min. In Comparative Example 6 at / min, foreign matter was generated. Further, as shown in Tables 1 and 2, Comparative Examples 1 to 4 in which the rate of temperature rise from 270 ° C. to 360 ° C. is 1.50 ° C./min, and Comparative Examples 7 and 1 in which 0.30 ° C./min. Foreign matter was also generated in Comparative Example 10 at 29 ° C./min.
As shown in Table 2, in Comparative Example 8 in which the rate of temperature rise from 140 ° C. to 200 ° C. is 0.30 ° C./min and Comparative Example 9 in which the temperature rise rate is 0.89 ° C./min, foreign matter is generated. It was. Further, as shown in Tables 1 and 2, Comparative Example 2 in which the rate of temperature rise from 200 ° C. to 270 ° C. is 0.60 ° C./min, and Comparative Example 5, 1.30 ° C. in which the temperature rise rate is 0.69 ° C./min. In Comparative Example 6 at / min, foreign matter was generated. Further, as shown in Tables 1 and 2, Comparative Examples 1 to 4 in which the rate of temperature rise from 270 ° C. to 360 ° C. is 1.50 ° C./min, and Comparative Examples 7 and 1 in which 0.30 ° C./min. Foreign matter was also generated in Comparative Example 10 at 29 ° C./min.
Claims (8)
- 必須の構成成分として、下記構成単位（Ｉ）、（ＩＩ）、（ＩＩＩ）及び（ＩＶ）からなり、
全構成単位に対して構成単位（Ｉ）の含有量は４０～７５モル％であり、
全構成単位に対して構成単位（ＩＩ）の含有量は０．５～７．５モル％であり、
全構成単位に対して構成単位（ＩＩＩ）の含有量は８．５～３０モル％であり、
全構成単位に対して構成単位（ＩＶ）の含有量は８．５～３０モル％であり、
全構成単位に対して構成単位（Ｉ）、（ＩＩ）、（ＩＩＩ）及び（ＩＶ）の合計の含有量は１００モル％であることを特徴とする、
全芳香族ポリエステルであって、
構成単位（ＩＩＩ）の含有量と構成単位（ＩＶ）の含有量との差が０．１５０モル％以下である、全芳香族ポリエステル。
The content of the constituent unit (I) is 40 to 75 mol% with respect to all the constituent units.
The content of the constituent unit (II) is 0.5 to 7.5 mol% with respect to all the constituent units.
The content of the constituent unit (III) is 8.5 to 30 mol% with respect to all the constituent units.
The content of the constituent unit (IV) is 8.5 to 30 mol% with respect to all the constituent units.
The total content of the constituent units (I), (II), (III) and (IV) with respect to all the constituent units is 100 mol%.
All aromatic polyester
A total aromatic polyester in which the difference between the content of the structural unit (III) and the content of the structural unit (IV) is 0.150 mol% or less.
- 請求項１に記載の全芳香族ポリエステルを含有するポリエステル樹脂組成物。 A polyester resin composition containing the total aromatic polyester according to claim 1.
- 請求項１または２に記載の全芳香族ポリエステルまたはポリエステル樹脂組成物を成形して得られるポリエステル成形品。 A polyester molded product obtained by molding the all-aromatic polyester or polyester resin composition according to claim 1 or 2.
- 全芳香族ポリエステルの製造方法であって、
６－ヒドロキシ－２－ナフトエ酸、４－ヒドロキシ安息香酸、及び４，４’－ジヒドロキシビフェニルを脂肪酸無水物でアシル化して、１，４－フェニレンジカルボン酸とエステル交換する工程を含み、
６－ヒドロキシ－２－ナフトエ酸、４－ヒドロキシ安息香酸、１，４－フェニレンジカルボン酸、及び４，４’－ジヒドロキシビフェニルからなる全モノマーに対し、
６－ヒドロキシ－２－ナフトエ酸の使用量が４０～７５モル％、
４－ヒドロキシ安息香酸の使用量が０．５～７．５モル％、
１，４－フェニレンジカルボン酸の使用量が８．５～３０モル％、
４，４’－ジヒドロキシビフェニルの使用量が８．５～３０モル％、
６－ヒドロキシ－２－ナフトエ酸、４－ヒドロキシ安息香酸、１，４－フェニレンジカルボン酸、及び４，４’－ジヒドロキシビフェニルの合計の使用量が１００モル％であり、
１４０℃から３６０℃まで段階的に分けて昇温することを特徴とする、全芳香族ポリエステルの製造方法。 A method for producing all-aromatic polyester.
It comprises the steps of acylating 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, and 4,4'-dihydroxybiphenyl with fatty acid anhydride and transesterifying with 1,4-phenylenedicarboxylic acid.
For all monomers consisting of 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 1,4-phenylenedicarboxylic acid, and 4,4'-dihydroxybiphenyl.
The amount of 6-hydroxy-2-naphthoic acid used is 40-75 mol%,
The amount of 4-hydroxybenzoic acid used is 0.5 to 7.5 mol%,
The amount of 1,4-phenylenedicarboxylic acid used is 8.5 to 30 mol%,
The amount of 4,4'-dihydroxybiphenyl used is 8.5 to 30 mol%,
The total amount of 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, 1,4-phenylenedicarboxylic acid, and 4,4'-dihydroxybiphenyl used is 100 mol%.
A method for producing a totally aromatic polyester, which comprises gradually raising the temperature from 140 ° C. to 360 ° C. in a stepwise manner. - 段階的に分けられた昇温が、１４０℃から２００℃、２００℃から２７０℃、２７０℃から３６０℃に分けられた昇温である、請求項４に記載の全芳香族ポリエステルの製造方法。 The method for producing an all-aromatic polyester according to claim 4, wherein the temperature rise divided in stages is a temperature rise divided into 140 ° C to 200 ° C, 200 ° C to 270 ° C, and 270 ° C to 360 ° C.
- １４０℃から２００℃への昇温速度が、０．４℃／分以上０．８℃／分未満である、請求項４または５に記載の全芳香族ポリエステルの製造方法。 The method for producing an all-aromatic polyester according to claim 4 or 5, wherein the rate of temperature rise from 140 ° C. to 200 ° C. is 0.4 ° C./min or more and less than 0.8 ° C./min.
- ２００℃から２７０℃への昇温速度が、０．８℃／分以上１．２℃／分以下である、請求項４から６のいずれか一項に記載の全芳香族ポリエステルの製造方法。 The method for producing an all-aromatic polyester according to any one of claims 4 to 6, wherein the rate of temperature rise from 200 ° C. to 270 ° C. is 0.8 ° C./min or more and 1.2 ° C./min or less.
- ２７０℃から３６０℃への昇温速度が、０．４℃／分以上１．２℃／分以下である、請求項４から７のいずれか一項に記載の全芳香族ポリエステルの製造方法。 The method for producing an all-aromatic polyester according to any one of claims 4 to 7, wherein the rate of temperature rise from 270 ° C. to 360 ° C. is 0.4 ° C./min or more and 1.2 ° C./min or less.
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| JP3730150B2 (en) | 2000-09-22 | 2005-12-21 | ポリプラスチックス株式会社 | Totally aromatic polyester and polyester resin composition |
| JP4463637B2 (en) * | 2004-07-30 | 2010-05-19 | ポリプラスチックス株式会社 | Liquid crystalline polyester resin composition |
| JP5165492B2 (en) * | 2008-05-23 | 2013-03-21 | ポリプラスチックス株式会社 | Planar connector |
| JP2010037364A (en) * | 2008-07-31 | 2010-02-18 | Polyplastics Co | Connector |
| JP5753144B2 (en) * | 2012-09-21 | 2015-07-22 | ポリプラスチックス株式会社 | Totally aromatic polyester and polyester resin composition, and polyester molded article |
| CN108026258B (en) * | 2015-10-21 | 2019-03-26 | 宝理塑料株式会社 | Wholly aromatic polyester and its manufacturing method |
-
2020
- 2020-04-02 MY MYPI2021005229A patent/MY191157A/en unknown
- 2020-04-02 CN CN202080026381.4A patent/CN113710724B/en active Active
- 2020-04-02 WO PCT/JP2020/015149 patent/WO2020204124A1/en active Application Filing
- 2020-04-02 KR KR1020217033623A patent/KR20210150422A/en unknown
- 2020-04-02 JP JP2020553566A patent/JP6837189B1/en active Active
- 2020-04-06 TW TW109111471A patent/TW202104347A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012137637A1 (en) * | 2011-04-01 | 2012-10-11 | ポリプラスチックス株式会社 | Planar connector |
| WO2012137636A1 (en) * | 2011-04-01 | 2012-10-11 | ポリプラスチックス株式会社 | Fully aromatic polyester and polyester resin composition |
| WO2018139393A1 (en) * | 2017-01-26 | 2018-08-02 | ポリプラスチックス株式会社 | Wholly aromatic polyester and polyester resin composition |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210075162A1 (en) * | 2019-09-10 | 2021-03-11 | Ticona Llc | Electrical Connector Formed from a Polymer Composition having a Low Dielectric Constant and Dissipation Factor |
| JP6944615B1 (en) * | 2019-10-31 | 2021-10-06 | ポリプラスチックス株式会社 | Resin composition and connector |
| JP6944616B1 (en) * | 2019-10-31 | 2021-10-06 | ポリプラスチックス株式会社 | Resin composition and planar connector |
| WO2022113802A1 (en) * | 2020-11-25 | 2022-06-02 | 株式会社クラレ | Liquid crystal polyester fibers and method for producing same |
| WO2022113803A1 (en) * | 2020-11-25 | 2022-06-02 | 株式会社クラレ | Liquid crystal polyester resin comosition, liquid crystal polyester fibers, fiber structure and melt molded body |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2020204124A1 (en) | 2021-04-30 |
| MY191157A (en) | 2022-06-02 |
| CN113710724B (en) | 2023-11-03 |
| JP6837189B1 (en) | 2021-03-03 |
| CN113710724A (en) | 2021-11-26 |
| KR20210150422A (en) | 2021-12-10 |
| TW202104347A (en) | 2021-02-01 |
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