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WO2021241269A1 - Fully aromatic polyester resin, resin composition containing same, and molded product - Google Patents

Fully aromatic polyester resin, resin composition containing same, and molded product Download PDF

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Publication number
WO2021241269A1
WO2021241269A1 PCT/JP2021/018369 JP2021018369W WO2021241269A1 WO 2021241269 A1 WO2021241269 A1 WO 2021241269A1 JP 2021018369 W JP2021018369 W JP 2021018369W WO 2021241269 A1 WO2021241269 A1 WO 2021241269A1
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WO
WIPO (PCT)
Prior art keywords
mol
structural unit
polyester resin
less
unit represented
Prior art date
Application number
PCT/JP2021/018369
Other languages
French (fr)
Japanese (ja)
Inventor
新治 大友
Original Assignee
住友化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to KR1020227042309A priority Critical patent/KR20230015929A/en
Priority to CN202180038114.3A priority patent/CN115667359B/en
Publication of WO2021241269A1 publication Critical patent/WO2021241269A1/en

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

  • the present invention relates to a total aromatic polyester resin and a resin composition containing the same.
  • the present invention also relates to a molded product containing the resin composition.
  • Patent Document 1 contains specific repeating units (I) to (V) in a specific composition ratio as a resin material having excellent mechanical properties and dielectric properties in a high frequency band, and ASTM.
  • a liquid crystal polyester resin having a tensile strength of 180 MPa or more at 23 ° C. according to D638 is described.
  • An object of the present invention is to provide a polyester resin having good dielectric properties in a high frequency band. Another object of the present invention is to provide a resin composition containing the polyester resin and a molded product containing the resin composition.
  • the present invention provides a total aromatic polyester resin, a resin composition and a molded product shown below.
  • Ar 1 represents at least one group selected from the group consisting of 1,4-phenylene group, 1,3-phenylene group and 2,6-naphthalenediyl group.
  • the total content of the structural unit represented by the formula (IIa) and the structural unit represented by the formula (IIb) is 0.1 mol% or more and 10 mol% or less.
  • the content of the structural unit represented by the formula (III) is 10 mol% or more and 25 mol% or less.
  • the total aromatic polyester resin according to [2], wherein the total content of the structural unit represented by the formula (IVa) and the structural unit represented by the formula (IVb) is 5 mol% or more and 20 mol% or less. ..
  • the total aromatic polyester resin (hereinafter, also simply referred to as “polyester resin”) according to the present invention is a structural unit represented by the following formula (I) (hereinafter, also referred to as “constituent unit (I)”).
  • the structural unit represented by the following formula (IIa) (hereinafter, also referred to as “constituent unit (IIa)”) and the structural unit represented by the following formula (IIb) (hereinafter, also referred to as “constituent unit (IIb)”.
  • At least one structural unit selected from the group consisting of) and a structural unit represented by the following formula (III) (hereinafter, also referred to as “constituent unit (III)”).
  • Ar 1 represents at least one group selected from the group consisting of 1,4-phenylene group, 1,3-phenylene group and 2,6-naphthalenediyl group. ]
  • the polyester resin is made of a polyester polymer in which aromatic groups contained in each of the above-mentioned structural units are linked to each other by an ester bond.
  • the polyester resin may contain two or more kinds of the polyester polymer.
  • the polyester resin preferably exhibits liquid crystallinity.
  • the polyester resin contains the above-mentioned predetermined structural units, it has good dielectric properties in the high frequency band. Specifically, the polyester resin can have a low dielectric loss tangent and a low permittivity at frequencies in the gigahertz (GHz) band, and in particular can have a low dielectric loss tangent.
  • GHz gigahertz
  • the polyester resin may contain other structural units other than the structural units (I), (IIa), (IIb) and (III). Examples of other structural units are a structural unit represented by the formula (IVa) described later and a structural unit represented by the formula (IVb).
  • the structural unit (I) is a structural unit derived from 6-hydroxy-2-naphthoic acid.
  • “Derived from 6-hydroxy-2-naphthoic acid” is a configuration formed by polymerization based on polycondensation or transesterification reaction from 6-hydroxy-2-naphthoic acid or a monomer which is a derivative thereof exemplified below. Refers to the unit. Hereinafter, the meaning of "derived” is the same for other monomers.
  • Examples of the monomer giving the structural unit (I) include 6-hydroxy-2-naphthoic acid, and acylated products thereof, acid halides, acid anhydrides, esterified products, and the like.
  • the content of the structural unit (I) in the polyester resin is usually 40 mol% or more and 96 mol% or less when the total content of all the structural units contained in the polyester resin is 100 mol%, and is dielectric in the high frequency band. From the viewpoint of improving the characteristics, particularly from the viewpoint of reducing the dielectric adjacency in the high frequency band, it is preferably 45 mol% or more and 96 mol% or less, more preferably 50 mol% or more and 90 mol% or less, and further preferably. It is 50 mol% or more and 80 mol% or less, more preferably 50 mol% or more and 70 mol% or less, and particularly preferably 55 mol% or more and 65 mol% or less.
  • Structural units (IIa) and (IIb) The structural unit (IIa) and the structural unit (IIb) are 2,3,5-trimethylhydroquinone, 2,2,', 3,3', 5,5'-hexamethyl-1,1'-biphenyl-4, respectively. , 4'-diol is a structural unit derived from diol. Examples of the monomer giving the structural unit (IIa) include 2,3,5-trimethylhydroquinone and its acylated products and esterified products.
  • Examples of the monomer giving the structural unit (IIb) include 2,2,', 3,3', 5,5'-hexamethyl-1,1'-biphenyl-4,4'-diol and its acylated products and esterified products. Can be mentioned.
  • the polyester resin may contain either one of the structural unit (IIa) and the structural unit (IIb), or may contain both.
  • the total content of the structural units (IIa) and the structural units (IIb) in the polyester resin is usually 0.1 mol% or more and 30 mol% when the total content of all the structural units contained in the polyester resin is 100 mol%.
  • the following is preferably 0.5 mol% or more and 30 mol% from the viewpoint of ease of manufacturing the polyester resin and from the viewpoint of improving the dielectric property in the high frequency band, particularly from the viewpoint of reducing the dielectric adjacency in the high frequency band. It is more preferably 1 mol% or more and 30 mol% or less, further preferably 2 mol% or more and 30 mol% or less, still more preferably 2 mol% or more and 20 mol% or less, and particularly preferably. It is 2 mol% or more and 15 mol% or less (for example, 3 mol% or more and 10 mol% or less).
  • the structural unit (III) is a structural unit represented by the above formula (III).
  • Ar 1 represents at least one group selected from the group consisting of 1,4-phenylene group, 1,3-phenylene group and 2,6-naphthalenedyl group.
  • the polyester resin may contain one type of structural unit (III) or may contain two or more types of structural unit (III).
  • the structural unit (III) is a structural unit derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid.
  • the structural unit (III) preferably includes a structural unit derived from terephthalic acid from the viewpoint of improving the dielectric property in the high frequency band, particularly from the viewpoint of reducing the dielectric loss tangent in the high frequency band.
  • the content of the structural unit derived from terephthalic acid in the structural unit (III) is preferably 10 mol% or more and 100 mol% or less, and more preferably 20 mol% or more and 100 mol% or less.
  • Examples of the monomer giving the structural unit (III) include terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid, and their acid halides, acid anhydrides and esterified products.
  • the content of the structural unit (III) in the polyester resin is usually 1 mol% or more and 30 mol% or less when the total content of all the structural units contained in the polyester resin is 100 mol%, and is dielectric in the high frequency band. From the viewpoint of improving the characteristics, particularly from the viewpoint of reducing the dielectric adjacency in the high frequency band, it is preferably 2 mol% or more and 30 mol% or less, more preferably 2 mol% or more and 25 mol% or less, and further preferably. It is 5 mol% or more and 25 mol% or less, more preferably 10 mol% or more and 25 mol% or less, and particularly preferably 15 mol% or more and 25 mol% or less.
  • the polyester resin has a structural unit represented by the following formula (IVa) (hereinafter, also referred to as “constituent unit (IVa)”) and a structural unit represented by the following formula (IVb) (hereinafter, “constituent unit (IVb)”. It is also possible to further include at least one structural unit selected from the group consisting of).
  • the polyester resin further contains at least one structural unit selected from the group consisting of a structural unit (IVa) and a structural unit (IVb), preferably from the viewpoint of improving the fluidity of the resin during injection molding.
  • the structural unit (IVa) and the structural unit (IVb) are structural units derived from hydroquinone and 1,1'-biphenyl-4,4'-diol, respectively.
  • Examples of the monomer giving the structural unit (IVa) include hydroquinone, an acylated product thereof, and an esterified product.
  • Examples of the monomer giving the structural unit (IVb) include 1,1'-biphenyl-4,4'-diol, an acylated product thereof, and an esterified product.
  • the polyester resin may contain either one of the structural unit (IVa) and the structural unit (IVb), or may contain both.
  • the total content of the structural units (IVa) and the structural units (IVb) in the polyester resin is usually 0.1 mol% or more and 30 mol% when the total content of all the structural units contained in the polyester resin is 100 mol%. From the viewpoint of improving the fluidity of the resin during injection molding, it is preferably 1 mol% or more and 30 mol% or less, more preferably 2 mol% or more and 30 mol% or less, and further preferably 2 mol%. It is 25 mol% or more, more preferably 2 mol% or more and 20 mol% or less, and particularly preferably 5 mol% or more and 20 mol% or less.
  • the polyester resin may further contain other structural units other than those described above.
  • Other building blocks include o-Hydroxybenzoic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 5-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 4'-hydroxyphenyl-4-benzoic acid, 3'- Hydroxyphenyl-4-benzoic acid, 4'-hydroxyphenyl-3-benzoic acid, 1-hydroxy-4-naphthoic acid, 4-hydroxy-4'-carboxydiphenyl ether, 4-hydroxy-4'-biphenylcarboxylic acid, and Aromatic hydroxycarboxylic acids such as their acylates, acid halides, acid anhydrides and esters; 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,1'-biphenyl
  • the content of the structural units other than the structural units (I), (IIa), (IIb), (III), (IVa) and (IVb) in the polyester resin is the total content of all the structural units contained in the polyester resin.
  • the ratio is 100 mol%, it is preferably 10 mol% or less, more preferably 5 mol% or less, from the viewpoint of improving the dielectric property in the high frequency band, particularly from the viewpoint of reducing the dielectric loss tangent in the high frequency band. It is more preferably 2 mol% or less, further preferably 1 mol% or less, and particularly preferably 0 mol% or less.
  • the content of the structural units other than the structural units (I), (IIa), (IIb), (III), (IVa) and (IVb) in the polyester resin is the content of all the structural units contained in the polyester resin.
  • the total content is 100 mol%, it is preferably 0 mol% or more and 10 mol% or less, more preferably 0 mol% or more and 5 mol% or less, and further preferably 0 mol% or more and 2 mol% or less. Yes, and even more preferably 0 mol% or more and 1 mol% or less.
  • polyester resin according to the first embodiment is composed of a constituent unit (I) and at least one constituent unit selected from the group consisting of the constituent unit (IIa) and the constituent unit (IIb). It includes the unit (III) and preferably consists of these constituent units. In the latter case, the total content of the structural unit (I), the structural unit (IIa), the structural unit (IIb) and the structural unit (III) is 100 mol%.
  • each constituent unit The content rate is, for example, as follows.
  • the polyester resin according to the second embodiment includes a constituent unit (I), at least one constituent unit selected from the group consisting of the constituent unit (IIa) and the constituent unit (IIb), and the constituent unit (III). , At least one constituent unit selected from the group consisting of the constituent units (IVa) and the constituent units (IVb), preferably composed of these constituent units.
  • the total content of the building blocks (I), building blocks (IIa), building blocks (IIb), building blocks (III), building blocks (IVa) and building blocks (IVb) is 100 mol%.
  • the content of each constituent unit is, for example, as follows.
  • Total of unit (IVa) and constituent unit (IVb) From the viewpoint of improving the fluidity of the resin during injection molding, it is preferably 1 mol% or more and 30 mol% or less, more preferably 2 mol% or more and 30 mol% or less, and further. It is preferably 2 mol% or more and 25 mol% or less, more preferably 2 mol% or more and 20 mol% or less, and particularly preferably 5 mol% or more and 20 mol% or less.
  • the polyester resin was heated and melted at a temperature rise rate of 4 ° C./min, and the polyester resin was extruded from a nozzle having an inner diameter of 1 mm and a length of 10 mm under a load of 9.8 MPa.
  • the temperature at which the melt viscosity measured using a capillary resin meter shows 4800 Pa ⁇ s (hereinafter, also referred to as “flow start temperature”.
  • flow start temperature 4800 Pa ⁇ s
  • the polyester resin has a TD molding shrinkage of preferably 2% or less, more preferably 1. It is 5% or less, more preferably 1.3% or less.
  • the polyester resin has a tensile strength at 23 ° C. measured according to the method described in the following [Example], preferably 100 MPa or more, more preferably 105 MPa or more, still more preferably 105 MPa or more. It is 110 MPa or more.
  • the tensile strength is usually 300 MPa or less. That is, the tensile strength is preferably 100 MPa or more and 300 MPa or less, more preferably 105 MPa or more and 300 MPa or less, and further preferably 110 MPa or more and 300 MPa or less.
  • the polyester resin has a tensile elongation at 23 ° C. measured according to the method described in the section of [Example] below, preferably 3.0% or more, more preferably 3.1. % Or more, more preferably 3.5% or more.
  • the tensile elongation is usually 10% or less. That is, the tensile elongation is preferably 3.0% or more and 10% or less, more preferably 3.1% or more and 10% or less, and further preferably 3.5% or more and 10% or less.
  • the polyester resin has a bending strength at 23 ° C. measured according to the method described in the following [Examples], preferably 140 MPa or more, more preferably 150 MPa or more, still more preferably. It is 160 MPa or more.
  • the bending strength is usually 300 MPa or less. That is, the bending strength is preferably 140 MPa or more and 300 MPa or less, more preferably 150 MPa or more and 300 MPa or less, and further preferably 160 MPa or more and 300 MPa or less.
  • the polyester resin has an Izod impact strength (without notch) at 23 ° C. measured according to the method described in the following [Example], preferably 140 J / m or more, more preferably. Is 150 J / m or more, more preferably 160 J / m or more.
  • the Izod impact strength is usually 300 J / m or less. That is, the Izod impact strength (without notch) is preferably 140 J / m or more and 300 J / m or less, more preferably 150 J / m or more and 300 J / m or less, and further preferably 160 J / m or more and 300 J / m or less. be.
  • the polyester resin has a deflection temperature under load measured according to the method described in the section of [Example] below, preferably 130 ° C. or higher, more preferably 150 ° C. or higher, still more preferably 200 ° C. That is all.
  • the deflection temperature under load is usually 360 ° C. or lower. That is, the deflection temperature under load is preferably 130 ° C. or higher and 360 ° C. or lower, more preferably 150 ° C. or higher and 360 ° C. or lower, and further preferably 200 ° C. or higher and 360 ° C. or lower.
  • the polyester resin has a dielectric loss tangent at 1 GHz measured according to the method described in the section of [Example] below, preferably 0.0009 or less, and more preferably 0.0008 or less.
  • the dielectric loss tangent is usually 0.0002 or more. That is, the dielectric loss tangent at 1 GHz is preferably 0.0002 or less and 0.0002 or more, and more preferably 0.0008 or less and 0.0002 or more.
  • the polyester resin has a dielectric constant at 1 GHz measured according to the method described in the section of [Example] below, preferably 3.3 or less, more preferably 3.2 or less, still more preferably 3. It is 0.1 or less, more preferably 3.0 or less, and particularly preferably 2.9 or less.
  • the dielectric constant is usually 2.5 or more. That is, the dielectric constant at 1 GHz is preferably 3.3 or less and 2.5 or more, more preferably 3.2 or less and 2.5 or more, still more preferably 3.1 or less and 2.5 or more, and even more so. It is preferably 3.0 or less and 2.5 or more, and particularly preferably 2.9 or less and 2.5 or more.
  • the polyester resin is at least one selected from the group consisting of a monomer giving a structural unit (I), a monomer giving a structural unit (IIa), and a monomer giving a structural unit (IIb). , At least one selected from the group consisting of a monomer giving the structural unit (III), and optionally a monomer giving the structural unit (IVa) and a monomer giving the structural unit (IVb), and other structural units. It can be produced by polymerizing the monomer by a conventionally known method such as melt polymerization, solid phase polymerization, solution polymerization, slurry polymerization and the like.
  • a polyester resin may be produced by combining a plurality of types of polymerization methods.
  • the method for producing a polyester resin preferably comprises melt polymerization.
  • the polyester resin is at least one selected from the group consisting of a monomer giving a structural unit (I), a monomer giving a structural unit (IIa), and a monomer giving a structural unit (IIb), and a configuration used as needed.
  • a hydroxyl group having at least one selected from the group consisting of a monomer giving a unit (IVa) and a monomer giving a constituent unit (IVb) was acylated with an excess amount of fatty acid anhydride to obtain an acylated product, and then obtained.
  • the acylated product may be produced by polycondensing (transesterification reaction) with a monomer giving the structural unit (III).
  • the fatty acid anhydride used in the acylation reaction is not particularly limited, and is, for example, acetic acid anhydride, propionic acid anhydride, butyric acid anhydride, isobutyric acid anhydride, valeric acid anhydride, pivalic acid anhydride, diethylhexanoic acid anhydride, monochloroacetic acid anhydride.
  • One type or two or more types of fatty acid anhydride can be used.
  • the fatty acid anhydride is preferably acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, and more preferably acetic anhydride.
  • polycondensation transesterification reaction
  • the polycondensation reaction is performed while distilling off by-produced fatty acids and unreacted fatty acid anhydrides.
  • the acylation reaction and polycondensation (transesterification reaction) may be carried out in the presence of a catalyst.
  • a catalyst known as a polyester polymerization catalyst can be used, for example.
  • Metal salt catalysts such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, antimony trioxide; Examples thereof include organic compound catalysts such as N, N-dimethylaminopyridine and N-methylimidazole.
  • heterocyclic compounds containing two or more nitrogen atoms in the molecule such as N, N-dimethylaminopyridine and N-methylimidazole, are preferably used.
  • the catalyst is usually charged at the time of charging the monomer, and it is not always necessary to remove the catalyst even after acylation. If the catalyst is not removed, polycondensation (transesterification reaction) can be carried out as it is.
  • the polycondensation may be performed, for example, by using melt polymerization and solid phase polymerization in combination.
  • solid phase polymerization By further performing solid phase polymerization after melt polymerization, it is possible to increase the molecular weight of the polyester resin, improve the mechanical strength and heat resistance, and raise the flow start temperature.
  • the solid phase polymerization is preferably carried out by a known solid phase polymerization method after extracting the polymer from the melt polymerization step and then pulverizing the polymer into a powder or flake. Specific examples thereof include a method of heat-treating in a solid phase state for 1 hour or more and 30 hours or less at a temperature of 200 ° C. or higher and 350 ° C. or lower in an inert atmosphere such as nitrogen.
  • Solid-phase polymerization may be carried out with stirring or in a stationary state without stirring.
  • the melt polymerization tank and the solid phase polymerization tank can be made into the same reaction tank by providing an appropriate stirring mechanism.
  • the polyester resin can be produced, for example, by using a batch device, a continuous device, or the like.
  • the obtained polyester resin may be processed into pellets, flakes, powders, etc. by a known method.
  • the resin composition according to the present invention includes the polyester resin according to the present invention and a filler.
  • the filler may be an organic filler or an inorganic filler.
  • the resin composition may contain one or more fillers.
  • the filler examples include titanium oxide, barium sulfate, calcium carbonate, glass balloon, glass beads, glass flakes, talc, mica, clay, wollastonite, dolomite, graphite, glass fiber, carbon fiber, alumina fiber, and silica alumina.
  • Other examples include various metals or metal compound powders.
  • the content of the filler in the resin composition is, for example, 1 part by mass or more and 150 parts by mass or less, preferably 5 parts by mass or more and 100 parts by mass or less, and more preferably 10 parts by mass with respect to 100 parts by mass of the polyester resin. It is 20 parts by mass or more and 70 parts by mass or less, and more preferably 20 parts by mass or more and 70 parts by mass or less.
  • the resin composition may contain one or more resins other than the polyester resin according to the present invention.
  • the resin include polyester resins other than the polyester resin according to the present invention, polyolefins, cyclic polyolefins, polyvinyl chlorides, polysulfones, (meth) acrylic resins, polyphenylene ether resins, polyacetal resins, polyamide resins, imide resins, and polystyrenes.
  • examples thereof include resins, cellulose resins, polyether ether ketone resins, fluororesins, polycarbonate resins, thermosetting resins and the like.
  • the resin composition may contain one or more additives other than the filler.
  • additives include colorants, dispersants, plasticizers, antioxidants, curing agents, flame retardants, heat stabilizers, ultraviolet absorbers, antistatic agents, surfactants, lubricants, mold release agents and the like. Can be mentioned.
  • the resin composition is not particularly limited as long as it contains a polyester resin, a filler and other components added as needed, and includes, for example, a polyester resin, a filler and other components added as needed. It may be a melt-kneaded mixture.
  • the molded product according to the present invention includes the polyester resin according to the present invention or the resin composition according to the present invention.
  • the molded product can be, for example, a film, a sheet, a plate, a fiber, or the like.
  • the molded product can be manufactured from a polyester resin or a resin composition by an injection molding method, a compression molding method, an extrusion molding method, a blow molding method, a solution casting method, or the like.
  • the polyester resin, resin composition and molded product can be suitably applied to communication equipment, electronic equipment and their parts.
  • the component include an antenna, a connector, a capacitor, a transformer, a circuit board, a flexible printed circuit board, and the like.
  • Example 1 A reactor equipped with a stirrer, torque meter, nitrogen gas introduction tube, thermometer and reflux condenser, 6-hydroxy-2-naphthoic acid 1035.0 g (5.50 mol), hydroquinone 137.6 g (1.25 mol). Mol), 2,3,5-trimethylhydroquinone 152.2 g (1.00 mol), terephthalic acid 83.1 g (0.50 mol), 2,6-naphthalenedicarboxylic acid 378.3 g (1.75 mol), 1174.0 (11.50 mol) of anhydrous acetic acid and 0.054 g of 1-methylimidazole as a catalyst were added, and the temperature was raised with stirring. When the internal temperature reached 140 ° C., the mixture was stirred for 1 hour while maintaining 140 ° C.
  • the temperature was raised from 140 ° C. to 300 ° C. over 4 hours and 20 minutes while distilling off distillate by-product acetic acid and unreacted acetic anhydride.
  • the whole aromatic polyester resin was obtained by incubating at 300 ° C. for 2 hours.
  • the obtained total aromatic polyester resin was cooled to room temperature and pulverized with a pulverizer to obtain a powder (particle size of about 0.1 mm to about 2 mm) of the total aromatic polyester resin.
  • the flow start temperature of this powder was measured and found to be 246 ° C.
  • the obtained powder was heated from 25 ° C. to 240 ° C. over 1 hour, then heated from 240 ° C. to 280 ° C. over 5 hours and 8 minutes, and then kept at 280 ° C. for 10 hours for solid phase polymerization. .. Then, the powder after solid-phase polymerization was cooled, and the flow start temperature of the cooled powder (total aromatic polyester resin, "polyester resin 1”) was measured and found to be 314 ° C.
  • Example 2 A reactor equipped with a stirrer, torque meter, nitrogen gas introduction tube, thermometer and reflux condenser, 6-hydroxy-2-naphthoic acid 1129.1 g (6.00 mol), 1,1'-biphenyl-4. , 4'-diol 186.2 g (1.00 mol), 2,3,5-trimethylhydroquinone 152.2 g (1.00 mol), terephthalic acid 332.3 g (2.00 mol), anhydrous acetic acid 1123.0 (11.00 mol) and 0.054 g of 1-methylimidazole as a catalyst were added, and the temperature was raised with stirring. When the internal temperature reached 140 ° C., the mixture was stirred for 1 hour while maintaining 140 ° C.
  • the temperature was raised from 140 ° C. to 300 ° C. over 4 hours while distilling off distillate by-product acetic acid and unreacted acetic anhydride.
  • the whole aromatic polyester resin was obtained by incubating at 300 ° C. for 1 hour.
  • the obtained total aromatic polyester resin was cooled to room temperature and pulverized with a pulverizer to obtain a powder (particle size of about 0.1 mm to about 2 mm) of the total aromatic polyester resin.
  • the flow start temperature of this powder was measured and found to be 237 ° C.
  • the obtained powder was heated from 25 ° C. to 220 ° C. over 1 hour, then heated from 220 ° C. to 290 ° C. over 11 hours and 40 minutes, and then kept at 290 ° C. for 5 hours for solid phase polymerization. .. Then, the powder after solid-phase polymerization was cooled, and the flow start temperature of the cooled powder (total aromatic polyester resin, "polyester resin 2”) was measured and found to be 288 ° C.
  • Example 3 A reactor equipped with a stirrer, torque meter, nitrogen gas introduction tube, thermometer and reflux condenser, 6-hydroxy-2-naphthoic acid 1129.1 g (6.00 mol), 1,1'-biphenyl-4. , 4'-diol 335.2 g (1.80 mol), 2,2', 3,3', 5,5'-hexamethyl-1,1'-biphenyl-4,4'-diol 54.1 g ( 0.20 mol), terephthalic acid 332.3 g (2.00 mol), anhydrous acetic acid 1123.0 (11.00 mol) and 1-methylimidazole 0.056 g as a catalyst were added, and the temperature was raised with stirring. .. When the internal temperature reached 140 ° C., the mixture was stirred for 1 hour while maintaining 140 ° C.
  • the temperature was raised from 140 ° C. to 300 ° C. over 4 hours while distilling off distillate by-product acetic acid and unreacted acetic anhydride.
  • the whole aromatic polyester resin was obtained by incubating at 300 ° C. for 2 hours.
  • the obtained total aromatic polyester resin was cooled to room temperature and pulverized with a pulverizer to obtain a powder (particle size of about 0.1 mm to about 2 mm) of the total aromatic polyester resin.
  • the flow start temperature of this powder was measured and found to be 232 ° C.
  • the obtained powder was heated from 25 ° C. to 230 ° C. over 1 hour, then heated from 230 ° C. to 303 ° C. over 12 hours and 10 minutes, and then kept at 303 ° C. for 5 hours for solid phase polymerization. .. Then, the powder after solid-phase polymerization was cooled, and the flow start temperature of the cooled powder (total aromatic polyester resin, "polyester resin 3”) was measured and found to be 330 ° C.
  • Example 4 A reactor equipped with a stirrer, torque meter, nitrogen gas introduction tube, thermometer and reflux condenser, 6-hydroxy-2-naphthoic acid 1129.1 g (6.00 mol), 1,1'-biphenyl-4. , 4'-diol 316.6 g (1.70 mol), 2,2', 3,3', 5,5'-hexamethyl-1,1'-biphenyl-4,4'-diol 81.1 g ( 0.30 mol), terephthalic acid 332.3 g (2.00 mol), anhydrous acetic acid 1123.0 (11.00 mol) and 1-methylimidazole 0.056 g as a catalyst were added, and the temperature was raised with stirring. .. When the internal temperature reached 140 ° C., the mixture was stirred for 1 hour while maintaining 140 ° C.
  • the temperature was raised from 140 ° C. to 300 ° C. over 4 hours while distilling off distillate by-product acetic acid and unreacted acetic anhydride.
  • the whole aromatic polyester resin was obtained by incubating at 300 ° C. for 1 hour.
  • the obtained total aromatic polyester resin was cooled to room temperature and pulverized with a pulverizer to obtain a powder (particle size of about 0.1 mm to about 2 mm) of the total aromatic polyester resin.
  • the flow start temperature of this powder was measured and found to be 222 ° C.
  • the obtained powder was heated from 25 ° C. to 230 ° C. over 1 hour, then heated from 230 ° C. to 304 ° C. over 12 hours and 20 minutes, and then kept at 304 ° C. for 5 hours for solid phase polymerization. .. Then, the powder after solid-phase polymerization was cooled, and the flow start temperature of the cooled powder (total aromatic polyester resin, "polyester resin 4") was measured and found to be 331 ° C.
  • Example 5 A reactor equipped with a stirrer, torque meter, nitrogen gas introduction tube, thermometer and reflux condenser, 6-hydroxy-2-naphthoic acid 1129.1 g (6.00 mol), 1,1'-biphenyl-4.
  • the temperature was raised from 140 ° C. to 300 ° C. over 5 hours and 7 minutes while distilling off distillate by-product acetic acid and unreacted acetic anhydride.
  • the whole aromatic polyester resin was obtained by incubating at 300 ° C. for 1 hour.
  • the obtained total aromatic polyester resin was cooled to room temperature and pulverized with a pulverizer to obtain a powder (particle size of about 0.1 mm to about 2 mm) of the total aromatic polyester resin.
  • the flow start temperature of this powder was measured and found to be 233 ° C.
  • the obtained powder was heated from 25 ° C. to 230 ° C. over 1 hour, then heated from 230 ° C. to 310 ° C. over 13 hours and 20 minutes, and then kept at 310 ° C. for 5 hours for solid phase polymerization. .. Then, the powder after solid-phase polymerization was cooled, and the flow start temperature of the cooled powder (total aromatic polyester resin, "polyester resin 5”) was measured and found to be 331 ° C.
  • the temperature was raised from 140 ° C. to 300 ° C. over 5 hours while distilling off distillate by-product acetic acid and unreacted acetic anhydride.
  • the whole aromatic polyester resin was obtained by incubating at 300 ° C. for 1 hour and 30 minutes.
  • the obtained total aromatic polyester resin was cooled to room temperature and pulverized with a pulverizer to obtain a powder (particle size of about 0.1 mm to about 2 mm) of the total aromatic polyester resin.
  • the flow start temperature of this powder was measured and found to be 250 ° C.
  • the obtained powder was heated from 25 ° C. to 240 ° C. over 1 hour, then heated from 240 ° C. to 285 ° C. over 5 hours and 46 minutes, and then kept warm at 285 ° C. for 5 hours for solid phase polymerization. .. Then, the powder after solid-phase polymerization was cooled, and the flow start temperature of the cooled powder (total aromatic polyester resin, "polyester resin 6") was measured and found to be 320 ° C.
  • the temperature was raised from 140 ° C. to 300 ° C. over 4 hours while distilling off distillate by-product acetic acid and unreacted acetic anhydride.
  • the whole aromatic polyester resin was obtained by incubating at 300 ° C. for 2 hours.
  • the obtained total aromatic polyester resin was cooled to room temperature and pulverized with a pulverizer to obtain a powder (particle size of about 0.1 mm to about 2 mm) of the total aromatic polyester resin.
  • the flow start temperature of this powder was measured and found to be 252 ° C.
  • the obtained powder was heated from 25 ° C. to 230 ° C. over 1 hour, then heated from 230 ° C. to 304 ° C. over 12 hours and 20 minutes, and then kept at 304 ° C. for 5 hours for solid phase polymerization. .. Then, the powder after solid-phase polymerization was cooled, and the flow start temperature of the cooled powder (total aromatic polyester resin, "polyester resin 7”) was measured and found to be 330 ° C.
  • Table 1 shows the composition of the monomers used in the production of the polyester resins 1 to 7 (unit: mol%). The table also shows the flow start temperatures of the polyester resins 1 to 7 measured by the method described later.
  • Table 1 The details of the abbreviations shown in Table 1 are as follows.
  • BON 6-hydroxy-2-naphthoic acid TMHQ: 2,3,5-trimethylhydroquinone
  • TMP-BP 2,2', 3,3', 5,5'-hexamethyl-1,1'-biphenyl-4 , 4'-diol
  • TPA terephthalic acid
  • NDCA 2,6-naphthalenedicarboxylic acid HQ: hydroquinone
  • DOD 1,1'-biphenyl-4,4'-diol
  • TD molding shrinkage rate (shrinkage rate in TD during molding) 40 parts by mass of milled glass fiber (EFH75-01 manufactured by Central Glass Fiber Co., Ltd.) is mixed with 60 parts by mass of powdered polyester resin, and a biaxial extruder in the same direction (PCM-30 manufactured by Ikekai Iron Works Co., Ltd.) is mixed. ) Was melt-kneaded at a temperature of + 15 ° C., which is the flow start temperature of the powdery polyester resin, extruded into a strand shape, cooled, and then cut to obtain a pellet-shaped polyester resin composition.
  • PCM-30 manufactured by Ikekai Iron Works Co., Ltd.
  • the obtained polyester resin composition is injected using a PS405ASE type injection molding machine manufactured by Nissei Resin Industry Co., Ltd. under the conditions that the cylinder temperature is the flow start temperature of the powdered polyester resin + 20 ° C. and the mold temperature is 130 ° C.
  • the lengths of two sides of the TD of a 64 mm (MD) ⁇ 64 mm (TD) ⁇ 3 mm (thickness) flat plate-shaped test piece (hereinafter, may be referred to as a “molded product”) produced by molding were measured.
  • the average value was obtained, and the TD molding shrinkage rate was calculated from the average value and the length of the TD of the mold cavity by the following formula.
  • TD molding shrinkage rate (%) ([Mold cavity TD length ( ⁇ m)]-[Average value of two sides of molded product TD ( ⁇ m)]) / [Mold cavity TD Length ( ⁇ m)] x 100
  • the cylinder temperature is the flow start temperature of the powdered polyester resin + 20 ° C. and the mold temperature is 130 ° C.
  • a STM No. 4 dumbbell was formed by molding, and the tensile strength and tensile elongation at 23 ° C. were measured according to ATM D638.
  • the bending strength of the 127 mm (length) ⁇ 12.7 mm (width) ⁇ 6.4 mm (thickness) test piece produced by molding at 23 ° C. was measured according to ASTM D790.
  • Izod Impact Strength 40 parts by mass of milled glass fiber (EFH75-01 manufactured by Central Glass Fiber Co., Ltd.) is mixed with 60 parts by mass of powdered polyester resin, and a twin-screw extruder in the same direction (Ikekai Iron Works (Ikekai Iron Works) Using PCM-30) manufactured by PCM-30), melt-kneaded the powdery polyester resin at the flow start temperature of + 15 ° C., extrude it into strands, cool it, and cut it to obtain a pellet-shaped aromatic polyester composition. Obtained.
  • the obtained polyester resin composition is injected using a PS405ASE type injection molding machine manufactured by Nissei Resin Industry Co., Ltd.
  • the Izod impact strength of a molded 64 mm (length) ⁇ 12.7 mm (width) ⁇ 6.4 mm (thickness) test piece (without notch) at 23 ° C. was measured according to ASTM D256.
  • the deflection temperature under load of a 12.7 mm (length) x 12.7 mm (width) x 6.4 mm (thickness) test piece produced by molding is based on ASTM D648, with a load of 1.82 MPa and a heating rate. It was measured at 2 ° C./min.
  • Dielectric Dissipation Factor and Dielectric Permittivity The polyester resin was hot-pressed under the condition of (flow start temperature +20) ° C. to form a tablet having a diameter of 1 cm and a thickness of 2 mm. Using the obtained tablet sample, the dielectric loss tangent and the dielectric constant at 1 GHz were measured under the following conditions.
  • Measuring device Impedance analyzer (Agilent model: E4991A) Measurement method: Capacitive method
  • Electrode model: 16453A Measurement environment: 23 ° C, 50% RH Applied voltage: 1V

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Abstract

Provided is a fully aromatic polyester resin that includes: at least one structural unit selected from the group consisting of structural units represented by formula (I), structural units represented by formula (IIa), and structural units represented by formula (IIb); and a structural unit represented by formula (III) [in formula (III), Ar1 represents at least one group selected from the group consisting of 1,4-phenylene groups, 1,3-phenylene groups, and 2,6-naphthalenediyl groups].

Description

全芳香族ポリエステル樹脂及びそれを含む樹脂組成物、並びに成形品All aromatic polyester resin, resin composition containing it, and molded product
　本発明は、全芳香族ポリエステル樹脂及びそれを含む樹脂組成物に関する。また本発明は、該樹脂組成物を含む成形品にも関する。 The present invention relates to a total aromatic polyester resin and a resin composition containing the same. The present invention also relates to a molded product containing the resin composition.
　近年、情報伝送のための周波数の高周波化が進んでいる。これに伴い、通信機器、電子機器及びそれらの部品等に用いられる樹脂材料において、高周波帯域での誘電特性の向上が求められている。 In recent years, the frequency for information transmission has been increasing. Along with this, in resin materials used for communication equipment, electronic equipment, and parts thereof, improvement of dielectric properties in a high frequency band is required.
　特開２０１９－１８９７３５号公報（特許文献１）には、機械特性及び高周波帯域での誘電特性に優れる樹脂材料として、特定の繰返し単位（Ｉ）～（Ｖ）を特定の組成比で含み、ＡＳＴＭ　Ｄ６３８に準拠した２３℃における引張強度が１８０ＭＰａ以上である液晶ポリエステル樹脂が記載されている。 Japanese Patent Application Laid-Open No. 2019-189735 (Patent Document 1) contains specific repeating units (I) to (V) in a specific composition ratio as a resin material having excellent mechanical properties and dielectric properties in a high frequency band, and ASTM. A liquid crystal polyester resin having a tensile strength of 180 MPa or more at 23 ° C. according to D638 is described.
特開２０１９－１８９７３５号公報Japanese Unexamined Patent Publication No. 2019-189735
　本発明の目的は、高周波帯域での誘電特性が良好なポリエステル樹脂を提供することにある。本発明の他の目的は、該ポリエステル樹脂を含む樹脂組成物、及び該樹脂組成物を含む成形品を提供することにある。 An object of the present invention is to provide a polyester resin having good dielectric properties in a high frequency band. Another object of the present invention is to provide a resin composition containing the polyester resin and a molded product containing the resin composition.
　本発明は、以下に示す全芳香族ポリエステル樹脂、樹脂組成物及び成形品を提供する。
　［１］　下記式（Ｉ）で表される構成単位と、
　下記式（ＩＩａ）で表される構成単位及び下記式（ＩＩｂ）で表される構成単位からなる群より選択される少なくとも１種の構成単位と、
　下記式（ＩＩＩ）で表される構成単位と、
を含む、全芳香族ポリエステル樹脂。
Figure JPOXMLDOC01-appb-C000003
［式（ＩＩＩ）中、Ａｒ１は、１，４－フェニレン基、１，３－フェニレン基及び２，６－ナフタレンジイル基からなる群より選択される少なくとも１種の基を表す。］
　［２］　下記式（ＩＶａ）で表される構成単位及び下記式（ＩＶｂ）で表される構成単位からなる群より選択される少なくとも１種の構成単位をさらに含む、［１］に記載の全芳香族ポリエステル樹脂。
Figure JPOXMLDOC01-appb-C000004
　［３］　前記式（Ｉ）で表される構成単位、前記式（ＩＩａ）で表される構成単位、前記式（ＩＩｂ）で表される構成単位、前記式（ＩＩＩ）で表される構成単位、前記式（ＩＶａ）で表される構成単位及び前記式（ＩＶｂ）で表される構成単位の合計含有率を１００モル％とするとき、
　前記式（Ｉ）で表される構成単位の含有率が５０モル％以上８０モル％以下であり、
　前記式（ＩＩａ）で表される構成単位及び前記式（ＩＩｂ）で表される構成単位の合計含有率が０．１モル％以上１０モル％以下であり、
　前記式（ＩＩＩ）で表される構成単位の含有率が１０モル％以上２５モル％以下であり、
　前記式（ＩＶａ）で表される構成単位及び前記式（ＩＶｂ）で表される構成単位の合計含有率が５モル％以上２０モル％以下である、［２］に記載の全芳香族ポリエステル樹脂。
　［４］　４℃／分の昇温速度で加熱溶融された前記全芳香族ポリエステル樹脂を、９．８ＭＰａの荷重下、内径１ｍｍ、長さ１０ｍｍのノズルから押し出したときに、毛細管型レオメータを用いて測定される溶融粘度が４８００Ｐａ・ｓを示す温度が２９０℃以上３５０℃以下である、［１］～［３］のいずれかに記載の全芳香族ポリエステル樹脂。
　［５］　［１］～［４］のいずれかに記載の全芳香族ポリエステル樹脂１００質量部と、
　充填剤１０質量部以上７０質量部以下と、
を含む、樹脂組成物。
　［６］　［１］～［４］のいずれかに記載の全芳香族ポリエステル樹脂又は［５］に記載の樹脂組成物を含む、成形品。
　［７］　フィルムである、［６］に記載の成形品。 The present invention provides a total aromatic polyester resin, a resin composition and a molded product shown below.
[1] The structural unit represented by the following formula (I) and
At least one structural unit selected from the group consisting of the structural unit represented by the following formula (IIa) and the structural unit represented by the following formula (IIb), and
The structural unit represented by the following formula (III) and
All aromatic polyester resin, including.
Figure JPOXMLDOC01-appb-C000003
[In formula (III), Ar 1 represents at least one group selected from the group consisting of 1,4-phenylene group, 1,3-phenylene group and 2,6-naphthalenediyl group. ]
[2] All of the description in [1], further comprising at least one structural unit selected from the group consisting of the structural unit represented by the following formula (IVa) and the structural unit represented by the following formula (IVb). Aromatic polyester resin.
Figure JPOXMLDOC01-appb-C000004
[3] The structural unit represented by the formula (I), the structural unit represented by the formula (IIa), the structural unit represented by the formula (IIb), and the structural unit represented by the formula (III). When the total content of the structural unit represented by the formula (IVa) and the structural unit represented by the formula (IVb) is 100 mol%,
The content of the structural unit represented by the formula (I) is 50 mol% or more and 80 mol% or less.
The total content of the structural unit represented by the formula (IIa) and the structural unit represented by the formula (IIb) is 0.1 mol% or more and 10 mol% or less.
The content of the structural unit represented by the formula (III) is 10 mol% or more and 25 mol% or less.
The total aromatic polyester resin according to [2], wherein the total content of the structural unit represented by the formula (IVa) and the structural unit represented by the formula (IVb) is 5 mol% or more and 20 mol% or less. ..
[4] When the all-aromatic polyester resin heated and melted at a temperature rise rate of 4 ° C./min is extruded from a nozzle having an inner diameter of 1 mm and a length of 10 mm under a load of 9.8 MPa, a capillary rheometer is used. The all-aromatic polyester resin according to any one of [1] to [3], wherein the temperature at which the melt viscosity measured is 4800 Pa · s is 290 ° C. or higher and 350 ° C. or lower.
[5] 100 parts by mass of the total aromatic polyester resin according to any one of [1] to [4].
10 parts by mass or more and 70 parts by mass or less of the filler,
A resin composition comprising.
[6] A molded product containing the all-aromatic polyester resin according to any one of [1] to [4] or the resin composition according to [5].
[7] The molded product according to [6], which is a film.
　高周波帯域での誘電特性が良好なポリエステル樹脂、該ポリエステル樹脂を含む樹脂組成物、及び該樹脂組成物を含む成形品を提供することができる。 It is possible to provide a polyester resin having good dielectric properties in a high frequency band, a resin composition containing the polyester resin, and a molded product containing the resin composition.
　＜全芳香族ポリエステル樹脂＞
　本発明に係る全芳香族ポリエステル樹脂（以下、単に「ポリエステル樹脂」ともいう。）は、下記式（Ｉ）で表される構成単位（以下、「構成単位（Ｉ）」ともいう。）と、下記式（ＩＩａ）で表される構成単位（以下、「構成単位（ＩＩａ）」ともいう。）及び下記式（ＩＩｂ）で表される構成単位（以下、「構成単位（ＩＩｂ）」ともいう。）からなる群より選択される少なくとも１種の構成単位と、下記式（ＩＩＩ）で表される構成単位（以下、「構成単位（ＩＩＩ）」ともいう。）とを含む。
Figure JPOXMLDOC01-appb-C000005
［式（ＩＩＩ）中、Ａｒ１は、１，４－フェニレン基、１，３－フェニレン基及び２，６－ナフタレンジイル基からなる群より選択される少なくとも１種の基を表す。］ <All aromatic polyester resin>
The total aromatic polyester resin (hereinafter, also simply referred to as “polyester resin”) according to the present invention is a structural unit represented by the following formula (I) (hereinafter, also referred to as “constituent unit (I)”). The structural unit represented by the following formula (IIa) (hereinafter, also referred to as “constituent unit (IIa)”) and the structural unit represented by the following formula (IIb) (hereinafter, also referred to as “constituent unit (IIb)”. ), At least one structural unit selected from the group consisting of) and a structural unit represented by the following formula (III) (hereinafter, also referred to as “constituent unit (III)”).
Figure JPOXMLDOC01-appb-C000005
[In formula (III), Ar 1 represents at least one group selected from the group consisting of 1,4-phenylene group, 1,3-phenylene group and 2,6-naphthalenediyl group. ]
　ポリエステル樹脂は、上記の各構成単位に含まれる芳香族基がエステル結合によって互いに連結されてなるポリエステルポリマーからなる。ポリエステル樹脂は、該ポリエステルポリマーを２種以上含んでいてもよい。ポリエステル樹脂は、液晶性を示すことが好ましい。 The polyester resin is made of a polyester polymer in which aromatic groups contained in each of the above-mentioned structural units are linked to each other by an ester bond. The polyester resin may contain two or more kinds of the polyester polymer. The polyester resin preferably exhibits liquid crystallinity.
　ポリエステル樹脂は、上記所定の構成単位を含んでいるため、高周波帯域での誘電特性が良好である。具体的には、ポリエステル樹脂は、ギガヘルツ（ＧＨｚ）帯の周波数において低い誘電正接及び低い誘電率を有することができ、とりわけ、低い誘電正接を有することができる。 Since the polyester resin contains the above-mentioned predetermined structural units, it has good dielectric properties in the high frequency band. Specifically, the polyester resin can have a low dielectric loss tangent and a low permittivity at frequencies in the gigahertz (GHz) band, and in particular can have a low dielectric loss tangent.
　ポリエステル樹脂は、構成単位（Ｉ）、（ＩＩａ）、（ＩＩｂ）及び（ＩＩＩ）以外の他の構成単位を含み得る。他の構成単位の例は、後述する式（ＩＶａ）で表される構成単位、式（ＩＶｂ）で表される構成単位である。 The polyester resin may contain other structural units other than the structural units (I), (IIa), (IIb) and (III). Examples of other structural units are a structural unit represented by the formula (IVa) described later and a structural unit represented by the formula (IVb).
　〔１〕構成単位（Ｉ）
　構成単位（Ｉ）は、６－ヒドロキシ－２－ナフトエ酸に由来する構成単位である。「６－ヒドロキシ－２－ナフトエ酸に由来する」とは、６－ヒドロキシ－２－ナフトエ酸又は下記に例示するその誘導体であるモノマーから、重縮合又はエステル交換反応に基づく重合によって形成される構成単位をいう。以下、他のモノマーについても「由来する」の意味は同様である。
　構成単位（Ｉ）を与えるモノマーとしては、６－ヒドロキシ－２－ナフトエ酸、並びにそのアシル化物、酸ハロゲン化物、酸無水物及びエステル化物等が挙げられる。 [1] Structural unit (I)
The structural unit (I) is a structural unit derived from 6-hydroxy-2-naphthoic acid. "Derived from 6-hydroxy-2-naphthoic acid" is a configuration formed by polymerization based on polycondensation or transesterification reaction from 6-hydroxy-2-naphthoic acid or a monomer which is a derivative thereof exemplified below. Refers to the unit. Hereinafter, the meaning of "derived" is the same for other monomers.
Examples of the monomer giving the structural unit (I) include 6-hydroxy-2-naphthoic acid, and acylated products thereof, acid halides, acid anhydrides, esterified products, and the like.
　ポリエステル樹脂における構成単位（Ｉ）の含有率は、ポリエステル樹脂に含まれる全構成単位の合計含有率を１００モル％とするとき、通常４０モル％以上９６モル％以下であり、高周波帯域での誘電特性を向上させる観点、とりわけ、高周波帯域での誘電正接を小さくする観点から、好ましくは４５モル％以上９６モル％以下であり、より好ましくは５０モル％以上９０モル％以下であり、さらに好ましくは５０モル％以上８０モル％以下であり、なおさらに好ましくは５０モル％以上７０モル％以下であり、特に好ましくは５５モル％以上６５モル％以下である。 The content of the structural unit (I) in the polyester resin is usually 40 mol% or more and 96 mol% or less when the total content of all the structural units contained in the polyester resin is 100 mol%, and is dielectric in the high frequency band. From the viewpoint of improving the characteristics, particularly from the viewpoint of reducing the dielectric adjacency in the high frequency band, it is preferably 45 mol% or more and 96 mol% or less, more preferably 50 mol% or more and 90 mol% or less, and further preferably. It is 50 mol% or more and 80 mol% or less, more preferably 50 mol% or more and 70 mol% or less, and particularly preferably 55 mol% or more and 65 mol% or less.
　〔２〕構成単位（ＩＩａ）及び（ＩＩｂ）
　構成単位（ＩＩａ）、構成単位（ＩＩｂ）は、それぞれ、２，３，５－トリメチルハイドロキノン、２，２，’，３，３’，５，５’－ヘキサメチル－１，１’－ビフェニル－４，４’－ジオールに由来する構成単位である。
　構成単位（ＩＩａ）を与えるモノマーとしては、２，３，５－トリメチルハイドロキノン及びそのアシル化物、エステル化物等が挙げられる。
　構成単位（ＩＩｂ）を与えるモノマーとしては、２，２，’，３，３’，５，５’－ヘキサメチル－１，１’－ビフェニル－４，４’－ジオール及びそのアシル化物、エステル化物等が挙げられる。 [2] Structural units (IIa) and (IIb)
The structural unit (IIa) and the structural unit (IIb) are 2,3,5-trimethylhydroquinone, 2,2,', 3,3', 5,5'-hexamethyl-1,1'-biphenyl-4, respectively. , 4'-diol is a structural unit derived from diol.
Examples of the monomer giving the structural unit (IIa) include 2,3,5-trimethylhydroquinone and its acylated products and esterified products.
Examples of the monomer giving the structural unit (IIb) include 2,2,', 3,3', 5,5'-hexamethyl-1,1'-biphenyl-4,4'-diol and its acylated products and esterified products. Can be mentioned.
　ポリエステル樹脂は、構成単位（ＩＩａ）及び構成単位（ＩＩｂ）のいずれか一方を含んでいてもよいし、両方を含んでいてもよい。 The polyester resin may contain either one of the structural unit (IIa) and the structural unit (IIb), or may contain both.
　ポリエステル樹脂における構成単位（ＩＩａ）及び構成単位（ＩＩｂ）の合計含有率は、ポリエステル樹脂に含まれる全構成単位の合計含有率を１００モル％とするとき、通常０．１モル％以上３０モル％以下であり、ポリエステル樹脂の製造容易性の観点、並びに高周波帯域での誘電特性を向上させる観点、とりわけ、高周波帯域での誘電正接を小さくする観点から、好ましくは０．５モル％以上３０モル％以下であり、より好ましくは１モル％以上３０モル％以下であり、さらに好ましくは２モル％以上３０モル％以下であり、なおさらに好ましくは２モル％以上２０モル％以下であり、特に好ましくは２モル％以上１５モル％以下（例えば３モル％以上１０モル％以下）である。 The total content of the structural units (IIa) and the structural units (IIb) in the polyester resin is usually 0.1 mol% or more and 30 mol% when the total content of all the structural units contained in the polyester resin is 100 mol%. The following is preferably 0.5 mol% or more and 30 mol% from the viewpoint of ease of manufacturing the polyester resin and from the viewpoint of improving the dielectric property in the high frequency band, particularly from the viewpoint of reducing the dielectric adjacency in the high frequency band. It is more preferably 1 mol% or more and 30 mol% or less, further preferably 2 mol% or more and 30 mol% or less, still more preferably 2 mol% or more and 20 mol% or less, and particularly preferably. It is 2 mol% or more and 15 mol% or less (for example, 3 mol% or more and 10 mol% or less).
　〔３〕構成単位（ＩＩＩ）
　構成単位（ＩＩＩ）は、上記式（ＩＩＩ）で表される構成単位である。式（ＩＩＩ）中、Ａｒ１は、１，４－フェニレン基、１，３－フェニレン基及び２，６－ナフタレンジイル基からなる群より選択される少なくとも１種の基を表す。
　ポリエステル樹脂は、１種の構成単位（ＩＩＩ）を含んでいてもよいし、２種以上の構成単位（ＩＩＩ）を含んでいてもよい。 [3] Structural unit (III)
The structural unit (III) is a structural unit represented by the above formula (III). In formula (III), Ar 1 represents at least one group selected from the group consisting of 1,4-phenylene group, 1,3-phenylene group and 2,6-naphthalenedyl group.
The polyester resin may contain one type of structural unit (III) or may contain two or more types of structural unit (III).
　構成単位（ＩＩＩ）は、テレフタル酸、イソフタル酸及び２，６－ナフタレンジカルボン酸からなる群より選択される少なくとも１種のジカルボン酸に由来する構成単位である。
　高周波帯域での誘電特性を向上させる観点、とりわけ、高周波帯域での誘電正接を小さくする観点から、構成単位（ＩＩＩ）は、好ましくはテレフタル酸に由来する構成単位を含む。構成単位（ＩＩＩ）におけるテレフタル酸に由来する構成単位の含有率は、好ましくは１０モル％以上１００モル％以下であり、より好ましくは２０モル％以上１００モル％以下である。
　構成単位（ＩＩＩ）を与えるモノマーとしては、テレフタル酸、イソフタル酸及び２，６－ナフタレンジカルボン酸、並びに、それらの酸ハロゲン化物、酸無水物及びエステル化物等が挙げられる。 The structural unit (III) is a structural unit derived from at least one dicarboxylic acid selected from the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid.
The structural unit (III) preferably includes a structural unit derived from terephthalic acid from the viewpoint of improving the dielectric property in the high frequency band, particularly from the viewpoint of reducing the dielectric loss tangent in the high frequency band. The content of the structural unit derived from terephthalic acid in the structural unit (III) is preferably 10 mol% or more and 100 mol% or less, and more preferably 20 mol% or more and 100 mol% or less.
Examples of the monomer giving the structural unit (III) include terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid, and their acid halides, acid anhydrides and esterified products.
　ポリエステル樹脂における構成単位（ＩＩＩ）の含有率は、ポリエステル樹脂に含まれる全構成単位の合計含有率を１００モル％とするとき、通常１モル％以上３０モル％以下であり、高周波帯域での誘電特性を向上させる観点、とりわけ、高周波帯域での誘電正接を小さくする観点から、好ましくは２モル％以上３０モル％以下であり、より好ましくは２モル％以上２５モル％以下であり、さらに好ましくは５モル％以上２５モル％以下であり、なおさらに好ましくは１０モル％以上２５モル％以下であり、特に好ましくは１５モル％以上２５モル％以下である。 The content of the structural unit (III) in the polyester resin is usually 1 mol% or more and 30 mol% or less when the total content of all the structural units contained in the polyester resin is 100 mol%, and is dielectric in the high frequency band. From the viewpoint of improving the characteristics, particularly from the viewpoint of reducing the dielectric adjacency in the high frequency band, it is preferably 2 mol% or more and 30 mol% or less, more preferably 2 mol% or more and 25 mol% or less, and further preferably. It is 5 mol% or more and 25 mol% or less, more preferably 10 mol% or more and 25 mol% or less, and particularly preferably 15 mol% or more and 25 mol% or less.
　〔４〕構成単位（ＩＶａ）及び（ＩＶｂ）
　ポリエステル樹脂は、下記式（ＩＶａ）で表される構成単位（以下、「構成単位（ＩＶａ）」ともいう。）及び下記式（ＩＶｂ）で表される構成単位（以下、「構成単位（ＩＶｂ）」ともいう。）からなる群より選択される少なくとも１種の構成単位をさらに含むことができる。
Figure JPOXMLDOC01-appb-C000006
 [4] Structural units (IVa) and (IVb)
The polyester resin has a structural unit represented by the following formula (IVa) (hereinafter, also referred to as “constituent unit (IVa)”) and a structural unit represented by the following formula (IVb) (hereinafter, “constituent unit (IVb)”. It is also possible to further include at least one structural unit selected from the group consisting of).
Figure JPOXMLDOC01-appb-C000006
　ポリエステル樹脂は、射出成形時の樹脂の流動性向上の観点から、好ましくは構成単位（ＩＶａ）及び構成単位（ＩＶｂ）からなる群より選択される少なくとも１種の構成単位をさらに含む。 The polyester resin further contains at least one structural unit selected from the group consisting of a structural unit (IVa) and a structural unit (IVb), preferably from the viewpoint of improving the fluidity of the resin during injection molding.
　構成単位（ＩＶａ）、構成単位（ＩＶｂ）は、それぞれ、ハイドロキノン、１，１’－ビフェニル－４，４’－ジオールに由来する構成単位である。
　構成単位（ＩＶａ）を与えるモノマーとしては、ハイドロキノン及びそのアシル化物、エステル化物等が挙げられる。
　構成単位（ＩＶｂ）を与えるモノマーとしては、１，１’－ビフェニル－４，４’－ジオール及びそのアシル化物、エステル化物等が挙げられる。 The structural unit (IVa) and the structural unit (IVb) are structural units derived from hydroquinone and 1,1'-biphenyl-4,4'-diol, respectively.
Examples of the monomer giving the structural unit (IVa) include hydroquinone, an acylated product thereof, and an esterified product.
Examples of the monomer giving the structural unit (IVb) include 1,1'-biphenyl-4,4'-diol, an acylated product thereof, and an esterified product.
　ポリエステル樹脂は、構成単位（ＩＶａ）及び構成単位（ＩＶｂ）のいずれか一方を含んでいてもよいし、両方を含んでいてもよい。 The polyester resin may contain either one of the structural unit (IVa) and the structural unit (IVb), or may contain both.
　ポリエステル樹脂における構成単位（ＩＶａ）及び構成単位（ＩＶｂ）の合計含有率は、ポリエステル樹脂に含まれる全構成単位の合計含有率を１００モル％とするとき、通常０．１モル％以上３０モル％以下であり、射出成形時の樹脂の流動性向上の観点から、好ましくは１モル％以上３０モル％以下であり、より好ましくは２モル％以上３０モル％以下であり、さらに好ましくは２モル％以上２５モル％以下であり、なおさらに好ましくは２モル％以上２０モル％以下であり、特に好ましくは５モル％以上２０モル％以下である。 The total content of the structural units (IVa) and the structural units (IVb) in the polyester resin is usually 0.1 mol% or more and 30 mol% when the total content of all the structural units contained in the polyester resin is 100 mol%. From the viewpoint of improving the fluidity of the resin during injection molding, it is preferably 1 mol% or more and 30 mol% or less, more preferably 2 mol% or more and 30 mol% or less, and further preferably 2 mol%. It is 25 mol% or more, more preferably 2 mol% or more and 20 mol% or less, and particularly preferably 5 mol% or more and 20 mol% or less.
　〔５〕その他の構成単位
　ポリエステル樹脂は、上記した以外のその他の構成単位をさらに含むことができる。
　その他の構成単位としては、
　ｏ－ヒドロキシ安息香酸、ｍ－ヒドロキシ安息香酸、ｐ－ヒドロキシ安息香酸、５－ヒドロキシ－２－ナフトエ酸、３－ヒドロキシ－２－ナフトエ酸、４’－ヒドロキシフェニル－４－安息香酸、３’－ヒドロキシフェニル－４－安息香酸、４’－ヒドロキシフェニル－３－安息香酸、１－ヒドロキシ－４－ナフトエ酸、４－ヒドロキシ－４’－カルボキシジフェニルエーテル、４－ヒドロキシ－４’－ビフェニルカルボン酸、及びそれらのアシル化物、酸ハロゲン化物、酸無水物及びエステル化物等の芳香族ヒドロキシカルボン酸；
　１，６－ナフタレンジカルボン酸、２，７－ナフタレンジカルボン酸、１，４－ナフタレンジカルボン酸、１，１’－ビフェニル－４，４’－ジカルボン酸、１，５－ナフタレンジカルボン酸、ジフェニルエーテル－４，４’－ジカルボン酸、ジフェニルスルホン－４，４’－ジカルボン酸、ジフェニルケトン－４，４’－ジカルボン酸、２，２’－ジフェニルプロパン－４，４’－ジカルボン酸等の芳香族ジカルボン酸；
　レゾルシン、２，６－ジヒドロキシナフタレン、２，７－ジヒドロキシナフタレン、１，６－ジヒドロキシナフタレン、１，４－ジヒドロキシナフタレン、１，１’－ビフェニル－３，３’－ジオール、１，１’－ビフェニル－３，４’－ジオール、３，３’－ジメチル－１，１’－ビフェニル－４，４’－ジオール、４，４’－ジヒドロキシビフェニルエーテル、２，２－ビス（４－ヒドロキシフェニル）プロパン、２，２－ビス（４－ヒドロキシ－３，５－ジメチルフェニル）プロパン、２，２－ビス（４－ヒドロキシ－３－メチルフェニル）プロパン、ビス－（４－ヒドロキシフェニル）メタン、ビス－（４－ヒドロキシ－３，５－ジメチルフェニル）メタン、ビス－（４－ヒドロキシ－３－メチルフェニル）メタン、ビス－（４－ヒドロキシフェニル）スルフィド、ビス－（４－ヒドロキシフェニル）スルホン等の芳香族ジオール
に由来する構成単位が挙げられる。 [5] Other Structural Units The polyester resin may further contain other structural units other than those described above.
Other building blocks include
o-Hydroxybenzoic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 5-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 4'-hydroxyphenyl-4-benzoic acid, 3'- Hydroxyphenyl-4-benzoic acid, 4'-hydroxyphenyl-3-benzoic acid, 1-hydroxy-4-naphthoic acid, 4-hydroxy-4'-carboxydiphenyl ether, 4-hydroxy-4'-biphenylcarboxylic acid, and Aromatic hydroxycarboxylic acids such as their acylates, acid halides, acid anhydrides and esters;
1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,1'-biphenyl-4,4'-dicarboxylic acid, 1,5-naphthalenedicarboxylic acid, diphenylether-4 , 4'-Dicarboxylic acid, diphenylsulfon-4,4'-dicarboxylic acid, diphenylketone-4,4'-dicarboxylic acid, 2,2'-diphenylpropane-4,4'-dicarboxylic acid and other aromatic dicarboxylic acids ;
Resolcin, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,1'-biphenyl-3,3'-diol, 1,1'-biphenyl -3,4'-diol, 3,3'-dimethyl-1,1'-biphenyl-4,4'-diol, 4,4'-dihydroxybiphenyl ether, 2,2-bis (4-hydroxyphenyl) propane , 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis- (4-hydroxyphenyl) methane, bis- ( Aromatic compounds such as 4-hydroxy-3,5-dimethylphenyl) methane, bis- (4-hydroxy-3-methylphenyl) methane, bis- (4-hydroxyphenyl) sulfide, and bis- (4-hydroxyphenyl) sulfone. Examples thereof include structural units derived from diols.
　ポリエステル樹脂における構成単位（Ｉ）、（ＩＩａ）、（ＩＩｂ）、（ＩＩＩ）、（ＩＶａ）及び（ＩＶｂ）以外のその他の構成単位の含有率は、ポリエステル樹脂に含まれる全構成単位の合計含有率を１００モル％とするとき、高周波帯域での誘電特性を向上させる観点、とりわけ、高周波帯域での誘電正接を小さくする観点から、好ましくは１０モル％以下であり、より好ましくは５モル％以下であり、さらに好ましくは２モル％以下であり、なおさらに好ましくは１モル％以下であり、特に好ましくは０モル％である。
　すなわち、ポリエステル樹脂における構成単位（Ｉ）、（ＩＩａ）、（ＩＩｂ）、（ＩＩＩ）、（ＩＶａ）及び（ＩＶｂ）以外のその他の構成単位の含有率は、ポリエステル樹脂に含まれる全構成単位の合計含有率を１００モル％とするとき、好ましくは０モル％以上１０モル％以下であり、より好ましくは０モル％以上５モル％以下であり、さらに好ましくは０モル％以上２モル％以下であり、なおさらに好ましくは０モル％以上１モル％以下である。 The content of the structural units other than the structural units (I), (IIa), (IIb), (III), (IVa) and (IVb) in the polyester resin is the total content of all the structural units contained in the polyester resin. When the ratio is 100 mol%, it is preferably 10 mol% or less, more preferably 5 mol% or less, from the viewpoint of improving the dielectric property in the high frequency band, particularly from the viewpoint of reducing the dielectric loss tangent in the high frequency band. It is more preferably 2 mol% or less, further preferably 1 mol% or less, and particularly preferably 0 mol% or less.
That is, the content of the structural units other than the structural units (I), (IIa), (IIb), (III), (IVa) and (IVb) in the polyester resin is the content of all the structural units contained in the polyester resin. When the total content is 100 mol%, it is preferably 0 mol% or more and 10 mol% or less, more preferably 0 mol% or more and 5 mol% or less, and further preferably 0 mol% or more and 2 mol% or less. Yes, and even more preferably 0 mol% or more and 1 mol% or less.
　〔６〕ポリエステル樹脂
　第１の実施形態に係るポリエステル樹脂は、構成単位（Ｉ）と、構成単位（ＩＩａ）及び構成単位（ＩＩｂ）からなる群より選択される少なくとも１種の構成単位と、構成単位（ＩＩＩ）とを含み、好ましくは、これらの構成単位からなる。後者の場合、構成単位（Ｉ）、構成単位（ＩＩａ）、構成単位（ＩＩｂ）及び構成単位（ＩＩＩ）の合計含有率は１００モル％である。 [6] Polyester Resin The polyester resin according to the first embodiment is composed of a constituent unit (I) and at least one constituent unit selected from the group consisting of the constituent unit (IIa) and the constituent unit (IIb). It includes the unit (III) and preferably consists of these constituent units. In the latter case, the total content of the structural unit (I), the structural unit (IIa), the structural unit (IIb) and the structural unit (III) is 100 mol%.
　第１の実施形態に係るポリエステル樹脂において、構成単位（Ｉ）、構成単位（ＩＩａ）、構成単位（ＩＩｂ）及び構成単位（ＩＩＩ）の合計含有率を１００モル％とするとき、各構成単位の含有率は、例えば次のとおりである。
　構成単位（Ｉ）：４０モル％以上９６モル％以下、高周波帯域での誘電特性を向上させる観点、とりわけ、高周波帯域での誘電正接を小さくする観点から、好ましくは４５モル％以上９６モル％以下、より好ましくは５０モル％以上９０モル％以下、さらに好ましくは５０モル％以上８０モル％以下、なおさらに好ましくは５０モル％以上７０モル％以下、特に好ましくは５５モル％以上６５モル％以下
　構成単位（ＩＩａ）及び構成単位（ＩＩｂ）の合計：ポリエステル樹脂の製造容易性の観点、並びに高周波帯域での誘電特性を向上させる観点、とりわけ、高周波帯域での誘電正接を小さくする観点から、好ましくは２モル％以上３０モル％以下、なおさらに好ましくは２モル％以上２０モル％以下、特に好ましくは２モル％以上１５モル％以下（例えば３モル％以上１０モル％以下）
　構成単位（ＩＩＩ）：高周波帯域での誘電特性を向上させる観点、とりわけ、高周波帯域での誘電正接を小さくする観点から、好ましくは２モル％以上３０モル％以下、より好ましくは２モル％以上２５モル％以下、さらに好ましくは５モル％以上２５モル％以下、なおさらに好ましくは１０モル％以上２５モル％以下、特に好ましくは１５モル％以上２５モル％以下 In the polyester resin according to the first embodiment, when the total content of the constituent units (I), the constituent units (IIa), the constituent units (IIb) and the constituent units (III) is 100 mol%, each constituent unit The content rate is, for example, as follows.
Structural unit (I): 40 mol% or more and 96 mol% or less, preferably 45 mol% or more and 96 mol% or less from the viewpoint of improving the dielectric property in the high frequency band, particularly from the viewpoint of reducing the dielectric loss tangent in the high frequency band. , More preferably 50 mol% or more and 90 mol% or less, further preferably 50 mol% or more and 80 mol% or less, still more preferably 50 mol% or more and 70 mol% or less, and particularly preferably 55 mol% or more and 65 mol% or less. Total of unit (IIa) and structural unit (IIb): From the viewpoint of ease of manufacturing polyester resin and from the viewpoint of improving the dielectric property in the high frequency band, particularly from the viewpoint of reducing the dielectric loss tangent in the high frequency band, it is preferable. 2 mol% or more and 30 mol% or less, more preferably 2 mol% or more and 20 mol% or less, particularly preferably 2 mol% or more and 15 mol% or less (for example, 3 mol% or more and 10 mol% or less)
Structural unit (III): From the viewpoint of improving the dielectric property in the high frequency band, particularly from the viewpoint of reducing the dielectric adjacency in the high frequency band, preferably 2 mol% or more and 30 mol% or less, more preferably 2 mol% or more and 25. Mol% or less, more preferably 5 mol% or more and 25 mol% or less, still more preferably 10 mol% or more and 25 mol% or less, particularly preferably 15 mol% or more and 25 mol% or less.
　第２の実施形態に係るポリエステル樹脂は、構成単位（Ｉ）と、構成単位（ＩＩａ）及び構成単位（ＩＩｂ）からなる群より選択される少なくとも１種の構成単位と、構成単位（ＩＩＩ）と、構成単位（ＩＶａ）及び構成単位（ＩＶｂ）からなる群より選択される少なくとも１種の構成単位とを含み、好ましくは、これらの構成単位からなる。後者の場合、構成単位（Ｉ）、構成単位（ＩＩａ）、構成単位（ＩＩｂ）、構成単位（ＩＩＩ）、構成単位（ＩＶａ）及び構成単位（ＩＶｂ）の合計含有率は１００モル％である。 The polyester resin according to the second embodiment includes a constituent unit (I), at least one constituent unit selected from the group consisting of the constituent unit (IIa) and the constituent unit (IIb), and the constituent unit (III). , At least one constituent unit selected from the group consisting of the constituent units (IVa) and the constituent units (IVb), preferably composed of these constituent units. In the latter case, the total content of the building blocks (I), building blocks (IIa), building blocks (IIb), building blocks (III), building blocks (IVa) and building blocks (IVb) is 100 mol%.
　第２の実施形態に係るポリエステル樹脂において、構成単位（Ｉ）、構成単位（ＩＩａ）、構成単位（ＩＩｂ）、構成単位（ＩＩＩ）、構成単位（ＩＶａ）及び構成単位（ＩＶｂ）の合計含有率を１００モル％とするとき、各構成単位の含有率は、例えば次のとおりである。
　構成単位（Ｉ）：高周波帯域での誘電特性を向上させる観点、とりわけ、高周波帯域での誘電正接を小さくする観点から、好ましくは５０モル％以上８０モル％以下、より好ましくは５０モル％以上７５モル％以下、さらに好ましくは５０モル％以上７０モル％以下、なおさらに好ましくは５０モル％以上６５モル％以下、特に好ましくは５５モル％以上６５モル％以下
　構成単位（ＩＩａ）及び構成単位（ＩＩｂ）の合計：ポリエステル樹脂の製造容易性の観点、並びに高周波帯域での誘電特性を向上させる観点、とりわけ、高周波帯域での誘電正接を小さくする観点から、好ましくは０．１モル％以上２０モル％以下、より好ましくは０．５モル％以上２０モル％以下、さらに好ましくは１モル％以上２０モル％以下、なおさらに好ましくは１モル％以上１５モル％以下、特に好ましくは２モル％以上１５モル％以下（例えば３モル％以上１０モル％以下）
　構成単位（ＩＩＩ）：１モル％以上３０モル％以下、高周波帯域での誘電特性を向上させる観点、とりわけ、高周波帯域での誘電正接を小さくする観点から、好ましくは２モル％以上３０モル％以下、より好ましくは２モル％以上２５モル％以下、さらに好ましくは５モル％以上２５モル％以下、なおさらに好ましくは１０モル％以上２５モル％以下、特に好ましくは１５モル％以上２５モル％以下
　構成単位（ＩＶａ）及び構成単位（ＩＶｂ）の合計：射出成形時の樹脂の流動性向上の観点から、好ましくは１モル％以上３０モル％以下、より好ましくは２モル％以上３０モル％以下、さらに好ましくは２モル％以上２５モル％以下、なおさらに好ましくは２モル％以上２０モル％以下、特に好ましくは５モル％以上２０モル％以下 In the polyester resin according to the second embodiment, the total content of the constituent unit (I), the constituent unit (IIa), the constituent unit (IIb), the constituent unit (III), the constituent unit (IVa) and the constituent unit (IVb). Is 100 mol%, the content of each constituent unit is, for example, as follows.
Structural unit (I): From the viewpoint of improving the dielectric property in the high frequency band, particularly from the viewpoint of reducing the dielectric loss tangent in the high frequency band, preferably 50 mol% or more and 80 mol% or less, more preferably 50 mol% or more and 75. Mol% or less, more preferably 50 mol% or more and 70 mol% or less, still more preferably 50 mol% or more and 65 mol% or less, particularly preferably 55 mol% or more and 65 mol% or less constituent units (IIa) and constituent units (IIb). ): From the viewpoint of ease of manufacturing polyester resin and from the viewpoint of improving the dielectric property in the high frequency band, particularly from the viewpoint of reducing the dielectric loss tangent in the high frequency band, preferably 0.1 mol% or more and 20 mol%. Below, more preferably 0.5 mol% or more and 20 mol% or less, still more preferably 1 mol% or more and 20 mol% or less, still more preferably 1 mol% or more and 15 mol% or less, and particularly preferably 2 mol% or more and 15 mol. % Or less (for example, 3 mol% or more and 10 mol% or less)
Structural unit (III): 1 mol% or more and 30 mol% or less, preferably 2 mol% or more and 30 mol% or less from the viewpoint of improving the dielectric property in the high frequency band, particularly from the viewpoint of reducing the dielectric adjacency in the high frequency band. , More preferably 2 mol% or more and 25 mol% or less, further preferably 5 mol% or more and 25 mol% or less, still more preferably 10 mol% or more and 25 mol% or less, and particularly preferably 15 mol% or more and 25 mol% or less. Total of unit (IVa) and constituent unit (IVb): From the viewpoint of improving the fluidity of the resin during injection molding, it is preferably 1 mol% or more and 30 mol% or less, more preferably 2 mol% or more and 30 mol% or less, and further. It is preferably 2 mol% or more and 25 mol% or less, more preferably 2 mol% or more and 20 mol% or less, and particularly preferably 5 mol% or more and 20 mol% or less.
　ポリエステル樹脂は、成形性及び耐熱性の観点から、４℃／分の昇温速度で加熱溶融された該ポリエステル樹脂を、荷重９．８ＭＰａの荷重下、内径１ｍｍ、長さ１０ｍｍのノズルから押し出したときに、毛細管型レオメータを用いて測定される溶融粘度が４８００Ｐａ・ｓを示す温度（以下、「流動開始温度」ともいう。例えば、小出直之編「液晶ポリマー－合成・成形・応用－」第９５頁、株式会社シーエムシー、１９８７年６月５日発行を参照）が、好ましくは２８５℃以上３８０℃以下であり、より好ましくは２８５℃以上３６０℃以下であり、さらに好ましくは２９０℃以上３５０℃以下である。 From the viewpoint of moldability and heat resistance, the polyester resin was heated and melted at a temperature rise rate of 4 ° C./min, and the polyester resin was extruded from a nozzle having an inner diameter of 1 mm and a length of 10 mm under a load of 9.8 MPa. Occasionally, the temperature at which the melt viscosity measured using a capillary resin meter shows 4800 Pa · s (hereinafter, also referred to as “flow start temperature”. For example, “Liquid crystal polymer-synthesis / molding / application-” edited by Naoyuki Koide. See page 95, CMC Co., Ltd., published June 5, 1987), preferably 285 ° C or higher and 380 ° C or lower, more preferably 285 ° C or higher and 360 ° C or lower, and further preferably 290 ° C or higher and 350 ° C or lower. It is below ° C.
　ポリエステル樹脂は、成形時における寸法安定性の観点から、下記の［実施例］の項に記載される方法に従って測定されるＴＤ成形収縮率が、好ましくは２％以下であり、より好ましくは１．５％以下であり、さらに好ましくは１．３％以下である。 From the viewpoint of dimensional stability during molding, the polyester resin has a TD molding shrinkage of preferably 2% or less, more preferably 1. It is 5% or less, more preferably 1.3% or less.
　ポリエステル樹脂は、機械的強度の観点から、下記の［実施例］の項に記載される方法に従って測定される２３℃での引張強度が、好ましくは１００ＭＰａ以上、より好ましくは１０５ＭＰａ以上、さらに好ましくは１１０ＭＰａ以上である。該引張強度は、通常、３００ＭＰａ以下である。すなわち、該引張強度は、好ましくは１００ＭＰａ以上３００ＭＰａ以下であり、より好ましくは１０５ＭＰａ以上３００ＭＰａ以下であり、さらに好ましくは１１０ＭＰａ以上３００ＭＰａ以下である。 From the viewpoint of mechanical strength, the polyester resin has a tensile strength at 23 ° C. measured according to the method described in the following [Example], preferably 100 MPa or more, more preferably 105 MPa or more, still more preferably 105 MPa or more. It is 110 MPa or more. The tensile strength is usually 300 MPa or less. That is, the tensile strength is preferably 100 MPa or more and 300 MPa or less, more preferably 105 MPa or more and 300 MPa or less, and further preferably 110 MPa or more and 300 MPa or less.
　ポリエステル樹脂は、機械的強度の観点から、下記の［実施例］の項に記載される方法に従って測定される２３℃での引張伸びが、好ましくは３．０％以上、より好ましくは３．１％以上、さらに好ましくは３．５％以上である。該引張伸びは、通常、１０％以下である。すなわち、該引張伸びは、好ましくは３．０％以上１０％以下であり、より好ましくは３．１％以上１０％以下であり、さらに好ましくは３．５％以上１０％以下である。 From the viewpoint of mechanical strength, the polyester resin has a tensile elongation at 23 ° C. measured according to the method described in the section of [Example] below, preferably 3.0% or more, more preferably 3.1. % Or more, more preferably 3.5% or more. The tensile elongation is usually 10% or less. That is, the tensile elongation is preferably 3.0% or more and 10% or less, more preferably 3.1% or more and 10% or less, and further preferably 3.5% or more and 10% or less.
　ポリエステル樹脂は、機械的強度の観点から、下記の［実施例］の項に記載される方法に従って測定される２３℃での曲げ強度が、好ましくは１４０ＭＰａ以上、より好ましくは１５０ＭＰａ以上、さらに好ましくは１６０ＭＰａ以上である。該曲げ強度は、通常、３００ＭＰａ以下である。すなわち、該曲げ強度は、好ましくは１４０ＭＰａ以上３００ＭＰａ以下であり、より好ましくは１５０ＭＰａ以上３００ＭＰａ以下であり、さらに好ましくは１６０ＭＰａ以上３００ＭＰａ以下である。 From the viewpoint of mechanical strength, the polyester resin has a bending strength at 23 ° C. measured according to the method described in the following [Examples], preferably 140 MPa or more, more preferably 150 MPa or more, still more preferably. It is 160 MPa or more. The bending strength is usually 300 MPa or less. That is, the bending strength is preferably 140 MPa or more and 300 MPa or less, more preferably 150 MPa or more and 300 MPa or less, and further preferably 160 MPa or more and 300 MPa or less.
　ポリエステル樹脂は、機械的強度の観点から、下記の［実施例］の項に記載される方法に従って測定される２３℃でのＩｚｏｄ衝撃強度（ノッチなし）が、好ましくは１４０Ｊ／ｍ以上、より好ましくは１５０Ｊ／ｍ以上、さらに好ましくは１６０Ｊ／ｍ以上である。該Ｉｚｏｄ衝撃強度は、通常３００Ｊ／ｍ以下である。すなわち、該Ｉｚｏｄ衝撃強度（ノッチなし）は、好ましくは１４０Ｊ／ｍ以上３００Ｊ／ｍ以下であり、より好ましくは１５０Ｊ／ｍ以上３００Ｊ／ｍ以下あり、さらに好ましくは１６０Ｊ／ｍ以上３００Ｊ／ｍ以下である。 From the viewpoint of mechanical strength, the polyester resin has an Izod impact strength (without notch) at 23 ° C. measured according to the method described in the following [Example], preferably 140 J / m or more, more preferably. Is 150 J / m or more, more preferably 160 J / m or more. The Izod impact strength is usually 300 J / m or less. That is, the Izod impact strength (without notch) is preferably 140 J / m or more and 300 J / m or less, more preferably 150 J / m or more and 300 J / m or less, and further preferably 160 J / m or more and 300 J / m or less. be.
　ポリエステル樹脂は、耐熱性の観点から、下記の［実施例］の項に記載される方法に従って測定される荷重たわみ温度が、好ましくは１３０℃以上、より好ましくは１５０℃以上、さらに好ましくは２００℃以上である。該荷重たわみ温度は、通常３６０℃以下である。すなわち、該荷重たわみ温度は、好ましくは１３０℃以上３６０℃以下であり、より好ましくは１５０℃以上３６０℃以下であり、さらに好ましくは２００℃以上３６０℃以下である。 From the viewpoint of heat resistance, the polyester resin has a deflection temperature under load measured according to the method described in the section of [Example] below, preferably 130 ° C. or higher, more preferably 150 ° C. or higher, still more preferably 200 ° C. That is all. The deflection temperature under load is usually 360 ° C. or lower. That is, the deflection temperature under load is preferably 130 ° C. or higher and 360 ° C. or lower, more preferably 150 ° C. or higher and 360 ° C. or lower, and further preferably 200 ° C. or higher and 360 ° C. or lower.
　ポリエステル樹脂は、下記の［実施例］の項に記載される方法に従って測定される１ＧＨｚにおける誘電正接が、好ましくは０．０００９以下であり、より好ましくは０．０００８以下である。該誘電正接は、通常０．０００２以上である。すなわち、１ＧＨｚにおける誘電正接は、好ましくは０．０００９以下０．０００２以上であり、より好ましくは０．０００８以下０．０００２以上である。
　ポリエステル樹脂は、下記の［実施例］の項に記載される方法に従って測定される１ＧＨｚにおける誘電率が、好ましくは３．３以下であり、より好ましくは３．２以下であり、さらに好ましくは３．１以下であり、なおさらに好ましくは３．０以下であり、特に好ましくは２．９以下である。該誘電率は、通常２．５以上である。すなわち、１ＧＨｚにおける誘電率は、好ましくは３．３以下２．５以上であり、より好ましくは３．２以下２．５以上であり、さらに好ましくは３．１以下２．５以上であり、なおさらに好ましくは３．０以下２．５以上であり、特に好ましくは２．９以下２．５以上である。 The polyester resin has a dielectric loss tangent at 1 GHz measured according to the method described in the section of [Example] below, preferably 0.0009 or less, and more preferably 0.0008 or less. The dielectric loss tangent is usually 0.0002 or more. That is, the dielectric loss tangent at 1 GHz is preferably 0.0002 or less and 0.0002 or more, and more preferably 0.0008 or less and 0.0002 or more.
The polyester resin has a dielectric constant at 1 GHz measured according to the method described in the section of [Example] below, preferably 3.3 or less, more preferably 3.2 or less, still more preferably 3. It is 0.1 or less, more preferably 3.0 or less, and particularly preferably 2.9 or less. The dielectric constant is usually 2.5 or more. That is, the dielectric constant at 1 GHz is preferably 3.3 or less and 2.5 or more, more preferably 3.2 or less and 2.5 or more, still more preferably 3.1 or less and 2.5 or more, and even more so. It is preferably 3.0 or less and 2.5 or more, and particularly preferably 2.9 or less and 2.5 or more.
　〔７〕ポリエステル樹脂の製造方法
　ポリエステル樹脂は、構成単位（Ｉ）を与えるモノマーと、構成単位（ＩＩａ）を与えるモノマー及び構成単位（ＩＩｂ）を与えるモノマーからなる群より選択される少なくとも１種と、構成単位（ＩＩＩ）を与えるモノマーと、さらに必要に応じて構成単位（ＩＶａ）を与えるモノマー及び構成単位（ＩＶｂ）を与えるモノマーからなる群より選択される少なくとも１種並びにその他の構成単位を与えるモノマーを、溶融重合、固相重合、溶液重合、スラリー重合等、従来公知の方法で重合させることにより製造できる。複数種の重合法を組み合わせてポリエステル樹脂を製造してもよい。
　ポリエステル樹脂の製造方法は、好ましくは溶融重合を含む。 [7] Method for Producing Polyester Resin The polyester resin is at least one selected from the group consisting of a monomer giving a structural unit (I), a monomer giving a structural unit (IIa), and a monomer giving a structural unit (IIb). , At least one selected from the group consisting of a monomer giving the structural unit (III), and optionally a monomer giving the structural unit (IVa) and a monomer giving the structural unit (IVb), and other structural units. It can be produced by polymerizing the monomer by a conventionally known method such as melt polymerization, solid phase polymerization, solution polymerization, slurry polymerization and the like. A polyester resin may be produced by combining a plurality of types of polymerization methods.
The method for producing a polyester resin preferably comprises melt polymerization.
　ポリエステル樹脂は、構成単位（Ｉ）を与えるモノマー、構成単位（ＩＩａ）を与えるモノマー及び構成単位（ＩＩｂ）を与えるモノマーからなる群より選択される少なくとも１種、並びに必要に応じて使用される構成単位（ＩＶａ）を与えるモノマー及び構成単位（ＩＶｂ）を与えるモノマーからなる群より選択される少なくとも１種等が有する水酸基を過剰量の脂肪酸無水物によりアシル化してアシル化物を得、次いで得られたアシル化物を構成単位（ＩＩＩ）を与えるモノマーとともに重縮合（エステル交換反応）させることによって製造されてもよい。 The polyester resin is at least one selected from the group consisting of a monomer giving a structural unit (I), a monomer giving a structural unit (IIa), and a monomer giving a structural unit (IIb), and a configuration used as needed. A hydroxyl group having at least one selected from the group consisting of a monomer giving a unit (IVa) and a monomer giving a constituent unit (IVb) was acylated with an excess amount of fatty acid anhydride to obtain an acylated product, and then obtained. The acylated product may be produced by polycondensing (transesterification reaction) with a monomer giving the structural unit (III).
　アシル化反応に使用される脂肪酸無水物は、特に限定されないが、例えば、無水酢酸、無水プロピオン酸、無水酪酸、無水イソ酪酸、無水吉草酸、無水ピバル酸、無水２エチルヘキサン酸、無水モノクロル酢酸、無水ジクロル酢酸、無水トリクロル酢酸、無水モノブロモ酢酸、無水ジブロモ酢酸、無水トリブロモ酢酸、無水モノフルオロ酢酸、無水ジフルオロ酢酸、無水トリフルオロ酢酸、無水グルタル酸、無水マレイン酸、無水コハク酸、無水β－ブロモプロピオン酸等が挙げられる。
　脂肪酸無水物は、１種又は２種類以上使用することができる。
　脂肪酸無水物は、好ましくは、無水酢酸、無水プロピオン酸、無水酪酸、無水イソ酪酸であり、より好ましくは無水酢酸である。 The fatty acid anhydride used in the acylation reaction is not particularly limited, and is, for example, acetic acid anhydride, propionic acid anhydride, butyric acid anhydride, isobutyric acid anhydride, valeric acid anhydride, pivalic acid anhydride, diethylhexanoic acid anhydride, monochloroacetic acid anhydride. , Anhydrous dichloracetic acid, Anhydrous trichloroacetic acid, Anhydrous monobromoacetic acid, Anhydrous dibromoacetic acid, Anhydrous tribromoacetic acid, Anhydrous monofluoroacetic acid, Anhydrous difluoroacetic acid, Anhydrous trifluoroacetic acid, Anhydrous glutaric acid, Anhydrous maleic acid, Anhydrous succinic acid, Anhydrous β- Bromopropionic acid and the like can be mentioned.
One type or two or more types of fatty acid anhydride can be used.
The fatty acid anhydride is preferably acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, and more preferably acetic anhydride.
　アシル化反応後に重縮合（エステル交換反応）を行う場合、副生する脂肪酸及び未反応の脂肪酸無水物を留去させながら重縮合反応を行う。 When polycondensation (transesterification reaction) is performed after the acylation reaction, the polycondensation reaction is performed while distilling off by-produced fatty acids and unreacted fatty acid anhydrides.
　アシル化反応及び重縮合（エステル交換反応）は、触媒の存在下に行われてもよい。
　該触媒としては、ポリエステルの重合用触媒として公知のものを使用することができ、例えば、
　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、酢酸カリウム、三酸化アンチモン等の金属塩触媒；
　Ｎ，Ｎ－ジメチルアミノピリジン、Ｎ－メチルイミダゾール等の有機化合物触媒
等が挙げられる。
　中でも、Ｎ，Ｎ－ジメチルアミノピリジン、Ｎ－メチルイミダゾール等の、分子内に窒素原子を２個以上含む複素環状化合物が好ましく使用される。
　該触媒は、通常、モノマーの投入時に投入され、アシル化後も除去することは必ずしも必要ではなく、該触媒を除去しない場合にはそのまま重縮合（エステル交換反応）を行うことができる。 The acylation reaction and polycondensation (transesterification reaction) may be carried out in the presence of a catalyst.
As the catalyst, a catalyst known as a polyester polymerization catalyst can be used, for example.
Metal salt catalysts such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, antimony trioxide;
Examples thereof include organic compound catalysts such as N, N-dimethylaminopyridine and N-methylimidazole.
Among them, heterocyclic compounds containing two or more nitrogen atoms in the molecule, such as N, N-dimethylaminopyridine and N-methylimidazole, are preferably used.
The catalyst is usually charged at the time of charging the monomer, and it is not always necessary to remove the catalyst even after acylation. If the catalyst is not removed, polycondensation (transesterification reaction) can be carried out as it is.
　重縮合（エステル交換反応）は、例えば、溶融重合と固相重合とを併用により行われてもよい。溶融重合の後に固相重合をさらに実施することにより、ポリエステル樹脂の高分子量化、機械的強度及び耐熱性の向上、流動開始温度の上昇を図り得る。
　固相重合は、好ましくは、溶融重合工程からポリマーを抜き出し、その後、粉砕してパウダー状又はフレーク状等にした後、公知の固相重合方法により行われる。具体的には、例えば、窒素等の不活性雰囲気下、２００℃以上３５０℃以下の温度で、１時間以上３０時間以下、固相状態で熱処理する方法等が挙げられる。
　固相重合は、攪拌しながらでも、攪拌することなく静置した状態で行ってもよい。
　なお適当な攪拌機構を備えることにより溶融重合槽と固相重合槽とを同一の反応槽とすることもできる。ポリエステル樹脂の製造は、例えば、回分装置、連続装置等を用いて行うことができる。
　得られたポリエステル樹脂は、公知の方法によりペレット状、フレーク状、粉末状等に加工されてもよい。 The polycondensation (transesterification reaction) may be performed, for example, by using melt polymerization and solid phase polymerization in combination. By further performing solid phase polymerization after melt polymerization, it is possible to increase the molecular weight of the polyester resin, improve the mechanical strength and heat resistance, and raise the flow start temperature.
The solid phase polymerization is preferably carried out by a known solid phase polymerization method after extracting the polymer from the melt polymerization step and then pulverizing the polymer into a powder or flake. Specific examples thereof include a method of heat-treating in a solid phase state for 1 hour or more and 30 hours or less at a temperature of 200 ° C. or higher and 350 ° C. or lower in an inert atmosphere such as nitrogen.
Solid-phase polymerization may be carried out with stirring or in a stationary state without stirring.
The melt polymerization tank and the solid phase polymerization tank can be made into the same reaction tank by providing an appropriate stirring mechanism. The polyester resin can be produced, for example, by using a batch device, a continuous device, or the like.
The obtained polyester resin may be processed into pellets, flakes, powders, etc. by a known method.
　＜樹脂組成物＞
　本発明に係る樹脂組成物（以下、単に「樹脂組成物」ともいう。）は、上記本発明に係るポリエステル樹脂と、充填剤とを含む。充填剤は、有機充填剤であってもよいし、無機充填剤であってもよい。
　樹脂組成物は、充填剤を１種又は２種以上含むことができる。 <Resin composition>
The resin composition according to the present invention (hereinafter, also simply referred to as “resin composition”) includes the polyester resin according to the present invention and a filler. The filler may be an organic filler or an inorganic filler.
The resin composition may contain one or more fillers.
　充填剤としては、例えば、酸化チタン、硫酸バリウム、炭酸カルシウム、ガラスバルーン、ガラスビーズ、ガラスフレーク、タルク、マイカ、クレイ、ウォラストナイト、ドロマイト、グラファイト、ガラス繊維、炭素繊維、アルミナ繊維、シリカアルミナ繊維、チタン酸カリウム繊維、ホウ酸アルミニウム繊維、アラミド繊維、カーボンブラック、黒鉛、シリカ、石英粉末、ケイ酸カルシウム、ケイ酸アルミニウム、クレー、酸化鉄、酸化亜鉛、三酸化アンチモン、アルミナ、硫酸カルシウム、その他各種の金属又は金属化合物粉末等が挙げられる。 Examples of the filler include titanium oxide, barium sulfate, calcium carbonate, glass balloon, glass beads, glass flakes, talc, mica, clay, wollastonite, dolomite, graphite, glass fiber, carbon fiber, alumina fiber, and silica alumina. Fiber, potassium titanate fiber, aluminum borate fiber, aramid fiber, carbon black, graphite, silica, quartz powder, calcium silicate, aluminum silicate, clay, iron oxide, zinc oxide, antimony trioxide, alumina, calcium sulfate, Other examples include various metals or metal compound powders.
　樹脂組成物における充填剤の含有量は、ポリエステル樹脂１００質量部に対して、例えば１質量部以上１５０質量部以下であり、好ましくは５質量部以上１００質量部以下であり、より好ましくは１０質量部以上７０質量部以下であり、さらに好ましくは２０質量部以上７０質量部以下である。 The content of the filler in the resin composition is, for example, 1 part by mass or more and 150 parts by mass or less, preferably 5 parts by mass or more and 100 parts by mass or less, and more preferably 10 parts by mass with respect to 100 parts by mass of the polyester resin. It is 20 parts by mass or more and 70 parts by mass or less, and more preferably 20 parts by mass or more and 70 parts by mass or less.
　樹脂組成物は、上記本発明に係るポリエステル樹脂以外の樹脂を１種又は２種以上含み得る。該樹脂としては、例えば、上記本発明に係るポリエステル樹脂以外のポリエステル樹脂、ポリオレフィン、環状ポリオレフィン、ポリ塩化ビニル、ポリスルホン、（メタ）アクリル樹脂、ポリフェニレンエーテル樹脂、ポリアセタール樹脂、ポリアミド樹脂、イミド樹脂、ポリスチレン樹脂、セルロース樹脂、ポリエーテルエーテルケトン樹脂、フッ素樹脂、ポリカーボネート樹脂、熱硬化性樹脂等が挙げられる。 The resin composition may contain one or more resins other than the polyester resin according to the present invention. Examples of the resin include polyester resins other than the polyester resin according to the present invention, polyolefins, cyclic polyolefins, polyvinyl chlorides, polysulfones, (meth) acrylic resins, polyphenylene ether resins, polyacetal resins, polyamide resins, imide resins, and polystyrenes. Examples thereof include resins, cellulose resins, polyether ether ketone resins, fluororesins, polycarbonate resins, thermosetting resins and the like.
　樹脂組成物は、充填剤以外の添加剤を１種又は２種以上含み得る。該添加剤としては、例えば、着色剤、分散剤、可塑剤、酸化防止剤、硬化剤、難燃剤、熱安定剤、紫外線吸収剤、帯電防止剤、界面活性剤、滑剤、離型剤等が挙げられる。 The resin composition may contain one or more additives other than the filler. Examples of the additive include colorants, dispersants, plasticizers, antioxidants, curing agents, flame retardants, heat stabilizers, ultraviolet absorbers, antistatic agents, surfactants, lubricants, mold release agents and the like. Can be mentioned.
　樹脂組成物は、ポリエステル樹脂、充填剤及び必要に応じて添加される他の成分を含むものである限り特に制限されないが、例えば、ポリエステル樹脂、充填剤及び必要に応じて添加される他の成分を含む混合物の溶融混練物であってもよい。 The resin composition is not particularly limited as long as it contains a polyester resin, a filler and other components added as needed, and includes, for example, a polyester resin, a filler and other components added as needed. It may be a melt-kneaded mixture.
　＜成形品＞
　本発明に係る成形品（以下、単に「成形品」ともいう。）は、上記本発明に係るポリエステル樹脂又は上記本発明に係る樹脂組成物を含む。
　成形品は、例えば、フィルム、シート、板、繊維等であることができる。 <Molded product>
The molded product according to the present invention (hereinafter, also simply referred to as “molded product”) includes the polyester resin according to the present invention or the resin composition according to the present invention.
The molded product can be, for example, a film, a sheet, a plate, a fiber, or the like.
　成形品は、ポリエステル樹脂又は樹脂組成物から、射出成形法、圧縮成形法、押出成形法、ブロー成形法、溶液キャスト法等によって製造することができる。 The molded product can be manufactured from a polyester resin or a resin composition by an injection molding method, a compression molding method, an extrusion molding method, a blow molding method, a solution casting method, or the like.
　ポリエステル樹脂、樹脂組成物及び成形品は、通信機器、電子機器及びそれらの部品等に好適に適用することができる。該部品としては、例えば、アンテナ、コネクタ、コンデンサ、トランス、回路基板、フレキシブルプリント基板等が挙げられる。 The polyester resin, resin composition and molded product can be suitably applied to communication equipment, electronic equipment and their parts. Examples of the component include an antenna, a connector, a capacitor, a transformer, a circuit board, a flexible printed circuit board, and the like.
　以下、実施例を示して本発明をさらに具体的に説明するが、本発明はこれらの例によって限定されるものではない。例中、含有量ないし使用量を表す％及び部は、特記ない限り、質量基準である。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples,% and parts representing the content or the amount used are based on mass unless otherwise specified.
　＜実施例１＞
　攪拌装置、トルクメータ、窒素ガス導入管、温度計及び還流冷却器を備えた反応器に、６－ヒドロキシ－２－ナフトエ酸１０３５．０ｇ（５．５０モル）、ハイドロキノン１３７．６ｇ（１．２５モル）、２，３，５－トリメチルハイドロキノン１５２．２ｇ（１．００モル）、テレフタル酸８３．１ｇ（０．５０モル）、２，６－ナフタレンジカルボン酸３７８．３ｇ（１．７５モル）、無水酢酸１１７４．０（１１．５０モル）及び触媒としての１－メチルイミダゾール０．０５４ｇを添加し、攪拌しながら昇温した。内温が１４０℃となったところで、１４０℃を保持したまま１時間攪拌した。 <Example 1>
A reactor equipped with a stirrer, torque meter, nitrogen gas introduction tube, thermometer and reflux condenser, 6-hydroxy-2-naphthoic acid 1035.0 g (5.50 mol), hydroquinone 137.6 g (1.25 mol). Mol), 2,3,5-trimethylhydroquinone 152.2 g (1.00 mol), terephthalic acid 83.1 g (0.50 mol), 2,6-naphthalenedicarboxylic acid 378.3 g (1.75 mol), 1174.0 (11.50 mol) of anhydrous acetic acid and 0.054 g of 1-methylimidazole as a catalyst were added, and the temperature was raised with stirring. When the internal temperature reached 140 ° C., the mixture was stirred for 1 hour while maintaining 140 ° C.
　次に、留出する副生酢酸、未反応の無水酢酸を留去しながら、１４０℃から３００℃まで４時間２０分かけて昇温した。３００℃で２時間保温して全芳香族ポリエステル樹脂を得た。得られた全芳香族ポリエステル樹脂を室温に冷却し、粉砕機で粉砕して、全芳香族ポリエステル樹脂の粉末（粒子径は約０．１ｍｍ～約２ｍｍ）を得た。
　この粉末（全芳香族ポリエステル樹脂）の流動開始温度を測定したところ、２４６℃であった。 Next, the temperature was raised from 140 ° C. to 300 ° C. over 4 hours and 20 minutes while distilling off distillate by-product acetic acid and unreacted acetic anhydride. The whole aromatic polyester resin was obtained by incubating at 300 ° C. for 2 hours. The obtained total aromatic polyester resin was cooled to room temperature and pulverized with a pulverizer to obtain a powder (particle size of about 0.1 mm to about 2 mm) of the total aromatic polyester resin.
The flow start temperature of this powder (total aromatic polyester resin) was measured and found to be 246 ° C.
　得られた粉末を２５℃から２４０℃まで１時間かけて昇温したのち、２４０℃から２８０℃まで５時間８分かけて昇温し、次いで２８０℃で１０時間保温して固相重合させた。その後、固相重合した後の粉末を冷却し、冷却後の粉末（全芳香族ポリエステル樹脂、「ポリエステル樹脂１」）の流動開始温度を測定したところ、３１４℃であった。 The obtained powder was heated from 25 ° C. to 240 ° C. over 1 hour, then heated from 240 ° C. to 280 ° C. over 5 hours and 8 minutes, and then kept at 280 ° C. for 10 hours for solid phase polymerization. .. Then, the powder after solid-phase polymerization was cooled, and the flow start temperature of the cooled powder (total aromatic polyester resin, "polyester resin 1") was measured and found to be 314 ° C.
　＜実施例２＞
　攪拌装置、トルクメータ、窒素ガス導入管、温度計及び還流冷却器を備えた反応器に、６－ヒドロキシ－２－ナフトエ酸１１２９．１ｇ（６．００モル）、１，１’－ビフェニル－４，４’－ジオール１８６．２ｇ（１．００モル）、２，３，５－トリメチルハイドロキノン１５２．２ｇ（１．００モル）、テレフタル酸３３２．３ｇ（２．００モル）、無水酢酸１１２３．０（１１．００モル）及び触媒としての１－メチルイミダゾール０．０５４ｇを添加し、攪拌しながら昇温した。内温が１４０℃となったところで、１４０℃を保持したまま１時間攪拌した。 <Example 2>
A reactor equipped with a stirrer, torque meter, nitrogen gas introduction tube, thermometer and reflux condenser, 6-hydroxy-2-naphthoic acid 1129.1 g (6.00 mol), 1,1'-biphenyl-4. , 4'-diol 186.2 g (1.00 mol), 2,3,5-trimethylhydroquinone 152.2 g (1.00 mol), terephthalic acid 332.3 g (2.00 mol), anhydrous acetic acid 1123.0 (11.00 mol) and 0.054 g of 1-methylimidazole as a catalyst were added, and the temperature was raised with stirring. When the internal temperature reached 140 ° C., the mixture was stirred for 1 hour while maintaining 140 ° C.
　次に、留出する副生酢酸、未反応の無水酢酸を留去しながら、１４０℃から３００℃まで４時間かけて昇温した。３００℃で１時間保温して全芳香族ポリエステル樹脂を得た。得られた全芳香族ポリエステル樹脂を室温に冷却し、粉砕機で粉砕して、全芳香族ポリエステル樹脂の粉末（粒子径は約０．１ｍｍ～約２ｍｍ）を得た。
　この粉末（全芳香族ポリエステル樹脂）の流動開始温度を測定したところ、２３７℃であった。 Next, the temperature was raised from 140 ° C. to 300 ° C. over 4 hours while distilling off distillate by-product acetic acid and unreacted acetic anhydride. The whole aromatic polyester resin was obtained by incubating at 300 ° C. for 1 hour. The obtained total aromatic polyester resin was cooled to room temperature and pulverized with a pulverizer to obtain a powder (particle size of about 0.1 mm to about 2 mm) of the total aromatic polyester resin.
The flow start temperature of this powder (total aromatic polyester resin) was measured and found to be 237 ° C.
　得られた粉末を２５℃から２２０℃まで１時間かけて昇温したのち、２２０℃から２９０℃まで１１時間４０分かけて昇温し、次いで２９０℃で５時間保温して固相重合させた。その後、固相重合した後の粉末を冷却し、冷却後の粉末（全芳香族ポリエステル樹脂、「ポリエステル樹脂２」）の流動開始温度を測定したところ、２８８℃であった。 The obtained powder was heated from 25 ° C. to 220 ° C. over 1 hour, then heated from 220 ° C. to 290 ° C. over 11 hours and 40 minutes, and then kept at 290 ° C. for 5 hours for solid phase polymerization. .. Then, the powder after solid-phase polymerization was cooled, and the flow start temperature of the cooled powder (total aromatic polyester resin, "polyester resin 2") was measured and found to be 288 ° C.
　＜実施例３＞
　攪拌装置、トルクメータ、窒素ガス導入管、温度計及び還流冷却器を備えた反応器に、６－ヒドロキシ－２－ナフトエ酸１１２９．１ｇ（６．００モル）、１，１’－ビフェニル－４，４’－ジオール３３５．２ｇ（１．８０モル）、２，２，’，３，３’，５，５’－ヘキサメチル－１，１’－ビフェニル－４，４’－ジオール５４．１ｇ（０．２０モル）、テレフタル酸３３２．３ｇ（２．００モル）、無水酢酸１１２３．０（１１．００モル）及び触媒としての１－メチルイミダゾール０．０５６ｇを添加し、攪拌しながら昇温した。内温が１４０℃となったところで、１４０℃を保持したまま１時間攪拌した。 <Example 3>
A reactor equipped with a stirrer, torque meter, nitrogen gas introduction tube, thermometer and reflux condenser, 6-hydroxy-2-naphthoic acid 1129.1 g (6.00 mol), 1,1'-biphenyl-4. , 4'-diol 335.2 g (1.80 mol), 2,2', 3,3', 5,5'-hexamethyl-1,1'-biphenyl-4,4'-diol 54.1 g ( 0.20 mol), terephthalic acid 332.3 g (2.00 mol), anhydrous acetic acid 1123.0 (11.00 mol) and 1-methylimidazole 0.056 g as a catalyst were added, and the temperature was raised with stirring. .. When the internal temperature reached 140 ° C., the mixture was stirred for 1 hour while maintaining 140 ° C.
　次に、留出する副生酢酸、未反応の無水酢酸を留去しながら、１４０℃から３００℃まで４時間かけて昇温した。３００℃で２時間保温して全芳香族ポリエステル樹脂を得た。得られた全芳香族ポリエステル樹脂を室温に冷却し、粉砕機で粉砕して、全芳香族ポリエステル樹脂の粉末（粒子径は約０．１ｍｍ～約２ｍｍ）を得た。
　この粉末（全芳香族ポリエステル樹脂）の流動開始温度を測定したところ、２３２℃であった。 Next, the temperature was raised from 140 ° C. to 300 ° C. over 4 hours while distilling off distillate by-product acetic acid and unreacted acetic anhydride. The whole aromatic polyester resin was obtained by incubating at 300 ° C. for 2 hours. The obtained total aromatic polyester resin was cooled to room temperature and pulverized with a pulverizer to obtain a powder (particle size of about 0.1 mm to about 2 mm) of the total aromatic polyester resin.
The flow start temperature of this powder (total aromatic polyester resin) was measured and found to be 232 ° C.
　得られた粉末を２５℃から２３０℃まで１時間かけて昇温したのち、２３０℃から３０３℃まで１２時間１０分かけて昇温し、次いで３０３℃で５時間保温して固相重合させた。その後、固相重合した後の粉末を冷却し、冷却後の粉末（全芳香族ポリエステル樹脂、「ポリエステル樹脂３」）の流動開始温度を測定したところ、３３０℃であった。 The obtained powder was heated from 25 ° C. to 230 ° C. over 1 hour, then heated from 230 ° C. to 303 ° C. over 12 hours and 10 minutes, and then kept at 303 ° C. for 5 hours for solid phase polymerization. .. Then, the powder after solid-phase polymerization was cooled, and the flow start temperature of the cooled powder (total aromatic polyester resin, "polyester resin 3") was measured and found to be 330 ° C.
　＜実施例４＞
　攪拌装置、トルクメータ、窒素ガス導入管、温度計及び還流冷却器を備えた反応器に、６－ヒドロキシ－２－ナフトエ酸１１２９．１ｇ（６．００モル）、１，１’－ビフェニル－４，４’－ジオール３１６．６ｇ（１．７０モル）、２，２，’，３，３’，５，５’－ヘキサメチル－１，１’－ビフェニル－４，４’－ジオール８１．１ｇ（０．３０モル）、テレフタル酸３３２．３ｇ（２．００モル）、無水酢酸１１２３．０（１１．００モル）及び触媒としての１－メチルイミダゾール０．０５６ｇを添加し、攪拌しながら昇温した。内温が１４０℃となったところで、１４０℃を保持したまま１時間攪拌した。 <Example 4>
A reactor equipped with a stirrer, torque meter, nitrogen gas introduction tube, thermometer and reflux condenser, 6-hydroxy-2-naphthoic acid 1129.1 g (6.00 mol), 1,1'-biphenyl-4. , 4'-diol 316.6 g (1.70 mol), 2,2', 3,3', 5,5'-hexamethyl-1,1'-biphenyl-4,4'-diol 81.1 g ( 0.30 mol), terephthalic acid 332.3 g (2.00 mol), anhydrous acetic acid 1123.0 (11.00 mol) and 1-methylimidazole 0.056 g as a catalyst were added, and the temperature was raised with stirring. .. When the internal temperature reached 140 ° C., the mixture was stirred for 1 hour while maintaining 140 ° C.
　次に、留出する副生酢酸、未反応の無水酢酸を留去しながら、１４０℃から３００℃まで４時間かけて昇温した。３００℃で１時間保温して全芳香族ポリエステル樹脂を得た。得られた全芳香族ポリエステル樹脂を室温に冷却し、粉砕機で粉砕して、全芳香族ポリエステル樹脂の粉末（粒子径は約０．１ｍｍ～約２ｍｍ）を得た。
　この粉末（全芳香族ポリエステル樹脂）の流動開始温度を測定したところ、２２２℃であった。 Next, the temperature was raised from 140 ° C. to 300 ° C. over 4 hours while distilling off distillate by-product acetic acid and unreacted acetic anhydride. The whole aromatic polyester resin was obtained by incubating at 300 ° C. for 1 hour. The obtained total aromatic polyester resin was cooled to room temperature and pulverized with a pulverizer to obtain a powder (particle size of about 0.1 mm to about 2 mm) of the total aromatic polyester resin.
The flow start temperature of this powder (total aromatic polyester resin) was measured and found to be 222 ° C.
　得られた粉末を２５℃から２３０℃まで１時間かけて昇温したのち、２３０℃から３０４℃まで１２時間２０分かけて昇温し、次いで３０４℃で５時間保温して固相重合させた。その後、固相重合した後の粉末を冷却し、冷却後の粉末（全芳香族ポリエステル樹脂、「ポリエステル樹脂４」）の流動開始温度を測定したところ、３３１℃であった。 The obtained powder was heated from 25 ° C. to 230 ° C. over 1 hour, then heated from 230 ° C. to 304 ° C. over 12 hours and 20 minutes, and then kept at 304 ° C. for 5 hours for solid phase polymerization. .. Then, the powder after solid-phase polymerization was cooled, and the flow start temperature of the cooled powder (total aromatic polyester resin, "polyester resin 4") was measured and found to be 331 ° C.
　＜実施例５＞
　攪拌装置、トルクメータ、窒素ガス導入管、温度計及び還流冷却器を備えた反応器に、６－ヒドロキシ－２－ナフトエ酸１１２９．１ｇ（６．００モル）、１，１’－ビフェニル－４，４’－ジオール２７９．３ｇ（１．５０モル）、２，２，’，３，３’，５，５’－ヘキサメチル－１，１’－ビフェニル－４，４’－ジオール１３５．２ｇ（０．５０モル）、テレフタル酸３３２．３ｇ（２．００モル）、無水酢酸１１２３．０（１１．００モル）及び触媒としての１－メチルイミダゾール０．０５６ｇを添加し、攪拌しながら昇温した。内温が１４０℃となったところで、１４０℃を保持したまま１時間攪拌した。 <Example 5>
A reactor equipped with a stirrer, torque meter, nitrogen gas introduction tube, thermometer and reflux condenser, 6-hydroxy-2-naphthoic acid 1129.1 g (6.00 mol), 1,1'-biphenyl-4. , 4'-diol 279.3 g (1.50 mol), 2,2', 3,3', 5,5'-hexamethyl-1,1'-biphenyl-4,4'-diol 135.2 g ( 0.50 mol), terephthalic acid 332.3 g (2.00 mol), anhydrous acetic acid 1123.0 (11.00 mol) and 1-methylimidazole 0.056 g as a catalyst were added, and the temperature was raised with stirring. .. When the internal temperature reached 140 ° C., the mixture was stirred for 1 hour while maintaining 140 ° C.
　次に、留出する副生酢酸、未反応の無水酢酸を留去しながら、１４０℃から３００℃まで５時間７分かけて昇温した。３００℃で１時間保温して全芳香族ポリエステル樹脂を得た。得られた全芳香族ポリエステル樹脂を室温に冷却し、粉砕機で粉砕して、全芳香族ポリエステル樹脂の粉末（粒子径は約０．１ｍｍ～約２ｍｍ）を得た。
　この粉末（全芳香族ポリエステル樹脂）の流動開始温度を測定したところ、２３３℃であった。 Next, the temperature was raised from 140 ° C. to 300 ° C. over 5 hours and 7 minutes while distilling off distillate by-product acetic acid and unreacted acetic anhydride. The whole aromatic polyester resin was obtained by incubating at 300 ° C. for 1 hour. The obtained total aromatic polyester resin was cooled to room temperature and pulverized with a pulverizer to obtain a powder (particle size of about 0.1 mm to about 2 mm) of the total aromatic polyester resin.
The flow start temperature of this powder (total aromatic polyester resin) was measured and found to be 233 ° C.
　得られた粉末を２５℃から２３０℃まで１時間かけて昇温したのち、２３０℃から３１０℃まで１３時間２０分かけて昇温し、次いで３１０℃で５時間保温して固相重合させた。その後、固相重合した後の粉末を冷却し、冷却後の粉末（全芳香族ポリエステル樹脂、「ポリエステル樹脂５」）の流動開始温度を測定したところ、３３１℃であった。 The obtained powder was heated from 25 ° C. to 230 ° C. over 1 hour, then heated from 230 ° C. to 310 ° C. over 13 hours and 20 minutes, and then kept at 310 ° C. for 5 hours for solid phase polymerization. .. Then, the powder after solid-phase polymerization was cooled, and the flow start temperature of the cooled powder (total aromatic polyester resin, "polyester resin 5") was measured and found to be 331 ° C.
　＜比較例１＞
　攪拌装置、トルクメータ、窒素ガス導入管、温度計及び還流冷却器を備えた反応器に、６－ヒドロキシ－２－ナフトエ酸１０３５．０ｇ（５．５０モル）、ハイドロキノン２４７．７ｇ（２．２５モル）、テレフタル酸８３．１ｇ（０．５０モル）、２，６－ナフタレンジカルボン酸３７８．３ｇ（１．７５モル）、無水酢酸１１２３．０（１１．００モル）及び触媒としての１－メチルイミダゾール０．０５４ｇを添加し、攪拌しながら昇温した。内温が１４０℃となったところで、１４０℃を保持したまま３時間攪拌した。 <Comparative Example 1>
A reactor equipped with a stirrer, torque meter, nitrogen gas introduction tube, thermometer and reflux condenser, 6-hydroxy-2-naphthoic acid 1035.0 g (5.50 mol), hydroquinone 247.7 g (2.25). Mol), terephthalic acid 83.1 g (0.50 mol), 2,6-naphthalenedicarboxylic acid 378.3 g (1.75 mol), anhydrous acetate 1123.0 (11.00 mol) and 1-methyl as a catalyst. 0.054 g of imidazole was added, and the temperature was raised while stirring. When the internal temperature reached 140 ° C., the mixture was stirred for 3 hours while maintaining 140 ° C.
　次に、留出する副生酢酸、未反応の無水酢酸を留去しながら、１４０℃から３００℃まで５時間かけて昇温した。３００℃で１時間３０分保温して全芳香族ポリエステル樹脂を得た。得られた全芳香族ポリエステル樹脂を室温に冷却し、粉砕機で粉砕して、全芳香族ポリエステル樹脂の粉末（粒子径は約０．１ｍｍ～約２ｍｍ）を得た。
　この粉末（全芳香族ポリエステル樹脂）の流動開始温度を測定したところ、２５０℃であった。 Next, the temperature was raised from 140 ° C. to 300 ° C. over 5 hours while distilling off distillate by-product acetic acid and unreacted acetic anhydride. The whole aromatic polyester resin was obtained by incubating at 300 ° C. for 1 hour and 30 minutes. The obtained total aromatic polyester resin was cooled to room temperature and pulverized with a pulverizer to obtain a powder (particle size of about 0.1 mm to about 2 mm) of the total aromatic polyester resin.
The flow start temperature of this powder (total aromatic polyester resin) was measured and found to be 250 ° C.
　得られた粉末を２５℃から２４０℃まで１時間かけて昇温したのち、２４０℃から２８５℃まで５時間４６分かけて昇温し、次いで２８５℃で５時間保温して固相重合させた。その後、固相重合した後の粉末を冷却し、冷却後の粉末（全芳香族ポリエステル樹脂、「ポリエステル樹脂６」）の流動開始温度を測定したところ、３２０℃であった。 The obtained powder was heated from 25 ° C. to 240 ° C. over 1 hour, then heated from 240 ° C. to 285 ° C. over 5 hours and 46 minutes, and then kept warm at 285 ° C. for 5 hours for solid phase polymerization. .. Then, the powder after solid-phase polymerization was cooled, and the flow start temperature of the cooled powder (total aromatic polyester resin, "polyester resin 6") was measured and found to be 320 ° C.
　＜比較例２＞
　攪拌装置、トルクメータ、窒素ガス導入管、温度計及び還流冷却器を備えた反応器に、６－ヒドロキシ－２－ナフトエ酸１１２９．１ｇ（６．００モル）、１，１’－ビフェニル－４，４’－ジオール３７２．４ｇ（２．００モル）、テレフタル酸３３２．３ｇ（２．００モル）、無水酢酸１１２０．０（１１．００モル）及び触媒としての１－メチルイミダゾール０．０５５ｇを添加し、攪拌しながら昇温した。内温が１４０℃となったところで、１４０℃を保持したまま１時間攪拌した。 <Comparative Example 2>
A reactor equipped with a stirrer, torque meter, nitrogen gas introduction tube, thermometer and reflux condenser, 6-hydroxy-2-naphthoic acid 1129.1 g (6.00 mol), 1,1'-biphenyl-4. , 4'-diol 372.4 g (2.00 mol), terephthalic acid 332.3 g (2.00 mol), anhydrous acetic acid 1120.0 (11.00 mol) and 1-methylimidazole 0.055 g as a catalyst. The temperature was raised while adding and stirring. When the internal temperature reached 140 ° C., the mixture was stirred for 1 hour while maintaining 140 ° C.
　次に、留出する副生酢酸、未反応の無水酢酸を留去しながら、１４０℃から３００℃まで４時間かけて昇温した。３００℃で２時間保温して全芳香族ポリエステル樹脂を得た。得られた全芳香族ポリエステル樹脂を室温に冷却し、粉砕機で粉砕して、全芳香族ポリエステル樹脂の粉末（粒子径は約０．１ｍｍ～約２ｍｍ）を得た。
　この粉末（全芳香族ポリエステル樹脂）の流動開始温度を測定したところ、２５２℃であった。 Next, the temperature was raised from 140 ° C. to 300 ° C. over 4 hours while distilling off distillate by-product acetic acid and unreacted acetic anhydride. The whole aromatic polyester resin was obtained by incubating at 300 ° C. for 2 hours. The obtained total aromatic polyester resin was cooled to room temperature and pulverized with a pulverizer to obtain a powder (particle size of about 0.1 mm to about 2 mm) of the total aromatic polyester resin.
The flow start temperature of this powder (total aromatic polyester resin) was measured and found to be 252 ° C.
　得られた粉末を２５℃から２３０℃まで１時間かけて昇温したのち、２３０℃から３０４℃まで１２時間２０分かけて昇温し、次いで３０４℃で５時間保温して固相重合させた。その後、固相重合した後の粉末を冷却し、冷却後の粉末（全芳香族ポリエステル樹脂、「ポリエステル樹脂７」）の流動開始温度を測定したところ、３３０℃であった。 The obtained powder was heated from 25 ° C. to 230 ° C. over 1 hour, then heated from 230 ° C. to 304 ° C. over 12 hours and 20 minutes, and then kept at 304 ° C. for 5 hours for solid phase polymerization. .. Then, the powder after solid-phase polymerization was cooled, and the flow start temperature of the cooled powder (total aromatic polyester resin, "polyester resin 7") was measured and found to be 330 ° C.
　表１に、ポリエステル樹脂１～７の製造に使用したモノマーの組成を示す（単位：モル％）。また同表に、後述する方法によって測定したポリエステル樹脂１～７の流動開始温度を示す。 Table 1 shows the composition of the monomers used in the production of the polyester resins 1 to 7 (unit: mol%). The table also shows the flow start temperatures of the polyester resins 1 to 7 measured by the method described later.
　表１に示される略称の詳細は次のとおりである。
　ＢＯＮ：６－ヒドロキシ－２－ナフトエ酸
　ＴＭＨＱ：２，３，５－トリメチルハイドロキノン
　ＴＭＰ－ＢＰ：２，２，’，３，３’，５，５’－ヘキサメチル－１，１’－ビフェニル－４，４’－ジオール
　ＴＰＡ：テレフタル酸
　ＮＤＣＡ：２，６－ナフタレンジカルボン酸
　ＨＱ：ハイドロキノン
　ＤＯＤ：１，１’－ビフェニル－４，４’－ジオール The details of the abbreviations shown in Table 1 are as follows.
BON: 6-hydroxy-2-naphthoic acid TMHQ: 2,3,5-trimethylhydroquinone TMP-BP: 2,2', 3,3', 5,5'-hexamethyl-1,1'-biphenyl-4 , 4'-diol TPA: terephthalic acid NDCA: 2,6-naphthalenedicarboxylic acid HQ: hydroquinone DOD: 1,1'-biphenyl-4,4'-diol
　〔測定〕
　ポリエステル樹脂１～７について次の測定を行った。測定結果を表１に示す。
　（１）流動開始温度
　４℃／分の昇温速度で加熱溶融されたポリエステル樹脂を、荷重９．８ＭＰａの荷重下、内径１ｍｍ、長さ１０ｍｍのノズルから押し出したときに、毛細管型レオメータを用いて測定される溶融粘度が４８００Ｐａ・ｓを示す温度を測定し、これを流動開始温度とした。 〔measurement〕
The following measurements were made on the polyester resins 1 to 7. The measurement results are shown in Table 1.
(1) When a polyester resin heated and melted at a flow start temperature of 4 ° C./min is extruded from a nozzle having an inner diameter of 1 mm and a length of 10 mm under a load of 9.8 MPa, a capillary rheometer is used. The temperature at which the melt viscosity measured was 4800 Pa · s was measured, and this was taken as the flow start temperature.
　（２）ＴＤ成形収縮率（成形時のＴＤにおける収縮率）
　粉末状のポリエステル樹脂６０質量部に対して、ミルドガラスファイバー（セントラル　グラス　ファイバー（株）製　ＥＦＨ７５－０１）４０質量部を混合し、同方向２軸押出機（池貝鉄工（株）製　ＰＣＭ－３０）を用いて粉末状のポリエステル樹脂の流動開始温度＋１５℃の温度にて溶融混練し、ストランド状に押し出し、冷却後、裁断して、ペレット状のポリエステル樹脂組成物を得た。 (2) TD molding shrinkage rate (shrinkage rate in TD during molding)
40 parts by mass of milled glass fiber (EFH75-01 manufactured by Central Glass Fiber Co., Ltd.) is mixed with 60 parts by mass of powdered polyester resin, and a biaxial extruder in the same direction (PCM-30 manufactured by Ikekai Iron Works Co., Ltd.) is mixed. ) Was melt-kneaded at a temperature of + 15 ° C., which is the flow start temperature of the powdery polyester resin, extruded into a strand shape, cooled, and then cut to obtain a pellet-shaped polyester resin composition.
　得られたポリエステル樹脂組成物を、日精樹脂工業（株）製　ＰＳ４０５ＡＳＥ型射出成型機を用いて、シリンダー温度を粉末状のポリエステル樹脂の流動開始温度＋２０℃、金型温度を１３０℃の条件で射出成形して作製した６４ｍｍ（ＭＤ）×６４ｍｍ（ＴＤ）×３ｍｍ（厚み）の平板状試験片（以下、「成形品」と称することがある。）について、ＴＤの２辺の長さを測定し、その平均値を求め、この平均値と、金型キャビティのＴＤの長さとから、下記式によりＴＤ成形収縮率を算出した。ここで、ＭＤは、射出成形時におけるポリエステル樹脂組成物の流れ方向を表し、ＴＤは、ポリエステル樹脂組成物の流れ方向に対して垂直な方向を表す。
　ＴＤ成形収縮率（％）＝（［金型キャビティのＴＤの長さ（μｍ）］－［成形品のＴＤの２辺の長さの平均値（μｍ）］）／［金型キャビティのＴＤの長さ（μｍ）］×１００ The obtained polyester resin composition is injected using a PS405ASE type injection molding machine manufactured by Nissei Resin Industry Co., Ltd. under the conditions that the cylinder temperature is the flow start temperature of the powdered polyester resin + 20 ° C. and the mold temperature is 130 ° C. The lengths of two sides of the TD of a 64 mm (MD) × 64 mm (TD) × 3 mm (thickness) flat plate-shaped test piece (hereinafter, may be referred to as a “molded product”) produced by molding were measured. , The average value was obtained, and the TD molding shrinkage rate was calculated from the average value and the length of the TD of the mold cavity by the following formula. Here, MD represents the flow direction of the polyester resin composition at the time of injection molding, and TD represents the direction perpendicular to the flow direction of the polyester resin composition.
TD molding shrinkage rate (%) = ([Mold cavity TD length (μm)]-[Average value of two sides of molded product TD (μm)]) / [Mold cavity TD Length (μm)] x 100
　（３）引張強度及び引張伸び
　粉末状のポリエステル樹脂６０質量部に対して、ミルドガラスファイバー（セントラル　グラス　ファイバー（株）製　ＥＦＨ７５－０１）４０質量部を混合し、同方向２軸押出機（池貝鉄工（株）製　ＰＣＭ－３０）を用いて粉末状のポリエステル樹脂の流動開始温度＋１５℃の温度にて溶融混練し、ストランド状に押し出し、冷却後、裁断して、ペレット状の芳香族ポリエステル組成物を得た。
　得られたポリエステル樹脂組成物を、日精樹脂工業（株）製　ＰＳ４０５ＡＳＥ型射出成型機を用いて、シリンダー温度を粉末状のポリエステル樹脂の流動開始温度＋２０℃、金型温度を１３０℃の条件で射出成形してＡＳＴＭ　４号ダンベルを作製し、ＡＳＴＭ　Ｄ６３８に準拠して２３℃における引張強度及び引張伸びを測定した。 (3) Tensile strength and tensile elongation 40 parts by mass of milled glass fiber (EFH75-01 manufactured by Central Glass Fiber Co., Ltd.) is mixed with 60 parts by mass of powdered polyester resin, and a biaxial extruder in the same direction (Ikekai). Using PCM-30) manufactured by Iron Works Co., Ltd., the powdery polyester resin is melt-kneaded at the flow start temperature of + 15 ° C., extruded into strands, cooled, and then cut to form a pellet-shaped aromatic polyester composition. I got something.
The obtained polyester resin composition is injected using a PS405ASE type injection molding machine manufactured by Nissei Resin Industry Co., Ltd. under the conditions that the cylinder temperature is the flow start temperature of the powdered polyester resin + 20 ° C. and the mold temperature is 130 ° C. A STM No. 4 dumbbell was formed by molding, and the tensile strength and tensile elongation at 23 ° C. were measured according to ATM D638.
　（４）曲げ強度
　粉末状のポリエステル樹脂６０質量部に対して、ミルドガラスファイバー（セントラル　グラス　ファイバー（株）製　ＥＦＨ７５－０１）４０質量部を混合し、同方向２軸押出機（池貝鉄工（株）製　ＰＣＭ－３０）を用いて粉末状のポリエステル樹脂の流動開始温度＋１５℃の温度にて溶融混練し、ストランド状に押し出し、冷却後、裁断して、ペレット状の芳香族ポリエステル組成物を得た。
　得られたポリエステル樹脂組成物を、日精樹脂工業（株）製　ＰＳ４０５ＡＳＥ型射出成型機を用いて、シリンダー温度を粉末状のポリエステル樹脂の流動開始温度＋２０℃、金型温度を１３０℃の条件で射出成形して作製した１２７ｍｍ（長さ）×１２．７ｍｍ（幅）×６．４ｍｍ（厚み）の試験片の２３℃での曲げ強度を、ＡＳＴＭ　Ｄ７９０に準拠して測定した。 (4) Bending strength 40 parts by mass of milled glass fiber (EFH75-01 manufactured by Central Glass Fiber Co., Ltd.) is mixed with 60 parts by mass of powdered polyester resin, and a twin-screw extruder in the same direction (Ikekai Iron Works Co., Ltd.) ) Made of PCM-30), melt-kneaded the powdery polyester resin at the flow start temperature + 15 ° C., extruded into strands, cooled, and cut to obtain a pellet-shaped aromatic polyester composition. rice field.
The obtained polyester resin composition is injected using a PS405ASE type injection molding machine manufactured by Nissei Resin Industry Co., Ltd. under the conditions that the cylinder temperature is the flow start temperature of the powdered polyester resin + 20 ° C. and the mold temperature is 130 ° C. The bending strength of the 127 mm (length) × 12.7 mm (width) × 6.4 mm (thickness) test piece produced by molding at 23 ° C. was measured according to ASTM D790.
　（５）Ｉｚｏｄ衝撃強度
　粉末状のポリエステル樹脂６０質量部に対して、ミルドガラスファイバー（セントラル　グラス　ファイバー（株）製　ＥＦＨ７５－０１）４０質量部を混合し、同方向２軸押出機（池貝鉄工（株）製　ＰＣＭ－３０）を用いて粉末状のポリエステル樹脂の流動開始温度＋１５℃の温度にて溶融混練し、ストランド状に押し出し、冷却後、裁断して、ペレット状の芳香族ポリエステル組成物を得た。
　得られたポリエステル樹脂組成物を、日精樹脂工業（株）製　ＰＳ４０５ＡＳＥ型射出成型機を用いて、シリンダー温度を粉末状のポリエステル樹脂の流動開始温度＋２０℃、金型温度を１３０℃の条件で射出成形して作製した６４ｍｍ（長さ）×１２．７ｍｍ（幅）×６．４ｍｍ（厚み）の試験片（ノッチなし）の２３℃でのＩｚｏｄ衝撃強度を、ＡＳＴＭ　Ｄ２５６に準拠して測定した。 (5) Izod Impact Strength 40 parts by mass of milled glass fiber (EFH75-01 manufactured by Central Glass Fiber Co., Ltd.) is mixed with 60 parts by mass of powdered polyester resin, and a twin-screw extruder in the same direction (Ikekai Iron Works (Ikekai Iron Works) Using PCM-30) manufactured by PCM-30), melt-kneaded the powdery polyester resin at the flow start temperature of + 15 ° C., extrude it into strands, cool it, and cut it to obtain a pellet-shaped aromatic polyester composition. Obtained.
The obtained polyester resin composition is injected using a PS405ASE type injection molding machine manufactured by Nissei Resin Industry Co., Ltd. under the conditions that the cylinder temperature is the flow start temperature of the powdery polyester resin + 20 ° C. and the mold temperature is 130 ° C. The Izod impact strength of a molded 64 mm (length) × 12.7 mm (width) × 6.4 mm (thickness) test piece (without notch) at 23 ° C. was measured according to ASTM D256.
　（６）荷重たわみ温度
　粉末状のポリエステル樹脂６０質量部に対して、ミルドガラスファイバー（セントラル　グラス　ファイバー（株）製　ＥＦＨ７５－０１）４０質量部を混合し、同方向２軸押出機（池貝鉄工（株）製　ＰＣＭ－３０）を用いて粉末状のポリエステル樹脂の流動開始温度＋１５℃の温度にて溶融混練し、ストランド状に押し出し、冷却後、裁断して、ペレット状の芳香族ポリエステル組成物を得た。
　得られたポリエステル樹脂組成物を、日精樹脂工業（株）製　ＰＳ４０５ＡＳＥ型射出成型機を用いて、シリンダー温度を粉末状のポリエステル樹脂の流動開始温度＋２０℃、金型温度を１３０℃の条件で射出成形して作製した１２．７ｍｍ（長さ）×１２．７ｍｍ（幅）×６．４ｍｍ（厚み）の試験片の荷重たわみ温度を、ＡＳＴＭ　Ｄ６４８に準拠し、１．８２ＭＰａの荷重、昇温速度２℃／分で測定した。 (6) Deflection temperature under load 40 parts by mass of milled glass fiber (EFH75-01 manufactured by Central Glass Fiber Co., Ltd.) is mixed with 60 parts by mass of powdered polyester resin, and a twin-screw extruder in the same direction (Ikekai Iron Works (Ikekai Iron Works) Using PCM-30) manufactured by PCM-30), the powdery polyester resin is melt-kneaded at a temperature of + 15 ° C., extruded into strands, cooled, and then cut to obtain a pellet-shaped aromatic polyester composition. Obtained.
The obtained polyester resin composition is injected using a PS405ASE type injection molding machine manufactured by Nissei Resin Industry Co., Ltd. under the conditions that the cylinder temperature is the flow start temperature of the powdered polyester resin + 20 ° C and the mold temperature is 130 ° C. The deflection temperature under load of a 12.7 mm (length) x 12.7 mm (width) x 6.4 mm (thickness) test piece produced by molding is based on ASTM D648, with a load of 1.82 MPa and a heating rate. It was measured at 2 ° C./min.
　（７）誘電正接及び誘電率
　ポリエステル樹脂を（流動開始温度＋２０）℃の条件で熱プレスし、直径１ｃｍ、厚み２ｍｍの錠剤に成形した。得られた錠剤サンプルを用い、下記条件にて１ＧＨｚにおける誘電正接及び誘電率を測定した。
　測定装置：インピーダンスアナライザー（Ａｇｉｌｅｎｔ社製　型式：Ｅ４９９１Ａ）
　測定方法：容量法
　電極型式：１６４５３Ａ
　測定環境：２３℃、５０％ＲＨ
　印加電圧：１Ｖ (7) Dielectric Dissipation Factor and Dielectric Permittivity The polyester resin was hot-pressed under the condition of (flow start temperature +20) ° C. to form a tablet having a diameter of 1 cm and a thickness of 2 mm. Using the obtained tablet sample, the dielectric loss tangent and the dielectric constant at 1 GHz were measured under the following conditions.
Measuring device: Impedance analyzer (Agilent model: E4991A)
Measurement method: Capacitive method Electrode model: 16453A
Measurement environment: 23 ° C, 50% RH
Applied voltage: 1V
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007

Claims (7)

  1. 　下記式（Ｉ）で表される構成単位と、
    　下記式（ＩＩａ）で表される構成単位及び下記式（ＩＩｂ）で表される構成単位からなる群より選択される少なくとも１種の構成単位と、
    　下記式（ＩＩＩ）で表される構成単位と、
    を含む、全芳香族ポリエステル樹脂。
    Figure JPOXMLDOC01-appb-C000001
    ［式（ＩＩＩ）中、Ａｒ１は、１，４－フェニレン基、１，３－フェニレン基及び２，６－ナフタレンジイル基からなる群より選択される少なくとも１種の基を表す。］     The structural unit represented by the following formula (I) and
    At least one structural unit selected from the group consisting of the structural unit represented by the following formula (IIa) and the structural unit represented by the following formula (IIb), and
    The structural unit represented by the following formula (III) and
    All aromatic polyester resin, including.
    Figure JPOXMLDOC01-appb-C000001
    [In formula (III), Ar 1 represents at least one group selected from the group consisting of 1,4-phenylene group, 1,3-phenylene group and 2,6-naphthalenediyl group. ]
  2. 　下記式（ＩＶａ）で表される構成単位及び下記式（ＩＶｂ）で表される構成単位からなる群より選択される少なくとも１種の構成単位をさらに含む、請求項１に記載の全芳香族ポリエステル樹脂。
    Figure JPOXMLDOC01-appb-C000002
         The total aromatic polyester according to claim 1, further comprising at least one structural unit selected from the group consisting of the structural unit represented by the following formula (IVa) and the structural unit represented by the following formula (IVb). resin.
    Figure JPOXMLDOC01-appb-C000002
  3. 　前記式（Ｉ）で表される構成単位、前記式（ＩＩａ）で表される構成単位、前記式（ＩＩｂ）で表される構成単位、前記式（ＩＩＩ）で表される構成単位、前記式（ＩＶａ）で表される構成単位及び前記式（ＩＶｂ）で表される構成単位の合計含有率を１００モル％とするとき、
    　前記式（Ｉ）で表される構成単位の含有率が５０モル％以上８０モル％以下であり、
    　前記式（ＩＩａ）で表される構成単位及び前記式（ＩＩｂ）で表される構成単位の合計含有率が０．１モル％以上１０モル％以下であり、
    　前記式（ＩＩＩ）で表される構成単位の含有率が１０モル％以上２５モル％以下であり、
    　前記式（ＩＶａ）で表される構成単位及び前記式（ＩＶｂ）で表される構成単位の合計含有率が５モル％以上２０モル％以下である、請求項２に記載の全芳香族ポリエステル樹脂。     The structural unit represented by the formula (I), the structural unit represented by the formula (IIa), the structural unit represented by the formula (IIb), the structural unit represented by the formula (III), and the formula. When the total content of the structural unit represented by (IVa) and the structural unit represented by the above formula (IVb) is 100 mol%.
    The content of the structural unit represented by the formula (I) is 50 mol% or more and 80 mol% or less.
    The total content of the structural unit represented by the formula (IIa) and the structural unit represented by the formula (IIb) is 0.1 mol% or more and 10 mol% or less.
    The content of the structural unit represented by the formula (III) is 10 mol% or more and 25 mol% or less.
    The total aromatic polyester resin according to claim 2, wherein the total content of the structural unit represented by the formula (IVa) and the structural unit represented by the formula (IVb) is 5 mol% or more and 20 mol% or less. ..
  4. 　４℃／分の昇温速度で加熱溶融された前記全芳香族ポリエステル樹脂を、９．８ＭＰａの荷重下、内径１ｍｍ、長さ１０ｍｍのノズルから押し出したときに、毛細管型レオメータを用いて測定される溶融粘度が４８００Ｐａ・ｓを示す温度が２９０℃以上３５０℃以下である、請求項１～３のいずれか１項に記載の全芳香族ポリエステル樹脂。 When the all-aromatic polyester resin heated and melted at a temperature rise rate of 4 ° C./min was extruded from a nozzle having an inner diameter of 1 mm and a length of 10 mm under a load of 9.8 MPa, it was measured using a capillary rheometer. The fully aromatic polyester resin according to any one of claims 1 to 3, wherein the temperature at which the melt viscosity is 4800 Pa · s is 290 ° C. or higher and 350 ° C. or lower.
  5. 　請求項１～４のいずれか１項に記載の全芳香族ポリエステル樹脂１００質量部と、
    　充填剤１０質量部以上７０質量部以下と、
    を含む、樹脂組成物。     100 parts by mass of the total aromatic polyester resin according to any one of claims 1 to 4.
    10 parts by mass or more and 70 parts by mass or less of the filler,
    A resin composition comprising.
  6. 　請求項１～４のいずれか１項に記載の全芳香族ポリエステル樹脂又は請求項５に記載の樹脂組成物を含む、成形品。 A molded product containing the all-aromatic polyester resin according to any one of claims 1 to 4 or the resin composition according to claim 5.
  7. 　フィルムである、請求項６に記載の成形品。 The molded product according to claim 6, which is a film.
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JPS6357633A (en) * 1986-08-28 1988-03-12 バスフ　アクチェンゲゼルシャフト Fully aromatic thermotropic polyester
JPS63182335A (en) * 1987-01-14 1988-07-27 ビーエーエスエフ　アクチェンゲゼルシャフト Fully aromatic thermotropic polyester
JPH04337320A (en) * 1991-05-14 1992-11-25 Mitsubishi Petrochem Co Ltd Fully aromatic polyester
JPH05331267A (en) * 1992-06-04 1993-12-14 Mitsubishi Petrochem Co Ltd Wholly aromatic polyester
JP2004013068A (en) * 2002-06-11 2004-01-15 Canon Inc Electrophotographic photoreceptor, processing cartridge, and electrophotographic device
JP2018185373A (en) * 2017-04-24 2018-11-22 キヤノン株式会社 Electrophotographic photoreceptor, process cartridge, and electrophotographic device

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7156814B2 (en) 2018-04-24 2022-10-19 上野製薬株式会社 Liquid crystalline polyester resin with excellent mechanical and dielectric properties

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6357633A (en) * 1986-08-28 1988-03-12 バスフ　アクチェンゲゼルシャフト Fully aromatic thermotropic polyester
JPS63182335A (en) * 1987-01-14 1988-07-27 ビーエーエスエフ　アクチェンゲゼルシャフト Fully aromatic thermotropic polyester
JPH04337320A (en) * 1991-05-14 1992-11-25 Mitsubishi Petrochem Co Ltd Fully aromatic polyester
JPH05331267A (en) * 1992-06-04 1993-12-14 Mitsubishi Petrochem Co Ltd Wholly aromatic polyester
JP2004013068A (en) * 2002-06-11 2004-01-15 Canon Inc Electrophotographic photoreceptor, processing cartridge, and electrophotographic device
JP2018185373A (en) * 2017-04-24 2018-11-22 キヤノン株式会社 Electrophotographic photoreceptor, process cartridge, and electrophotographic device

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