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WO2025121326A1 - Polyester resin composition, method for producing same, and molded body - Google Patents

Polyester resin composition, method for producing same, and molded body Download PDF

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Publication number
WO2025121326A1
WO2025121326A1 PCT/JP2024/042735 JP2024042735W WO2025121326A1 WO 2025121326 A1 WO2025121326 A1 WO 2025121326A1 JP 2024042735 W JP2024042735 W JP 2024042735W WO 2025121326 A1 WO2025121326 A1 WO 2025121326A1
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WO
WIPO (PCT)
Prior art keywords
polyester resin
mass
component
resin composition
content
Prior art date
Legal status (The legal status 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 status listed.)
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PCT/JP2024/042735
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French (fr)
Japanese (ja)
Inventor
真之 大石
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Toagosei Co Ltd
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Toagosei Co Ltd
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Publication of WO2025121326A1 publication Critical patent/WO2025121326A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters

Definitions

  • This disclosure relates to a polyester resin composition, a method for producing the same, and a molded article.
  • Synthetic fibers such as polyester, nylon, and acrylic are widely used for clothing, industrial materials, bedding, and other purposes due to their excellent properties such as heat resistance and chemical resistance.
  • fibers that have been provided with deodorizing functions against sweat odor, aging odor, fatigue odor, and the like have been distributed.
  • resin compositions in which a tetravalent metal phosphate compound, which is used as a deodorizer for quickly deodorizing basic gases such as ammonia, which are the causative substances of sweat odor and fatigue odor, is mixed into a resin, and deodorizing fibers that are melt-spun using the resin compositions.
  • Various proposals have been made with the aim of imparting functionality and improving the properties of these resin compositions and deodorizing fibers.
  • Patent Document 1 discloses a method for producing functional yarn using a masterbatch made of a polyester with an intrinsic viscosity of 0.70 to 0.95 dL/g and a blend amount of zirconium phosphate.
  • Patent Document 2 also discloses an eccentric sheath-core type antibacterial composite polyester fiber and its preparation method, including a nano antibacterial masterbatch manufacturing process in which a resin composition is made by pre-kneading a specified amount of an antibacterial agent containing silver-loaded zirconium phosphate and polytrimethylene terephthalate (PTT polyester) at a kneading temperature of 60°C to 150°C for 30 to 120 minutes, and then melt-blending the resulting resin composition in a twin-screw extruder.
  • a nano antibacterial masterbatch manufacturing process in which a resin composition is made by pre-kneading a specified amount of an antibacterial agent containing silver-loaded zirconium phosphate and polytrimethylene terephthalate (PTT polyester) at a kneading temperature of 60°C to 150°C for 30 to 120 minutes, and then melt-blending the resulting resin composition in a twin-screw extruder.
  • PTT polyester polyt
  • a polyester resin composition comprising: (Component A) a tetravalent metal phosphate compound satisfying the following (a-1) and (a-2); (Component B) a polyester resin satisfying the following (b-1) and (b-2); and (Component C) a dispersant, in which the content of Component A is 40% by mass to 72% by mass, based on the total mass of the composition, the content of Component B is 25% by mass to 50% by mass, and the content of Component C is 3% by mass to 25% by mass, based on the total mass of the composition.
  • (a-1) A compound represented by the following formula (1): MH a (PO 4 ) b ⁇ nH 2 O (1)
  • M represents one or more tetravalent metals
  • (a-2) has a median diameter (D 50 ) of 1.5 ⁇ m or less
  • (b-1) is crystalline
  • (b-2) is copolymerized with one or more monomers other than terephthalic acid and ethylene glycol.
  • a polyester resin composition comprising: (Component A) a tetravalent metal phosphate compound that satisfies the following (a-1) and (a-2); (Component B) a polyester resin that satisfies the following (b-1) and (b-2); (Component C) a dispersant; and (Component D) a polyester resin that satisfies the following (d-1), wherein the content of Component A is 0.4% by mass to 30% by mass, relative to the total mass of the composition, the content of Component B is 7% by mass to 35% by mass, relative to the total mass of the composition, the content of Component C is 0.1% by mass to 11% by mass, and the content of Component D is 37% by mass to 83.6% by mass, relative to the total mass of the composition.
  • (a-1) A compound represented by the following formula (1): MH a (PO 4 ) b ⁇ nH 2 O (1)
  • M represents one or more tetravalent metals
  • (a-2) the median diameter ( D50 ) is 1.5 ⁇ m or less;
  • (b-1) the component is crystalline;
  • (d-1) the component has a melting point of 240° C. or more as measured by a differential scanning calorimeter.
  • ⁇ 3> The polyester resin composition according to ⁇ 1> or ⁇ 2>, wherein component C is a dispersant having a polar group in its molecular structure.
  • component C is a dispersant having a polar group in its molecular structure.
  • the polar group is at least one group selected from the group consisting of an ester group, an ether group, a hydroxyl group, and an imino group.
  • component D satisfies the following (d-2): (d-2) An intrinsic viscosity (IV) of 0.6 dL/g or more.
  • component B contains a polyester resin that satisfies the following (b-3): (b-3) A melting point measured by a differential scanning calorimeter is 200° C. or less.
  • a polyester resin composition comprising a tetravalent metal phosphate compound and a polyester resin, wherein in a cross-sectional SEM image of the polyester resin composition having a field of view size of 0.4 mm x 0.3 mm, the number of particles of the tetravalent metal phosphate compound having a particle size of 20 ⁇ m2 or more is less than 1.
  • ⁇ 11> The polyester resin composition according to ⁇ 9> or ⁇ 10>, wherein the number of particles having a particle size of 2 ⁇ m2 or more of the tetravalent metal phosphate compound is 10 or less.
  • ⁇ 12> The polyester resin composition according to any one of ⁇ 1> to ⁇ 11>, further comprising an additional polyester resin different from the polyester resin in addition to the polyester resin.
  • ⁇ 13> A molded article obtained by molding the polyester resin composition according to ⁇ 12>.
  • ⁇ 14> The molded article according to ⁇ 13>, wherein the molding process is melt spinning.
  • ⁇ 15> A molded article obtained by subjecting the molded article according to ⁇ 13> to advanced processing.
  • ⁇ 16> The molded article according to ⁇ 15>, which is a woven fabric or a nonwoven fabric.
  • a method for producing a polyester resin composition comprising a step of kneading (component A) a tetravalent metal phosphate compound that satisfies the following (a-1) and (a-2), (component B) a polyester resin that satisfies the following (b-1) and (b-2), and (component C) a dispersant by batch kneading means to obtain a polyester resin composition a, in which the content of component A is 40% by mass to 72% by mass, the content of component B is 25% by mass to 50% by mass, and the content of component C is 3% by mass to 25% by mass, relative to the total mass of the composition.
  • (a-1) A compound represented by the following formula (1): MH a (PO 4 ) b ⁇ nH 2 O (1)
  • M represents one or more tetravalent metals
  • (a-2) the median diameter (D 50 ) is 1.5 ⁇ m or less
  • (b-1) the polyester is crystalline
  • (a-1) A compound represented by the following formula (1): MH a (PO 4 ) b ⁇ nH 2 O (1)
  • M represents one or more tetravalent metals
  • (a-2) the median diameter (D 50 ) is 1.5 ⁇ m or less;
  • (b-1) the component is crystalline;
  • (b-3) the melting point measured by a differential scanning calorimeter is 200° C.
  • a polyester resin composition having excellent dispersibility of a tetravalent metal phosphate compound and a method for producing the same.
  • the present disclosure also provides a molded article using the polyester resin composition.
  • FIG. 1 is an SEM image of a cross section of a polyester resin composition pellet of Example 28 taken at 300x magnification.
  • FIG. 2 is an image obtained by subjecting the comparative SEM image of FIG. 1 to image analysis and binarization.
  • FIG. 3 is an SEM image of a cross section of the polyester resin composition pellet of Comparative Example 6 taken at 300x magnification.
  • FIG. 4 is an image obtained by subjecting the SEM image of FIG. 3 to image analysis and binarization.
  • a numerical range expressed using "to” means a range that includes the numerical values before and after "to” as the lower and upper limits.
  • the amount of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified.
  • the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages.
  • the upper or lower limit value of the numerical range may be replaced with a value shown in the examples. In this disclosure, combinations of preferred aspects are more preferred aspects.
  • each component may be used alone or in combination of two or more types.
  • dispersibility of the tetravalent metal phosphate compound in the present disclosure is used as a concept including the dispersibility and distribution of the compound. That is, in the present disclosure, dispersibility and distribution are collectively referred to simply as "dispersibility". Dispersibility means that individual tetravalent metal phosphate compound particles (primary particles) do not form coarse particles (secondary particles) by aggregation, but tend to be monodispersed, and distribution means that tetravalent metal phosphate particles tend to be uniformly present throughout the substrate of the polyester resin composition.
  • polyyester resin composition according to the present disclosure it refers to all of the first embodiment, the second embodiment, and the third embodiment described below.
  • a first embodiment of the polyester resin composition according to the present disclosure comprises (component A) a tetravalent metal phosphate compound satisfying the following (a-1) and (a-2), (component B) a polyester resin satisfying the following (b-1) and (b-2), and (component C) a dispersant, wherein the content of component A is 40% by mass to 72% by mass, the content of component B is 25% by mass to 50% by mass, and the content of component C is 3% by mass to 25% by mass, based on the total mass of the composition.
  • (a-1) A compound represented by the following formula (1): MH a (PO 4 ) b ⁇ nH 2 O (1)
  • M represents one or more tetravalent metals
  • (a-2) The median diameter (D 50 ) is 1.5 ⁇ m or less.
  • (b-1) It is crystalline.
  • (b-2) At least one monomer other than terephthalic acid and ethylene glycol is copolymerized.
  • a second embodiment of the polyester resin composition according to the present disclosure contains (component A) a tetravalent metal phosphate compound satisfying the following (a-1) and (a-2), (component B) a polyester resin satisfying the following (b-1) and (b-2), (component C) a dispersant, and (component D) a polyester resin satisfying the following (d-1), and the content of component A is 0.4% by mass to 30% by mass with respect to the total mass of the composition, the content of component B is 7% by mass to 35% by mass with respect to the total mass of the composition, the content of component C is 0.1% by mass to 11% by mass with respect to the total mass of the composition, and the content of component D is 37% by mass to 83.6% by mass with respect to the total mass of the composition.
  • (a-1) is a compound represented by the following formula (1): MH a (PO 4 ) b ⁇ nH 2 O (1)
  • M represents one or more tetravalent metals
  • (a-2) The median diameter (D 50 ) is 1.5 ⁇ m or less.
  • (b-1) It is crystalline.
  • (b-2) At least one monomer other than terephthalic acid and ethylene glycol is copolymerized.
  • (d-1) It has a melting point of 240° C. or more as measured by a differential scanning calorimeter.
  • a third embodiment of the polyester resin composition according to the present disclosure is a polyester resin composition comprising a tetravalent metal phosphate compound and a polyester resin, wherein in a cross-sectional SEM image of the polyester resin composition having a field of view size of 0.4 mm x 0.3 mm, the number of particles of the tetravalent metal phosphate compound represented by zirconium phosphate having a particle size of 20 ⁇ m 2 or more is less than 1.
  • the second and third embodiments of the polyester resin composition according to the present disclosure are preferably used as a so-called masterbatch.
  • the first embodiment of the polyester resin composition according to the present disclosure is preferably used as an intermediate for producing a masterbatch.
  • the second and third embodiments of the polyester resin composition according to the present disclosure are preferably produced using the first embodiment of the polyester resin composition according to the present disclosure from the viewpoint of dispersibility of the tetravalent metal phosphate compound.
  • component A or the like refers to all of the first embodiment, the second embodiment, and the third embodiment.
  • the present inventors have conducted detailed studies and have found that in the first or second embodiment of the polyester resin composition according to the present disclosure, coarse particles (secondary particles) which are aggregates of primary particles of a tetravalent metal phosphate compound are pulverized by shear and elongation energy during kneading, the primary particles of the tetravalent metal phosphate compound are uniformly dispersed, and the above-mentioned blending ratio is satisfied, whereby the surface of the tetravalent metal phosphate compound is thoroughly wetted and coated with the polyester resin, which is an organic substance, and a dispersant, thereby reducing the interfacial energy of the tetravalent metal phosphate compound and improving its affinity with the polyester resin.
  • the amount of coarse particles (secondary particles) which are aggregates of the primary particles of the tetravalent metal phosphate compound is sufficiently small, and it can be confirmed that the particles of the tetravalent metal phosphate compound represented by zirconium phosphate particles in the polyester resin composition have good dispersibility.
  • the size of the particles of the tetravalent metal phosphate compound contained in the polyester resin composition is small, in other words, the dispersibility of the particles of the tetravalent metal phosphate compound is good, and the aggregation of the particles of the tetravalent metal phosphate compound is suppressed, and the dispersibility of the tetravalent metal phosphate compound is excellent.
  • Particles of tetravalent metal phosphate compounds exhibit a deodorizing function in polyester resin compositions.
  • the particles of tetravalent metal phosphate compounds do not aggregate, and the number of particles with a particle size of 20 ⁇ m2 or more in the above viewing angle of the cross-sectional SEM image is less than one, and more preferably, the particle size of all particles in the cross-sectional SEM image is less than 20 ⁇ m2 , so that when the polyester resin composition is used for spinning, there is less thread breakage, and when the particles of tetravalent metal phosphate compounds are used at the same content, the surface area of the particles is increased, and the deodorizing effect is improved.
  • particles of a tetravalent metal phosphate compound such as zirconium phosphate, have ion adsorptive, antibacterial, antiviral, and antiallergenic properties, and similar functions are also exhibited in polyester resin compositions containing a tetravalent metal phosphate compound.
  • the first and second embodiments of the polyester resin composition according to the present disclosure contain (Component A) a tetravalent metal phosphate compound that satisfies the following (a-1) and (a-2).
  • a third embodiment of the polyester resin composition according to the present disclosure preferably contains (Component A) a tetravalent metal phosphate compound that satisfies the following (a-1) and (a-2).
  • (a-1) A compound represented by the following formula (1): MH a (PO 4 ) b ⁇ nH 2 O (1)
  • M represents one or more tetravalent metals
  • b represents a number greater than 2.0 and equal to or less than 2.1
  • n represents an integer of 0 to 2.
  • (a-2) The median diameter (D 50 ) is 1.5 ⁇ m or less.
  • M is a tetravalent metal, but from the viewpoint of dispersibility and deodorizing properties, it is preferably at least one tetravalent metal selected from the group consisting of zirconium, titanium, and hafnium, more preferably zirconium and hafnium, and particularly preferably Zr 1-x Hf x , where x represents a number from 0 to 0.2.
  • the b in formula (1) is 2 ⁇ b ⁇ 2.1, preferably 2.0 ⁇ b ⁇ 2.1, and more preferably 2.01 ⁇ b ⁇ 2.06.
  • the larger b is, that is, the more phosphoric acid there is, the higher the ion exchange performance is, but other physical properties such as the tendency for phosphate ions to dissolve are reduced.
  • n is 0 ⁇ n ⁇ 2, and n is preferably less than 1, more preferably 0.01 to 0.5, and even more preferably in the range of 0.03 to 0.3. If n exceeds 2, the absolute amount of water contained in the tetravalent metal phosphate compound is large, and there is a risk of foaming, hydrolysis, etc. occurring during processing, etc.
  • the compound represented by formula (1) is preferably a compound represented by formula (2) or (3) below, and more preferably a compound represented by formula (2) below.
  • X is 0 ⁇ n ⁇ 1
  • x is 0 ⁇ x ⁇ 1, preferably 0 ⁇ x ⁇ 0.2, more preferably 0.005 ⁇ x ⁇ 0.1, and even more preferably 0.005 ⁇ x ⁇ 0.03.
  • hafnium content improves ion exchange performance, but hafnium contains radioactive isotopes, so if it is used in electronic components, too much of it may have adverse effects.
  • the method for analyzing the composition formula of Component A in the present disclosure is not particularly limited, but can be measured, for example, by the following method. This is carried out by elemental analysis using X-ray fluorescence and hydration water analysis using thermogravimetric differential thermal analysis (TG-DTA).
  • TG-DTA thermogravimetric differential thermal analysis
  • X-ray fluorescence analysis is performed under the following conditions.
  • TG-DTA Thermogravimetric differential thermal analysis
  • TG-DTA Thermogravimetric-differential thermal analysis
  • zirconium phosphate include the following: Zr 0.99 Hf 0.01 H 2.03 (PO 4 ) 2.01 ⁇ 0.05H 2 O Zr 0.99 Hf 0.01 H 2.06 (PO 4 ) 2.02 ⁇ 0.05H 2 O Zr 0.99 Hf 0.01 H 2.12 (PO 4 ) 2.04 ⁇ 0.05H 2 O Zr 0.99 Hf 0.01 H 2.24 (PO 4 ) 2.08 ⁇ 0.05H 2 O Zr 0.98 Hf 0.02 H 2.03 (PO 4 ) 2.01 ⁇ 0.05H 2 O Zr 0.98 Hf 0.02 H 2.06 (PO 4 ) 2.02 ⁇ 0.05H 2 O Zr 0.98 Hf 0.02 H 2.12 (PO 4 ) 2.04 ⁇ 0.05H 2 O Zr 0.98 Hf 0.02 H 2.24 (PO 4 ) 2.08 ⁇ 0.05H 2 O Zr 0.97 Hf 0.03 H 2.03 (PO 4 ) 2.01 ⁇ 0.05H 2 O Zr 0.94 Hf 0.06 H 2.0
  • tetravalent metal phosphate compounds obtained by contacting an ⁇ -type, ⁇ -type, ⁇ -type or amorphous tetravalent metal phosphate compound having basic gas adsorption ability with a basic liquid of pH 9 or more and then contacting the compound with an acidic liquid of pH 6 or less, and more preferred are ⁇ -type tetravalent metal phosphate compounds.
  • the compound represented by formula (1) is a compound represented by formula (2)
  • the crystal structure of the compound represented by formula (2) is an ⁇ -type.
  • the method for measuring the crystal structure of component A in the present disclosure is not particularly limited, but can be evaluated, for example, by powder X-ray diffraction.
  • the X-ray diffraction apparatus used is a D8 ADVANCE manufactured by BRUKER.
  • An X-ray diffraction pattern is obtained using CuK ⁇ generated at an applied voltage of 40 kV and a current value of 40 mA using a Cu-encapsulated X-ray source.
  • the detailed measurement conditions are as follows.
  • X-ray source Enclosed X-ray source (Cu ray source), 0.4 x 12 mm 2 , Long Fine Focus Rating: 2.2kW Output power: 40kV-40mA (1.6kW) Goniometer radius: 280 mm
  • the median diameter (D 50 ) of component A is 1.5 ⁇ m or less, and from the viewpoint of deodorizing properties, it is preferably 1.0 ⁇ m or less, more preferably 0.1 ⁇ m to 1.0 ⁇ m, and even more preferably 0.2 ⁇ m to 0.8 ⁇ m.
  • the method for measuring the median size is not particularly limited, but can be measured, for example, by the following method.
  • a dispersion liquid containing particles to be measured such as a tetravalent metal phosphate compound, is dispersed for 5 minutes using an ultrasonic generator, and the particles are measured using a laser diffraction particle size distribution measuring device "Mastersizer 2000" (manufactured by Malvern Instruments), and the results are analyzed on a volume basis.
  • Dispersion medium Water Particle concentration: 1% by mass (1 g of tetravalent metal phosphate compound per 100 g of water) Particle refractive index: 2.4 Stirring: 2,450 rpm (revolutions per minute) Ultrasonic: 50% output x 1 minute repetition
  • the drying loss rate of component A is preferably 5.0 mass% or less, more preferably 3.0 mass% or less, even more preferably 1.0 mass% or less, and particularly preferably 0.5 mass% or less, relative to the total mass of component A.
  • the method for measuring the drying loss is not particularly limited, but it can be measured, for example, by JIS K0067:1992 (Testing method for weight loss and residue of chemical products) 4.1.1(1) Method 1.
  • the tetravalent metal phosphate compound is left to stand for 24 hours in a room at a temperature of 25°C and a humidity of 50%, and then heated at 250°C under normal pressure for 2 hours.
  • the masses before and after heating are measured, and the drying loss rate Y of the tetravalent metal phosphate compound is calculated from the following formula (4).
  • Drying reduction rate Y (mass%) ⁇ (B 0 - B 1 )/B 0 ⁇ 100 (4)
  • B 0 Mass of tetravalent metal phosphate compound before heating
  • B 1 Mass of tetravalent metal phosphate compound after heating
  • the content of component A in the first embodiment of the polyester resin composition according to the present disclosure is 40% by mass to 72% by mass relative to the total mass of the composition, and from the viewpoints of dispersibility, deodorizing properties, and moldability, is preferably 40% by mass to 63% by mass, and more preferably 45% by mass to 63% by mass.
  • the content of component A in the second embodiment of the polyester resin composition according to the present disclosure is 0.4% by mass to 30% by mass relative to the total mass of the composition, and from the viewpoints of dispersibility, deodorizing properties, and moldability, is preferably 0.8% by mass to 30% by mass, more preferably 1.2% by mass to 27% by mass, and even more preferably 2.0% by mass to 24% by mass.
  • the content of component A in the third embodiment of the polyester resin composition according to the present disclosure is preferably 0.4% by mass to 30% by mass, more preferably 0.8% by mass to 30% by mass, even more preferably 1.2% by mass to 27% by mass, and particularly preferably 2.0% by mass to 24% by mass, based on the total mass of the composition, from the viewpoints of dispersibility, deodorization, and moldability.
  • the method for identifying the type of resin from an unknown resin composition is not particularly limited, but examples thereof include a method using a Fourier transform infrared spectrometer (FT-IR) or nuclear magnetic resonance spectroscopy (hereinafter abbreviated as NMR).
  • FT-IR Fourier transform infrared spectrometer
  • NMR nuclear magnetic resonance spectroscopy
  • Methods for confirming the presence and amount of a tetravalent metal phosphate compound in an unknown resin composition include scanning electron microscope energy-dispersive X-ray spectroscopy (SEM-EDX) and ash measurement.
  • SEM-EDX scanning electron microscope energy-dispersive X-ray spectroscopy
  • An example of a measurement method using SEM-EDX is a method in which elemental analysis and composition analysis are performed using a SEM (“JSM-7900F” manufactured by JEOL Ltd.) and EDX (EDS, "ULTIM100 type energy dispersive X-ray microanalyzer” manufactured by Oxford Instruments) to confirm whether the particles are a tetravalent metal phosphate compound.
  • Ash content (residue mass ⁇ resin composition material amount) ⁇ 100
  • the first and second embodiments of the polyester resin composition according to the present disclosure contain a polyester resin (component B) that satisfies the following (b-1) and (b-2).
  • a polyester resin that satisfies the following (b-1) and (b-2) (Component B).
  • (b-1) It is crystalline.
  • (b-2) At least one monomer other than terephthalic acid and ethylene glycol is copolymerized.
  • Component B is a polyester resin which is crystalline and has a melting point.
  • the melting point of component B as measured by a differential scanning calorimeter (DSC) is preferably 200° C. or lower, more preferably 160° C. or lower, and even more preferably 100° C. to 160° C., from the viewpoints of dispersibility and suppression of thermal deterioration and hydrolysis of the polyester resin.
  • the melting point is measured using a differential scanning calorimeter (DSC), and the endothermic peak on the high temperature side in the second run (second temperature rise) is regarded as the melting point.
  • the differential scanning calorimeter is not particularly limited, but may be measured, for example, in accordance with JIS K7121.
  • the endothermic peak on the high temperature side in the 2nd RUN (at the second temperature rise) is regarded as the melting point.
  • DSC “DSC 214 Polyma” manufactured by NETZSCH -1st RUN- Heating rate: 10°C/min Measurement temperature: 30°C to 300°C Measurement atmosphere: Nitrogen Holding: 5 minutes after reaching 300°C Cooling rate: 30°C/min Cooling temperature: 300°C to 30°C -2nd RUN- Heating rate: 10°C/min Measurement temperature: 30°C to 300°C Measurement atmosphere: Nitrogen
  • Polyester resin is a polycondensation product mainly composed of polyvalent carboxylic acid components and polyhydric alcohol components.
  • Commercially available polyester resins include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), and polytrimethylene terephthalate (PTT), and can be used alone or in a blend of two or more types.
  • polycarboxylic acid component examples include alicyclic dicarboxylic acids such as terephthalic acid and their substituted derivatives. Although there are no particular limitations, examples include oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, anhydrides thereof, or lower alkyl esters thereof (e.g., carbon number 1 to 5
  • polyhydric alcohol components include aliphatic diols such as ethylene glycol and diethylene glycol, and alicyclic diols such as 1,4-cyclohexanedimethanol.
  • examples include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosanedecanediol, glycerin, trimethylolethane, trimethylolpropane
  • Copolymer polyester resin is a polycondensation product of either the polyvalent carboxylic acid component of polyester resin or the polyhydric alcohol component of polyester resin, or a combination of two or more of both components.
  • Commercially available copolymer polyester resins include glycol-modified polyethylene terephthalate (PETG) and polyester-based thermoplastic elastomers (TPEE, TPC), and can be used alone or in a blend of two or more types.
  • terminal hydroxyl groups or carboxylic acid groups of polyester resins and copolymer polyester resins may be end-capped with epoxy compounds, carbodiimide compounds, isocyanate compounds, etc.
  • the method for measuring the copolymerization monomer components of the polyester resin is not particularly limited, but for example, it can be calculated from the peak intensity of each component by measuring 1 H-NMR and 13 C-NMR using nuclear magnetic resonance spectroscopy (hereinafter abbreviated as NMR).
  • NMR nuclear magnetic resonance spectroscopy
  • Component B may be a copolymerized polyester resin in which one or more monomers other than terephthalic acid and ethylene glycol are copolymerized.
  • the monomer other than terephthalic acid and ethylene glycol is preferably a polyhydric alcohol other than ethylene glycol, more preferably a dihydric alcohol other than ethylene glycol, and particularly preferably 1,4-butanediol, polybutanediol, or polytetramethylene ether glycol.
  • the amount of copolymerization of monomers other than terephthalic acid and ethylene glycol in component B is not particularly limited, but is preferably 0.1 mol% to 90 mol%, more preferably 0.5 mol% to 80 mol%, and even more preferably 1 mol% to 80 mol%, relative to the total amount of monomers forming component B.
  • component B suitable as a polyester resin to be added when preparing a masterbatch (third embodiment) using an intermediate (first embodiment) include polyester resins that satisfy the following (b-3) and (b-4).
  • b-3 The melting point measured by a differential scanning calorimeter is 200° C. or less.
  • b-4 The intrinsic viscosity (IV) is 1 dL/g or more.
  • the melting point of the polyester resin satisfying (b-3) and (b-4) as measured by a differential scanning calorimeter (DSC) is preferably 160° C. or lower, and more preferably 100° C. to 160° C., from the viewpoints of dispersibility and intrinsic viscosity.
  • the intrinsic viscosity (IV) of the polyester resin satisfying (b-3) and (b-4) is preferably 1.1 dL/g or more, more preferably 1.3 dL/g or more, and even more preferably 1.5 dL/g to 2.0 dL/g, from the viewpoint of dispersibility.
  • the method for measuring the intrinsic viscosity (IV) is not particularly limited as long as it is the intrinsic viscosity (IV) at 30° C., and for example, it can be measured using an Ubbelohde viscometer under the following measurement conditions in accordance with JIS K7367-5.
  • Solvent: 1,1,2,2-tetrachloroethane/phenol 1/1 mixed solvent Concentration (resin concentration): 0.5 g/dL (adjusted to 0.5 g/dL with resin component) Temperature: 30°C
  • the content of component B in the first embodiment of the polyester resin composition according to the present disclosure is 25% by mass to 50% by mass relative to the total mass of the composition, and from the viewpoints of dispersibility, deodorizing properties, and moldability, is preferably 25% by mass to 45% by mass, and more preferably 27% by mass to 40% by mass.
  • the content of component B in the second embodiment of the polyester resin composition according to the present disclosure is 7% by mass to 35% by mass relative to the total mass of the composition, and from the viewpoints of dispersibility, deodorizing properties, and moldability, is preferably 10% by mass to 32% by mass, and more preferably 12% by mass to 30% by mass.
  • the content of component B in the third embodiment of the polyester resin composition according to the present disclosure is preferably 7% by mass to 35% by mass, more preferably 10% by mass to 32% by mass, and even more preferably 12% by mass to 30% by mass, based on the total mass of the composition, from the viewpoints of dispersibility, deodorization, and moldability.
  • the first and second embodiments of the polyester resin composition according to the present disclosure contain a dispersant (Component C).
  • the third embodiment of the polyester resin composition according to the present disclosure preferably contains a dispersant (Component C).
  • Component C is not particularly limited and any known dispersant can be used, but from the viewpoint of dispersibility, it preferably has a polar group containing atoms other than carbon and hydrogen atoms.
  • the polar group is preferably at least one group selected from the group consisting of ester, ether, hydroxyl group and imino group, and more preferably ester or hydroxyl group.
  • component C is preferably an ester-based dispersant, and more preferably an aliphatic ester-based dispersant. From the viewpoint of dispersibility, it is particularly preferable that component C has a bulky molecular structure having a branched structure, a cyclic structure, or the like, which causes greater steric hindrance than a straight-chain structure. Commercially available products can also be suitably used as Component C.
  • the polyester resin composition according to the present disclosure preferably contains, as Component C, two or more types of dispersants, more preferably contains two or more types of aliphatic ester-based dispersants, and particularly preferably contains two types of aliphatic ester-based dispersants.
  • the method for measuring the polar group of the dispersant is not particularly limited, but for example, it can be determined from the peak intensity of each component by measuring 1 H-NMR and 13 C-NMR using nuclear magnetic resonance spectroscopy (hereinafter abbreviated as NMR).
  • NMR nuclear magnetic resonance spectroscopy
  • Device name Bruker "AVANCE III 400" Measurement nuclides: 1H , 13C Resonance frequency: 400MHz ( 1H ), 100.6MHz ( 13C )
  • Measurement solvent CDCl 3
  • an infrared spectrum may be measured using a Fourier transform infrared spectrometer (FT-IR), and the determination may also be made from the peak intensity of each component.
  • FT-IR Fourier transform infrared spectrometer
  • the content of component C in the first embodiment of the polyester resin composition according to the present disclosure is 3% by mass to 25% by mass relative to the total mass of the composition, and from the viewpoints of dispersibility, deodorizing properties, and moldability, is preferably 3% by mass to 19% by mass, and more preferably 7% by mass to 16% by mass.
  • the content of component C in the second embodiment of the polyester resin composition according to the present disclosure is 0.1% by mass to 11% by mass relative to the total mass of the composition, and from the viewpoints of dispersibility, deodorizing properties, and moldability, is preferably 0.2% by mass to 11% by mass, more preferably 0.3% by mass to 10% by mass, and even more preferably 0.5% by mass to 8% by mass.
  • the content of component C in the third embodiment of the polyester resin composition according to the present disclosure is preferably 0.1% by mass to 11% by mass, more preferably 0.2% by mass to 11% by mass, even more preferably 0.3% by mass to 10% by mass, and particularly preferably 0.5% by mass to 8% by mass, based on the total mass of the composition, from the viewpoints of dispersibility, deodorization, and moldability.
  • a second embodiment of the polyester resin composition according to the present disclosure contains (component D) a polyester resin that satisfies the following (d-1).
  • (d-1) The melting point measured by a differential scanning calorimeter is 240° C. or higher. From the viewpoint of dispersibility, it is preferable that Component D satisfies the following (d-2): (d-2) Intrinsic viscosity (IV) is 0.6 dL/g or more
  • the melting point of component D is preferably 240° C. to 260° C. from the viewpoint of heat resistance.
  • the intrinsic viscosity (IV) of component D is preferably 0.6 dL/g to 1.2 dL/g, and more preferably 0.6 dL/g to 1.1 dL/g.
  • component D is preferably polyethylene terephthalate (PET) made of terephthalic acid and ethylene glycol.
  • PET polyethylene terephthalate
  • polyethylene terephthalate may contain a copolymerization monomer within a range that does not impair physical properties.
  • ethylene glycol used as a raw material is partially converted to diethylene glycol during polymerization and copolymerized.
  • Diethylene glycol constituent units are often contained in the constituent units derived from ethylene glycol at about 2 mol%, and polyethylene terephthalate may contain 3 mol% or less of the constituent units derived from diethylene glycol.
  • Component D is preferably a polyester resin other than Component B.
  • the content of component D in the second embodiment of the polyester resin composition according to the present disclosure is 37% by mass to 83.6% by mass relative to the total mass of the composition, and from the viewpoints of dispersibility, deodorizing properties, and moldability, is preferably 42% by mass to 83.6% by mass, more preferably 47% by mass to 75% by mass, and even more preferably 50% by mass to 68% by mass.
  • the content of component D in the third embodiment of the polyester resin composition according to the present disclosure is preferably 37% by mass to 83.6% by mass, more preferably 42% by mass to 83.6% by mass, even more preferably 47% by mass to 75% by mass, and particularly preferably 50% by mass to 68% by mass, based on the total mass of the composition, from the viewpoints of dispersibility, deodorization, and moldability.
  • the polyester resin composition according to the present disclosure may contain other components in addition to those described above.
  • other components that can be added include conventionally known components that can be blended with polyester resins, such as extender pigments, coloring pigments, dyes, antioxidants, plasticizers, lubricants, flame retardants, antistatic agents, crystal nucleating agents, blocking agents for terminal carboxylic acids such as epoxy compounds or carbodiimide compounds, reinforcing materials such as glass fibers, deodorants, antibacterial agents, antifungal agents, antiviral processing agents, and antiallergen agents.
  • the deodorizer is not particularly limited, and any known deodorizer can be used.
  • the deodorizer include acidic gas deodorizers, basic gas deodorizers, sulfur-based gas deodorizers, aldehyde gas deodorizers, ketone gas deodorizers, and aromatics.
  • Compounds that cause bad odors include basic gases such as ammonia gas and trimethylamine; acidic gases such as acetic acid and isovaleric acid; aldehyde gases such as formaldehyde, acetaldehyde and nonenal; and sulfur gases such as hydrogen sulfide and methyl mercaptan.
  • the composition may contain other deodorants that have deodorizing properties against these compounds.
  • deodorizers for basic gases include amorphous composite oxides such as zeolite, Al2O3 , SiO2 , MgO , CaO, SrO , BaO, ZrO2 , TiO2, WO2 , CeO2, Li2O , Na2O , and K2O .
  • deodorants for acidic gases include zirconium hydroxide, zirconium oxide, and hydrotalcite compounds such as magnesium-aluminum hydrotalcite.
  • deodorizers for aldehyde gases include hydrazine compounds such as adipic acid dihydrazide, carbohydrazide, succinic acid dihydrazide, and oxalic acid dihydrazide, and aminoguanidine salts such as aminoguanidine hydrochloride, aminoguanidine sulfate, and aminoguanidine bicarbonate.
  • deodorants for sulfur-based gases include copper silicate, copper zirconium phosphate hydrate, zinc oxide, zinc aluminum oxide, zinc silicate, zinc aluminum silicate, and layered zinc aluminosilicate.
  • the resin pressure difference ( ⁇ P) of the high density polyethylene (HDPE) before and after pouring the polyester resin composition is preferably 1.6 MPa or less, more preferably 1.5 MPa or less, even more preferably 1.0 MPa or less, and particularly preferably less than 1.0 MPa, from the viewpoint of dispersibility.
  • the method for measuring the differential pressure ( ⁇ P) in the present disclosure is not particularly limited, but for example, the differential pressure ( ⁇ P) can be measured by the following method.
  • a single-screw extruder unit model "D2025" is connected to a basic device model "10S100"
  • P9210 high density polyethylene (HDPE)) manufactured by Keiyo Polyethylene Co., Ltd. is fed at an extrusion temperature of 287°C, a rotation speed of 50 rpm, and a 40/730/40 mesh until the resin pressure stabilizes.
  • the system After confirming that the resin pressure has stabilized, the system is switched to a polyester resin composition weighed so that the tetravalent metal phosphate compound content is 200 g, and the entire amount is fed. Then, P9210 (HDPE) manufactured by Keiyo Polyethylene Co., Ltd. is fed again until the resin pressure stabilizes, and the HDPE resin pressure before and after the flow of the tetravalent metal phosphate compound-containing polyester resin composition (master batch) is measured as a differential pressure ( ⁇ P).
  • HDPE high density polyethylene
  • the intrinsic viscosity (IV) is preferably 0.50 dL/g or more, more preferably 0.55 dL/g to 0.74 dL/g, even more preferably 0.59 dL/g to 0.70 dL/g, and particularly preferably 0.59 dL/g to 0.69 dL/g, from the viewpoint of dispersibility.
  • the number of particles of a tetravalent metal phosphate compound represented by zirconium phosphate having a particle size of 20 ⁇ m2 or more is less than 1 , preferably less than 0.5, more preferably less than 0.1, and even more preferably 0, that is, none.
  • the number of particles having a particle size of 20 ⁇ m 2 or more of zirconium phosphate is confirmed by photographing the cross-section of the pellet of the polyester resin composition with a scanning electron microscope (SEM) to obtain an SEM image, and the obtained SEM image is subjected to image analysis to count the number of particles having a particle size of 20 ⁇ m 2 or more within the viewing angle.
  • the number of particles having a particle size of 20 ⁇ m 2 or more is less than 1, which is an indication that the dispersibility of the zirconium phosphate particles is good.
  • the number of particles is 0, that is, when the number of particles having a particle size of 20 ⁇ m 2 or more is not observed, the dispersibility of the zirconium phosphate particles is evaluated to be more excellent.
  • the number of particles having a particle size of 10 ⁇ m 2 or more of zirconium phosphate is 1 or less. It is more preferable that the number of zirconium phosphate particles having a particle size of 2 ⁇ m 2 or more is 10 or less when observed by image analysis of the obtained SEM image. It is more preferable that the number of zirconium phosphate particles having a particle size of 1 ⁇ m2 or more is 30 or less, and it is particularly preferable that the number of zirconium phosphate particles having a particle size of 0.5 ⁇ m2 or more is 50 or less, as observed by image analysis of the obtained SEM image.
  • a pellet of the polyester resin composition obtained by the method described in the Examples below can be cut perpendicularly to the flow direction (machine direction, MD) of the pellet, and an SEM image can be obtained at a magnification of 300 times using an SEM.
  • the pellets can be obtained by mixing the polyester resin composition according to the present disclosure, which is the subject of the measurement, and then heating and melt-extruding the mixture using a twin-screw extruder, followed by pelletizing the mixture using a strand-cut method.
  • the flow direction (MD) of the pellets coincides with the flow direction (MD) of the strands, and the longitudinal direction of the pellets is usually the MD.
  • the method of producing the pellets will be described later in the Examples.
  • the pellet when evaluating already produced pellets, i.e., pellets whose strand flow direction and pellet flow direction are unknown, the pellet can be cut in any direction to prepare a cross section, and the obtained cross section can be evaluated by the above-mentioned method.
  • the obtained SEM image is binarized using the image analysis software "Image J Fiji" within a range of a viewing angle of 0.4 mm (400 ⁇ m) ⁇ 0.3 mm (300 ⁇ m) and a viewing size of 0.12 mm2 , and the particles are measured.
  • the number of particles in the field of view having a particle size of 20 ⁇ m2 or more is 0, and the number of particles having a particle size of 10 ⁇ m2 or more is preferably 1 or less, more preferably 10 or less, even more preferably 30 or less, and particularly preferably 50 or less, of zirconium phosphate having a particle size of 0.5 ⁇ m2 or more.
  • the polyester resin composition of the present disclosure may further include, in addition to the polyester resins of Components B and D, an additional polyester resin different from the polyester resins.
  • the additional polyester resin may be the same as or different from the polyester resin contained in the polyester resin composition of the present disclosure.
  • the additional polyester resin is preferably a polyester resin that improves molding processability when a molded body or the like is obtained using the polyester resin composition of the present disclosure.
  • the intrinsic viscosity (IV) of the additional polyester resin is preferably 0.50 L/g or more, more preferably 0.55 dL/g to 0.74 dL/g, even more preferably 0.57 dL/g to 0.70 dL/g, and particularly preferably 0.57 dL/g to 0.65 dL/g.
  • the additional polyester resin a known polyester resin can be appropriately selected and used depending on the purpose of processing.
  • the additional polyester resin may be crystalline or amorphous.
  • the additional polyester resin may be a commercially available product, and examples of the commercially available product include, but are not limited to, the following: Crystalline copolymer polyester resin (Vylon GM-913 manufactured by Toyobo Co., Ltd.), amorphous copolymer polyester resin (GN001 manufactured by Eastman Chemical Japan Co., Ltd.), polyethylene terephthalate (MA-2101M manufactured by Unitika Ltd.), crystalline copolymer polyester resin (SB654 manufactured by Toray Celanese Co., Ltd.), crystalline copolymer polyester resin (Vylon GA-6300 manufactured by Toyobo Co., Ltd.), etc.
  • the method for producing a polyester resin composition according to the present disclosure is not particularly limited, but preferably includes a step of kneading (component A) a tetravalent metal phosphate compound satisfying the following (a-1) and (a-2), (component B) a polyester resin satisfying the following (b-1) and (b-2), and (component C) a dispersant by batch kneading means to obtain a polyester resin composition ⁇ in which the content of component A is 40% by mass to 72% by mass, the content of component B is 25% by mass to 50% by mass, and the content of component C is 3% by mass to 25% by mass, relative to the total mass of the composition.
  • the method for producing a polyester resin composition preferably includes a step of adding (component D) a polyester resin that satisfies the following (d-1) and (b-4) as component B to a polyester resin composition ⁇ that contains (component A) a tetravalent metal phosphate compound that satisfies the following (a-1) and (a-2), (component B) a polyester resin that satisfies the following (b-1) and (b-2), and (component C) a dispersant, the content of component A being 40% by mass to 72% by mass, the content of component B being 25% by mass to 50% by mass, and the content of component C being 3% by mass to 25% by mass, relative to the total mass of the composition, and kneading the resulting polyester resin composition.
  • (a-1) A compound represented by the following formula (1): MH a (PO 4 ) b ⁇ nH 2 O (1)
  • M represents one or more tetravalent metals
  • (a-2) the median diameter (D 50 ) is 1.0 ⁇ m or less;
  • (b-1) the polyester resin composition is crystalline;
  • (b-3) the melting point measured by a differential scanning calorimeter is 200° C.
  • the polyester resin composition ⁇ corresponds to the first embodiment of the polyester resin composition according to the present disclosure, and preferred embodiments are the same as those described above.
  • the polyester resin composition obtained after the kneading step by the production method for a polyester resin composition according to the present disclosure corresponds to the second or third embodiment of the polyester resin composition according to the present disclosure, and preferred embodiments are also similar to the preferred embodiments described above.
  • the kneading step is preferably a step of kneading by a continuous kneading means. From the viewpoint of dispersibility, it is more preferable to include a step of obtaining the polyester resin composition ⁇ prior to the kneading step.
  • the batch-type kneading means used in the present disclosure include a Henschel mixer, a pressure kneader, a Banbury mixer, a planetary mixer, a colloid mill, a planetary mixer, a centrifugal mixer, a thin film rotary mixer, and the like.
  • the order of adding components A to C to the batch kneading means is not particularly limited, and the components may be added all at once, or each component may be added successively or continuously.
  • the heating temperature in the step of kneading by the batch-type kneading means may be selected depending on the components used, but from the viewpoints of dispersibility and decomposability, it is preferably 100°C to 200°C, more preferably 130°C to 190°C, and even more preferably 140°C to 180°C. From the viewpoints of dispersibility and decomposition, the heating temperature is preferably equal to or higher than the melting point of component B.
  • the kneading time in the step of kneading by a batch-type kneading means is not particularly limited, but is, for example, preferably 0.1 hour to 12 hours, more preferably 0.3 hour to 6 hours, and even more preferably 0.5 hour to 2 hours.
  • Step of kneading by continuous kneading means examples include a single-screw kneading extruder, a twin-screw kneading extruder, a multi-screw kneading extruder, and a tandem kneading extruder.
  • the polyester resin composition obtained in the step of kneading by batch kneading means with component D it is preferable to mix and knead the polyester resin composition obtained in the step of kneading by batch kneading means with component D, and it is more preferable to mix and knead the polyester resin composition obtained in the step of kneading by batch kneading means with component D and a polyester resin satisfying the above-mentioned (b-3) and (b-4).
  • the amount of the polyester resin composition obtained by the step of kneading by batch kneading means added to the step of kneading by continuous kneading means is preferably 2% by mass to 50% by mass, more preferably 3% by mass to 45% by mass, and particularly preferably 5% by mass to 40% by mass, based on the total mass of the obtained composition, from the viewpoints of dispersibility, deodorizing properties, and moldability.
  • the amount of component D added in the step of kneading by continuous kneading means is, from the viewpoints of dispersibility, deodorizing properties, and moldability, preferably 37% by mass to 83.6% by mass, more preferably 42% by mass to 83.6% by mass, even more preferably 47% by mass to 75% by mass, and particularly preferably 50% by mass to 68% by mass, relative to the total mass of the composition to be obtained.
  • the amount of polyester resin satisfying the above (b-3) and (b-4) added in the step of kneading by a continuous kneading means is preferably 0% by mass to 25% by mass, more preferably 1.5% by mass to 20% by mass, and particularly preferably 1.8% by mass to 15% by mass, based on the total mass of the obtained composition, from the viewpoints of dispersibility, deodorizing properties, and moldability.
  • the components are preferably mixed in advance and then fed into the continuous kneading means.
  • the heating temperature in the step of kneading by the continuous kneading means may be selected depending on the components used, but from the viewpoint of dispersibility, it is preferably 240°C to 300°C, more preferably 250°C to 280°C, and particularly preferably 257°C to 270°C. From the viewpoint of dispersibility, the heating temperature is preferably equal to or higher than the melting point of component D.
  • the kneading time in the step of kneading by the continuous kneading means is not particularly limited, and the discharge amount and the like may be appropriately selected depending on the continuous kneading means to be used, etc.
  • the method for producing the polyester resin composition according to the present disclosure may include other steps, such as pelletizing the obtained polyester resin composition, as necessary.
  • the molded article according to the present disclosure is a molded article obtained by molding a polyester resin composition selected from the first embodiment of the polyester resin composition according to the present disclosure, the second embodiment of the polyester resin composition according to the present disclosure, and the third embodiment of the polyester resin composition according to the present disclosure.
  • the molded article according to the present disclosure may be a molded article obtained by molding the polyester resin composition according to the present disclosure, or may be a molded article obtained by mixing the polyester resin composition according to the present disclosure and the additional polyester resin and molding the mixture.
  • the molded article according to the present disclosure is preferably a molded article obtained by mixing the second or third embodiment of the polyester resin composition according to the present disclosure and the additional polyester resin and molding the mixture.
  • the molding method of the polyester resin composition is appropriately selected depending on the type of molded article, and examples thereof include extrusion molding, injection molding, compression molding, transfer molding, stampable molding, blow molding, inflation molding, stretched film molding, lamination molding, calendar molding, foam molding, cast molding, powder molding, paste molding, melt spinning, and the like. They may be used alone or in combination of two or more.
  • the molding process is preferably melt spinning.
  • a molded article obtained by advanced processing of the molded article according to the present disclosure is also preferably included. Examples of the molded article obtained by advanced processing include yarn and textile products obtained by further processing the fiber of the molded article.
  • the thickness, length, cross-sectional shape (circular, irregular, etc.), cross-sectional layer structure (single layer, multi-layer, core-sheath, hollow, etc.), stretching method (sequential, simultaneous), and stretching ratio of the fibers and yarns in the molded product may be appropriately selected as desired.
  • the fibers and threads in the molded article may be long fibers (filaments) or short fibers (staples), and the long fibers (filaments) may be monofilaments or multifilaments, which may be appropriately selected as desired.
  • the filaments may be undrawn yarn (UDY: Undrawn Yarn), fully oriented yarn (FOY: Fully Oriented Yarn) in which UDY is drawn and twisted in a separate process to obtain a highly oriented yarn, direct spin drawn (DSD: Direct Spin Draw) in which spinning and drawing are directly combined to obtain a drawn yarn in one process, partially oriented yarn (POY: Partially Oriented Yarn), drawn textured yarn (DTY: Drawn Textured Yarn), or drawn textured yarn (DTY: Drawn Textured Yarn) in which POY is drawn and twisted in a separate process, or one step OSY (One Step) which does not require drawing.
  • the yarn formed including the polyester resin composition according to the present disclosure may be a single yarn, a two-ply yarn, or a spun yarn.
  • the fibers and yarns in the molded article may be a mixed fiber containing other fibers, and the type of other fibers is not particularly limited and may be appropriately selected from natural fibers and synthetic fibers as desired.
  • the additional polyester resin to be mixed with the first embodiment, the second embodiment, or the third embodiment of the polyester resin composition according to the present disclosure is not particularly limited and can be appropriately selected depending on the molded body to be produced.
  • the intrinsic viscosity (IV) of the additional polyester resin to be mixed with the second or third embodiment of the polyester resin composition according to the present disclosure is preferably 0.50 dL/g or more, more preferably 0.55 dL/g to 0.74 dL/g, even more preferably 0.57 dL/g to 0.70 dL/g, and particularly preferably 0.57 dL/g to 0.65 dL/g, from the viewpoint of spinnability.
  • the molded article according to the present disclosure can be used, for example, as a deodorant molded article, an ion-adsorbing molded article, an antibacterial molded article, an antiviral molded article, an antiallergenic molded article, and the like.
  • the molded article include fibers, threads, textile products, films, plates, and three-dimensional structures (for example, bags, containers, housing materials, and automobile parts).
  • preferred examples of the molded article include fibers, threads, and textile products, and more preferred examples include woven fabrics and nonwoven fabrics.
  • Examples of textile products include woven fabrics, nonwoven fabrics, and clothing and bedding made from these.
  • Examples of clothing items include stockings, underwear, pants, brassieres, girdles, spats, jumpers, down jackets, sweaters, cardigans, trousers, vests, hats, gloves, socks, dresses, shoes, sandals, work clothes, uniforms, lab coats, pajamas, scarves, neck warmers, underwear, wigs, T-shirts, dress shirts, suits, formal wear, neckties, masks, belly warmers, obi, kimonos, tabi, sportswear, jerseys, bandanas, sweatshirts, sweatshirts, and wristbands.
  • bedding examples include pillows, futons, pillowcases, futon covers, sheets, blankets, towel blankets, mattress pads, futon storage bags, towels, handkerchiefs, gowns, and slippers. If necessary, these may be subjected to a dyeing process, mainly for the purpose of coloring, or a finishing process, mainly for the purpose of maintaining the characteristics of the fiber material and imparting functionality.
  • Tetravalent metal phosphate compound Synthesis Example 1 (Preparation of Tetravalent Metal Phosphate Compound)
  • the zirconium phosphate particles having a median diameter of 0.8 ⁇ m were Kesmon NS-10 manufactured by Toagosei Co., Ltd.
  • Synthesis Example 2 (Preparation of Tetravalent Metal Phosphate Compound) As zirconium phosphate particles having a median diameter of 1.5 ⁇ m, Kesmon NS-10TZ manufactured by Toagosei Co., Ltd. was used.
  • Zirconium phosphate particles having a median diameter of 0.51 ⁇ m were prepared by the following method.
  • a 6 m3 reactor was charged with 3,480 kg of deionized water and 520 kg of 35% hydrochloric acid, and 865 kg of a 20% aqueous solution of zirconium oxychloride octahydrate containing 0.18% hafnium was added, followed by dissolving 358 kg of oxalic acid dihydrate. While stirring the solution well, 403 kg of 75% phosphoric acid was added. The temperature was raised to 98°C in 2 hours, and the mixture was refluxed with stirring for 12 hours.
  • the resulting precipitate was thoroughly washed with water and then dried at 105°C to obtain zirconium phosphate particles.
  • the particles were crushed with a pulverizer. Then, the particles were sieved.
  • the obtained zirconium phosphate particles were measured with a powder X-ray diffraction device, and it was confirmed that they were ⁇ -zirconium phosphate particles.
  • Zirconium phosphate particles having a median diameter of 0.22 ⁇ m were prepared by the following method.
  • a 6 m3 reactor was charged with 3,168 kg of deionized water and 556 kg of 35% hydrochloric acid, and 968 kg of a 20% aqueous solution of zirconium oxychloride octahydrate containing 0.18% hafnium was added, followed by dissolving 328 kg of oxalic acid dihydrate. 482 kg of 75% phosphoric acid was added while stirring the solution well. The temperature was raised to 98°C in 2 hours, and the mixture was refluxed with stirring for 12 hours.
  • the resulting precipitate was thoroughly washed with water and then dried at 105°C to obtain zirconium phosphate particles.
  • the particles were crushed with a pulverizer. Then, the particles were sieved.
  • the obtained zirconium phosphate particles were measured with a powder X-ray diffractometer, and it was confirmed that they were ⁇ -zirconium phosphate particles.
  • Titanium phosphate particles having a median diameter of 0.56 ⁇ m were prepared by the following method. A 6 m3 reactor was charged with 2,745 kg of deionized water, and 2,432 kg of 75% phosphoric acid was added. While stirring the solution well, 823 kg of titanyl sulfate was added, and stirring was continued for 10 minutes. The temperature was then raised to 100°C in 1 hour, and the mixture was refluxed with stirring for 44 hours. After cooling, the resulting precipitate was thoroughly washed with water, and then dried at 105°C to obtain titanium phosphate particles. The precipitate was crushed with a grinder. Then, the mixture was sieved. The obtained titanium phosphate particles were measured with a powder X-ray diffractometer, and it was confirmed that they were ⁇ -titanium phosphate particles.
  • Zirconium phosphate particles having a median diameter of 0.11 ⁇ m were prepared by the following method. 228 kg of deionized water was placed in a 6 m3 reactor, and 4,320 kg of 75% phosphoric acid was added. While stirring this solution well, 864 kg of a 20% aqueous solution of zirconium oxychloride octahydrate containing 0.18% hafnium was added, and stirring was continued for 10 minutes. The temperature was then raised to 98°C in 1 hour, and the mixture was refluxed with stirring for 12 hours. After cooling, the obtained precipitate was thoroughly washed with water and then dried at 105°C to obtain zirconium phosphate particles.
  • the particles were crushed with a pulverizer. Then, the particles were sieved. The obtained zirconium phosphate particles were measured with a powder X-ray diffraction device, and it was confirmed that they were ⁇ -zirconium phosphate particles.
  • Zirconium phosphate particles having a median diameter of 1.0 ⁇ m were prepared by the following method.
  • a 6 m3 reactor was charged with 3,600 kg of deionized water and 362 kg of 35% hydrochloric acid, and 600 kg of a 20% aqueous solution of zirconium oxychloride octahydrate containing 0.18% hafnium was added, followed by dissolving 250 kg of oxalic acid dihydrate. 274 kg of 75% phosphoric acid was added while stirring the solution well. The temperature was raised to 98°C in 2 hours, and the mixture was refluxed with stirring for 12 hours.
  • the resulting precipitate was thoroughly washed with water and then dried at 105°C to obtain zirconium phosphate particles.
  • the particles were crushed with a pulverizer. Then, the particles were sieved.
  • the obtained zirconium phosphate particles were measured with a powder X-ray diffractometer, and it was confirmed that they were ⁇ -zirconium phosphate particles.
  • the particle composition identified by X-ray fluorescence analysis and thermogravimetric differential thermal analysis, is shown in Table 1.
  • the contents were molded into a sheet with a thickness of 3 mm using two 10-inch rolls at a roll temperature of 110°C, and then shredded and pelletized to obtain a polyester resin composition (intermediate) containing a tetravalent metal phosphate compound.
  • a tetravalent metal phosphate compound-containing polyester resin composition (intermediate) and a polyester resin shown in Table 3 or Table 4 were mixed in the blending ratio shown in Table 3 or Table 4, and pelletized using a ⁇ 18 mm twin-screw extruder (continuous kneader, "TEM-18SS-12/1V" manufactured by Shibaura Machine Co., Ltd.) at an extrusion temperature of 260°C, a screw rotation speed of 400 rpm, a discharge rate of 7.0 kg/h, and a strand cut method to obtain a tetravalent metal phosphate compound-containing polyester resin composition (master batch).
  • a ⁇ 18 mm twin-screw extruder continuous kneader, "TEM-18SS-12/1V” manufactured by Shibaura Machine Co., Ltd.
  • a tetravalent metal phosphate compound and a polyester resin shown in Table 5 were mixed in the compounding ratio shown in Table 5, and the mixture was pelletized using a ⁇ 18 mm twin-screw extruder (continuous kneader, "TEM-18SS-12/1V" manufactured by Shibaura Machine Co., Ltd.) at an extrusion temperature of 260° C., a screw rotation speed of 400 rpm, a discharge rate of 7.0 kg/h, and a strand cut method to obtain a tetravalent metal phosphate compound-containing polyester resin composition (master batch).
  • a ⁇ 18 mm twin-screw extruder continuous kneader, "TEM-18SS-12/1V” manufactured by Shibaura Machine Co., Ltd.
  • a polyester resin composition (master batch) containing a tetravalent metal phosphate compound and a polyester resin shown in Table 3 or Table 4 were mixed in the blending ratio shown in Table 3 or Table 4, and a ⁇ 20 mm melt spinning equipment ("ALM-S3500-T1" manufactured by AIKI Liotech Co., Ltd.) equipped with a 30/325/30 mesh on a 48 filament nozzle was used.
  • the extrusion temperature was 280° C.
  • the gear pump rotation speed was adjusted to a discharge rate of 1.5 kg/h.
  • the fiber was air-cooled in a quench box, and taken up at a godet roller speed of 743 m/min while oiling.
  • the fiber was stretched in the stretching section at a godet roller temperature of 120° C. and a speed of 2,970 m/min to an apparent stretch ratio of 4.0 times.
  • the fiber was heat-set in the heat-setting section at a godet roller temperature of 120° C. and a speed of 2,970 m/min, and taken up at 3,000 m/min to obtain a polyester fiber containing a tetravalent metal phosphate compound having a fineness of 75 denier and 48 filaments.
  • Dispersion liquid to which the tetravalent metal phosphate compound was added was dispersed using an ultrasonic generator, and the dispersion was measured using a laser diffraction particle size distribution measuring device "Mastersizer 2000" (manufactured by Malvern Instruments), and the results were analyzed on a volume basis.
  • Dispersion medium Water Particle concentration: 1% by mass (1 g of tetravalent metal phosphate compound per 100 g of water) Particle refractive index: 2.4 Stirring: 2,450 rpm Ultrasonic: 50% output x 1 minute repetition
  • the evaluation was performed by powder X-ray diffraction.
  • the X-ray diffraction apparatus used was a D8 ADVANCE manufactured by BRUKER.
  • An X-ray diffraction pattern was obtained using CuK ⁇ generated at an applied voltage of 40 kV and a current value of 40 mA using a Cu-encapsulated X-ray source.
  • the detailed measurement conditions are as follows.
  • X-ray source Encapsulated X-ray source (Cu ray source), 0.4 x 12 mm 2 , Long Fine Focus Rating: 2.2kW Output power: 40kV-40mA (1.6kW) Goniometer radius: 280 mm
  • composition formula was determined by elemental analysis using X-ray fluorescence and hydration water analysis using thermogravimetric differential thermal analysis (TG-DTA).
  • TG-DTA Thermogravimetric differential thermal analysis
  • TG-DTA Thermogravimetric-differential thermal analysis
  • DSC differential scanning calorimeter
  • ⁇ P -Differential pressure
  • the polyester resin compositions of Examples 1 to 48 had a low differential pressure ( ⁇ P) and were excellent in dispersibility of the tetravalent metal phosphate compound. Moreover, the polyester resin compositions of Examples 1 to 48 had good spinnability during melt spinning, and the tensile strength was at a level that would not cause any practical problems. Furthermore, the polyester resin compositions of Examples 1 to 6, 9, 10, 12 to 32, and 34 to 48 were spun into fibers having a high deodorizing rate. On the other hand, the polyester resin compositions of Comparative Examples 1, 2, and 5 to 11 were capable of melt spinning, but had a higher differential pressure ( ⁇ P) than the Examples, and were inferior in dispersibility of the tetravalent metal phosphate compound. As shown in Table 3 or Table 5, the polyester resin compositions of Comparative Examples 3, 4 and 12 to 15 could not be melt spun, and therefore could not be evaluated at all.
  • R972 Silica particles (R972 manufactured by Nippon Aerosil Co., Ltd.)
  • GM-913 Crystalline copolymer polyester resin (Vylon GM-913 manufactured by Toyobo Co., Ltd.) )
  • GN001 Amorphous copolymer polyester resin (GN001 manufactured by Eastman Chemical Japan Co., Ltd.)
  • MA-2101M Polyethylene terephthalate (MA-2101M manufactured by Unitika Ltd.)
  • SB654 Crystalline copolymer polyester resin (SB654 manufactured by Toray Celanese Co., Ltd.)
  • GA-6300 crystalline copolymer polyester resin (Vylon GA-6300 manufactured by Toyobo Co., Ltd.)
  • TG-12 12-hydroxystearic acid triglyceride (Rikemal TG-12, manufactured by Riken Vitamin Co., Ltd.)
  • Polyethylene polyethylene wax (Sanyo Chemical Industries, Ltd., Sanwax 171-P) H-476:
  • O-80V Sorbitan oleate (Poem O-80V manufactured by Riken Vitamin Co., Ltd.) M-300: Glycerin monolaurate (Poem M-300, manufactured by Riken Vitamin Co., Ltd.) SOLSPERSE 28000: Polymeric dispersant (manufactured by Lubrizol) Solplus L400: Polymeric dispersant (manufactured by Lubrizol) Pelestat 300: Polyether/polyolefin block polymer (manufactured by Sanyo Chemical Industries, Ltd.) NES-2040: Polyethylene terephthalate (NES-2040 manufactured by Unitika Ltd.) NEH-2070: Polyethylene terephthalate (NEH-2070 manufactured by Unitika Ltd.) SA1206: Polyethylene terephthalate (SA-1206 manufactured by Unitika Ltd.) SA-863JP: Crystalline polyester resin (SA-863JP manufactured by Unitika Ltd.)
  • the polyester resin compositions of Examples 1 to 48 are superior in dispersibility of the tetravalent metal phosphate compound as compared with the polyester resin compositions of Comparative Examples 1 to 15. Furthermore, as shown in Tables 3 and 4, the polyester resin compositions of Examples 1 to 48 are excellent in tensile strength and spinnability.
  • component B was not copolymerized with one or more monomers other than terephthalic acid and ethylene glycol, i.e., polyethylene terephthalate (homo-PET) composed of terephthalic acid and ethylene glycol, the differential pressure ⁇ P was high and the deodorizing rate was low.
  • homo-PET polyethylene terephthalate
  • the differential pressure ⁇ P increased when the content of component A in the master batch exceeded 30 mass%.
  • the differential pressure ⁇ P was high when the content of component D in the master batch was less than 37 mass%.
  • the pellets of the polyester resin composition were sufficiently cooled using dry ice or liquid nitrogen.
  • the pellets were cut perpendicular to the flow direction (machine direction, MD) of the cooled pellets using a single-edged trimming razor (manufactured by Nisshin EM Co., Ltd.) to prepare a pellet cross section as a SEM measurement surface.
  • the cut pellets were sandwiched between a sample stage and fixed to the sample stage so that the pellet cross section could be observed with an SEM.
  • SEM carbon double-sided tape manufactured by Nisshin EM Co., Ltd. was attached so that both ends of the measurement surface and the sample stage were in contact.
  • Platinum was evaporated onto the cross section of the pellet using a precious metal thin film coating device "MSP-1S” (manufactured by Vacuum Device Co., Ltd.) for SEM observation.
  • MSP-1S precious metal thin film coating device
  • JSM-7900F scanning electron microscope
  • the SEM image was focused at a magnification of 15,000 to 25,000 times, and gradually changed to a magnification of 300 times, so that the quality of the measurement surface of the pellet cross section and the quality of the SEM image were confirmed while measuring, and if satisfactory quality was not obtained, the preparation of the pellet cross section was started over.
  • SEM images were photographed at five or more different locations in different regions, and the one that was considered to be the most average was selected by visual inspection. If the quality of the SEM image is poor due to poor condition of the pellet cross section, microtome, cryomicrotome or ion milling may be used to improve the quality of the cross section.
  • SEM JEOL Schottky field emission scanning electron microscope "JSM-7900F”
  • Vacuum mode Low vacuum Vacuum setting: 30 Pa
  • Observation mode SEM Acceleration voltage: 5.0 kV
  • Detector Low vacuum backscattered electron detector (LVBED-C) Magnification: x300 (effective viewing angle 0.4mm (400 ⁇ m) x 0.3mm (300 ⁇ m)
  • the selected SEM image was binarized using the image analysis software "Image J Fiji" within a viewing angle of 0.4 mm (400 ⁇ m) ⁇ 0.3 mm (300 ⁇ m) and a viewing size of 0.12 mm2 , and the size (area) of each detected particle was measured.
  • the selected SEM image was read into image analysis software, and the conversion scale of the image analysis software was set based on the conversion scale bar written on the SEM image. Unnecessary parts containing information on the time of SEM image capture were deleted to obtain an image with an effective viewing angle of 0.4 mm (400 ⁇ m) ⁇ 0.3 mm (300 ⁇ m) and a viewing size of 0.12 mm2 .
  • binarization was performed so that the particles were white.
  • the threshold value of binarization was performed while visually comparing the SEM image before image analysis with the binarized image so that the number and size of the particles were appropriate. All particles after binarization were detected using a particle measurement algorithm built into the image analysis software, and the size (area) of each particle was measured, and the calculation result of the particle size was obtained.
  • the Fourier transform and filter processing built into the image analysis software are not performed, but the SEM image before image analysis is divided, the above image analysis is performed, and the SEM image and the binarized image are compared in each divided area, and the image of the SEM image before image analysis is divided until the number and size of particles match well.
  • Image analysis is performed in each divided area for the SEM image that has been divided until the number and size of particles match well, and the calculation result of the particle size is obtained as the result of image analysis within the effective field of view by adding up all the respective measurement results obtained.
  • Fig. 1 is an SEM image of the cross section of the polyester resin composition pellet of Example 27 taken at 300x magnification.
  • the SEM image shown in Fig. 1 was divided into five images and binarized using the above software, and the resulting images are shown in Fig. 2.
  • Fig. 2 is an image of the cross section of the polyester resin composition pellet of Example 27 that was subjected to image analysis and binarized. In Fig. 2, each zirconium phosphate particle could be confirmed as a clear white image.
  • Fig. 3 is an SEM image of the cross section of the polyester resin composition pellet of Comparative Example 6 taken at 300x magnification. The SEM image of Fig.
  • Fig. 4 shows that there are more coarse particles of zirconium phosphate than in Fig. 2.
  • the particle size in the image obtained by binarization was measured.
  • the number of zirconium phosphate particles having a particle size of 20 ⁇ m2 or more, the number of particles having a particle size of 10 ⁇ m2 or more, the number of particles having a particle size of 2 ⁇ m2 or more, the number of particles having a particle size of 1 ⁇ m2 or more, and the number of particles having a particle size of 0.5 ⁇ m2 or more in the field of view were counted.
  • the results are shown in Table 6 below.
  • the differential pressure ( ⁇ P) of the resin pressure of high density polyethylene (HDPE) before and after pouring the polyester resin composition is also shown in the table.
  • polyester resin compositions of the Examples contain zirconium phosphate particles of 20 ⁇ m2 or more. Also, the polyester resin of Example 8 does not contain titanium phosphate particles of 20 ⁇ m2 or more.
  • each of the polyester resin compositions of the Comparative Examples contained one or more zirconium phosphate particles of 20 ⁇ m2 or more. The pressure difference ( ⁇ P) in each Example was smaller than that in each Comparative Example, indicating that the zirconium phosphate or titanium phosphate particles had good dispersibility. Since the dispersibility was good, fewer coarse particles of zirconium phosphate or titanium phosphate were captured by the mesh, and the mesh was less likely to become clogged.
  • the number of particles by image analysis correlates well with the dispersibility of the tetravalent metal phosphate compound in the polyester resin composition, and the polyester resin composition of each Example is expected to have good spinnability during melt spinning. It was also confirmed that the polyester resin composition of each Example can produce a molded product with excellent deodorizing properties.

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Abstract

Provided are: a polyester resin composition which contains a tetravalent metal phosphate compound having a median diameter of 1.5 μm or less (component A), a crystalline copolymer polyester resin (component B), a dispersant (component C), and a polyester resin having a melting point of 240°C or more (component D), wherein the content of the component A is 0.4 mass% to 30 mass% with respect to the total mass of the composition, the content of the component B is 7 mass% to 35 mass% with respect to the total mass of the composition, the content of the component C is 0.1 mass% to 11 mass% with respect to the total mass of the composition, and the content of the component D is 42 mass% to 83.6 mass% with respect to the total mass of the composition; a method for producing the polyester resin composition; and a molded body using the polyester resin composition.

Description

ポリエステル樹脂組成物及びその製造方法、並びに、成形体Polyester resin composition, its manufacturing method, and molded body

　本開示は、ポリエステル樹脂組成物及びその製造方法、並びに、成形体に関する。 This disclosure relates to a polyester resin composition, a method for producing the same, and a molded article.

　ポリエステル、ナイロン、アクリルなどの合成繊維は、耐熱性、耐薬品性などの特性に優れているため衣料、産業用資材、寝装具などの用途に広く利用されている。
　近年、これらの繊維用途において、汗臭、加齢臭、疲労臭などに対する消臭機能を付与した繊維が流通している。
　例えば、汗臭及び疲労臭の原因物質であるアンモニア等の塩基性ガスを迅速に消臭することを目的とした消臭剤として用いられる４価金属リン酸塩化合物を樹脂へ混合した樹脂組成物やこの樹脂組成物を用いて溶融紡糸加工した消臭繊維が挙げられる。これらの樹脂組成物や消臭繊維の機能性付与、及び特性向上を目指して種々の提案がなされている Synthetic fibers such as polyester, nylon, and acrylic are widely used for clothing, industrial materials, bedding, and other purposes due to their excellent properties such as heat resistance and chemical resistance.
In recent years, in these textile applications, fibers that have been provided with deodorizing functions against sweat odor, aging odor, fatigue odor, and the like have been distributed.
For example, there are resin compositions in which a tetravalent metal phosphate compound, which is used as a deodorizer for quickly deodorizing basic gases such as ammonia, which are the causative substances of sweat odor and fatigue odor, is mixed into a resin, and deodorizing fibers that are melt-spun using the resin compositions. Various proposals have been made with the aim of imparting functionality and improving the properties of these resin compositions and deodorizing fibers.

　例えば、特許文献１は、リン酸ジルコニウムの配合量と固有粘度０．７０～０．９５ｄＬ／ｇのポリエステルで作製したマスターバッチを用いた機能性原糸の製造方法を開示している。 For example, Patent Document 1 discloses a method for producing functional yarn using a masterbatch made of a polyester with an intrinsic viscosity of 0.70 to 0.95 dL/g and a blend amount of zirconium phosphate.

　また、特許文献２は、銀担持リン酸ジルコニウムを含む抗菌剤とポリトリメチレンテレフタレート（ＰＴＴポリエステル）を所定の配合量で混練温度６０℃～１５０℃、３０～１２０ｍｉｎであらかじめ捏和した樹脂組成物をそのままツインスクリュー押出機溶融ブレンドして作製したナノ抗菌マスターバッチ製造過程を含む偏心鞘芯型抗菌機能複合したポリエステルファイバ及びその調製方法が開示されている。 Patent Document 2 also discloses an eccentric sheath-core type antibacterial composite polyester fiber and its preparation method, including a nano antibacterial masterbatch manufacturing process in which a resin composition is made by pre-kneading a specified amount of an antibacterial agent containing silver-loaded zirconium phosphate and polytrimethylene terephthalate (PTT polyester) at a kneading temperature of 60°C to 150°C for 30 to 120 minutes, and then melt-blending the resulting resin composition in a twin-screw extruder.

国際公開第２０１６／０７６５７２号International Publication No. 2016/076572 中国特許出願公開第１０３３４３３９８号明細書Chinese Patent Publication No. 103343398

　本開示が解決しようとする課題は、４価金属リン酸塩化合物の分散性に優れるポリエステル樹脂組成物及びその製造方法を提供することである。
　本開示が解決しようとする他の課題は、前記ポリエステル樹脂組成物を用いた成形体を提供することである。 The problem to be solved by the present disclosure is to provide a polyester resin composition having excellent dispersibility of a tetravalent metal phosphate compound, and a method for producing the same.
Another problem to be solved by the present disclosure is to provide a molded article using the polyester resin composition.

　上記課題を解決するための具体的な手段には、以下の態様が含まれる。
＜１＞　（成分Ａ）下記（ａ－１）及び（ａ－２）を満たす４価金属リン酸塩化合物、（成分Ｂ）下記（ｂ－１）及び（ｂ－２）を満たすポリエステル樹脂、並びに、（成分Ｃ）分散剤を含有し、成分Ａの含有量が、組成物の全質量に対し、４０質量％～７２質量％であり、成分Ｂの含有量が、組成物の全質量に対し、２５質量％～５０質量％であり、成分Ｃの含有量が、組成物の全質量に対し、３質量％～２５質量％であるポリエステル樹脂組成物。
（ａ－１）下記式（１）で表される化合物である
　ＭＨａ（ＰＯ４）ｂ・ｎＨ２Ｏ　（１）
　式（１）中、Ｍは１種以上の４価金属を表し、ａ及びｂは３ｂ－ａ＝４を満たす正数であり、ｂは２＜ｂ≦２．１であり、ｎは０≦ｎ≦２である。
（ａ－２）メジアン径（Ｄ５０）が１．５μｍ以下である
（ｂ－１）結晶性である
（ｂ－２）テレフタル酸及びエチレングリコール以外のモノマーが１種類以上共重合されている
＜２＞　（成分Ａ）下記（ａ－１）及び（ａ－２）を満たす４価金属リン酸塩化合物、（成分Ｂ）下記（ｂ－１）及び（ｂ－２）を満たすポリエステル樹脂、（成分Ｃ）分散剤、並びに、（成分Ｄ）下記（ｄ－１）を満たすポリエステル樹脂を含有し、成分Ａの含有量が、組成物の全質量に対し、０．４質量％～３０質量％であり、成分Ｂの含有量が、組成物の全質量に対し、７質量％～３５質量％であり、成分Ｃの含有量が、組成物の全質量に対し、０．１質量％～１１質量％であり、成分Ｄの含有量が、組成物の全質量に対し、３７質量％～８３．６質量％であるポリエステル樹脂組成物。
（ａ－１）下記式（１）で表される化合物である
　ＭＨａ（ＰＯ４）ｂ・ｎＨ２Ｏ　（１）
　式（１）中、Ｍは１種以上の４価金属を表し、ａ及びｂは３ｂ－ａ＝４を満たす正数であり、ｂは２＜ｂ≦２．１であり、ｎは０≦ｎ≦２である。
（ａ－２）メジアン径（Ｄ５０）が１．５μｍ以下である
（ｂ－１）結晶性である
（ｂ－２）テレフタル酸及びエチレングリコール以外のモノマーが１種類以上共重合されている
（ｄ－１）示差走査熱量計で測定した融点が２４０℃以上である
＜３＞　成分Ｃが、分子構造中に極性基を有する分散剤である＜１＞又は＜２＞に記載のポリエステル樹脂組成物。
＜４＞　前記極性基が、エステル、エーテル、水酸基及びイミノ基よりなる群から選ばれた少なくとも１種の基である＜３＞に記載のポリエステル樹脂組成物。
＜５＞　成分Ｄが、下記（ｄ－２）を満たす＜２＞に記載のポリエステル樹脂組成物。
（ｄ－２）固有粘度（ＩＶ）が０．６ｄＬ／ｇ以上である
＜６＞　前記Ｍが、ジルコニウム、チタン及びハフニウムよりなる群から選ばれた１種以上の４価金属である＜１＞～＜５＞のいずれか１つに記載のポリエステル樹脂組成物。
＜７＞　成分Ｂが、下記（ｂ－３）を満たすポリエステル樹脂を含む＜１＞～＜６＞のいずれか１つに記載のポリエステル樹脂組成物。
（ｂ－３）示差走査熱量計で測定した融点が２００℃以下である
＜８＞　成分Ｂが、下記（ｂ－４）を満たすポリエステル樹脂を含む＜１＞～＜７＞のいずれか１つに記載のポリエステル樹脂組成物。
（ｂ－４）固有粘度（ＩＶ）が１ｄＬ／ｇ以上である Specific means for solving the above problems include the following aspects.
<1> A polyester resin composition comprising: (Component A) a tetravalent metal phosphate compound satisfying the following (a-1) and (a-2); (Component B) a polyester resin satisfying the following (b-1) and (b-2); and (Component C) a dispersant, in which the content of Component A is 40% by mass to 72% by mass, based on the total mass of the composition, the content of Component B is 25% by mass to 50% by mass, and the content of Component C is 3% by mass to 25% by mass, based on the total mass of the composition.
(a-1) A compound represented by the following formula (1): MH a (PO 4 ) b ·nH 2 O (1)
In formula (1), M represents one or more tetravalent metals, a and b are positive numbers satisfying 3b-a=4, b is 2<b≦2.1, and n is 0≦n≦2.
(a-2) has a median diameter (D 50 ) of 1.5 μm or less, (b-1) is crystalline, and (b-2) is copolymerized with one or more monomers other than terephthalic acid and ethylene glycol. <2> A polyester resin composition comprising: (Component A) a tetravalent metal phosphate compound that satisfies the following (a-1) and (a-2); (Component B) a polyester resin that satisfies the following (b-1) and (b-2); (Component C) a dispersant; and (Component D) a polyester resin that satisfies the following (d-1), wherein the content of Component A is 0.4% by mass to 30% by mass, relative to the total mass of the composition, the content of Component B is 7% by mass to 35% by mass, relative to the total mass of the composition, the content of Component C is 0.1% by mass to 11% by mass, and the content of Component D is 37% by mass to 83.6% by mass, relative to the total mass of the composition.
(a-1) A compound represented by the following formula (1): MH a (PO 4 ) b ·nH 2 O (1)
In formula (1), M represents one or more tetravalent metals, a and b are positive numbers satisfying 3b-a=4, b is 2<b≦2.1, and n is 0≦n≦2.
(a-2) the median diameter ( D50 ) is 1.5 μm or less; (b-1) the component is crystalline; (b-2) one or more monomers other than terephthalic acid and ethylene glycol are copolymerized therein; and (d-1) the component has a melting point of 240° C. or more as measured by a differential scanning calorimeter. <3> The polyester resin composition according to <1> or <2>, wherein component C is a dispersant having a polar group in its molecular structure.
<4> The polyester resin composition according to <3>, wherein the polar group is at least one group selected from the group consisting of an ester group, an ether group, a hydroxyl group, and an imino group.
<5> The polyester resin composition according to <2>, in which component D satisfies the following (d-2):
(d-2) An intrinsic viscosity (IV) of 0.6 dL/g or more. <6> The polyester resin composition according to any one of <1> to <5>, wherein M is one or more tetravalent metals selected from the group consisting of zirconium, titanium, and hafnium.
<7> The polyester resin composition according to any one of <1> to <6>, wherein component B contains a polyester resin that satisfies the following (b-3):
(b-3) A melting point measured by a differential scanning calorimeter is 200° C. or less. <8> The polyester resin composition according to any one of <1> to <7>, wherein component B contains a polyester resin that satisfies the following (b-4):
(b-4) Intrinsic viscosity (IV) is 1 dL/g or more

＜９＞　４価金属リン酸塩化合物及びポリエステル樹脂を含み、視野サイズが０．４ｍｍ×０．３ｍｍのポリエステル樹脂組成物の断面ＳＥＭ像において、前記４価金属リン酸塩化合物の粒子サイズが２０μｍ２以上となる粒子数が１個未満であるポリエステル樹脂組成物。
＜１０＞　前記４価金属リン酸塩化合物の粒子サイズが１０μｍ２以上となる粒子数が１個以下である＜９＞に記載のポリエステル樹脂組成物。
＜１１＞　前記４価金属リン酸塩化合物の粒子サイズが２μｍ２以上となる粒子数が１０個以下である＜９＞又は＜１０＞に記載のポリエステル樹脂組成物。
＜１２＞　前記ポリエステル樹脂に加え、前記ポリエステル樹脂とは異なる追加のポリエステル樹脂を更に含む＜１＞～＜１１＞のいずれか１つに記載のポリエステル樹脂組成物。
＜１３＞　＜１２＞に記載のポリエステル樹脂組成物を成形加工してなる成形体。
＜１４＞　前記成形加工が、溶融紡糸である＜１３＞に記載の成形体。
＜１５＞　＜１３＞に記載の成形体を高次加工してなる成形体。
＜１６＞　織布又は不織布である＜１５＞に記載の成形体。 <9> A polyester resin composition comprising a tetravalent metal phosphate compound and a polyester resin, wherein in a cross-sectional SEM image of the polyester resin composition having a field of view size of 0.4 mm x 0.3 mm, the number of particles of the tetravalent metal phosphate compound having a particle size of 20 μm2 or more is less than 1.
<10> The polyester resin composition according to <9>, wherein the number of particles having a particle size of 10 μm 2 or more of the tetravalent metal phosphate compound is 1 or less.
<11> The polyester resin composition according to <9> or <10>, wherein the number of particles having a particle size of 2 μm2 or more of the tetravalent metal phosphate compound is 10 or less.
<12> The polyester resin composition according to any one of <1> to <11>, further comprising an additional polyester resin different from the polyester resin in addition to the polyester resin.
<13> A molded article obtained by molding the polyester resin composition according to <12>.
<14> The molded article according to <13>, wherein the molding process is melt spinning.
<15> A molded article obtained by subjecting the molded article according to <13> to advanced processing.
<16> The molded article according to <15>, which is a woven fabric or a nonwoven fabric.

＜１７＞　（成分Ａ）下記（ａ－１）及び（ａ－２）を満たす４価金属リン酸塩化合物、（成分Ｂ）下記（ｂ－１）及び（ｂ－２）を満たすポリエステル樹脂、並びに、（成分Ｃ）分散剤をバッチ式混練手段により混練し、成分Ａの含有量が、組成物の全質量に対し、４０質量％～７２質量％であり、成分Ｂの含有量が、組成物の全質量に対し、２５質量％～５０質量％であり、成分Ｃの含有量が、組成物の全質量に対し、３質量％～２５質量％であるポリエステル樹脂組成物αを得る工程を含むポリエステル樹脂組成物の製造方法。
（ａ－１）下記式（１）で表される化合物である
　ＭＨａ（ＰＯ４）ｂ・ｎＨ２Ｏ　（１）
　式（１）中、Ｍは１種以上の４価金属を表し、ａ及びｂは３ｂ－ａ＝４を満たす正数であり、ｂは２＜ｂ≦２．１であり、ｎは０≦ｎ≦２である。
（ａ－２）メジアン径（Ｄ５０）が１．５μｍ以下である
（ｂ－１）結晶性である
（ｂ－２）テレフタル酸及びエチレングリコール以外のモノマーが１種類以上共重合されている
＜１８＞　（成分Ａ）下記（ａ－１）及び（ａ－２）を満たす４価金属リン酸塩化合物、（成分Ｂ）下記（ｂ－１）及び（ｂ－２）を満たすポリエステル樹脂、並びに、（成分Ｃ）分散剤を含有し、成分Ａの含有量が、組成物の全質量に対し、４０質量％～７２質量％であり、成分Ｂの含有量が、組成物の全質量に対し、２５質量％～５０質量％であり、成分Ｃの含有量が、組成物の全質量に対し、３質量％～２５質量％であるポリエステル樹脂組成物αに、（成分Ｄ）下記（ｄ－１）を満たすポリエステル樹脂と、成分Ｂとして、下記（ｂ－３）及び（ｂ－４）を満たすポリエステル樹脂とを添加して混練する工程を含むポリエステル樹脂組成物の製造方法。
（ａ－１）下記式（１）で表される化合物である
　ＭＨａ（ＰＯ４）ｂ・ｎＨ２Ｏ　（１）
　式（１）中、Ｍは１種以上の４価金属を表し、ａ及びｂは３ｂ－ａ＝４を満たす正数であり、ｂは２＜ｂ≦２．１であり、ｎは０≦ｎ≦２である。
（ａ－２）メジアン径（Ｄ５０）が１．５μｍ以下である
（ｂ－１）結晶性である
（ｂ－２）テレフタル酸及びエチレングリコール以外のモノマーが１種類以上共重合されている
（ｂ－３）示差走査熱量計で測定した融点が２００℃以下である
（ｂ－４）固有粘度（ＩＶ）が１ｄＬ／ｇ以上である
（ｄ－１）示差走査熱量計で測定した融点が２４０℃以上である
＜１９＞　成分Ｄが、下記（ｄ－２）を満たす＜１８＞に記載のポリエステル樹脂組成物の製造方法。
（ｄ－２）固有粘度（ＩＶ）が０．６ｄＬ／ｇ以上である
＜２０＞　前記混練する工程が、連続式混練手段により混練する工程である＜１８＞又は＜１９＞に記載のポリエステル樹脂組成物の製造方法。 <17> A method for producing a polyester resin composition, comprising a step of kneading (component A) a tetravalent metal phosphate compound that satisfies the following (a-1) and (a-2), (component B) a polyester resin that satisfies the following (b-1) and (b-2), and (component C) a dispersant by batch kneading means to obtain a polyester resin composition a, in which the content of component A is 40% by mass to 72% by mass, the content of component B is 25% by mass to 50% by mass, and the content of component C is 3% by mass to 25% by mass, relative to the total mass of the composition.
(a-1) A compound represented by the following formula (1): MH a (PO 4 ) b ·nH 2 O (1)
In formula (1), M represents one or more tetravalent metals, a and b are positive numbers satisfying 3b-a=4, b is 2<b≦2.1, and n is 0≦n≦2.
(a-2) the median diameter (D 50 ) is 1.5 μm or less, (b-1) the polyester is crystalline, and (b-2) one or more monomers other than terephthalic acid and ethylene glycol are copolymerized therein. <18> A method for producing a polyester resin composition comprising: (Component A) a tetravalent metal phosphate compound that satisfies the following (a-1) and (a-2); (Component B) a polyester resin that satisfies the following (b-1) and (b-2); and (Component C) a dispersant, the method comprising the steps of: adding, to a polyester resin composition α in which the content of Component A is 40% by mass to 72% by mass, the content of Component B is 25% by mass to 50% by mass, and the content of Component C is 3% by mass to 25% by mass, based on the total mass of the composition; and kneading the resulting polyester resin composition with (Component D) a polyester resin that satisfies the following (d-1); and, as Component B, a polyester resin that satisfies the following (b-3) and (b-4).
(a-1) A compound represented by the following formula (1): MH a (PO 4 ) b ·nH 2 O (1)
In formula (1), M represents one or more tetravalent metals, a and b are positive numbers satisfying 3b-a=4, b is 2<b≦2.1, and n is 0≦n≦2.
(a-2) the median diameter (D 50 ) is 1.5 μm or less; (b-1) the component is crystalline; (b-2) one or more monomers other than terephthalic acid and ethylene glycol are copolymerized therein; (b-3) the melting point measured by a differential scanning calorimeter is 200° C. or less; (b-4) the intrinsic viscosity (IV) is 1 dL/g or more; (d-1) the melting point measured by a differential scanning calorimeter is 240° C. or more. <19> The method for producing a polyester resin composition according to <18>, wherein component D satisfies the following (d-2):
<20> The method for producing a polyester resin composition according to <18> or <19>, wherein the kneading step is a step of kneading by a continuous kneading means, and (d-2) an intrinsic viscosity (IV) is 0.6 dL/g or more.

　本開示によれば、４価金属リン酸塩化合物の分散性に優れるポリエステル樹脂組成物及びその製造方法が提供される。
　また、本開示によれば、前記ポリエステル樹脂組成物を用いた成形体が提供される。 According to the present disclosure, there are provided a polyester resin composition having excellent dispersibility of a tetravalent metal phosphate compound and a method for producing the same.
The present disclosure also provides a molded article using the polyester resin composition.

図１は、実施例２８のポリエステル樹脂組成物ペレットの断面を３００倍で撮影したＳＥＭ像である。FIG. 1 is an SEM image of a cross section of a polyester resin composition pellet of Example 28 taken at 300x magnification. 図２は、図１の比較例ＳＥＭ像を画像解析し、二値化して得た画像である。FIG. 2 is an image obtained by subjecting the comparative SEM image of FIG. 1 to image analysis and binarization. 図３は、比較例６のポリエステル樹脂組成物ペレットの断面を３００倍で撮影したＳＥＭ像である。FIG. 3 is an SEM image of a cross section of the polyester resin composition pellet of Comparative Example 6 taken at 300x magnification. 図４は、図３のＳＥＭ像を画像解析し、二値化して得た画像である。FIG. 4 is an image obtained by subjecting the SEM image of FIG. 3 to image analysis and binarization.

　本開示において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
　本開示において、組成物中の各成分の量は、組成物中に各成分に該当する物質が複数存在する場合は、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。
　本開示中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上
限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。本開示中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
　本開示において、好ましい態様の組み合わせは、より好ましい態様である。
　本開示における基（原子団）の表記において、置換及び無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。
　本開示において、特に断りのない限り、各成分は、１種単独で使用しても、２種以上を併用してもよい。 In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values before and after "to" as the lower and upper limits.
In the present disclosure, when a plurality of substances corresponding to each component are present in the composition, the amount of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified.
In the numerical ranges described in stages in this disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. In the numerical ranges described in this disclosure, the upper or lower limit value of the numerical range may be replaced with a value shown in the examples.
In this disclosure, combinations of preferred aspects are more preferred aspects.
In the description of groups (atomic groups) in the present disclosure, a description without specifying whether substituted or unsubstituted encompasses both groups having no substituents and groups having a substituent.
In the present disclosure, unless otherwise specified, each component may be used alone or in combination of two or more types.

　本開示における４価金属リン酸塩化合物の「分散性」の文言は、上記化合物の分散性及び分配性を含む概念で用いられる。即ち、本開示では、分散性及び分配性をあわせて単に「分散性」と称する。分散性とは、個々の４価金属リン酸塩化合物粒子（一次粒子）が凝集した粗大粒子（二次粒子）を形成せず、単分散され易い性質を意味し、分配性とは、４価金属リン酸塩粒子がポリエステル樹脂組成物の基材全体に亘り均一に存在し易い性質を意味する。
　本明細書において、特に断りなく、単に「本開示に係るポリエステル樹脂組成物」という場合は、後述の第１の実施形態、第２の実施態様及び第３の実施態様の全てについて述べるものとする。 The term "dispersibility" of the tetravalent metal phosphate compound in the present disclosure is used as a concept including the dispersibility and distribution of the compound. That is, in the present disclosure, dispersibility and distribution are collectively referred to simply as "dispersibility". Dispersibility means that individual tetravalent metal phosphate compound particles (primary particles) do not form coarse particles (secondary particles) by aggregation, but tend to be monodispersed, and distribution means that tetravalent metal phosphate particles tend to be uniformly present throughout the substrate of the polyester resin composition.
In this specification, unless otherwise specified, when the term "polyester resin composition according to the present disclosure" is used, it refers to all of the first embodiment, the second embodiment, and the third embodiment described below.

（ポリエステル樹脂組成物）
　本開示に係るポリエステル樹脂組成物の第１の実施態様は、（成分Ａ）下記（ａ－１）及び（ａ－２）を満たす４価金属リン酸塩化合物、（成分Ｂ）下記（ｂ－１）及び（ｂ－２）を満たすポリエステル樹脂、並びに、（成分Ｃ）分散剤を含有し、成分Ａの含有量が、組成物の全質量に対し、４０質量％～７２質量％であり、成分Ｂの含有量が、組成物の全質量に対し、２５質量％～５０質量％であり、成分Ｃの含有量が、組成物の全質量に対し、３質量％～２５質量％である。
（ａ－１）下記式（１）で表される化合物である
　ＭＨａ（ＰＯ４）ｂ・ｎＨ２Ｏ　（１）
　式（１）中、Ｍは１種以上の４価金属を表し、ａ及びｂは３ｂ－ａ＝４を満たす正数であり、ｂは２＜ｂ≦２．１であり、ｎは０≦ｎ≦２である。
（ａ－２）メジアン径（Ｄ５０）が１．５μｍ以下である
（ｂ－１）結晶性である
（ｂ－２）テレフタル酸及びエチレングリコール以外のモノマーが１種類以上共重合されている (Polyester resin composition)
A first embodiment of the polyester resin composition according to the present disclosure comprises (component A) a tetravalent metal phosphate compound satisfying the following (a-1) and (a-2), (component B) a polyester resin satisfying the following (b-1) and (b-2), and (component C) a dispersant, wherein the content of component A is 40% by mass to 72% by mass, the content of component B is 25% by mass to 50% by mass, and the content of component C is 3% by mass to 25% by mass, based on the total mass of the composition.
(a-1) A compound represented by the following formula (1): MH a (PO 4 ) b ·nH 2 O (1)
In formula (1), M represents one or more tetravalent metals, a and b are positive numbers satisfying 3b-a=4, b is 2<b≦2.1, and n is 0≦n≦2.
(a-2) The median diameter (D 50 ) is 1.5 μm or less. (b-1) It is crystalline. (b-2) At least one monomer other than terephthalic acid and ethylene glycol is copolymerized.

　本開示に係るポリエステル樹脂組成物の第２の実施態様は、（成分Ａ）下記（ａ－１）及び（ａ－２）を満たす４価金属リン酸塩化合物、（成分Ｂ）下記（ｂ－１）及び（ｂ－２）を満たすポリエステル樹脂、（成分Ｃ）分散剤、並びに、（成分Ｄ）下記（ｄ－１）を満たすポリエステル樹脂を含有し、成分Ａの含有量が、組成物の全質量に対し、０．４質量％～３０質量％であり、成分Ｂの含有量が、組成物の全質量に対し、７質量％～３５質量％であり、成分Ｃの含有量が、組成物の全質量に対し、０．１質量％～１１質量％であり、成分Ｄの含有量が、組成物の全質量に対し、３７質量％～８３．６質量％である。（ａ－１）下記式（１）で表される化合物である
　ＭＨａ（ＰＯ４）ｂ・ｎＨ２Ｏ　（１）
　式（１）中、Ｍは１種以上の４価金属を表し、ａ及びｂは３ｂ－ａ＝４を満たす正数であり、ｂは２＜ｂ≦２．１であり、ｎは０≦ｎ≦２である。
（ａ－２）メジアン径（Ｄ５０）が１．５μｍ以下である
（ｂ－１）結晶性である
（ｂ－２）テレフタル酸及びエチレングリコール以外のモノマーが１種類以上共重合されている
（ｄ－１）示差走査熱量計で測定した融点が２４０℃以上である A second embodiment of the polyester resin composition according to the present disclosure contains (component A) a tetravalent metal phosphate compound satisfying the following (a-1) and (a-2), (component B) a polyester resin satisfying the following (b-1) and (b-2), (component C) a dispersant, and (component D) a polyester resin satisfying the following (d-1), and the content of component A is 0.4% by mass to 30% by mass with respect to the total mass of the composition, the content of component B is 7% by mass to 35% by mass with respect to the total mass of the composition, the content of component C is 0.1% by mass to 11% by mass with respect to the total mass of the composition, and the content of component D is 37% by mass to 83.6% by mass with respect to the total mass of the composition. (a-1) is a compound represented by the following formula (1): MH a (PO 4 ) b ·nH 2 O (1)
In formula (1), M represents one or more tetravalent metals, a and b are positive numbers satisfying 3b-a=4, b is 2<b≦2.1, and n is 0≦n≦2.
(a-2) The median diameter (D 50 ) is 1.5 μm or less. (b-1) It is crystalline. (b-2) At least one monomer other than terephthalic acid and ethylene glycol is copolymerized. (d-1) It has a melting point of 240° C. or more as measured by a differential scanning calorimeter.

　本開示に係るポリエステル樹脂組成物の第３の実施態様は、４価金属リン酸塩化合物及びポリエステル樹脂を含み、視野サイズが０．４ｍｍ×０．３ｍｍのポリエステル樹脂組成物の断面ＳＥＭ像において、リン酸ジルコニウムに代表される前記４価金属リン酸塩化合物の粒子サイズが２０μｍ２以上となる粒子数が１個未満であるポリエステル樹脂組成物である。 A third embodiment of the polyester resin composition according to the present disclosure is a polyester resin composition comprising a tetravalent metal phosphate compound and a polyester resin, wherein in a cross-sectional SEM image of the polyester resin composition having a field of view size of 0.4 mm x 0.3 mm, the number of particles of the tetravalent metal phosphate compound represented by zirconium phosphate having a particle size of 20 μm 2 or more is less than 1.

　本開示に係るポリエステル樹脂組成物の第２の実施態様及び第３の実施態様は、いわゆるマスターバッチとして使用されることが好ましい。
　本開示に係るポリエステル樹脂組成物の第１の実施態様は、マスターバッチを作製する中間体として使用されることが好ましい。
　本開示に係るポリエステル樹脂組成物の第２の実施態様及び第３の実施態様は、４価金属リン酸塩化合物の分散性の観点から、本開示に係るポリエステル樹脂組成物の第１の実施態様を用いて作製されることが好ましい。
　本開示において、特に断りなく、単に「成分Ａ」等という場合は、前記第１の実施態様、前記第２の実施態様及び前記第３の実施態様の全てについて述べるものとする。 The second and third embodiments of the polyester resin composition according to the present disclosure are preferably used as a so-called masterbatch.
The first embodiment of the polyester resin composition according to the present disclosure is preferably used as an intermediate for producing a masterbatch.
The second and third embodiments of the polyester resin composition according to the present disclosure are preferably produced using the first embodiment of the polyester resin composition according to the present disclosure from the viewpoint of dispersibility of the tetravalent metal phosphate compound.
In the present disclosure, unless otherwise specified, simply referring to "component A" or the like refers to all of the first embodiment, the second embodiment, and the third embodiment.

　本発明者の検討結果によれば、従来技術に記載のポリエステル樹脂組成物を用いて溶融紡糸加工を行う際、ポリエステル樹脂組成物中の４価金属リン酸塩化合物の分散性が悪いと一次粒子が凝集した粗大粒子（二次粒子）が原因で溶融紡糸加工に用いる押出機先端に設置したメッシュで捕捉されてメッシュが詰まり、樹脂圧力が上昇して昇圧することで樹脂組成物の吐出量不足やメッシュを通過した粗大粒子にて発生した糸切れによる生産性低下、及び、４価金属リン酸塩化合物がメッシュで捕捉された分の配合量不足による性能低下の問題があることを見出した。
　上記事情に鑑み、本発明者が詳細な検討を行った結果、本開示に係るポリエステル樹脂組成物の第１の実施態様又は第２の実施態様であると、混練時のせん断、及び、伸長エネルギーにより４価金属リン酸塩化合物の一次粒子の凝集体である粗大粒子（二次粒子）を粉砕し、４価金属リン酸塩化合物の一次粒子を均一に分散させ、前記配合比率を満たすことにより、４価金属リン酸塩化合物の表面を有機物であるポリエステル樹脂と分散剤でよく濡らしてコーティングすることで４価金属リン酸塩化合物の界面エネルギーを低減させてポリエステル樹脂との親和性を向上させることで、混練時のせん断、及び、伸長エネルギー起因でのメカノケミカルで発生すると考えられる４価金属リン酸塩化合物同士の再凝集による粗大粒子の生成を抑制し、４価金属リン酸塩化合物の分散性に優れると推定している。 According to the results of investigations by the present inventors, it has been found that when melt spinning is carried out using the polyester resin composition described in the prior art, if the dispersibility of the tetravalent metal phosphate compound in the polyester resin composition is poor, coarse particles (secondary particles) formed by agglomeration of primary particles are captured by a mesh installed at the tip of the extruder used in the melt spinning process, causing the mesh to become clogged, and the resin pressure increases and builds up, resulting in a shortage of the discharge rate of the resin composition and a decrease in productivity due to thread breakage caused by the coarse particles that pass through the mesh, and a decrease in performance due to an insufficient blending amount of the tetravalent metal phosphate compound captured by the mesh.
In view of the above circumstances, the present inventors have conducted detailed studies and have found that in the first or second embodiment of the polyester resin composition according to the present disclosure, coarse particles (secondary particles) which are aggregates of primary particles of a tetravalent metal phosphate compound are pulverized by shear and elongation energy during kneading, the primary particles of the tetravalent metal phosphate compound are uniformly dispersed, and the above-mentioned blending ratio is satisfied, whereby the surface of the tetravalent metal phosphate compound is thoroughly wetted and coated with the polyester resin, which is an organic substance, and a dispersant, thereby reducing the interfacial energy of the tetravalent metal phosphate compound and improving its affinity with the polyester resin. This suppresses the generation of coarse particles due to re-aggregation of the tetravalent metal phosphate compounds which is thought to occur mechanochemically due to shear and elongation energy during kneading, and thus results in excellent dispersibility of the tetravalent metal phosphate compound.

　また、本開示に係るポリエステル樹脂組成物の第３の実施態様であると、４価金属リン酸塩化合物の一次粒子の凝集体である粗大粒子（二次粒子）が十分に少なく、ポリエステル樹脂組成物中の、リン酸ジルコニウム粒子に代表される４価金属リン酸塩化合物の粒子の分散性が良好であることが確認できる。更に、ポリエステル樹脂組成物中に含まれる４価金属リン酸塩化合物の粒子のサイズが小さいこと、言い換えれば、４価金属リン酸塩化合物の粒子の分散性が良好であり、４価金属リン酸塩化合物の粒子の凝集が抑制されていることが確認でき、４価金属リン酸塩化合物の分散性に優れる。
　リン酸ジルコニウムに代表される４価金属リン酸塩化合物の粒子は、ポリエステル樹脂組成物において消臭機能を発現する。ポリエステル樹脂組成物中において、４価金属リン酸塩化合物の粒子が凝集せず、断面ＳＥＭ像の上記視野角中における粒子サイズが２０μｍ２以上の粒子の数が１個未満であること、更に好ましくは、全ての粒子の断面ＳＥＭ像における粒子サイズが２０μｍ２未満であることで、ポリエステル樹脂組成物を用いて紡糸した場合の糸切れが少なく、同じ含有量で４価金属リン酸塩化合物の粒子を用いた場合、粒子の表面積が広くなり、消臭効果が向上する。
　また、リン酸ジルコニウムに代表される４価金属リン酸塩化合物の粒子にはイオン吸着性、抗菌性、抗ウイルス性、抗アレルゲン性があり、４価金属リン酸塩化合物を含有するポリエステル樹脂組成物においても同様の機能が発現する。 In addition, in the third embodiment of the polyester resin composition according to the present disclosure, the amount of coarse particles (secondary particles) which are aggregates of the primary particles of the tetravalent metal phosphate compound is sufficiently small, and it can be confirmed that the particles of the tetravalent metal phosphate compound represented by zirconium phosphate particles in the polyester resin composition have good dispersibility.Furthermore, it can be confirmed that the size of the particles of the tetravalent metal phosphate compound contained in the polyester resin composition is small, in other words, the dispersibility of the particles of the tetravalent metal phosphate compound is good, and the aggregation of the particles of the tetravalent metal phosphate compound is suppressed, and the dispersibility of the tetravalent metal phosphate compound is excellent.
Particles of tetravalent metal phosphate compounds, such as zirconium phosphate, exhibit a deodorizing function in polyester resin compositions. In the polyester resin composition, the particles of tetravalent metal phosphate compounds do not aggregate, and the number of particles with a particle size of 20 μm2 or more in the above viewing angle of the cross-sectional SEM image is less than one, and more preferably, the particle size of all particles in the cross-sectional SEM image is less than 20 μm2 , so that when the polyester resin composition is used for spinning, there is less thread breakage, and when the particles of tetravalent metal phosphate compounds are used at the same content, the surface area of the particles is increased, and the deodorizing effect is improved.
In addition, particles of a tetravalent metal phosphate compound, such as zirconium phosphate, have ion adsorptive, antibacterial, antiviral, and antiallergenic properties, and similar functions are also exhibited in polyester resin compositions containing a tetravalent metal phosphate compound.

＜（成分Ａ）（ａ－１）及び（ａ－２）を満たす４価金属リン酸塩化合物＞
　本開示に係るポリエステル樹脂組成物の第１の実施態様及び第２の実施態様は、（成分Ａ）下記（ａ－１）及び（ａ－２）を満たす４価金属リン酸塩化合物を含有する。
　本開示に係るポリエステル樹脂組成物の第３の実施態様は、（成分Ａ）下記（ａ－１）及び（ａ－２）を満たす４価金属リン酸塩化合物を含有することが好ましい。
　（ａ－１）下記式（１）で表される化合物である
　ＭＨａ（ＰＯ４）ｂ・ｎＨ２Ｏ　（１）
　式（１）中、Ｍは１種以上の４価金属を表し、ａ及びｂは３ｂ－ａ＝４を満たす数を表し、ｂは２．０を超え２．１以下の数を表し、ｎは０～２の整数を表す。
　（ａ－２）メジアン径（Ｄ５０）が１．５μｍ以下である <(Component A) Tetravalent Metal Phosphate Compound Satisfying (a-1) and (a-2)>
The first and second embodiments of the polyester resin composition according to the present disclosure contain (Component A) a tetravalent metal phosphate compound that satisfies the following (a-1) and (a-2).
A third embodiment of the polyester resin composition according to the present disclosure preferably contains (Component A) a tetravalent metal phosphate compound that satisfies the following (a-1) and (a-2).
(a-1) A compound represented by the following formula (1): MH a (PO 4 ) b ·nH 2 O (1)
In formula (1), M represents one or more tetravalent metals, a and b represent numbers satisfying 3b-a=4, b represents a number greater than 2.0 and equal to or less than 2.1, and n represents an integer of 0 to 2.
(a-2) The median diameter (D 50 ) is 1.5 μm or less.

　Ｍとしては、４価の金属であれば特に制限はないが、分散性及び消臭性の観点から、ジルコニウム、チタン及びハフニウムよりなる群から選ばれた少なくとも１種の４価金属であることが好ましく、ジルコニウム及びハフニウムであることがより好ましく、Ｚｒ１－ｘＨｆｘであることが特に好ましい。なお、ｘは０以上０．２以下の数を表す。 There are no particular limitations on M as long as it is a tetravalent metal, but from the viewpoint of dispersibility and deodorizing properties, it is preferably at least one tetravalent metal selected from the group consisting of zirconium, titanium, and hafnium, more preferably zirconium and hafnium, and particularly preferably Zr 1-x Hf x , where x represents a number from 0 to 0.2.

　式（１）のｂは２＜ｂ≦２．１であり、好ましくは２．０≦ｂ≦２．１であり、より好ましくは２．０１≦ｂ≦２．０６である。ｂが大きい、つまりリン酸が多いほどイオン交換性能は上がるが、リン酸イオンが溶出しやすくなるなど他の物性が低下する。 The b in formula (1) is 2<b≦2.1, preferably 2.0≦b≦2.1, and more preferably 2.01≦b≦2.06. The larger b is, that is, the more phosphoric acid there is, the higher the ion exchange performance is, but other physical properties such as the tendency for phosphate ions to dissolve are reduced.

　式（１）のｎは、０≦ｎ≦２であり、ｎは１未満が好ましく、より好ましくは０．０１～０．５であり、０．０３～０．３の範囲が更に好ましい。ｎが２を超える場合、４価金属リン酸塩化合物に含まれる水分の絶対量が多く、加工時等に発泡や加水分解などを生じるおそれがある。 In formula (1), n is 0≦n≦2, and n is preferably less than 1, more preferably 0.01 to 0.5, and even more preferably in the range of 0.03 to 0.3. If n exceeds 2, the absolute amount of water contained in the tetravalent metal phosphate compound is large, and there is a risk of foaming, hydrolysis, etc. occurring during processing, etc.

　前記式（１）で表される化合物は、下記式（２）又は式（３）で表される化合物であることが好ましく、下記式（２）で表される化合物であることがより好ましい。
　Ｚｒ１－ＸＨｆＸＨａ（ＰＯ４）ｂ・ｎＨ２Ｏ　（２）
　Ｔｉ１－ＸＨｆＸＨａ（ＰＯ４）ｂ・ｎＨ２Ｏ　（３）
　式（２）及び式（３）中、Ｘは０≦ｎ＜１であり、ａ及びｂは３ｂ－ａ＝４を満たす正数であり、ｂは２＜ｂ≦２．１であり、ｎは０≦ｎ≦２である。 The compound represented by formula (1) is preferably a compound represented by formula (2) or (3) below, and more preferably a compound represented by formula (2) below.
Zr 1-X Hf X H a (PO 4 ) b・nH 2 O (2)
Ti 1-X Hf X H a (PO 4 ) b・nH 2 O (3)
In formulas (2) and (3), X is 0≦n<1, a and b are positive numbers satisfying 3b−a=4, b is 2<b≦2.1, and n is 0≦n≦2.

　式（２）及び式（３）のｘは、０＜ｘ＜１であり、好ましくは０＜ｘ≦０．２であり、より好ましくは０．００５≦ｘ≦０．１であり、更に好ましくは０．００５≦ｘ＜０．０３である。ハフニウムの含有量が多くなるとイオン交換性能は向上するが、ハフニウムには放射性の同位体が存在するので、電子部品に使用する場合は、多すぎると悪影響を及ぼす可能性がある。 In formulas (2) and (3), x is 0<x<1, preferably 0<x≦0.2, more preferably 0.005≦x≦0.1, and even more preferably 0.005≦x<0.03. Increasing the hafnium content improves ion exchange performance, but hafnium contains radioactive isotopes, so if it is used in electronic components, too much of it may have adverse effects.

　本開示における成分Ａの組成式の分析方法は、特に限定されないが、例えば、以下の方法で測定可能である。
　蛍光Ｘ線による元素分析と熱重量示差熱分析（ＴＧ－ＤＴＡ）による水和水分析にて実施する。 The method for analyzing the composition formula of Component A in the present disclosure is not particularly limited, but can be measured, for example, by the following method.
This is carried out by elemental analysis using X-ray fluorescence and hydration water analysis using thermogravimetric differential thermal analysis (TG-DTA).

－蛍光Ｘ線分析－
　蛍光Ｘ線分析は以下の条件で測定する。
　＜測定条件＞
　測定機器：リガク（株）製　ＺＳＸ　Ｐｒｉｍｕｓ　ＩＩ
　測定元素：Ｃ～Ｕ（Ｆ、Ｃｌ、Ｂｒ、Ｉに定角測定、ＢＧ　４ｓｅｃ、ピーク８ｓｅｃ）
　分析径：２０ｍｍ
　測定数：ｎ＝２で測定
　試料処理：錠剤成型機を用い、試料をペレット状に加圧成型し、測定に供する。
　＜解析＞
　ソフトウェア：ＺＳＸ　ｖｅｒｓｉｏｎ７．４９
　モデル：バルク - X-ray fluorescence analysis -
The X-ray fluorescence analysis is performed under the following conditions.
<Measurement conditions>
Measuring equipment: Rigaku Corporation ZSX Primus II
Measurement elements: C to U (measured at a fixed angle for F, Cl, Br, and I, BG 4 sec, peak 8 sec)
Analysis diameter: 20mm
Number of measurements: n=2 Sample treatment: The sample is compressed into pellets using a tablet press and then subjected to the measurement.
<Analysis>
Software: ZSX version 7.49
Model: Bulk

－熱重量示差熱分析（ＴＧ－ＤＴＡ）－
　熱重量示差熱分析（ＴＧ－ＤＴＡ）は以下の条件で測定する。
　測定機器：（株）日立ハイテクサイエンス製ＴＧ／ＤＴＡ　６３００
　測定方法：試料７ｍｇ～８ｍｇをＡｌパンに入れてセットし、２０℃／ｍｉｎで６００℃まで昇温し、室温～１００℃までの減量を水分量（付着水）とし、１００℃～２５０℃までの減量を結晶水（水和水）として見積もる。 -Thermogravimetric differential thermal analysis (TG-DTA)-
Thermogravimetric-differential thermal analysis (TG-DTA) is performed under the following conditions.
Measuring equipment: TG/DTA 6300 manufactured by Hitachi High-Tech Science Co., Ltd.
Measurement method: 7 mg to 8 mg of sample is placed in an Al pan and heated to 600°C at 20°C/min. The weight loss from room temperature to 100°C is estimated as the moisture content (adherent water), and the weight loss from 100°C to 250°C is estimated as water of crystallization (water of hydration).

　４価金属リン酸塩化合物の内、リン酸ジルコニウムの好ましい具体例として、以下のものが挙げられる。
　Ｚｒ０．９９Ｈｆ０．０１Ｈ２．０３（ＰＯ４）２．０１・０．０５Ｈ２Ｏ
　Ｚｒ０．９９Ｈｆ０．０１Ｈ２．０６（ＰＯ４）２．０２・０．０５Ｈ２Ｏ
　Ｚｒ０．９９Ｈｆ０．０１Ｈ２．１２（ＰＯ４）２．０４・０．０５Ｈ２Ｏ
　Ｚｒ０．９９Ｈｆ０．０１Ｈ２．２４（ＰＯ４）２．０８・０．０５Ｈ２Ｏ
　Ｚｒ０．９８Ｈｆ０．０２Ｈ２．０３（ＰＯ４）２．０１・０．０５Ｈ２Ｏ
　Ｚｒ０．９８Ｈｆ０．０２Ｈ２．０６（ＰＯ４）２．０２・０．０５Ｈ２Ｏ
　Ｚｒ０．９８Ｈｆ０．０２Ｈ２．１２（ＰＯ４）２．０４・０．０５Ｈ２Ｏ
　Ｚｒ０．９８Ｈｆ０．０２Ｈ２．２４（ＰＯ４）２．０８・０．０５Ｈ２Ｏ
　Ｚｒ０．９７Ｈｆ０．０３Ｈ２．０３（ＰＯ４）２．０１・０．０５Ｈ２Ｏ
　Ｚｒ０．９４Ｈｆ０．０６Ｈ２．０３（ＰＯ４）２．０１・０．０５Ｈ２Ｏ
　Ｚｒ０．９Ｈｆ０．１Ｈ２．０３（ＰＯ４）２．０１・０．０５Ｈ２Ｏ Among the tetravalent metal phosphate compounds, preferred specific examples of zirconium phosphate include the following:
Zr 0.99 Hf 0.01 H 2.03 (PO 4 ) 2.01・0.05H 2 O
Zr 0.99 Hf 0.01 H 2.06 (PO 4 ) 2.02・0.05H 2 O
Zr 0.99 Hf 0.01 H 2.12 (PO 4 ) 2.04・0.05H 2 O
Zr 0.99 Hf 0.01 H 2.24 (PO 4 ) 2.08・0.05H 2 O
Zr 0.98 Hf 0.02 H 2.03 (PO 4 ) 2.01・0.05H 2 O
Zr 0.98 Hf 0.02 H 2.06 (PO 4 ) 2.02・0.05H 2 O
Zr 0.98 Hf 0.02 H 2.12 (PO 4 ) 2.04・0.05H 2 O
Zr 0.98 Hf 0.02 H 2.24 (PO 4 ) 2.08・0.05H 2 O
Zr 0.97 Hf 0.03 H 2.03 (PO 4 ) 2.01・0.05H 2 O
Zr 0.94 Hf 0.06 H 2.03 (PO 4 ) 2.01・0.05H 2 O
Zr 0.9 Hf 0.1 H 2.03 (PO 4 ) 2.01・0.05H 2 O

　４価金属リン酸塩化合物の結晶構造に特に制限はないが、消臭性の観点から、塩基性ガス吸着能を有するα型、β型、γ型及び非晶質の４価金属リン酸塩化合物をｐＨ９以上の塩基性液体に接触させた後、更に、ｐＨ６以下の酸性液体に接触させることによって得られる４価金属リン酸塩化合物が好ましく、α型の４価金属リン酸塩化合物がより好ましい。
　また、前記式（１）で表される化合物が、前記式（２）で表される化合物であり、かつ前記式（２）で表される化合物の結晶構造は、α型であるであることが好ましい。 There are no particular limitations on the crystal structure of the tetravalent metal phosphate compound, but from the viewpoint of deodorizing properties, preferred are tetravalent metal phosphate compounds obtained by contacting an α-type, β-type, γ-type or amorphous tetravalent metal phosphate compound having basic gas adsorption ability with a basic liquid of pH 9 or more and then contacting the compound with an acidic liquid of pH 6 or less, and more preferred are α-type tetravalent metal phosphate compounds.
It is also preferred that the compound represented by formula (1) is a compound represented by formula (2), and the crystal structure of the compound represented by formula (2) is an α-type.

　本開示における成分Ａの結晶構造の測定方法は、特に限定されないが、例えば、粉末Ｘ線回折にて評価可能である。Ｘ線回折装置は、ＢＲＵＫＥＲ社製　Ｄ８　ＡＤＶＡＮＣＥを使用する。Ｃｕ封入型Ｘ線源を用い、印加電圧４０ｋＶ、電流値４０ｍＡで発生するＣｕＫαを用いてＸ線回折図を得る。詳細な測定条件は下記の通り。
　Ｘ線源：封入型Ｘ線源（Ｃｕ線源）、０．４×１２ｍｍ２、Ｌｏｎｇ　Ｆｉｎｅ　Ｆｏｃｕｓ
　定格：２．２ｋＷ
　使用出力：４０ｋＶ－４０ｍＡ（１．６ｋＷ）
　ゴニオメーター半径：２８０ｍｍ
　試料ステージ：ＦｌｉｐＳｔｉｃｋ＿Ｔｗｉｎ＿Ｔｗｉｎ－ＸＥ
　測定範囲２θ：５°～５５°
　ステップ幅：０．０２°
　ステップ時間：０．０５秒／ステップ
　入射側ソラースリット：２．５°
　散乱防止スリット：１０．５ｍｍ
　曲率：１．００
　検出器：ＬＹＮＸＥＹＥ　ＸＥ
　検出器スリット幅：５．７５８ｍｍ
　検出器ウインドウ幅：２．９° The method for measuring the crystal structure of component A in the present disclosure is not particularly limited, but can be evaluated, for example, by powder X-ray diffraction. The X-ray diffraction apparatus used is a D8 ADVANCE manufactured by BRUKER. An X-ray diffraction pattern is obtained using CuKα generated at an applied voltage of 40 kV and a current value of 40 mA using a Cu-encapsulated X-ray source. The detailed measurement conditions are as follows.
X-ray source: Enclosed X-ray source (Cu ray source), 0.4 x 12 mm 2 , Long Fine Focus
Rating: 2.2kW
Output power: 40kV-40mA (1.6kW)
Goniometer radius: 280 mm
Sample stage: FlipStick_Twin_Twin-XE
Measurement range 2θ: 5° to 55°
Step width: 0.02°
Step time: 0.05 sec/step Entrance side Soller slit: 2.5°
Anti-scattering slit: 10.5 mm
Curvature: 1.00
Detector: LYNXEYE XE
Detector slit width: 5.758 mm
Detector window width: 2.9°

　成分Ａのメジアン径（Ｄ５０）は、１．５μｍ以下であり、消臭性の観点から、１．０μｍ以下であることが好ましく、０．１μｍ～１．０μｍであることがより好ましく、０．２μｍ～０．８μｍであることが更に好ましい。 The median diameter (D 50 ) of component A is 1.5 μm or less, and from the viewpoint of deodorizing properties, it is preferably 1.0 μm or less, more preferably 0.1 μm to 1.0 μm, and even more preferably 0.2 μm to 0.8 μm.

　本開示におけるメジアン径（単に「粒子径」ともいう）の測定方法は、特に限定されないが、例えば、以下の方法で測定可能である。
　４価金属リン酸塩化合物等の測定対象となる粒子を添加した分散液を超音波発生装置で５分間分散させ、レーザー回折式粒度分布測定装置「マスターサイザー２０００」（マルバーン社製）で測定し、結果を体積基準で解析する。
　分散媒：水
　粒子濃度：１質量％（水１００ｇに対して４価金属リン酸塩化合物１ｇ）
　粒子屈折率：２．４
　撹拌：２，４５０ｒｐｍ（回転／分）
　超音波：出力５０％×１分の繰り返し The method for measuring the median size (also simply referred to as "particle size") in the present disclosure is not particularly limited, but can be measured, for example, by the following method.
A dispersion liquid containing particles to be measured, such as a tetravalent metal phosphate compound, is dispersed for 5 minutes using an ultrasonic generator, and the particles are measured using a laser diffraction particle size distribution measuring device "Mastersizer 2000" (manufactured by Malvern Instruments), and the results are analyzed on a volume basis.
Dispersion medium: Water Particle concentration: 1% by mass (1 g of tetravalent metal phosphate compound per 100 g of water)
Particle refractive index: 2.4
Stirring: 2,450 rpm (revolutions per minute)
Ultrasonic: 50% output x 1 minute repetition

　また、成分Ａの乾燥減分率は、分散性、及び、ポリエステル樹脂の加水分解抑制の観点から、成分Ａの全質量に対し、５．０質量％以下であることが好ましく、３．０質量％以下であることがより好ましく、１．０質量％以下であることが更に好ましく、０．５質量％以下であることが特に好ましい。 In addition, from the viewpoint of dispersibility and suppression of hydrolysis of the polyester resin, the drying loss rate of component A is preferably 5.0 mass% or less, more preferably 3.0 mass% or less, even more preferably 1.0 mass% or less, and particularly preferably 0.5 mass% or less, relative to the total mass of component A.

　乾燥減分率の測定方法は、特に限定されないが、例えば、ＪＩＳ　Ｋ００６７：１９９２（化学製品の減量及び残分試験方法）の４．１．１（１）第一法により測定可能である。４価金属リン酸塩化合物を温度２５℃、湿度５０％の室内に２４時間静置した後、常圧下、２５０℃で２時間加熱し、加熱前後の質量を測定して、下記式（４）から４価金属リン酸塩化合物の乾燥減分率Ｙを算出する。
　　乾燥減分率Ｙ（質量％）＝｛（Ｂ０－Ｂ１）／Ｂ０｝×１００　（４）
　Ｂ０：加熱前の４価金属リン酸塩化合物の質量
　Ｂ１：加熱後の４価金属リン酸塩化合物の質量 The method for measuring the drying loss is not particularly limited, but it can be measured, for example, by JIS K0067:1992 (Testing method for weight loss and residue of chemical products) 4.1.1(1) Method 1. The tetravalent metal phosphate compound is left to stand for 24 hours in a room at a temperature of 25°C and a humidity of 50%, and then heated at 250°C under normal pressure for 2 hours. The masses before and after heating are measured, and the drying loss rate Y of the tetravalent metal phosphate compound is calculated from the following formula (4).
Drying reduction rate Y (mass%) = {(B 0 - B 1 )/B 0 }×100 (4)
B 0 : Mass of tetravalent metal phosphate compound before heating B 1 : Mass of tetravalent metal phosphate compound after heating

　本開示に係るポリエステル樹脂組成物の第１の実施態様における成分Ａの含有量は、組成物の全質量に対し、４０質量％～７２質量％であり、分散性、消臭性及び成形加工性の観点から、４０質量％～６３質量％であることが好ましく、４５質量％～６３質量％であることがより好ましい。 The content of component A in the first embodiment of the polyester resin composition according to the present disclosure is 40% by mass to 72% by mass relative to the total mass of the composition, and from the viewpoints of dispersibility, deodorizing properties, and moldability, is preferably 40% by mass to 63% by mass, and more preferably 45% by mass to 63% by mass.

　本開示に係るポリエステル樹脂組成物の第２の実施態様における成分Ａの含有量は、組成物の全質量に対し、０．４質量％～３０質量％であり、分散性、消臭性及び成形加工性の観点から、０．８質量％～３０質量％であることが好ましく、１．２質量％～２７質量％であることがより好ましく、２．０質量％～２４質量％であることが更に好ましい。 The content of component A in the second embodiment of the polyester resin composition according to the present disclosure is 0.4% by mass to 30% by mass relative to the total mass of the composition, and from the viewpoints of dispersibility, deodorizing properties, and moldability, is preferably 0.8% by mass to 30% by mass, more preferably 1.2% by mass to 27% by mass, and even more preferably 2.0% by mass to 24% by mass.

　本開示に係るポリエステル樹脂組成物の第３の実施態様における成分Ａの含有量は、組成物の全質量に対し、分散性、消臭性及び成形加工性の観点から、０．４質量％～３０質量％であることが好ましく、０．８質量％～３０質量％であることがより好ましく、１．２質量％～２７質量％であることが更に好ましく、２．０質量％～２４質量％であることが特に好ましい。 The content of component A in the third embodiment of the polyester resin composition according to the present disclosure is preferably 0.4% by mass to 30% by mass, more preferably 0.8% by mass to 30% by mass, even more preferably 1.2% by mass to 27% by mass, and particularly preferably 2.0% by mass to 24% by mass, based on the total mass of the composition, from the viewpoints of dispersibility, deodorization, and moldability.

　未知の樹脂組成物から樹脂の種類を確認する方法としては、特に限定されないが、例えばフーリエ変換赤外分光分析装置（ＦＴ－ＩＲ）や核磁気共鳴分光法（以下、ＮＭＲと略称する。）で確認する方法が挙げられる。
　以下に記載の如きＦＴ－ＩＲを用いて分析する場合、樹脂組成物の赤外スペクトルを測定し、各成分のピーク強度から樹脂の種類を判断できる。
　装置名：サーモフィッシャーサイエンティフィック社製「Ｎｉｃｏｌｅｔ　ｉＳ５０　ＦＴ－ＩＲ」
　測定方法：ＡＴＲ法（ＤｕｒａＳｃｏｐｅユニット　ダイアモンドディスク）
　アクセサリー：μ－ＡＴＲ
　条件：分解能４ｃｍ－１、積算回数３２回 The method for identifying the type of resin from an unknown resin composition is not particularly limited, but examples thereof include a method using a Fourier transform infrared spectrometer (FT-IR) or nuclear magnetic resonance spectroscopy (hereinafter abbreviated as NMR).
When analyzing using FT-IR as described below, the infrared spectrum of the resin composition is measured, and the type of resin can be determined from the peak intensity of each component.
Device name: Thermo Fisher Scientific "Nicolet iS50 FT-IR"
Measurement method: ATR method (DuraScope unit diamond disc)
Accessories: μ-ATR
Conditions: resolution 4cm -1 , number of integrations 32 times

　ＮＭＲを用いて樹脂の種類を確認する場合、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲを測定し、各成分のピーク強度から判断できる。
　装置名：Ｂｒｕｋｅｒ社製「ＡＶＡＮＣＥ　ＩＩＩ　４００」
　測定核種：１Ｈ、１３Ｃ
　共鳴周波数：４００ＭＨｚ（１Ｈ）、１００．６ＭＨｚ（１３Ｃ）
　測定溶媒：ＣＤＣｌ３ When the type of resin is identified using NMR, it can be determined from the peak intensity of each component by measuring 1 H-NMR and 13 C-NMR.
Device name: Bruker "AVANCE III 400"
Measurement nuclides: 1H , 13C
Resonance frequency: 400MHz ( 1H ), 100.6MHz ( 13C )
Measurement solvent: CDCl 3

　未知の樹脂組成物から４価金属リン酸塩化合物の含有、及び含有量を確認する方法としては、走査型電子顕微鏡－エネルギー分散型Ｘ線分光法（Ｓｃａｎｎｉｎｇ　Ｅｌｅｃｔｒｏｎ　Ｍｉｃｒｏｓｃｏｐｅ　Ｅｎｅｒｇｙ－Ｄｉｓｐｅｒｓｉｖｅ　Ｘ－ｒａｙ　Ｓｐｅｃｔｒｏｓｃｏｐｙ：ＳＥＭ－ＥＤＸ）、及び灰分測定にて確認する方法が挙げられる。
　ＳＥＭ－ＥＤＸによる測定方法としては、例えば、ＳＥＭ（日本電子社製「ＪＳＭ－７９００Ｆ」）とＥＤＸ（ＥＤＳ、オックスフォードインスツルメンツ社製「ＵＬＴＩＭ１００型エネルギー分散Ｘ線マイクロアナライザー」）と、を用いて、元素分析や組成分析を行い、粒子が４価金属リン酸塩化合物であるかを確認する方法が挙げられる。
　灰分は、計量した樹脂組成物をるつぼに入れ、空気下で７５０℃、４時間加熱して樹脂成分を熱分解させて除去し、４価金属リン酸塩化合物由来の残渣を計量し、下記式から算出できる。
　灰分（ｗｔ％）＝（残渣質量÷樹脂組成物質量）×１００ Methods for confirming the presence and amount of a tetravalent metal phosphate compound in an unknown resin composition include scanning electron microscope energy-dispersive X-ray spectroscopy (SEM-EDX) and ash measurement.
An example of a measurement method using SEM-EDX is a method in which elemental analysis and composition analysis are performed using a SEM ("JSM-7900F" manufactured by JEOL Ltd.) and EDX (EDS, "ULTIM100 type energy dispersive X-ray microanalyzer" manufactured by Oxford Instruments) to confirm whether the particles are a tetravalent metal phosphate compound.
The ash content can be calculated from the following formula by placing a weighed amount of the resin composition in a crucible, heating it in air at 750°C for 4 hours to thermally decompose and remove the resin component, and weighing the residue derived from the tetravalent metal phosphate compound.
Ash content (wt%) = (residue mass ÷ resin composition material amount) × 100

＜（成分Ｂ）（ｂ－１）及び（ｂ－２）を満たすポリエステル樹脂＞
　本開示に係るポリエステル樹脂組成物の第１の実施態様及び第２の実施態様は、（成分Ｂ）下記（ｂ－１）及び（ｂ－２）を満たすポリエステル樹脂を含有する。
　本開示に係るポリエステル樹脂組成物の第３の実施態様は、前記ポリエステル樹脂として、（成分Ｂ）下記（ｂ－１）及び（ｂ－２）を満たすポリエステル樹脂を含有することが好ましい。
　（ｂ－１）結晶性である
　（ｂ－２）テレフタル酸及びエチレングリコール以外のモノマーが１種類以上共重合されている <(Component B) Polyester resin satisfying (b-1) and (b-2)>
The first and second embodiments of the polyester resin composition according to the present disclosure contain a polyester resin (component B) that satisfies the following (b-1) and (b-2).
In a third embodiment of the polyester resin composition according to the present disclosure, it is preferable to contain, as the polyester resin, a polyester resin that satisfies the following (b-1) and (b-2) (Component B).
(b-1) It is crystalline. (b-2) At least one monomer other than terephthalic acid and ethylene glycol is copolymerized.

　成分Ｂは、結晶性であり、融点を有するポリエステル樹脂である。
　成分Ｂの示差走査熱量計（ＤＳＣ）で測定した融点は、分散性、及び、ポリエステル樹脂の熱劣化や加水分解抑制の観点から、２００℃以下であることが好ましく、１６０℃以下であることがより好ましく、１００℃～１６０℃であることが更により好ましい。
　本開示における融点の測定方法は、示差走査熱量計（ＤＳＣ）を用いて測定し、２ｎｄＲＵＮ（２回目の昇温時）の高温側の吸熱ピークを融点とする。 Component B is a polyester resin which is crystalline and has a melting point.
The melting point of component B as measured by a differential scanning calorimeter (DSC) is preferably 200° C. or lower, more preferably 160° C. or lower, and even more preferably 100° C. to 160° C., from the viewpoints of dispersibility and suppression of thermal deterioration and hydrolysis of the polyester resin.
In the present disclosure, the melting point is measured using a differential scanning calorimeter (DSC), and the endothermic peak on the high temperature side in the second run (second temperature rise) is regarded as the melting point.

　示差走査熱量計（ＤＳＣ）は、特に限定されないが、例えば、ＪＩＳ　Ｋ７１２１に準拠して測定可能である。２ｎｄＲＵＮ（２回目の昇温時）の高温側の吸熱ピークを融点とする。
　ＤＳＣ：ＮＥＴＺＳＣＨ社製「ＤＳＣ　２１４　Ｐｏｌｙｍａ」
－１ｓｔＲＵＮ－
　昇温速度：１０℃／分
　測定温度：３０℃～３００℃
　測定雰囲気：窒素
　保持：３００℃到達後、５分
　降温速度：３０℃／分
　冷却温度：３００℃～３０℃
－２ｎｄＲＵＮ－
　昇温速度：１０℃／分
　測定温度：３０℃～３００℃
　測定雰囲気：窒素 The differential scanning calorimeter (DSC) is not particularly limited, but may be measured, for example, in accordance with JIS K7121. The endothermic peak on the high temperature side in the 2nd RUN (at the second temperature rise) is regarded as the melting point.
DSC: “DSC 214 Polyma” manufactured by NETZSCH
-1st RUN-
Heating rate: 10°C/min Measurement temperature: 30°C to 300°C
Measurement atmosphere: Nitrogen Holding: 5 minutes after reaching 300°C Cooling rate: 30°C/min Cooling temperature: 300°C to 30°C
-2nd RUN-
Heating rate: 10°C/min Measurement temperature: 30°C to 300°C
Measurement atmosphere: Nitrogen

　ポリエステル樹脂とは、多価カルボン酸成分と多価アルコール成分を主体とした重縮合物である。市販品のポリエステル樹脂にはポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリブチレンナフタレート（ＰＢＮ）、ポリトリメチレンテレフタレート（ＰＴＴ）などがあり、１種単独、もしくは２種類以上をブレンドして使用できる。 Polyester resin is a polycondensation product mainly composed of polyvalent carboxylic acid components and polyhydric alcohol components. Commercially available polyester resins include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), and polytrimethylene terephthalate (PTT), and can be used alone or in a blend of two or more types.

　多価カルボン酸成分としては、例えばテレフタル酸などの脂環式ジカルボン酸及びこれらの置換体等が挙げられる。特に制限はないが、例えば、シュウ酸、コハク酸、グルタル酸、アジピン酸、スベリン酸、アゼライン酸、セバシン酸、１，９－ノナンジカルボン酸、１，１０－デカンジカルボン酸、１，１２－ドデカンジカルボン酸、１，１４－テトラデカンジカルボン酸、１，１８－オクタデカンジカルボン酸、フタル酸、イソフタル酸、ナフタレン－２，６－ジカルボン酸、１，２，３－ベンゼントリカルボン酸、１，２，４－ベンゼントリカルボン酸、１，２，４－ナフタレントリカルボン酸、これらの無水物、又はこれらの低級（例えば炭素数１以上５以下）アルキルエステル、スルホン酸ナトリウム基を有する多価カルボン酸などが挙げられる。これらの多価カルボン酸成分は単独で又は２種以上を組み合わせて使用できる。 Examples of the polycarboxylic acid component include alicyclic dicarboxylic acids such as terephthalic acid and their substituted derivatives. Although there are no particular limitations, examples include oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, anhydrides thereof, or lower alkyl esters thereof (e.g., carbon number 1 to 5), polycarboxylic acids having sodium sulfonate groups, etc. These polycarboxylic acid components can be used alone or in combination of two or more.

　多価アルコール成分としては、例えば、エチレングリコール、ジエチレングリコール等の脂肪族ジオールや１，４－シクロヘキサンジメタノール等の脂環式ジオールなどが挙げられる。特に制限はないが、例えば、１，３－プロパンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、１，７－ヘプタンジオール、１，８－オクタンジオール、１，９－ノナンジオール、１，１０－デカンジオール、１，１１－ウンデカンジオール、１，１２－ドデカンジオール、１，１３－トリデカンジオール、１，１４－テトラデカンジオール、１，１８－オクタデカンジオール、１，１４－エイコサンデカンジオール、グリセリン、トリメチロールエタン、トリメチロールプロパン、ペンタエリスリトール、ポリエチレングリコール、ポリプロピレングリコール、ポリブタンジオール、ポリテトラメチレンエーテルグリコールなどが挙げられる。これらの多価アルコール成分は単独で又は２種以上を組み合わせて使用できる。 Examples of polyhydric alcohol components include aliphatic diols such as ethylene glycol and diethylene glycol, and alicyclic diols such as 1,4-cyclohexanedimethanol. Although there are no particular limitations, examples include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosanedecanediol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, polyethylene glycol, polypropylene glycol, polybutanediol, and polytetramethylene ether glycol. These polyhydric alcohol components can be used alone or in combination of two or more.

　共重合ポリエステル樹脂とは、ポリエステル樹脂の多価カルボン酸成分と多価アルコール成分のどちらか、あるいは両方の成分を２種類以上組み合わせた重縮合物である。市販品の共重合ポリエステル樹脂にはグリコール変性ポリエチレンテレフタレート（ＰＥＴＧ）、ポリエステル系熱可塑性エラストマー（ＴＰＥＥ、ＴＰＣ）などがあり、１種単独、もしくは２種類以上をブレンドして使用できる。 Copolymer polyester resin is a polycondensation product of either the polyvalent carboxylic acid component of polyester resin or the polyhydric alcohol component of polyester resin, or a combination of two or more of both components. Commercially available copolymer polyester resins include glycol-modified polyethylene terephthalate (PETG) and polyester-based thermoplastic elastomers (TPEE, TPC), and can be used alone or in a blend of two or more types.

　ポリエステル樹脂及び共重合ポリエステル樹脂は、エポキシ化合物、カルボジイミド化合物、イソシアネート化合物などで末端の水酸基やカルボン酸基が末端封鎖（エンドキャッピング）されていてもよい。 The terminal hydroxyl groups or carboxylic acid groups of polyester resins and copolymer polyester resins may be end-capped with epoxy compounds, carbodiimide compounds, isocyanate compounds, etc.

　ポリエステル樹脂の共重合モノマー成分の測定方法は、特に限定されないが、例えば、核磁気共鳴分光法（以下、ＮＭＲと略称する。）を用いて１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲを測定し、各成分のピーク強度より算出できる。
装置名：Ｂｒｕｋｅｒ社製「ＡＶＡＮＣＥ　ＩＩＩ　４００」
測定核種：１Ｈ、１３Ｃ
共鳴周波数：４００ＭＨｚ（１Ｈ）、１００．６ＭＨｚ（１３Ｃ）
測定溶媒：ＣＤＣｌ３ The method for measuring the copolymerization monomer components of the polyester resin is not particularly limited, but for example, it can be calculated from the peak intensity of each component by measuring 1 H-NMR and 13 C-NMR using nuclear magnetic resonance spectroscopy (hereinafter abbreviated as NMR).
Device name: Bruker "AVANCE III 400"
Measurement nuclides: 1 H, 13 C
Resonance frequency: 400MHz ( 1H ), 100.6MHz ( 13C )
Measurement solvent: CDCl3

　成分Ｂは、テレフタル酸及びエチレングリコール以外のモノマーが１種類以上共重合されている共重合ポリエステル樹脂であればよい。これらの中でも、テレフタル酸及びエチレングリコール以外のモノマーとしては、分散性の観点から、エチレングリコール以外の多価アルコールであることが好ましく、エチレングリコール以外の２価アルコールであることがより好ましく、１，４－ブタンジオール、ポリブタンジオール、又は、ポリテトラメチレンエーテルグリコールが特に好ましい。 Component B may be a copolymerized polyester resin in which one or more monomers other than terephthalic acid and ethylene glycol are copolymerized. Among these, from the viewpoint of dispersibility, the monomer other than terephthalic acid and ethylene glycol is preferably a polyhydric alcohol other than ethylene glycol, more preferably a dihydric alcohol other than ethylene glycol, and particularly preferably 1,4-butanediol, polybutanediol, or polytetramethylene ether glycol.

　成分Ｂにおけるテレフタル酸及びエチレングリコール以外のモノマーの共重合量は、特に制限はないが、成分Ｂを形成する全モノマー量に対し、０．１ｍｏｌ％～９０ｍｏｌ％であることが好ましく、０．５ｍｏｌ％～８０ｍｏｌ％であることがより好ましく、１ｍｏｌ％～８０ｍｏｌ％であることが更に好ましい。 The amount of copolymerization of monomers other than terephthalic acid and ethylene glycol in component B is not particularly limited, but is preferably 0.1 mol% to 90 mol%, more preferably 0.5 mol% to 80 mol%, and even more preferably 1 mol% to 80 mol%, relative to the total amount of monomers forming component B.

　また、後述するように、中間体（第１の実施態様）を用いてマスターバッチ（第３の実施態様）を作製する際に添加するポリエステル樹脂として好適な成分Ｂとしては、下記（ｂ－３）及び（ｂ－４）を満たすポリエステル樹脂が好ましく挙げられる。
（ｂ－３）示差走査熱量計で測定した融点が２００℃以下である
（ｂ－４）固有粘度（ＩＶ）が１ｄＬ／ｇ以上である As described later, preferred examples of component B suitable as a polyester resin to be added when preparing a masterbatch (third embodiment) using an intermediate (first embodiment) include polyester resins that satisfy the following (b-3) and (b-4).
(b-3) The melting point measured by a differential scanning calorimeter is 200° C. or less. (b-4) The intrinsic viscosity (IV) is 1 dL/g or more.

　（ｂ－３）及び（ｂ－４）を満たすポリエステル樹脂の示差走査熱量計（ＤＳＣ）で測
定した融点としては、分散性及び固有粘度の観点から、１６０℃以下であることが好ましく、１００℃～１６０℃であることがより好ましい。 The melting point of the polyester resin satisfying (b-3) and (b-4) as measured by a differential scanning calorimeter (DSC) is preferably 160° C. or lower, and more preferably 100° C. to 160° C., from the viewpoints of dispersibility and intrinsic viscosity.

　（ｂ－３）及び（ｂ－４）を満たすポリエステル樹脂の固有粘度（ＩＶ）としては、分散性の観点から、１．１ｄＬ／ｇ以上であることが好ましく、１．３ｄＬ／ｇ以上であることがより好ましく、１．５ｄＬ／ｇ～２．０ｄＬ／ｇであることが更に好ましい。
　本開示における固有粘度（ＩＶ）の測定方法は、３０℃における固有粘度（ＩＶ）であれば特に制限はないが、例えば、ウベローデ粘度計を用い、ＪＩＳ　Ｋ７３６７－５に準拠して下記の測定条件により測定可能である。
　溶媒：１，１，２，２－テトラクロロエタン／フェノール＝１／１混合溶媒
　濃度（樹脂濃度）：０．５ｇ／ｄＬ（樹脂成分で０．５ｇ／ｄＬとなるように調整）
　温度：３０℃ The intrinsic viscosity (IV) of the polyester resin satisfying (b-3) and (b-4) is preferably 1.1 dL/g or more, more preferably 1.3 dL/g or more, and even more preferably 1.5 dL/g to 2.0 dL/g, from the viewpoint of dispersibility.
In the present disclosure, the method for measuring the intrinsic viscosity (IV) is not particularly limited as long as it is the intrinsic viscosity (IV) at 30° C., and for example, it can be measured using an Ubbelohde viscometer under the following measurement conditions in accordance with JIS K7367-5.
Solvent: 1,1,2,2-tetrachloroethane/phenol = 1/1 mixed solvent Concentration (resin concentration): 0.5 g/dL (adjusted to 0.5 g/dL with resin component)
Temperature: 30℃

　本開示に係るポリエステル樹脂組成物の第１の実施態様における成分Ｂの含有量は、組成物の全質量に対し、２５質量％～５０質量％であり、分散性、消臭性及び成形加工性の観点から、２５質量％～４５質量％であることが好ましく、２７質量％～４０質量％であることがより好ましい。 The content of component B in the first embodiment of the polyester resin composition according to the present disclosure is 25% by mass to 50% by mass relative to the total mass of the composition, and from the viewpoints of dispersibility, deodorizing properties, and moldability, is preferably 25% by mass to 45% by mass, and more preferably 27% by mass to 40% by mass.

　本開示に係るポリエステル樹脂組成物の第２の実施態様における成分Ｂの含有量は、組成物の全質量に対し、７質量％～３５質量％であり、分散性、消臭性及び成形加工性の観点から、１０質量％～３２質量％であることが好ましく、１２質量％～３０質量％であることがより好ましい。 The content of component B in the second embodiment of the polyester resin composition according to the present disclosure is 7% by mass to 35% by mass relative to the total mass of the composition, and from the viewpoints of dispersibility, deodorizing properties, and moldability, is preferably 10% by mass to 32% by mass, and more preferably 12% by mass to 30% by mass.

　本開示に係るポリエステル樹脂組成物の第３の実施態様における成分Ｂの含有量は、組成物の全質量に対し、分散性、消臭性及び成形加工性の観点から、７質量％～３５質量％であることが好ましく、１０質量％～３２質量％であることがより好ましく、１２質量％～３０質量％であることが更に好ましい。 The content of component B in the third embodiment of the polyester resin composition according to the present disclosure is preferably 7% by mass to 35% by mass, more preferably 10% by mass to 32% by mass, and even more preferably 12% by mass to 30% by mass, based on the total mass of the composition, from the viewpoints of dispersibility, deodorization, and moldability.

＜（成分Ｃ）分散剤＞
　本開示に係るポリエステル樹脂組成物の第１の実施態様及び第２の実施態様は、（成分Ｃ）分散剤を含有する。
　本開示に係るポリエステル樹脂組成物の第３の実施態様は、（成分Ｃ）分散剤を含有することが好ましい。
　成分Ｃとしては、特に制限はなく、公知の分散剤を用いることができるが、分散性の観点から、炭素原子及び水素原子以外の原子を含む極性のある極性基を有することが好ましい。
　極性基としては、エステル、エーテル、水酸基及びイミノ基よりなる群から選ばれた少なくとも１種の基が好ましく、エステル又は水酸基がより好ましい。
　また、成分Ｃとしては、分散性の観点から、エステル系分散剤であることが好ましく、脂肪族エステル系分散剤であることがより好ましい。
　また、成分Ｃとしては、分散性の観点から、直鎖構造よりも立体障害が大きくなるような分岐構造、環状構造などを有するバルキーな分子構造であることが特に好ましい。
　成分Ｃは、市販品も好適に用いることができ、例えば、理研ビタミン（株）製リケマールＴＧ－１２、日油（株）製ユニスターＨ－４７６、日油（株）製ジンクステアレート、理研ビタミン（株）製ポエムＯ－８０Ｖ、理研ビタミン（株）製ポエムＭ－３００、Ｌｕｂｒｉｚｏｌ社製Ｓｏｌｐｌｕｓ　ＤＰ３１０、Ｌｕｂｒｉｚｏｌ社製Ｓｏｌｐｌｕｓ　Ｌ４００等が挙げられる。
　更に、本開示に係るポリエステル樹脂組成物は、分散性の観点から、成分Ｃとして、２種以上の分散剤を含有することが好ましく、２種以上の脂肪族エステル系分散剤を含有することがより好ましく、２種の脂肪族エステル系分散剤を含有することが特に好ましい。 <(Component C) Dispersant>
The first and second embodiments of the polyester resin composition according to the present disclosure contain a dispersant (Component C).
The third embodiment of the polyester resin composition according to the present disclosure preferably contains a dispersant (Component C).
Component C is not particularly limited and any known dispersant can be used, but from the viewpoint of dispersibility, it preferably has a polar group containing atoms other than carbon and hydrogen atoms.
The polar group is preferably at least one group selected from the group consisting of ester, ether, hydroxyl group and imino group, and more preferably ester or hydroxyl group.
From the viewpoint of dispersibility, component C is preferably an ester-based dispersant, and more preferably an aliphatic ester-based dispersant.
From the viewpoint of dispersibility, it is particularly preferable that component C has a bulky molecular structure having a branched structure, a cyclic structure, or the like, which causes greater steric hindrance than a straight-chain structure.
Commercially available products can also be suitably used as Component C. Examples thereof include Rikemal TG-12 manufactured by Riken Vitamin Co., Ltd., Unistar H-476 manufactured by NOF Corp., Zinc Stearate manufactured by NOF Corp., Poem O-80V manufactured by Riken Vitamin Co., Ltd., Poem M-300 manufactured by Riken Vitamin Co., Ltd., Solplus DP310 manufactured by Lubrizol, and Solplus L400 manufactured by Lubrizol.
Furthermore, from the viewpoint of dispersibility, the polyester resin composition according to the present disclosure preferably contains, as Component C, two or more types of dispersants, more preferably contains two or more types of aliphatic ester-based dispersants, and particularly preferably contains two types of aliphatic ester-based dispersants.

　分散剤の極性基の測定方法は、特に限定されないが、例えば、核磁気共鳴分光法（以下、ＮＭＲと略称する。）を用いて１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲを測定し、各成分のピーク強度より判断できる。
装置名：Ｂｒｕｋｅｒ社製「ＡＶＡＮＣＥ　ＩＩＩ　４００」
測定核種：１Ｈ、１３Ｃ
共鳴周波数：４００ＭＨｚ（１Ｈ）、１００．６ＭＨｚ（１３Ｃ）
測定溶媒：ＣＤＣｌ３
　また例えば、フーリエ変換赤外分光分析装置（ＦＴ－ＩＲ）を用いて、赤外スペクトルを測定し、各成分のピーク強度からも判断できる。
装置名：サーモフィッシャーサイエンティフィック(株）製「Ｎｉｃｏｌｅｔ　ｉＳ５０　ＦＴ－ＩＲ」
測定方法：ＡＴＲ法（ＤｕｒａＳｃｏｐｅユニット　ダイアモンドディスク）
アクセサリー：μ－ＡＴＲ
条件：分解能４ｃｍ－１、積算回数３２回 The method for measuring the polar group of the dispersant is not particularly limited, but for example, it can be determined from the peak intensity of each component by measuring 1 H-NMR and 13 C-NMR using nuclear magnetic resonance spectroscopy (hereinafter abbreviated as NMR).
Device name: Bruker "AVANCE III 400"
Measurement nuclides: 1H , 13C
Resonance frequency: 400MHz ( 1H ), 100.6MHz ( 13C )
Measurement solvent: CDCl 3
Alternatively, for example, an infrared spectrum may be measured using a Fourier transform infrared spectrometer (FT-IR), and the determination may also be made from the peak intensity of each component.
Device name: "Nicolet iS50 FT-IR" manufactured by Thermo Fisher Scientific Co., Ltd.
Measurement method: ATR method (DuraScope unit diamond disc)
Accessories: μ-ATR
Conditions: resolution 4cm -1 , number of integrations 32 times

　本開示に係るポリエステル樹脂組成物の第１の実施態様における成分Ｃの含有量は、組成物の全質量に対し、３質量％～２５質量％であり、分散性、消臭性及び成形加工性の観点から、３質量％～１９質量％であることが好ましく、７質量％～１６質量％であることがより好ましい。 The content of component C in the first embodiment of the polyester resin composition according to the present disclosure is 3% by mass to 25% by mass relative to the total mass of the composition, and from the viewpoints of dispersibility, deodorizing properties, and moldability, is preferably 3% by mass to 19% by mass, and more preferably 7% by mass to 16% by mass.

　本開示に係るポリエステル樹脂組成物の第２の実施態様における成分Ｃの含有量は、組成物の全質量に対し、０．１質量％～１１質量％であり、分散性、消臭性及び成形加工性の観点から、０．２質量％～１１質量％であることが好ましく、０．３質量％～１０質量％であることがより好ましく、０．５質量％～８質量％であることが更に好ましい。 The content of component C in the second embodiment of the polyester resin composition according to the present disclosure is 0.1% by mass to 11% by mass relative to the total mass of the composition, and from the viewpoints of dispersibility, deodorizing properties, and moldability, is preferably 0.2% by mass to 11% by mass, more preferably 0.3% by mass to 10% by mass, and even more preferably 0.5% by mass to 8% by mass.

　本開示に係るポリエステル樹脂組成物の第３の実施態様における成分Ｃの含有量は、組成物の全質量に対し、分散性、消臭性及び成形加工性の観点から、０．１質量％～１１質量％であることが好ましく、０．２質量％～１１質量％であることがより好ましく、０．３質量％～１０質量％であることが更に好ましく、０．５質量％～８質量％であることが特に好ましい。 The content of component C in the third embodiment of the polyester resin composition according to the present disclosure is preferably 0.1% by mass to 11% by mass, more preferably 0.2% by mass to 11% by mass, even more preferably 0.3% by mass to 10% by mass, and particularly preferably 0.5% by mass to 8% by mass, based on the total mass of the composition, from the viewpoints of dispersibility, deodorization, and moldability.

＜（成分Ｄ）（ｄ－１）を満たすポリエステル樹脂＞
　本開示に係るポリエステル樹脂組成物の第２の実施態様は、（成分Ｄ）下記（ｄ－１）を満たすポリエステル樹脂を含有する。
　本開示に係るポリエステル樹脂組成物の第３の実施態様は、前記ポリエステル樹脂として、（成分Ｄ）下記（ｄ－１）を満たすポリエステル樹脂を含有することが好ましい。
（ｄ－１）示差走査熱量計で測定した融点が２４０℃以上である
　また、成分Ｄは、分散性の観点から、下記（ｄ－２）を満たすことが好ましい。
（ｄ－２）固有粘度（ＩＶ）が０．６ｄＬ／ｇ以上である <(Component D) Polyester resin satisfying (d-1)>
A second embodiment of the polyester resin composition according to the present disclosure contains (component D) a polyester resin that satisfies the following (d-1).
In a third embodiment of the polyester resin composition according to the present disclosure, it is preferable to contain, as the polyester resin, a polyester resin that satisfies the following (d-1) (Component D).
(d-1) The melting point measured by a differential scanning calorimeter is 240° C. or higher. From the viewpoint of dispersibility, it is preferable that Component D satisfies the following (d-2):
(d-2) Intrinsic viscosity (IV) is 0.6 dL/g or more

　成分Ｄの示差走査熱量計で測定した融点としては、耐熱性の観点から、２４０℃～２６０℃であることが好ましい。
　成分Ｄの固有粘度（ＩＶ）としては、分散性の観点から、０．６ｄＬ／ｇ～１．２ｄＬ／ｇであることが好ましく、０．６ｄＬ／ｇ～１．１ｄＬ／ｇであることがより好ましい。 The melting point of component D, as measured by a differential scanning calorimeter, is preferably 240° C. to 260° C. from the viewpoint of heat resistance.
From the viewpoint of dispersibility, the intrinsic viscosity (IV) of component D is preferably 0.6 dL/g to 1.2 dL/g, and more preferably 0.6 dL/g to 1.1 dL/g.

　また、成分Ｄは、耐熱性、分散性の観点から、テレフタル酸及びエチレングリコールからなるポリエチレンテレフタレート（ＰＥＴ）であることが好ましい。
　なお、ポリエチレンテレフタレートは、物性を損なわない範囲で共重合モノマーを含んでいてもよい。例えば、原料として用いられるエチレングリコールは、重合中に一部がジエチレングリコールとなり、共重合される。エチレングリコール由来の構成単位中のジエチレングリコール構成単位は２モル％程度含まれていることが多く、ポリエチレンテレフタレートは、ジエチレングリコール由来の構成単位を３モル％以下含んでいてもよい。
　更に、成分Ｄは、成分Ｂ以外のポリエステル樹脂であることが好ましい。 From the viewpoints of heat resistance and dispersibility, component D is preferably polyethylene terephthalate (PET) made of terephthalic acid and ethylene glycol.
In addition, polyethylene terephthalate may contain a copolymerization monomer within a range that does not impair physical properties. For example, ethylene glycol used as a raw material is partially converted to diethylene glycol during polymerization and copolymerized. Diethylene glycol constituent units are often contained in the constituent units derived from ethylene glycol at about 2 mol%, and polyethylene terephthalate may contain 3 mol% or less of the constituent units derived from diethylene glycol.
Furthermore, Component D is preferably a polyester resin other than Component B.

　本開示に係るポリエステル樹脂組成物の第２の実施態様における成分Ｄの含有量は、組成物の全質量に対し、３７質量％～８３．６質量％であり、分散性、消臭性及び成形加工性の観点から、４２質量％～８３．６質量％であることが好ましく、４７質量％～７５質量％であることがより好ましく、５０質量％～６８質量％であることが更に好ましい。 The content of component D in the second embodiment of the polyester resin composition according to the present disclosure is 37% by mass to 83.6% by mass relative to the total mass of the composition, and from the viewpoints of dispersibility, deodorizing properties, and moldability, is preferably 42% by mass to 83.6% by mass, more preferably 47% by mass to 75% by mass, and even more preferably 50% by mass to 68% by mass.

　本開示に係るポリエステル樹脂組成物の第３の実施態様における成分Ｄの含有量は、組成物の全質量に対し、分散性、消臭性及び成形加工性の観点から、３７質量％～８３．６質量％であることが好ましく、４２質量％～８３．６質量％であることがより好ましく、４７質量％～７５質量％であることが更に好ましく、５０質量％～６８質量％であることが特に好ましい。 The content of component D in the third embodiment of the polyester resin composition according to the present disclosure is preferably 37% by mass to 83.6% by mass, more preferably 42% by mass to 83.6% by mass, even more preferably 47% by mass to 75% by mass, and particularly preferably 50% by mass to 68% by mass, based on the total mass of the composition, from the viewpoints of dispersibility, deodorization, and moldability.

＜その他の成分＞
　本開示に係るポリエステル樹脂組成物は、上述した以外のその他の成分を含有していてもよい。
　その他の成分としては、体質顔料、着色顔料、染料、酸化防止剤、可塑剤、滑剤、難燃剤、帯電防止剤、結晶核剤、エポキシ化合物あるいはカルボジイミド化合物等の末端カルボン酸の封鎖剤、ガラス繊維等の強化材、消臭剤、抗菌剤、防カビ剤、抗ウイルス加工剤、抗アレルゲン剤などのポリエステル樹脂に配合可能な従来公知の成分を加えることができる。 <Other ingredients>
The polyester resin composition according to the present disclosure may contain other components in addition to those described above.
Examples of other components that can be added include conventionally known components that can be blended with polyester resins, such as extender pigments, coloring pigments, dyes, antioxidants, plasticizers, lubricants, flame retardants, antistatic agents, crystal nucleating agents, blocking agents for terminal carboxylic acids such as epoxy compounds or carbodiimide compounds, reinforcing materials such as glass fibers, deodorants, antibacterial agents, antifungal agents, antiviral processing agents, and antiallergen agents.

　消臭剤としては、特に制限はなく、公知の消臭剤を用いることができ、例えば、酸性ガス消臭剤、塩基性ガス消臭剤、硫黄系ガス消臭剤、アルデヒド系ガス消臭剤、ケトン系ガス消臭剤、芳香剤等が挙げられる。
　悪臭等の原因となる化合物としては、アンモニアガス及びトリメチルアミン等の塩基性ガス；酢酸及びイソ吉草酸等の酸性ガス；ホルムアルデヒド、アセトアルデヒド及びノネナール等のアルデヒド系ガス；並びに硫化水素及びメチルメルカプタン等の硫黄系ガス等が挙げられ、これらに対する消臭性能を有する他の消臭剤を含有することができる。
　塩基性ガス用の消臭剤としては、ゼオライト、Ａｌ２Ｏ３、ＳｉＯ２、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ、ＺｒＯ２、ＴｉＯ２、ＷＯ２、ＣｅＯ２、Ｌｉ２Ｏ、Ｎａ２Ｏ、Ｋ２Ｏ等の非晶質複合酸化物が挙げられる。
　酸性ガス用の消臭剤としては、水酸化ジルコニウム、酸化ジルコニウム及びマグネシウム－アルミニウムハイドロタルサイト等のハイドロタルサイト系化合物等が挙げられる。
　アルデヒド系ガス用の消臭剤としては、アジピン酸ジヒドラジド、カルボヒドラジド、コハク酸ジヒドラジド及びシュウ酸ジヒドラジド等のヒドラジン系化合物、アミノグアニジン塩酸塩、アミノグアニジン硫酸塩、アミノグアニジン重炭酸塩等のアミノグアニジン塩等が挙げられる。
　硫黄系ガス用の消臭剤としては、ケイ酸銅、銅リン酸ジルコニウム水和物、酸化亜鉛、酸化アルミニウム亜鉛、ケイ酸亜鉛、ケイ酸アルミニウム亜鉛、層状アルミノケイ酸亜鉛等が挙げられる。 The deodorizer is not particularly limited, and any known deodorizer can be used. Examples of the deodorizer include acidic gas deodorizers, basic gas deodorizers, sulfur-based gas deodorizers, aldehyde gas deodorizers, ketone gas deodorizers, and aromatics.
Compounds that cause bad odors include basic gases such as ammonia gas and trimethylamine; acidic gases such as acetic acid and isovaleric acid; aldehyde gases such as formaldehyde, acetaldehyde and nonenal; and sulfur gases such as hydrogen sulfide and methyl mercaptan. The composition may contain other deodorants that have deodorizing properties against these compounds.
Examples of deodorizers for basic gases include amorphous composite oxides such as zeolite, Al2O3 , SiO2 , MgO , CaO, SrO , BaO, ZrO2 , TiO2, WO2 , CeO2, Li2O , Na2O , and K2O .
Examples of deodorants for acidic gases include zirconium hydroxide, zirconium oxide, and hydrotalcite compounds such as magnesium-aluminum hydrotalcite.
Examples of deodorizers for aldehyde gases include hydrazine compounds such as adipic acid dihydrazide, carbohydrazide, succinic acid dihydrazide, and oxalic acid dihydrazide, and aminoguanidine salts such as aminoguanidine hydrochloride, aminoguanidine sulfate, and aminoguanidine bicarbonate.
Examples of deodorants for sulfur-based gases include copper silicate, copper zirconium phosphate hydrate, zinc oxide, zinc aluminum oxide, zinc silicate, zinc aluminum silicate, and layered zinc aluminosilicate.

　本開示に係るポリエステル樹脂組成物の第２の実施態様及び第３の実施態様におけるポリエステル樹脂組成物を流す前と後の高密度ポリエチレン（ＨＤＰＥ）の樹脂圧力の差圧（ΔＰ）は、分散性の観点から、１．６ＭＰａ以下であることが好ましく、１．５ＭＰａ以下であることがより好ましく、１．０ＭＰａ以下であることが更に好ましく、１．０ＭＰａ未満であることが特に好ましい。 In the second and third embodiments of the polyester resin composition according to the present disclosure, the resin pressure difference (ΔP) of the high density polyethylene (HDPE) before and after pouring the polyester resin composition is preferably 1.6 MPa or less, more preferably 1.5 MPa or less, even more preferably 1.0 MPa or less, and particularly preferably less than 1.0 MPa, from the viewpoint of dispersibility.

　本開示における差圧（ΔＰ）の測定方法は、特に限定されないが、例えば、以下の方法で測定可能である。
　φ２０ｍｍ単軸押出機「ラボプラストミル」（（株）東洋精機製作所製、基本装置型式「１０Ｓ１００」に単軸押出機ユニット型式「Ｄ２０２５」を接続）を用い、押出温度２８７℃、回転数５０ｒｐｍ、４０／７３０／４０メッシュで京葉ポリエチレン（株）製Ｐ９２１０（高密度ポリエチレン（ＨＤＰＥ））を樹脂圧が安定するまで流し、樹脂圧が安定したことを確認した後に４価金属リン酸塩化合物含有量が２００ｇとなるように計量したポリエステル樹脂組成物に切り替えて全量流した後に、再度京葉ポリエチレン（株）製Ｐ９２１０（ＨＤＰＥ）を樹脂圧が安定するまで流し、４価金属リン酸塩化合物含有ポリエステル樹脂組成物（マスターバッチ）を流す前後のＨＤＰＥ樹脂圧力を差圧（ΔＰ）として測定する。
　差圧（ΔＰ）の値が小さいほど、メッシュで捕捉される４価金属リン酸塩化合物の粗大粒子が少なく、メッシュが閉塞しづらいことから、ポリエステル樹脂組成物中における４価金属リン酸塩化合物の分散性に優れる。 The method for measuring the differential pressure (ΔP) in the present disclosure is not particularly limited, but for example, the differential pressure (ΔP) can be measured by the following method.
Using a φ20 mm single-screw extruder "Labo Plastomill" (manufactured by Toyo Seiki Seisakusho Co., Ltd., a single-screw extruder unit model "D2025" is connected to a basic device model "10S100"), P9210 (high density polyethylene (HDPE)) manufactured by Keiyo Polyethylene Co., Ltd. is fed at an extrusion temperature of 287°C, a rotation speed of 50 rpm, and a 40/730/40 mesh until the resin pressure stabilizes. After confirming that the resin pressure has stabilized, the system is switched to a polyester resin composition weighed so that the tetravalent metal phosphate compound content is 200 g, and the entire amount is fed. Then, P9210 (HDPE) manufactured by Keiyo Polyethylene Co., Ltd. is fed again until the resin pressure stabilizes, and the HDPE resin pressure before and after the flow of the tetravalent metal phosphate compound-containing polyester resin composition (master batch) is measured as a differential pressure (ΔP).
The smaller the differential pressure (ΔP), the fewer coarse particles of the tetravalent metal phosphate compound are captured by the mesh, and the less likely the mesh is to become clogged, resulting in excellent dispersibility of the tetravalent metal phosphate compound in the polyester resin composition.

　本開示に係るポリエステル樹脂組成物の第２の実施態様及び第３の実施態様における固有粘度（ＩＶ）は、分散性の観点から、０．５０ｄＬ／ｇ以上であることが好ましく、０．５５ｄＬ／ｇ～０．７４ｄＬ／ｇであることがより好ましく、０．５９ｄＬ／ｇ～０．７０ｄＬ／ｇであることが更に好ましく、０．５９ｄＬ／ｇ～０．６９ｄＬ／ｇであることが特に好ましい。 In the second and third embodiments of the polyester resin composition according to the present disclosure, the intrinsic viscosity (IV) is preferably 0.50 dL/g or more, more preferably 0.55 dL/g to 0.74 dL/g, even more preferably 0.59 dL/g to 0.70 dL/g, and particularly preferably 0.59 dL/g to 0.69 dL/g, from the viewpoint of dispersibility.

　本開示に係るポリエステル樹脂組成物の第３の実施態様は、視野サイズが０．４ｍｍ×０．３ｍｍのポリエステル樹脂組成物の断面ＳＥＭ像において、リン酸ジルコニウムに代表される４価金属リン酸塩化合物の粒子サイズが２０μｍ２以上となる粒子数が１個未満であり、０．５個未満が好ましく、０．１個未満がより好ましく、０個すなわち、含まないことが更に好ましい。 In a third embodiment of the polyester resin composition according to the present disclosure, in a cross-sectional SEM image of the polyester resin composition having a visual field size of 0.4 mm x 0.3 mm, the number of particles of a tetravalent metal phosphate compound represented by zirconium phosphate having a particle size of 20 μm2 or more is less than 1 , preferably less than 0.5, more preferably less than 0.1, and even more preferably 0, that is, none.

　ポリエステル樹脂組成物の第３の実施態様において、ポリエステル樹脂組成物の断面ＳＥＭ像において、リン酸ジルコニウムの粒子サイズが２０μｍ２以上となる粒子数の確認方法としては、ポリエステル樹脂組成物のペレット断面を走査型電子顕微鏡（Ｓｃａｎｎｉｎｇ　Ｅｌｅｃｔｒｏｎ　Ｍｉｃｒｏｓｃｏｐｙ：ＳＥＭ）にて撮影してＳＥＭ像を得て、得られたＳＥＭ像を画像解析して、視野角内の粒子サイズが２０μｍ２以上となる粒子数をカウントする。ここで、粒子サイズが２０μｍ２以上となる粒子数が１個未満であることにより、リン酸ジルコニウムの粒子の分散性が良好であるとの目安とする。粒子数が０個、即ち、粒子サイズが２０μｍ２以上となる粒子数が観察されない場合、リン酸ジルコニウムの粒子の分散性により優れると評価される。 In the third embodiment of the polyester resin composition, in the cross-sectional SEM image of the polyester resin composition, the number of particles having a particle size of 20 μm 2 or more of zirconium phosphate is confirmed by photographing the cross-section of the pellet of the polyester resin composition with a scanning electron microscope (SEM) to obtain an SEM image, and the obtained SEM image is subjected to image analysis to count the number of particles having a particle size of 20 μm 2 or more within the viewing angle. Here, the number of particles having a particle size of 20 μm 2 or more is less than 1, which is an indication that the dispersibility of the zirconium phosphate particles is good. When the number of particles is 0, that is, when the number of particles having a particle size of 20 μm 2 or more is not observed, the dispersibility of the zirconium phosphate particles is evaluated to be more excellent.

　得られたＳＥＭ像の画像解析による観察で、リン酸ジルコニウムの粒子サイズが１０μｍ２以上となる粒子数が１個以下であることが好ましい。
　得られたＳＥＭ像の画像解析による観察で、リン酸ジルコニウムの粒子サイズが２μｍ２以上となる粒子数が１０個以下であることが、より好ましい。
　得られたＳＥＭ像の画像解析による観察で、リン酸ジルコニウムの粒子サイズが１μｍ２以上となる粒子数が３０個以下であることが更に好ましく、リン酸ジルコニウムの粒子サイズが０．５μｍ２以上となる粒子数が５０個以下であることが特に好ましい。 It is preferable that, when observed by image analysis of the obtained SEM image, the number of particles having a particle size of 10 μm 2 or more of zirconium phosphate is 1 or less.
It is more preferable that the number of zirconium phosphate particles having a particle size of 2 μm 2 or more is 10 or less when observed by image analysis of the obtained SEM image.
It is more preferable that the number of zirconium phosphate particles having a particle size of 1 μm2 or more is 30 or less, and it is particularly preferable that the number of zirconium phosphate particles having a particle size of 0.5 μm2 or more is 50 or less, as observed by image analysis of the obtained SEM image.

　より具体的には、後述の実施例に記載の方法で得られたポリエステル樹脂組成物のペレットを、ペレットの流れ方向（Ｍａｃｈｉｎｅ　Ｄｉｒｅｃｔｉｏｎ、ＭＤ）に対して、垂直に切断した断面を、ＳＥＭを用いて３００倍の倍率でＳＥＭ像を得ることができる。
　ペレットは、測定対象である本開示に係るポリエステル樹脂組成物を混合し、二軸押出機を用い、加熱し、溶融押出してストランドカット方式でペレット化することで得ることができる。つまり、ペレットの流れ方向（ＭＤ）はストランドの流れ方向（ＭＤ）と一致し、通常はペレットの長手方向がＭＤである。ペレットの製造方法については、実施例にて後述する。
　なお、既に製造されたペレット、即ち、ストランドの流れ方向及びペレットの流れ方向が不明なペレットを評価する場合には、任意の方向でペレットを切断して断面を作製し、得られた断面を上記方法で評価することもできる。 More specifically, a pellet of the polyester resin composition obtained by the method described in the Examples below can be cut perpendicularly to the flow direction (machine direction, MD) of the pellet, and an SEM image can be obtained at a magnification of 300 times using an SEM.
The pellets can be obtained by mixing the polyester resin composition according to the present disclosure, which is the subject of the measurement, and then heating and melt-extruding the mixture using a twin-screw extruder, followed by pelletizing the mixture using a strand-cut method. In other words, the flow direction (MD) of the pellets coincides with the flow direction (MD) of the strands, and the longitudinal direction of the pellets is usually the MD. The method of producing the pellets will be described later in the Examples.
In addition, when evaluating already produced pellets, i.e., pellets whose strand flow direction and pellet flow direction are unknown, the pellet can be cut in any direction to prepare a cross section, and the obtained cross section can be evaluated by the above-mentioned method.

　得られたＳＥＭ像の視野角０．４ｍｍ（４００μｍ）×０．３ｍｍ（３００μｍ）、視野サイズ：０．１２ｍｍ２の範囲を、画像解析ソフト「Ｉｍａｇｅ　Ｊ　Ｆｉｊｉ」を用いて二値化し、粒子を計測する方法をとる。
　二値化により計測された粒子サイズにおいて、視野サイズ中での、リン酸ジルコニウムの粒子サイズが２０μｍ２以上となる粒子数は０個であり、粒子サイズが１０μｍ２以上となる粒子数が１個以下であることが好ましく、粒子サイズが２μｍ２以上となる粒子数が１０個以下であることが、より好ましく、粒子サイズが１μｍ２以上となる粒子数が３０個以下であることが更に好ましく、粒子サイズが０．５μｍ２以上となる粒子数が５０個以下であることが特に好ましい。 The obtained SEM image is binarized using the image analysis software "Image J Fiji" within a range of a viewing angle of 0.4 mm (400 μm) × 0.3 mm (300 μm) and a viewing size of 0.12 mm2 , and the particles are measured.
In the particle size measured by binarization, the number of particles in the field of view having a particle size of 20 μm2 or more is 0, and the number of particles having a particle size of 10 μm2 or more is preferably 1 or less, more preferably 10 or less, even more preferably 30 or less, and particularly preferably 50 or less, of zirconium phosphate having a particle size of 0.5 μm2 or more.

　本開示のポリエステル樹脂組成物は、成分Ｂ及び成分Ｄの前記ポリエステル樹脂に加え、前記ポリエステル樹脂とは異なる追加のポリエステル樹脂を更に含むことができる。
　前記追加のポリエステル樹脂は、本開示のポリエステル樹脂組成物に含まれるポリエステル樹脂と同じであっても異なっていてもよい。前記追加のポリエステル樹脂は、本開示のポリエステル樹脂組成物を用いて、成形体等を得る際の成形加工性を向上させるポリエステル樹脂であることが好ましい。 The polyester resin composition of the present disclosure may further include, in addition to the polyester resins of Components B and D, an additional polyester resin different from the polyester resins.
The additional polyester resin may be the same as or different from the polyester resin contained in the polyester resin composition of the present disclosure. The additional polyester resin is preferably a polyester resin that improves molding processability when a molded body or the like is obtained using the polyester resin composition of the present disclosure.

　前記追加のポリエステル樹脂の固有粘度（ＩＶ）は、紡糸性の観点から、０．５０Ｌ／ｇ以上であることが好ましく、０．５５ｄＬ／ｇ～０．７４ｄＬ／ｇであることがより好ましく、０．５７ｄＬ／ｇ～０．７０ｄＬ／ｇであることが更に好ましく、０．５７ｄＬ／ｇ～０．６５ｄＬ／ｇであることが特に好ましい。
　前記追加のポリエステル樹脂としては、加工の目的に応じて公知のポリエステル樹脂を適宜選択して用いることができる。
　前記追加のポリエステル樹脂は、結晶性であってもよく、非晶性であってもよい。
　前記追加のポリエステル樹脂は市販品を用いてもよく、市販品としては、以下の例が挙げられるがこれらに限定されない。
　結晶性共重合ポリエステル樹脂（東洋紡（株）製バイロンＧＭ－９１３）、非晶性共重合ポリエステル樹脂（イーストマン・ケミカル・ジャパン（株）製ＧＮ００１）、ポリエチレンテレフタレート（ユニチカ（株）製ＭＡ－２１０１Ｍ）、結晶性共重合ポリエステル樹脂（東レ・セラニーズ（株）製ＳＢ６５４）、結晶性共重合ポリエステル樹脂（東洋紡（株）製バイロンＧＡ－６３００）等。 From the viewpoint of spinnability, the intrinsic viscosity (IV) of the additional polyester resin is preferably 0.50 L/g or more, more preferably 0.55 dL/g to 0.74 dL/g, even more preferably 0.57 dL/g to 0.70 dL/g, and particularly preferably 0.57 dL/g to 0.65 dL/g.
As the additional polyester resin, a known polyester resin can be appropriately selected and used depending on the purpose of processing.
The additional polyester resin may be crystalline or amorphous.
The additional polyester resin may be a commercially available product, and examples of the commercially available product include, but are not limited to, the following:
Crystalline copolymer polyester resin (Vylon GM-913 manufactured by Toyobo Co., Ltd.), amorphous copolymer polyester resin (GN001 manufactured by Eastman Chemical Japan Co., Ltd.), polyethylene terephthalate (MA-2101M manufactured by Unitika Ltd.), crystalline copolymer polyester resin (SB654 manufactured by Toray Celanese Co., Ltd.), crystalline copolymer polyester resin (Vylon GA-6300 manufactured by Toyobo Co., Ltd.), etc.

＜ポリエステル樹脂組成物の製造方法＞
　本開示に係るポリエステル樹脂組成物の製造方法は、特に制限はないが、（成分Ａ）下記（ａ－１）及び（ａ－２）を満たす４価金属リン酸塩化合物、（成分Ｂ）下記（ｂ－１）及び（ｂ－２）を満たすポリエステル樹脂、並びに、（成分Ｃ）分散剤をバッチ式混練手段により混練し、成分Ａの含有量が、組成物の全質量に対し、４０質量％～７２質量％であり、成分Ｂの含有量が、組成物の全質量に対し、２５質量％～５０質量％であり、成分Ｃの含有量が、組成物の全質量に対し、３質量％～２５質量％であるポリエステル樹脂組成物αを得る工程を含むことが好ましい。
　また、本開示に係るポリエステル樹脂組成物の製造方法は、（成分Ａ）下記（ａ－１）及び（ａ－２）を満たす４価金属リン酸塩化合物、（成分Ｂ）下記（ｂ－１）及び（ｂ－２）を満たすポリエステル樹脂、並びに、（成分Ｃ）分散剤を含有し、成分Ａの含有量が、組成物の全質量に対し、４０質量％～７２質量％であり、成分Ｂの含有量が、組成物の全質量に対し、２５質量％～５０質量％であり、成分Ｃの含有量が、組成物の全質量に対し、３質量％～２５質量％であるポリエステル樹脂組成物αに、（成分Ｄ）下記（ｄ－１）を満たすポリエステル樹脂と、成分Ｂとして、下記（ｂ－３）及び（ｂ－４）を満たすポリエステル樹脂とを添加して混練する工程を含むことが好ましい。
（ａ－１）下記式（１）で表される化合物である
　ＭＨａ（ＰＯ４）ｂ・ｎＨ２Ｏ　（１）
　式（１）中、Ｍは１種以上の４価金属を表し、ａ及びｂは３ｂ－ａ＝４を満たす正数であり、ｂは２＜ｂ≦２．１であり、ｎは０≦ｎ≦２である。
（ａ－２）メジアン径（Ｄ５０）が１．０μｍ以下である
（ｂ－１）結晶性である
（ｂ－２）テレフタル酸及びエチレングリコール以外のモノマーが１種類以上共重合されている
（ｂ－３）示差走査熱量計で測定した融点が２００℃以下である
（ｂ－４）固有粘度（ＩＶ）が１ｄＬ／ｇ以上である
（ｄ－１）示差走査熱量計で測定した融点が２４０℃以上である
　なお、前記ポリエステル樹脂組成物αは、本開示に係るポリエステル樹脂組成物の第１の実施態様に該当し、好ましい態様も前述した好ましい態様と同様である。
　また、本開示に係るポリエステル樹脂組成物の製造方法により前記混練する工程後に得られるポリエステル樹脂組成物は、本開示に係るポリエステル樹脂組成物の第２の実施態様又は第３の実施態様に該当し、好ましい態様も前述した好ましい態様と同様である。 <Method of producing polyester resin composition>
The method for producing a polyester resin composition according to the present disclosure is not particularly limited, but preferably includes a step of kneading (component A) a tetravalent metal phosphate compound satisfying the following (a-1) and (a-2), (component B) a polyester resin satisfying the following (b-1) and (b-2), and (component C) a dispersant by batch kneading means to obtain a polyester resin composition α in which the content of component A is 40% by mass to 72% by mass, the content of component B is 25% by mass to 50% by mass, and the content of component C is 3% by mass to 25% by mass, relative to the total mass of the composition.
In addition, the method for producing a polyester resin composition according to the present disclosure preferably includes a step of adding (component D) a polyester resin that satisfies the following (d-1) and (b-4) as component B to a polyester resin composition α that contains (component A) a tetravalent metal phosphate compound that satisfies the following (a-1) and (a-2), (component B) a polyester resin that satisfies the following (b-1) and (b-2), and (component C) a dispersant, the content of component A being 40% by mass to 72% by mass, the content of component B being 25% by mass to 50% by mass, and the content of component C being 3% by mass to 25% by mass, relative to the total mass of the composition, and kneading the resulting polyester resin composition.
(a-1) A compound represented by the following formula (1): MH a (PO 4 ) b ·nH 2 O (1)
In formula (1), M represents one or more tetravalent metals, a and b are positive numbers satisfying 3b-a=4, b is 2<b≦2.1, and n is 0≦n≦2.
(a-2) the median diameter (D 50 ) is 1.0 μm or less; (b-1) the polyester resin composition is crystalline; (b-2) one or more monomers other than terephthalic acid and ethylene glycol are copolymerized; (b-3) the melting point measured by a differential scanning calorimeter is 200° C. or less; (b-4) the intrinsic viscosity (IV) is 1 dL/g or more; (d-1) the melting point measured by a differential scanning calorimeter is 240° C. or more. The polyester resin composition α corresponds to the first embodiment of the polyester resin composition according to the present disclosure, and preferred embodiments are the same as those described above.
In addition, the polyester resin composition obtained after the kneading step by the production method for a polyester resin composition according to the present disclosure corresponds to the second or third embodiment of the polyester resin composition according to the present disclosure, and preferred embodiments are also similar to the preferred embodiments described above.

　前記混練する工程は、分散性の観点から、連続式混練手段により混練する工程であることが好ましい。
　また、分散性の観点から、前記混練する工程の前に、前記ポリエステル樹脂組成物αを得る工程を含むことがより好ましい。 From the viewpoint of dispersibility, the kneading step is preferably a step of kneading by a continuous kneading means.
From the viewpoint of dispersibility, it is more preferable to include a step of obtaining the polyester resin composition α prior to the kneading step.

＜＜バッチ式混練手段により混練し前記ポリエステル樹脂組成物αを得る工程＞＞
　本開示に用いられるバッチ式混練手段としては、ヘンシェルミキサー、加圧ニーダー、バンバリーミキサー、プラネタリーミキサー、コロイドミル、自転公転撹拌機、薄膜旋回型撹拌機等が挙げられる。
　バッチ式混練手段により混練する工程においては、成分Ａ～成分Ｃを混合し、混練することが好ましい。
　バッチ式混練手段への成分Ａ～成分Ｃの添加順序は、特に制限はなく、まとめて添加してもよいし、各成分を逐次的又は連続的に添加してもよい。
　バッチ式混練手段により混練する工程における加熱温度は、使用する成分に応じて選択すればよいが、分散性及び分解性の観点から、１００℃～２００℃であることが好ましく、１３０℃～１９０℃であることがより好ましく、１４０℃～１８０℃であることが更により好ましい。
　また、前記加熱温度は、分散性、及び分解性の観点から、成分Ｂの融点以上であること
が好ましい。
　バッチ式混練手段により混練する工程における混練時間は、特に制限はないが、例えば、０．１時間～１２時間であることが好ましく、０．３時間～６時間であることがより好ましく、０．５時間～２時間であることが更に好ましい。 <<Step of obtaining the polyester resin composition α by kneading using a batch kneading means>>
Examples of the batch-type kneading means used in the present disclosure include a Henschel mixer, a pressure kneader, a Banbury mixer, a planetary mixer, a colloid mill, a planetary mixer, a centrifugal mixer, a thin film rotary mixer, and the like.
In the step of kneading using a batch-type kneading means, it is preferable to mix and knead Components A to C.
The order of adding components A to C to the batch kneading means is not particularly limited, and the components may be added all at once, or each component may be added successively or continuously.
The heating temperature in the step of kneading by the batch-type kneading means may be selected depending on the components used, but from the viewpoints of dispersibility and decomposability, it is preferably 100°C to 200°C, more preferably 130°C to 190°C, and even more preferably 140°C to 180°C.
From the viewpoints of dispersibility and decomposition, the heating temperature is preferably equal to or higher than the melting point of component B.
The kneading time in the step of kneading by a batch-type kneading means is not particularly limited, but is, for example, preferably 0.1 hour to 12 hours, more preferably 0.3 hour to 6 hours, and even more preferably 0.5 hour to 2 hours.

＜＜連続式混練手段により混練する工程＞＞
　本開示に用いられる連続式混練手段としては、単軸混練押出機、二軸混練押出機、多軸式混練押出機、タンデム式混練押出機等が挙げられる。
　連続式混練手段により混練する工程においては、バッチ式混練手段により混練する工程により得られたポリエステル樹脂組成物と、成分Ｄとを混合し、混練することが好ましく、バッチ式混練手段により混練する工程により得られたポリエステル樹脂組成物と、成分Ｄと、前記（ｂ－３）及び（ｂ－４）を満たすポリエステル樹脂を混合し、混練することがより好ましい。
　連続式混練手段により混練する工程におけるバッチ式混練手段により混練する工程により得られたポリエステル樹脂組成物の添加量としては、得られる組成物の全質量に対し、分散性、消臭性及び成形加工性の観点から、２質量％～５０質量％であることが好ましく、３質量％～４５質量％であることがより好ましく、５質量％～４０質量％であることが特に好ましい。
　連続式混練手段により混練する工程における成分Ｄの添加量としては、得られる組成物の全質量に対し、分散性、消臭性及び成形加工性の観点から、３７質量％～８３．６質量％であることが好ましく、４２質量％～８３．６質量％であることがより好ましく、４７質量％～７５質量％であることが更に好ましく、５０質量％～６８質量％であることが特に好ましい。
　また、連続式混練手段により混練する工程における前記（ｂ－３）及び（ｂ－４）を満たすポリエステル樹脂の添加量としては、得られる組成物の全質量に対し、分散性、消臭性及び成形加工性の観点から、０質量％～２５質量％であることが好ましく、１．５質量％～２０質量％であることがより好ましく、１．８質量％～１５質量％であることが特に好ましい。 <<Step of kneading by continuous kneading means>>
Examples of the continuous kneading means used in the present disclosure include a single-screw kneading extruder, a twin-screw kneading extruder, a multi-screw kneading extruder, and a tandem kneading extruder.
In the step of kneading by continuous kneading means, it is preferable to mix and knead the polyester resin composition obtained in the step of kneading by batch kneading means with component D, and it is more preferable to mix and knead the polyester resin composition obtained in the step of kneading by batch kneading means with component D and a polyester resin satisfying the above-mentioned (b-3) and (b-4).
The amount of the polyester resin composition obtained by the step of kneading by batch kneading means added to the step of kneading by continuous kneading means is preferably 2% by mass to 50% by mass, more preferably 3% by mass to 45% by mass, and particularly preferably 5% by mass to 40% by mass, based on the total mass of the obtained composition, from the viewpoints of dispersibility, deodorizing properties, and moldability.
The amount of component D added in the step of kneading by continuous kneading means is, from the viewpoints of dispersibility, deodorizing properties, and moldability, preferably 37% by mass to 83.6% by mass, more preferably 42% by mass to 83.6% by mass, even more preferably 47% by mass to 75% by mass, and particularly preferably 50% by mass to 68% by mass, relative to the total mass of the composition to be obtained.
The amount of polyester resin satisfying the above (b-3) and (b-4) added in the step of kneading by a continuous kneading means is preferably 0% by mass to 25% by mass, more preferably 1.5% by mass to 20% by mass, and particularly preferably 1.8% by mass to 15% by mass, based on the total mass of the obtained composition, from the viewpoints of dispersibility, deodorizing properties, and moldability.

　連続式混練手段により混練する工程における各成分は、事前に混合し、連続式混練手段へ投入することが好ましい。
　連続式混練手段により混練する工程における加熱温度は、使用する成分に応じて選択すればよいが、分散性の観点から、２４０℃～３００℃であることが好ましく、２５０℃～２８０℃であることがより好ましく、２５７℃～２７０℃であることが特に好ましい。
　また、前記加熱温度は、分散性の観点から、成分Ｄの融点以上であることが好ましい。
　連続式混練手段により混練する工程における混練時間は、特に制限はなく、使用する連続式混練手段等に応じて、吐出量等を適宜選択すればよい。 In the step of kneading using a continuous kneading means, the components are preferably mixed in advance and then fed into the continuous kneading means.
The heating temperature in the step of kneading by the continuous kneading means may be selected depending on the components used, but from the viewpoint of dispersibility, it is preferably 240°C to 300°C, more preferably 250°C to 280°C, and particularly preferably 257°C to 270°C.
From the viewpoint of dispersibility, the heating temperature is preferably equal to or higher than the melting point of component D.
The kneading time in the step of kneading by the continuous kneading means is not particularly limited, and the discharge amount and the like may be appropriately selected depending on the continuous kneading means to be used, etc.

　本開示に係るポリエステル樹脂組成物の製造方法は、必要に応じ、得られたポリエステル樹脂組成物をペレット化する工程等のその他の工程を含んでいてもよい。 The method for producing the polyester resin composition according to the present disclosure may include other steps, such as pelletizing the obtained polyester resin composition, as necessary.

（成形体）
　本開示に係る成形体は、既述の本開示のポリエステル樹脂組成物の第１の実施形態、本開示のポリエステル樹脂組成物の第２の実施形態及び本開示のポリエステル樹脂組成物の第３の実施形態から選ばれるポリエステル樹脂組成物を成形加工してなる成形体である。
　本開示に係る成形体は、本開示に係るポリエステル樹脂組成物を成形加工してなる成形体であってもよく、本開示のポリエステル樹脂組成物と前記追加のポリエステル樹脂とを混合し成形加工してなる成形体であってもよい。
　中でも、本開示に係る成形体は、本開示に係るポリエステル樹脂組成物の第２実施態様又は第３の実施態様と前記追加のポリエステル樹脂とを混合し成形加工してなる成形体であることが好ましい。
　ポリエステル樹脂組成物の成形加工法は、成形体の種類等に応じて、適宜選択され、例えば、押出成形、射出成形、圧縮成形、トランスファー成形、スタンバブル成形、ブロー成形、インフレーション成形、延伸フィルム成形、積層成形、カレンダー成形、発泡成形、注型成形、粉末成形、ペースト成形、溶融紡糸等が挙げられ、これらの成形加工法を１
種単独で使用しても、２種以上を併用してもよい。
　中でも、本開示に係る成形体においては、前記成形加工が、溶融紡糸であることが好ましい。
　また、本開示に係る成形体を高次加工してなる成形体も好ましく挙げられる。高次加工してなる成形体としては、例えば、成形体である繊維を更に加工して得られる糸、及び、繊維製品等が挙げられる。
　成形体における繊維、及び糸の太さ、長さ、断面形状（円形、異形など）、断面層構造（単層、多層、芯鞘、中空など）、延伸方法（逐次、同時）、及び延伸倍率は、所望に応じ適宜選択すればよい。
　成形体における繊維、及び糸は長繊維（フィラメント）でも短繊維（ステープル）でもよく、長繊維（フィラメント）はモノフィラメントでもマルチフィラメントでもよく、所望に応じ適宜選択すればよい。
　長繊維（フィラメント）は、未延伸糸（ＵＤＹ：Ｕｎ　Ｄｒａｗｎ　Ｙａｒｎ）であっても、ＵＤＹを別工程で延伸や実撚付与等を行い、配向の進行した延伸糸（ＦＯＹ：Ｆｕｌｌｙ　Ｏｒｉｅｎｔｅｄ　Ｙａｒｎ）であっても、紡糸と延伸を直結して延伸糸を１工程で得る紡糸直延伸（ＤＳＤ：Ｄｉｒｅｃｔ　Ｓｐｉｎ　Ｄｒａｗ）であっても、部分配向糸（ＰＯＹ：Ｐａｒｔｉａｌｌｙ　Ｏｒｉｅｎｔｅｄ　Ｙａｒｎ）であっても、延伸加工糸（ＤＴＹ：Ｄｒａｗ　Ｔｅｘｔｕｒｅｄ　Ｙａｒｎ）であっても、ＰＯＹを別工程で延伸と仮撚加工まで施した延伸仮撚加工糸（ＤＴＹ：Ｄｒａｗ　Ｔｅｘｔｕｒｅｄ　Ｙａｒｎ）であっても、延伸を必要としないＯＳＹ（Ｏｎｅ　Ｓｔｅｐ　Ｙａｒｎ）であっても、カバリング糸（ＦＴＹ：Ｆｉｌａｍｅｎｔ　Ｔｗｉｓｔｅｄ　Ｙａｒｎ）であってもよい。また、本開示に係るポリエステル樹脂組成物を含んで形成される糸は、単糸、双糸、もしくは紡績糸であってもよい。
　成形体における繊維、及び糸は、他の繊維を含んだ混合繊維でもよく、他の繊維の種類は特に限定されず、天然繊維や合成繊維から所望に応じ適宜選択すればよい。 (Molded body)
The molded article according to the present disclosure is a molded article obtained by molding a polyester resin composition selected from the first embodiment of the polyester resin composition according to the present disclosure, the second embodiment of the polyester resin composition according to the present disclosure, and the third embodiment of the polyester resin composition according to the present disclosure.
The molded article according to the present disclosure may be a molded article obtained by molding the polyester resin composition according to the present disclosure, or may be a molded article obtained by mixing the polyester resin composition according to the present disclosure and the additional polyester resin and molding the mixture.
In particular, the molded article according to the present disclosure is preferably a molded article obtained by mixing the second or third embodiment of the polyester resin composition according to the present disclosure and the additional polyester resin and molding the mixture.
The molding method of the polyester resin composition is appropriately selected depending on the type of molded article, and examples thereof include extrusion molding, injection molding, compression molding, transfer molding, stampable molding, blow molding, inflation molding, stretched film molding, lamination molding, calendar molding, foam molding, cast molding, powder molding, paste molding, melt spinning, and the like.
They may be used alone or in combination of two or more.
In particular, in the molded article according to the present disclosure, the molding process is preferably melt spinning.
In addition, a molded article obtained by advanced processing of the molded article according to the present disclosure is also preferably included. Examples of the molded article obtained by advanced processing include yarn and textile products obtained by further processing the fiber of the molded article.
The thickness, length, cross-sectional shape (circular, irregular, etc.), cross-sectional layer structure (single layer, multi-layer, core-sheath, hollow, etc.), stretching method (sequential, simultaneous), and stretching ratio of the fibers and yarns in the molded product may be appropriately selected as desired.
The fibers and threads in the molded article may be long fibers (filaments) or short fibers (staples), and the long fibers (filaments) may be monofilaments or multifilaments, which may be appropriately selected as desired.
The filaments may be undrawn yarn (UDY: Undrawn Yarn), fully oriented yarn (FOY: Fully Oriented Yarn) in which UDY is drawn and twisted in a separate process to obtain a highly oriented yarn, direct spin drawn (DSD: Direct Spin Draw) in which spinning and drawing are directly combined to obtain a drawn yarn in one process, partially oriented yarn (POY: Partially Oriented Yarn), drawn textured yarn (DTY: Drawn Textured Yarn), or drawn textured yarn (DTY: Drawn Textured Yarn) in which POY is drawn and twisted in a separate process, or one step OSY (One Step) which does not require drawing. The yarn formed including the polyester resin composition according to the present disclosure may be a single yarn, a two-ply yarn, or a spun yarn.
The fibers and yarns in the molded article may be a mixed fiber containing other fibers, and the type of other fibers is not particularly limited and may be appropriately selected from natural fibers and synthetic fibers as desired.

　本開示に係るポリエステル樹脂組成物の第１の実施態様、第２の実施態様又は第３の実施態様と混合する追加のポリエステル樹脂としては、特に制限はなく、作製する成形体等に応じて、適宜選択することができる。
　本開示に係るポリエステル樹脂組成物の第２の実施態様又は第３の実施態様と混合する追加のポリエステル樹脂の固有粘度（ＩＶ）は、紡糸性の観点から、０．５０ｄＬ／ｇ以上であることが好ましく、０．５５ｄＬ／ｇ～０．７４ｄＬ／ｇであることがより好ましく、０．５７ｄＬ／ｇ～０．７０ｄＬ／ｇであることが更に好ましく、０．５７ｄＬ／ｇ～０．６５ｄＬ／ｇであることが特に好ましい。 The additional polyester resin to be mixed with the first embodiment, the second embodiment, or the third embodiment of the polyester resin composition according to the present disclosure is not particularly limited and can be appropriately selected depending on the molded body to be produced.
The intrinsic viscosity (IV) of the additional polyester resin to be mixed with the second or third embodiment of the polyester resin composition according to the present disclosure is preferably 0.50 dL/g or more, more preferably 0.55 dL/g to 0.74 dL/g, even more preferably 0.57 dL/g to 0.70 dL/g, and particularly preferably 0.57 dL/g to 0.65 dL/g, from the viewpoint of spinnability.

　本開示に係る成形体は、例えば、消臭性成形体、イオン吸着性成形体、抗菌性成形体、抗ウイルス性成形体、抗アレルゲン性成形体等として使用することができる。
　成形体としては、繊維、糸、繊維製品、フィルム、板、立体構造体（例えば、袋、容器、筐体、住宅建材、自動車部品等）等が挙げられる。
　中でも、成形体としては、繊維、糸、又は、繊維製品が好ましく挙げられ、織布、又は、不織布がより好ましく挙げられる。 The molded article according to the present disclosure can be used, for example, as a deodorant molded article, an ion-adsorbing molded article, an antibacterial molded article, an antiviral molded article, an antiallergenic molded article, and the like.
Examples of the molded article include fibers, threads, textile products, films, plates, and three-dimensional structures (for example, bags, containers, housing materials, and automobile parts).
Among these, preferred examples of the molded article include fibers, threads, and textile products, and more preferred examples include woven fabrics and nonwoven fabrics.

　繊維製品としては、例えば、織布、不織布、並びに、これらを使用した衣料用品及び寝具類等が挙げられる。
　衣料用品としては、例えば、ストッキング、下着、パンツ、ブラジャー、ガードル、スパッツ、ジャンパー、ダウンジャケット、セーター、カーディガン、ズボン、ベスト、帽子、手袋、靴下、ワンピース、靴、サンダル、作業着、制服、白衣、パジャマ、マフラー、ネックウォーマー、肌着、かつら（ウィッグ）、Ｔシャツ、Ｙシャツ、スーツ、礼服、ネクタイ、マスク、腹巻、帯、着物、足袋、スポーツウェア、ジャージ、バンダナ、トレーナー、スウェット及びリストバンド等が挙げられる。
　寝具類としては、例えば、枕、布団、枕カバー、布団カバー、シーツ、毛布、タオルケット、敷きパット、布団収納袋、タオル、ハンカチ、ガウン、及びスリッパ等が挙げられる。
　これらは必要に応じて主に着色を目的とした染色加工や、主に繊維素材の特性維持や機
能性付与を目的とした仕上げ加工を施してもよい。 Examples of textile products include woven fabrics, nonwoven fabrics, and clothing and bedding made from these.
Examples of clothing items include stockings, underwear, pants, brassieres, girdles, spats, jumpers, down jackets, sweaters, cardigans, trousers, vests, hats, gloves, socks, dresses, shoes, sandals, work clothes, uniforms, lab coats, pajamas, scarves, neck warmers, underwear, wigs, T-shirts, dress shirts, suits, formal wear, neckties, masks, belly warmers, obi, kimonos, tabi, sportswear, jerseys, bandanas, sweatshirts, sweatshirts, and wristbands.
Examples of bedding include pillows, futons, pillowcases, futon covers, sheets, blankets, towel blankets, mattress pads, futon storage bags, towels, handkerchiefs, gowns, and slippers.
If necessary, these may be subjected to a dyeing process, mainly for the purpose of coloring, or a finishing process, mainly for the purpose of maintaining the characteristics of the fiber material and imparting functionality.

　以下、本開示を実施例により更に具体的に説明するが、本開示はその主旨を越えない限り、以下の実施例に限定されるものではない。なお、特に断りのない限り、「％」は質量基準である。 The present disclosure will be explained in more detail below with reference to examples, but the present disclosure is not limited to the following examples as long as it does not deviate from the gist of the disclosure. Unless otherwise specified, "%" is based on mass.

（４価金属リン酸塩化合物）
＜合成例１（４価金属リン酸塩化合物の準備）＞
　メジアン径０．８μｍのリン酸ジルコニウム粒子は、東亞合成（株）製ケスモンＮＳ－１０を用いた。 (Tetravalent metal phosphate compound)
Synthesis Example 1 (Preparation of Tetravalent Metal Phosphate Compound)
The zirconium phosphate particles having a median diameter of 0.8 μm were Kesmon NS-10 manufactured by Toagosei Co., Ltd.

＜合成例２（４価金属リン酸塩化合物の準備）＞
　メジアン径１．５μｍのリン酸ジルコニウム粒子は、東亞合成（株）製ケスモンＮＳ－１０ＴＺを用いた。 Synthesis Example 2 (Preparation of Tetravalent Metal Phosphate Compound)
As zirconium phosphate particles having a median diameter of 1.5 μm, Kesmon NS-10TZ manufactured by Toagosei Co., Ltd. was used.

＜合成例３＞
　メジアン径０．５１μｍのリン酸ジルコニウム粒子は、以下の方法により作製した。
　６ｍ３反応器に脱イオン水３，４８０ｋｇ及び３５％塩酸５２０ｋｇを入れ、ハフニウム０．１８％含有オキシ塩化ジルコニウム８水和物２０％水溶液８６５ｋｇを追加後、シュウ酸２水和物３５８ｋｇを溶解させた。この溶液をよく撹拌しながら、７５％リン酸４０３ｋｇを加えた。これを２時間で９８℃に昇温し、１２時間撹拌還流した。冷却後、得られた沈殿物をよく水洗浄した後、１０５℃で乾燥することにより、リン酸ジルコニウム粒子を得た。これを粉砕機で解砕した。その後、篩分処理をした。この得られたリン酸ジルコニウム粒子について粉末Ｘ線回折装置で測定した結果、αリン酸ジルコニウム粒子であることを確認した。 <Synthesis Example 3>
Zirconium phosphate particles having a median diameter of 0.51 μm were prepared by the following method.
A 6 m3 reactor was charged with 3,480 kg of deionized water and 520 kg of 35% hydrochloric acid, and 865 kg of a 20% aqueous solution of zirconium oxychloride octahydrate containing 0.18% hafnium was added, followed by dissolving 358 kg of oxalic acid dihydrate. While stirring the solution well, 403 kg of 75% phosphoric acid was added. The temperature was raised to 98°C in 2 hours, and the mixture was refluxed with stirring for 12 hours. After cooling, the resulting precipitate was thoroughly washed with water and then dried at 105°C to obtain zirconium phosphate particles. The particles were crushed with a pulverizer. Then, the particles were sieved. The obtained zirconium phosphate particles were measured with a powder X-ray diffraction device, and it was confirmed that they were α-zirconium phosphate particles.

＜合成例４＞
　メジアン径０．２２μｍのリン酸ジルコニウム粒子は、以下の方法により作製した。
　６ｍ３反応器に脱イオン水３，１６８ｋｇ及び３５％塩酸５５６ｋｇを入れ、ハフニウム０．１８％含有オキシ塩化ジルコニウム８水和物２０％水溶液９６８ｋｇを追加後、シュウ酸２水和物３２８ｋｇを溶解させた。この溶液をよく撹拌しながら、７５％リン酸４８２ｋｇを加えた。これを２時間で９８℃に昇温し、１２時間撹拌還流した。冷却後、得られた沈殿物をよく水洗浄した後、１０５℃で乾燥することにより、リン酸ジルコニウム粒子を得た。これを粉砕機で解砕した。その後、篩分処理をした。この得られたリン酸ジルコニウム粒子について粉末Ｘ線回折装置で測定した結果、αリン酸ジルコニウム粒子であることを確認した。 <Synthesis Example 4>
Zirconium phosphate particles having a median diameter of 0.22 μm were prepared by the following method.
A 6 m3 reactor was charged with 3,168 kg of deionized water and 556 kg of 35% hydrochloric acid, and 968 kg of a 20% aqueous solution of zirconium oxychloride octahydrate containing 0.18% hafnium was added, followed by dissolving 328 kg of oxalic acid dihydrate. 482 kg of 75% phosphoric acid was added while stirring the solution well. The temperature was raised to 98°C in 2 hours, and the mixture was refluxed with stirring for 12 hours. After cooling, the resulting precipitate was thoroughly washed with water and then dried at 105°C to obtain zirconium phosphate particles. The particles were crushed with a pulverizer. Then, the particles were sieved. The obtained zirconium phosphate particles were measured with a powder X-ray diffractometer, and it was confirmed that they were α-zirconium phosphate particles.

＜合成例５＞
　メジアン径０．５６μｍのリン酸チタン粒子は、以下の方法により作製した。
　６ｍ３反応器に脱イオン水２，７４５ｋｇを入れ、７５％リン酸２，４３２ｋｇを加えた。この溶液をよく撹拌しながら、硫酸チタニル８２３ｋｇを投入し、１０分間撹拌を継続した。その後、１００℃まで１時間で昇温し、４４時間撹拌還流した。冷却後、得られた沈殿物をよく水洗浄した後、１０５℃で乾燥することにより、リン酸チタン粒子を得た。これを粉砕機で解砕した。その後、篩分処理をした。この得られたリン酸チタン粒子について粉末Ｘ線回折装置で測定した結果、αリン酸チタン粒子であることを確認した。 <Synthesis Example 5>
Titanium phosphate particles having a median diameter of 0.56 μm were prepared by the following method.
A 6 m3 reactor was charged with 2,745 kg of deionized water, and 2,432 kg of 75% phosphoric acid was added. While stirring the solution well, 823 kg of titanyl sulfate was added, and stirring was continued for 10 minutes. The temperature was then raised to 100°C in 1 hour, and the mixture was refluxed with stirring for 44 hours. After cooling, the resulting precipitate was thoroughly washed with water, and then dried at 105°C to obtain titanium phosphate particles. The precipitate was crushed with a grinder. Then, the mixture was sieved. The obtained titanium phosphate particles were measured with a powder X-ray diffractometer, and it was confirmed that they were α-titanium phosphate particles.

＜合成例６＞
　メジアン径０．１１μｍのリン酸ジルコニウム粒子は、以下の方法により作製した。
　６ｍ３反応器に脱イオン水２２８ｋｇを入れ、７５％リン酸４，３２０ｋｇを加えた。この溶液をよく撹拌しながら、ハフニウム０．１８％含有オキシ塩化ジルコニウム８水和物２０％水溶液８６４ｋｇを投入し、１０分間撹拌を継続した。その後、９８℃まで１時
間で昇温し、１２時間撹拌還流した。冷却後、得られた沈殿物をよく水洗浄した後、１０５℃で乾燥することにより、リン酸ジルコニウム粒子を得た。これを粉砕機で解砕した。その後、篩分処理をした。この得られたリン酸ジルコニウム粒子について粉末Ｘ線回折装置で測定した結果、αリン酸ジルコニウム粒子であることを確認した。 <Synthesis Example 6>
Zirconium phosphate particles having a median diameter of 0.11 μm were prepared by the following method.
228 kg of deionized water was placed in a 6 m3 reactor, and 4,320 kg of 75% phosphoric acid was added. While stirring this solution well, 864 kg of a 20% aqueous solution of zirconium oxychloride octahydrate containing 0.18% hafnium was added, and stirring was continued for 10 minutes. The temperature was then raised to 98°C in 1 hour, and the mixture was refluxed with stirring for 12 hours. After cooling, the obtained precipitate was thoroughly washed with water and then dried at 105°C to obtain zirconium phosphate particles. The particles were crushed with a pulverizer. Then, the particles were sieved. The obtained zirconium phosphate particles were measured with a powder X-ray diffraction device, and it was confirmed that they were α-zirconium phosphate particles.

＜合成例７＞
　メジアン径１．０μｍのリン酸ジルコニウム粒子は、以下の方法により作製した。
　６ｍ３反応器に脱イオン水３，６００ｋｇ及び３５％塩酸３６２ｋｇを入れ、ハフニウム０．１８％含有オキシ塩化ジルコニウム８水和物２０％水溶液６００ｋｇを追加後、シュウ酸２水和物２５０ｋｇを溶解させた。この溶液をよく撹拌しながら、７５％リン酸２７４ｋｇを加えた。これを２時間で９８℃に昇温し、１２時間撹拌還流した。冷却後、得られた沈殿物をよく水洗浄した後、１０５℃で乾燥することにより、リン酸ジルコニウム粒子を得た。これを粉砕機で解砕した。その後、篩分処理をした。この得られたリン酸ジルコニウム粒子について粉末Ｘ線回折装置で測定した結果、αリン酸ジルコニウム粒子であることを確認した。 <Synthesis Example 7>
Zirconium phosphate particles having a median diameter of 1.0 μm were prepared by the following method.
A 6 m3 reactor was charged with 3,600 kg of deionized water and 362 kg of 35% hydrochloric acid, and 600 kg of a 20% aqueous solution of zirconium oxychloride octahydrate containing 0.18% hafnium was added, followed by dissolving 250 kg of oxalic acid dihydrate. 274 kg of 75% phosphoric acid was added while stirring the solution well. The temperature was raised to 98°C in 2 hours, and the mixture was refluxed with stirring for 12 hours. After cooling, the resulting precipitate was thoroughly washed with water and then dried at 105°C to obtain zirconium phosphate particles. The particles were crushed with a pulverizer. Then, the particles were sieved. The obtained zirconium phosphate particles were measured with a powder X-ray diffractometer, and it was confirmed that they were α-zirconium phosphate particles.

　蛍光Ｘ線分析及び熱重量示差熱分析を行い同定した粒子の組成式を、表１に示す。 The particle composition, identified by X-ray fluorescence analysis and thermogravimetric differential thermal analysis, is shown in Table 1.

（実施例１～４８、及び、比較例１～１５）
＜中間体の作製：配合例＞
　表２に記載の４価金属リン酸塩化合物、ポリエステル樹脂及び分散剤、並びに、その他の成分を表２に記載の配合比率となるように３Ｌ加圧式ニーダー（バッチ式混練機、日本スピンドル製造社製「ＤＳ－３－１０ＭＷＢ－Ｅ型」）へ入れ、温度１５０℃、ブレード回転数３０ｒｐｍで４５分混練した。混練後、内容物をロール温度１１０℃の１０インチ２本ロールにて厚さ３ｍｍのシートへ成形後、細断してペレット化することで４価金属リン酸塩化合物含有ポリエステル樹脂組成物（中間体）を得た。 (Examples 1 to 48 and Comparative Examples 1 to 15)
<Preparation of intermediates: Mixture example>
The tetravalent metal phosphate compound, polyester resin, dispersant, and other components shown in Table 2 were placed in a 3L pressure kneader (batch kneader, "DS-3-10MWB-E" manufactured by Nihon Spindle Mfg. Co., Ltd.) in the blending ratios shown in Table 2, and kneaded for 45 minutes at a temperature of 150°C and a blade rotation speed of 30 rpm. After kneading, the contents were molded into a sheet with a thickness of 3 mm using two 10-inch rolls at a roll temperature of 110°C, and then shredded and pelletized to obtain a polyester resin composition (intermediate) containing a tetravalent metal phosphate compound.

＜マスターバッチの作製＞
　表３又は表４に記載の４価金属リン酸塩化合物含有ポリエステル樹脂組成物（中間体）、及びポリエステル樹脂を表３又は表４に記載の配合比率で混合し、φ１８ｍｍ二軸押出機（連続式混練機、芝浦機械（株）製「ＴＥＭ－１８ＳＳ－１２／１Ｖ」）を用い、押出温度２６０℃、スクリュー回転数４００ｒｐｍ、吐出量７．０ｋｇ／ｈ、ストランドカット方式でペレット化することで４価金属リン酸塩化合物含有ポリエステル樹脂組成物（マスターバッチ）を得た。
　また、表５に記載の４価金属リン酸塩化合物、及びポリエステル樹脂を表５に記載の配合比率で混合し、φ１８ｍｍ二軸押出機（連続式混練機、芝浦機械（株）製「ＴＥＭ－１８ＳＳ－１２／１Ｖ」）を用い、押出温度２６０℃、スクリュー回転数４００ｒｐｍ、吐出量７．０ｋｇ／ｈ、ストランドカット方式でペレット化することで４価金属リン酸塩化合物含有ポリエステル樹脂組成物（マスターバッチ）を得た。 <Preparation of Masterbatch>
A tetravalent metal phosphate compound-containing polyester resin composition (intermediate) and a polyester resin shown in Table 3 or Table 4 were mixed in the blending ratio shown in Table 3 or Table 4, and pelletized using a φ18 mm twin-screw extruder (continuous kneader, "TEM-18SS-12/1V" manufactured by Shibaura Machine Co., Ltd.) at an extrusion temperature of 260°C, a screw rotation speed of 400 rpm, a discharge rate of 7.0 kg/h, and a strand cut method to obtain a tetravalent metal phosphate compound-containing polyester resin composition (master batch).
In addition, a tetravalent metal phosphate compound and a polyester resin shown in Table 5 were mixed in the compounding ratio shown in Table 5, and the mixture was pelletized using a φ18 mm twin-screw extruder (continuous kneader, "TEM-18SS-12/1V" manufactured by Shibaura Machine Co., Ltd.) at an extrusion temperature of 260° C., a screw rotation speed of 400 rpm, a discharge rate of 7.0 kg/h, and a strand cut method to obtain a tetravalent metal phosphate compound-containing polyester resin composition (master batch).

＜繊維の作製＞
　表３又は表４に記載の４価金属リン酸塩化合物含有ポリエステル樹脂組成物（マスターバッチ）及びポリエステル樹脂を表３又は表４に記載の配合比率で混合し、４８フィラメント用の口金に３０／３２５／３０メッシュを備えたφ２０ｍｍ溶融紡糸設備（ＡＩＫＩリオテック社製「ＡＬＭ－Ｓ３５００－Ｔ１」）を用い、押出温度２８０℃、ギアポンプの回転数を吐出量１．５ｋｇ／ｈとなるように調整し、クエンチボックス内で空冷、オイリングしながらゴデッドローラー速度７４３ｍ／分で引き取り、延伸部のゴデッドローラー温度１２０℃、速度２，９７０ｍ／分で、みかけの延伸倍率が４．０倍となるように延伸し、熱固定部のゴデッドローラー温度１２０℃、速度２，９７０ｍ／分で熱固定を行い、３，０００ｍ／分で巻き取ることにより、繊度７５デニール、フィラメント数４８の４価金属リン酸塩化合物含有ポリエステル繊維を得た。 <Fabric Preparation>
A polyester resin composition (master batch) containing a tetravalent metal phosphate compound and a polyester resin shown in Table 3 or Table 4 were mixed in the blending ratio shown in Table 3 or Table 4, and a φ20 mm melt spinning equipment ("ALM-S3500-T1" manufactured by AIKI Liotech Co., Ltd.) equipped with a 30/325/30 mesh on a 48 filament nozzle was used. The extrusion temperature was 280° C., and the gear pump rotation speed was adjusted to a discharge rate of 1.5 kg/h. The fiber was air-cooled in a quench box, and taken up at a godet roller speed of 743 m/min while oiling. The fiber was stretched in the stretching section at a godet roller temperature of 120° C. and a speed of 2,970 m/min to an apparent stretch ratio of 4.0 times. The fiber was heat-set in the heat-setting section at a godet roller temperature of 120° C. and a speed of 2,970 m/min, and taken up at 3,000 m/min to obtain a polyester fiber containing a tetravalent metal phosphate compound having a fineness of 75 denier and 48 filaments.

＜評価＞
－メジアン径－
　４価金属リン酸塩化合物を添加した分散液を超音波発生装置で分散させ、レーザー回折式粒度分布測定装置「マスターサイザー２０００」（マルバーン社製）で測定し、結果を体積基準で解析した。
　分散媒：水
　粒子濃度：１質量％（水１００ｇに対して４価金属リン酸塩化合物１ｇ）
　粒子屈折率：２．４
　撹拌：２，４５０ｒｐｍ
　超音波：出力５０％×１分の繰り返し <Evaluation>
- Median diameter -
The dispersion liquid to which the tetravalent metal phosphate compound was added was dispersed using an ultrasonic generator, and the dispersion was measured using a laser diffraction particle size distribution measuring device "Mastersizer 2000" (manufactured by Malvern Instruments), and the results were analyzed on a volume basis.
Dispersion medium: Water Particle concentration: 1% by mass (1 g of tetravalent metal phosphate compound per 100 g of water)
Particle refractive index: 2.4
Stirring: 2,450 rpm
Ultrasonic: 50% output x 1 minute repetition

－結晶構造分析－
　粉末Ｘ線回折にて評価した。Ｘ線回折装置は、ＢＲＵＫＥＲ社製　Ｄ８　ＡＤＶＡＮＣＥを使用した。Ｃｕ封入型Ｘ線源を用い、印加電圧４０ｋＶ、電流値４０ｍＡで発生するＣｕＫαを用いてＸ線回折図を得た。詳細な測定条件は下記の通り。
　Ｘ線源：封入型Ｘ線源（Ｃｕ線源）、０．４×１２ｍｍ２、Ｌｏｎｇ　Ｆｉｎｅ　Ｆｏｃｕｓ
　定格：２．２ｋＷ
　使用出力：４０ｋＶ－４０ｍＡ（１．６ｋＷ）
　ゴニオメーター半径：２８０ｍｍ
　試料ステージ：ＦｌｉｐＳｔｉｃｋ＿Ｔｗｉｎ＿Ｔｗｉｎ－ＸＥ
　測定範囲２θ：５°～５５°
　ステップ幅：０．０２°
　ステップ時間：０．０５秒／ステップ
　入射側ソラースリット：２．５°
　散乱防止スリット：１０．５ｍｍ
　曲率：１．００
　検出器：ＬＹＮＸＥＹＥ　ＸＥ
　検出器スリット幅：５．７５８ｍｍ
　検出器ウインドウ幅：２．９° -Crystal structure analysis-
The evaluation was performed by powder X-ray diffraction. The X-ray diffraction apparatus used was a D8 ADVANCE manufactured by BRUKER. An X-ray diffraction pattern was obtained using CuKα generated at an applied voltage of 40 kV and a current value of 40 mA using a Cu-encapsulated X-ray source. The detailed measurement conditions are as follows.
X-ray source: Encapsulated X-ray source (Cu ray source), 0.4 x 12 mm 2 , Long Fine Focus
Rating: 2.2kW
Output power: 40kV-40mA (1.6kW)
Goniometer radius: 280 mm
Sample stage: FlipStick_Twin_Twin-XE
Measurement range 2θ: 5° to 55°
Step width: 0.02°
Step time: 0.05 sec/step Entrance side Soller slit: 2.5°
Anti-scattering slit: 10.5 mm
Curvature: 1.00
Detector: LYNXEYE XE
Detector slit width: 5.758 mm
Detector window width: 2.9°

　組成式は、蛍光Ｘ線による元素分析、及び、熱重量示差熱分析（ＴＧ－ＤＴＡ）による水和水分析にて実施した。 The composition formula was determined by elemental analysis using X-ray fluorescence and hydration water analysis using thermogravimetric differential thermal analysis (TG-DTA).

－蛍光Ｘ線分析－
　蛍光Ｘ線分析は以下の条件で測定した。
＜測定条件＞
　測定機器：（株）リガク製　ＺＳＸ　Ｐｒｉｍｕｓ　ＩＩ
　測定元素：Ｃ～Ｕ（Ｆ、Ｃｌ、Ｂｒ、Ｉに定角測定、ＢＧ　４ｓｅｃ、ピーク８ｓｅｃ）
　分析径：２０ｍｍ
　測定数：ｎ＝２で測定
　試料処理：錠剤成型機を用い、試料をペレット状に加圧成型し、測定に供した。
＜解析＞
　ソフトウェア：ＺＳＸ　ｖｅｒｓｉｏｎ７．４９
　モデル：バルク - X-ray fluorescence analysis -
The X-ray fluorescence analysis was performed under the following conditions.
<Measurement conditions>
Measuring equipment: Rigaku ZSX Primus II
Measurement elements: C to U (measured at a fixed angle for F, Cl, Br, and I, BG 4 sec, peak 8 sec)
Analysis diameter: 20mm
Number of measurements: n=2 Sample treatment: The sample was pressurized into pellets using a tablet press and subjected to the measurement.
<Analysis>
Software: ZSX version 7.49
Model: Bulk

－熱重量示差熱分析（ＴＧ－ＤＴＡ）－
　熱重量示差熱分析（ＴＧ－ＤＴＡ）は以下の条件で測定した。
　測定機器：（株）日立ハイテクサイエンス製ＴＧ／ＤＴＡ　６３００
　測定方法：試料７ｍｇ～８ｍｇをＡｌパンに入れてセットし、２０℃／ｍｉｎで６００℃まで昇温し、室温～１００℃までの減量を水分量（付着水）とし、１００℃～２５０℃までの減量を結晶水（水和水）として見積もった。 -Thermogravimetric differential thermal analysis (TG-DTA)-
Thermogravimetric-differential thermal analysis (TG-DTA) was performed under the following conditions.
Measuring equipment: TG/DTA 6300 manufactured by Hitachi High-Tech Science Co., Ltd.
Measurement method: 7 mg to 8 mg of sample was placed in an Al pan and heated to 600°C at 20°C/min. The weight loss from room temperature to 100°C was estimated as the moisture content (adherent water), and the weight loss from 100°C to 250°C was estimated as water of crystallization (water of hydration).

－融点－
　示差走査熱量計（ＤＳＣ）を用いて測定した。ＪＩＳ　Ｋ７１２１に準拠して下記の測定条件にて測定し、２ｎｄＲＵＮ（２回目の昇温時）の高温側の吸熱ピークを融点とした。
　ＤＳＣ：ＮＥＴＺＳＣＨ社製「ＤＳＣ　２１４　Ｐｏｌｙｍａ」
－１ｓｔＲＵＮ－
　昇温速度：１０℃／分
　測定温度：３０℃～３００℃
　測定雰囲気：窒素
　保持：３００℃到達後、５分
　降温速度：３０℃／分
　冷却温度：３００℃～３０℃
－２ｎｄＲＵＮ－
　昇温速度：１０℃／分
　測定温度：３０℃～３００℃
　測定雰囲気：窒素 -Melting point-
The measurement was performed using a differential scanning calorimeter (DSC) under the following measurement conditions in accordance with JIS K7121, and the endothermic peak on the high temperature side in the second run (second temperature rise) was taken as the melting point.
DSC: “DSC 214 Polyma” manufactured by NETZSCH
-1st RUN-
Heating rate: 10°C/min Measurement temperature: 30°C to 300°C
Measurement atmosphere: Nitrogen Holding: 5 minutes after reaching 300°C Cooling rate: 30°C/min Cooling temperature: 300°C to 30°C
-2nd RUN-
Heating rate: 10°C/min Measurement temperature: 30°C to 300°C
Measurement atmosphere: Nitrogen

－固有粘度（ＩＶ）－
　ウベローデ粘度計を用い、ＪＩＳ　Ｋ７３６７－５に準拠して下記の測定条件にて測定した。
　溶媒：１，１，２，２－テトラクロロエタン／フェノール＝１／１混合溶媒
　濃度（樹脂濃度）：０．５ｇ／ｄＬ（樹脂成分で０．５ｇ／ｄＬとなるように調整）
　温度：３０℃ -Intrinsic viscosity (IV)-
The measurement was carried out using an Ubbelohde viscometer in accordance with JIS K7367-5 under the following measurement conditions.
Solvent: 1,1,2,2-tetrachloroethane/phenol = 1/1 mixed solvent Concentration (resin concentration): 0.5 g/dL (adjusted to 0.5 g/dL with resin component)
Temperature: 30℃

－差圧（ΔＰ）：分散性－
　φ２０ｍｍ単軸押出機「ラボプラストミル」（（株）東洋精機製作所製、基本装置型式「１０Ｓ１００」に単軸押出機ユニット型式「Ｄ２０２５」を接続）を用い、押出温度２８７℃、回転数５０ｒｐｍ、４０／７３０／４０メッシュで京葉ポリエチレン（株）製Ｐ９２１０（高密度ポリエチレン（ＨＤＰＥ））を樹脂圧が安定するまで流し、樹脂圧が安定したことを確認した後に４価金属リン酸塩化合物含有量が２００ｇとなるように計量したポリエステル樹脂組成物に切り替えて全量流した後に、再度京葉ポリエチレン（株）製
Ｐ９２１０（ＨＤＰＥ）を樹脂圧が安定するまで流し、４価金属リン酸塩化合物含有ポリエステル樹脂組成物（マスターバッチ）を流す前後のＨＤＰＥ樹脂圧力を差圧（ΔＰ）として測定した。
　差圧（ΔＰ）の値が小さいほど、メッシュで捕捉される４価金属リン酸塩化合物の粗大粒子が少なく、メッシュが閉塞しづらいことから、ポリエステル樹脂組成物中における４価金属リン酸塩化合物の分散性に優れる。 -Differential pressure (ΔP): dispersibility-
Using a φ20 mm single-screw extruder "Labo Plastomill" (manufactured by Toyo Seiki Seisakusho Co., Ltd., a single-screw extruder unit model "D2025" connected to a basic device model "10S100"), P9210 (high density polyethylene (HDPE)) manufactured by Keiyo Polyethylene Co., Ltd. was fed at an extrusion temperature of 287°C, a rotation speed of 50 rpm, and a 40/730/40 mesh until the resin pressure stabilized. After confirming that the resin pressure had stabilized, the system was switched to a polyester resin composition weighed so that the tetravalent metal phosphate compound content was 200 g, and the entire amount was fed. Then, P9210 (HDPE) manufactured by Keiyo Polyethylene Co., Ltd. was fed again until the resin pressure stabilized, and the HDPE resin pressure before and after the flow of the tetravalent metal phosphate compound-containing polyester resin composition (master batch) was measured as a differential pressure (ΔP).
The smaller the differential pressure (ΔP), the fewer coarse particles of the tetravalent metal phosphate compound are captured by the mesh, and the less likely the mesh is to become clogged, resulting in excellent dispersibility of the tetravalent metal phosphate compound in the polyester resin composition.

－消臭率－
　消臭加工繊維製品認証基準（制定者：社団法人繊維評価技術協議会　製品認証部、制定日：平成１４年９月１日）に準拠した検知管法にて測定した。
　４価金属リン酸塩化合物含有ポリエステル繊維１ｇを計量してテドラーバックに入れてヒートシーラーで密封した。アンモニア初期濃度１００ｐｐｍに調整した試験ガスを所定量注入し、２時間後、及び、２４時間後の残存ガス濃度（ｐｐｍ）を成分対応検知管（ガステック社製）で測定し、残存ガス濃度の減少率を算出し、消臭率として表記した。測定はｎ＝３の平均値で算出した。なお、ガス充填量は３Ｌ、希釈ガスは乾燥空気を使用した。 - Deodorizing rate -
Measurements were performed using the detector tube method in accordance with the Deodorizing Textile Product Certification Standards (established by: Textile Evaluation Technology Council, Product Certification Department, established on September 1, 2002).
1 g of polyester fiber containing a tetravalent metal phosphate compound was weighed and placed in a Tedlar bag and sealed with a heat sealer. A predetermined amount of test gas adjusted to an initial ammonia concentration of 100 ppm was injected, and the remaining gas concentration (ppm) after 2 hours and 24 hours was measured using a component-specific detector tube (manufactured by Gastec Co., Ltd.), and the reduction rate of the remaining gas concentration was calculated and expressed as the deodorization rate. The measurement was calculated using the average value of n=3. The gas filling amount was 3 L, and dry air was used as the dilution gas.

－引張強度－
　テンシロン万能試験機「ＲＴＥ－１２１０」（エー・アンド・デイ社製）を用い、ＪＩＳ　Ｌ１０１３：２０１０準拠で測定した。初期チャック間隔２００ｍｍ、引張速度２００ｍｍ／ｍｉｎ、２３℃環境下で引っ張ることで測定を行い、試験回数３回の平均を測定値とした。 - Tensile strength -
Measurements were performed using a Tensilon universal testing machine "RTE-1210" (manufactured by A&D Corporation) in accordance with JIS L1013:2010. Measurements were performed by pulling at an initial chuck distance of 200 mm, a tensile speed of 200 mm/min, and in an environment of 23°C, and the average of three tests was taken as the measured value.

　評価結果を表３～表５にまとめて示す。 The evaluation results are summarized in Tables 3 to 5.

　表３～表５に示す如く、実施例１～実施例４８のポリエステル樹脂組成物は、差圧（ΔＰ）が低く、４価金属リン酸塩化合物の分散性に優れるものであった。
　また、実施例１～実施例４８のポリエステル樹脂組成物は、溶融紡糸時の紡糸性が良好であり、引張強度は実用上問題のないレベルであった。
　更に、実施例１～実施例６、実施例９、実施例１０、実施例１２～実施例３２及び実施例３４～実施例４８のポリエステル樹脂組成物は、紡糸により得られたポリエステル樹脂組成物からなる繊維は消臭率も高いものであった。
　他方、比較例１、比較例２及び比較例５～比較例１１のポリエステル樹脂組成物は、溶融紡糸は可能であったが、実施例に比較すると差圧（ΔＰ）が高く、４価金属リン酸塩化合物の分散性に劣るものであった。
　なお、表３又は表５に示す如く、比較例３、比較例４及び比較例１２～比較例１５のポリエステル樹脂組成物は、溶融紡糸ができず、評価自体ができなかった。 As shown in Tables 3 to 5, the polyester resin compositions of Examples 1 to 48 had a low differential pressure (ΔP) and were excellent in dispersibility of the tetravalent metal phosphate compound.
Moreover, the polyester resin compositions of Examples 1 to 48 had good spinnability during melt spinning, and the tensile strength was at a level that would not cause any practical problems.
Furthermore, the polyester resin compositions of Examples 1 to 6, 9, 10, 12 to 32, and 34 to 48 were spun into fibers having a high deodorizing rate.
On the other hand, the polyester resin compositions of Comparative Examples 1, 2, and 5 to 11 were capable of melt spinning, but had a higher differential pressure (ΔP) than the Examples, and were inferior in dispersibility of the tetravalent metal phosphate compound.
As shown in Table 3 or Table 5, the polyester resin compositions of Comparative Examples 3, 4 and 12 to 15 could not be melt spun, and therefore could not be evaluated at all.

　表２～表５に記載の略号の詳細を以下に示す。
　Ｒ９７２：シリカ粒子（日本アエロジル（株）製Ｒ９７２）
　ＧＭ－９１３：結晶性共重合ポリエステル樹脂（東洋紡（株）製バイロンＧＭ－９１３
）
　ＧＮ００１：非晶性共重合ポリエステル樹脂（イーストマン・ケミカル・ジャパン（株）製ＧＮ００１）
　ＭＡ－２１０１Ｍ：ポリエチレンテレフタレート（ユニチカ（株）製ＭＡ－２１０１Ｍ）
　ＳＢ６５４：結晶性共重合ポリエステル樹脂（東レ・セラニーズ（株）製ＳＢ６５４）
　ＧＡ－６３００：結晶性共重合ポリエステル樹脂（東洋紡（株）製バイロンＧＡ－６３００）
　ＴＧ－１２：１２－ヒドロキシステアリン酸トリグリセリド（理研ビタミン（株）製リケマールＴＧ－１２）
　ポリエチレン：ポリエチレン系ワックス（三洋化成工業（株）製サンワックス１７１－Ｐ）
　Ｈ－４７６：ペンタエリスリトールテトラステアレート（日油（株）製ユニスターＨ－４７６）
　ステアリン酸亜鉛：日油（株）製ジンクステアレート
　Ｏ－８０Ｖ：ソルビタンオレート（理研ビタミン（株）製ポエムＯ－８０Ｖ）
　Ｍ－３００：グリセリンモノラウレート（理研ビタミン（株）製ポエムＭ－３００）
　ＳＯＬＳＰＥＲＳＥ　２８０００：ポリマー分散剤（Ｌｕｂｒｉｚｏｌ社製）
　Ｓｏｌｐｌｕｓ　Ｌ４００：ポリマー分散剤（Ｌｕｂｒｉｚｏｌ社製）
　ペレスタット　３００：ポリエーテル／ポリオレフィンブロックポリマー（三洋化成工業社製）
　ＮＥＳ－２０４０：ポリエチレンテレフタレート（ユニチカ（株）製ＮＥＳ－２０４０）
　ＮＥＨ－２０７０：ポリエチレンテレフタレート（ユニチカ（株）製ＮＥＨ－２０７０）
　ＳＡ１２０６：ポリエチレンテレフタレート（ユニチカ（株）製ＳＡ－１２０６）
　ＳＡ－８６３ＪＰ：結晶性ポリエステル樹脂（ユニチカ（株）製ＳＡ－８６３ＪＰ） Details of the abbreviations used in Tables 2 to 5 are shown below.
R972: Silica particles (R972 manufactured by Nippon Aerosil Co., Ltd.)
GM-913: Crystalline copolymer polyester resin (Vylon GM-913 manufactured by Toyobo Co., Ltd.)
)
GN001: Amorphous copolymer polyester resin (GN001 manufactured by Eastman Chemical Japan Co., Ltd.)
MA-2101M: Polyethylene terephthalate (MA-2101M manufactured by Unitika Ltd.)
SB654: Crystalline copolymer polyester resin (SB654 manufactured by Toray Celanese Co., Ltd.)
GA-6300: crystalline copolymer polyester resin (Vylon GA-6300 manufactured by Toyobo Co., Ltd.)
TG-12: 12-hydroxystearic acid triglyceride (Rikemal TG-12, manufactured by Riken Vitamin Co., Ltd.)
Polyethylene: polyethylene wax (Sanyo Chemical Industries, Ltd., Sanwax 171-P)
H-476: Pentaerythritol tetrastearate (UNISTAR H-476, manufactured by NOF Corporation)
Zinc stearate: Zinc stearate manufactured by NOF Corp. O-80V: Sorbitan oleate (Poem O-80V manufactured by Riken Vitamin Co., Ltd.)
M-300: Glycerin monolaurate (Poem M-300, manufactured by Riken Vitamin Co., Ltd.)
SOLSPERSE 28000: Polymeric dispersant (manufactured by Lubrizol)
Solplus L400: Polymeric dispersant (manufactured by Lubrizol)
Pelestat 300: Polyether/polyolefin block polymer (manufactured by Sanyo Chemical Industries, Ltd.)
NES-2040: Polyethylene terephthalate (NES-2040 manufactured by Unitika Ltd.)
NEH-2070: Polyethylene terephthalate (NEH-2070 manufactured by Unitika Ltd.)
SA1206: Polyethylene terephthalate (SA-1206 manufactured by Unitika Ltd.)
SA-863JP: Crystalline polyester resin (SA-863JP manufactured by Unitika Ltd.)

　表３～表５に示すように、実施例１～４８のポリエステル樹脂組成物は、比較例１～１５のポリエステル樹脂組成物と比べ、４価金属リン酸塩化合物の分散性に優れる。
　更に、表３及び表４に示すように、実施例１～４８のポリエステル樹脂組成物は、引張強度にも優れ、紡糸性に優れる。 As shown in Tables 3 to 5, the polyester resin compositions of Examples 1 to 48 are superior in dispersibility of the tetravalent metal phosphate compound as compared with the polyester resin compositions of Comparative Examples 1 to 15.
Furthermore, as shown in Tables 3 and 4, the polyester resin compositions of Examples 1 to 48 are excellent in tensile strength and spinnability.

　実施例、並びに、比較例１及び比較例２より、中間体の成分Ｃの含有量が０．１質量％未満となると４価金属リン酸塩化合物の分散性が十分得られず、差圧ΔＰが高くなった。
　実施例及び比較例３より、中間体の成分Ａの含有量が７５質量％以上となると４価金属リン酸塩が過多となり、ポリエステル樹脂への充填が困難で中間体をペレット化することができず、その後のマスターバッチや繊維への成形加工ができなかった。 From the examples and comparative examples 1 and 2, when the content of component C in the intermediate was less than 0.1 mass %, the dispersibility of the tetravalent metal phosphate compound was not sufficient and the differential pressure ΔP increased.
From the examples and comparative example 3, when the content of component A in the intermediate was 75 mass% or more, the amount of tetravalent metal phosphate became excessive, which made it difficult to fill the polyester resin, and the intermediate could not be pelletized, and the subsequent molding processing into a master batch or fibers was not possible.

　実施例及び比較例４より、中間体の成分Ｂの含有量が５５質量％以上となるとポリエステル樹脂が過多となり、加圧式ニーダーへ付着し、回収が困難で中間体をペレット化することができず、その後のマスターバッチや繊維への成形加工ができなかった。 From the examples and comparative example 4, when the content of component B in the intermediate was 55% by mass or more, the polyester resin became excessive and adhered to the pressure kneader, making recovery difficult and making it impossible to pelletize the intermediate, and therefore impossible to process it into a master batch or fibers.

　実施例及び比較例５より、成分Ａは式（１）でなければ差圧ΔＰが高く、消臭率が低下した。 From the examples and comparative example 5, it was found that unless component A was of formula (1), the differential pressure ΔP was high and the deodorizing rate was low.

　実施例及び比較例６より、成分Ｂが結晶性でなければ差圧ΔＰが高くなった。 From the examples and comparative example 6, the differential pressure ΔP was high if component B was not crystalline.

　実施例及び比較例７より、成分Ｂがテレフタル酸及びエチレングリコール以外のモノマーが１種類以上共重合されていない、つまりテレフタル酸とエチレングリコールで構成されたポリエチレンテレフタレート（ホモＰＥＴ）だと、差圧ΔＰが高く、消臭率が低下した。 From the examples and comparative example 7, it was found that when component B was not copolymerized with one or more monomers other than terephthalic acid and ethylene glycol, i.e., polyethylene terephthalate (homo-PET) composed of terephthalic acid and ethylene glycol, the differential pressure ΔP was high and the deodorizing rate was low.

　実施例及び比較例８より、中間体の成分Ｃの含有量が３０質量％以上となると差圧ΔＰ測定時の単軸押出機のスクリュー上でスリップし、サンプルが押出機に供給されず、差圧ΔＰが測定できなかった。これは繊維への成形加工時にマスターバッチとベース樹脂の分級による繊維の品質不良の可能性が考えられる。 From the examples and comparative example 8, when the content of component C in the intermediate was 30 mass% or more, slippage occurred on the screw of the single screw extruder during measurement of the differential pressure ΔP, and the sample was not fed to the extruder, making it impossible to measure the differential pressure ΔP. This may be due to poor quality of the fiber caused by separation of the master batch and base resin during processing into fiber.

　実施例及び比較例９より、中間体及びマスターバッチにおいて、成分Ｃを含有しないと差圧ΔＰが高くなった。 From the examples and comparative example 9, the differential pressure ΔP increased when component C was not contained in the intermediate and master batch.

　実施例及び比較例１０より、マスターバッチの成分Ａの含有量が３０質量％を超えると差圧ΔＰが高くなった。 From the examples and comparative example 10, the differential pressure ΔP increased when the content of component A in the master batch exceeded 30 mass%.

　実施例及び比較例１１より、マスターバッチの成分Ｄの含有量が３７質量％未満では差圧ΔＰが高くなった。 From the examples and comparative example 11, the differential pressure ΔP was high when the content of component D in the master batch was less than 37 mass%.

　実施例及び比較例１２～１５より、成分Ｂ、及び成分Ｃを配合しないと差圧ΔＰが高く、繊維への成形加工が困難であり、繊維の評価ができなかった。 From Examples and Comparative Examples 12 to 15, it was found that if components B and C were not mixed, the differential pressure ΔP was high, making it difficult to process into fibers, and making it impossible to evaluate the fibers.

（ＳＥＭ像による画像解析）
　上記表３～表５に記載のペレット化されたポリエステル樹脂組成物の実施例及び比較例の中から、実施例３、実施例８、実施例１９、実施例２５～実施例２７、実施例３１、比較例２、比較例６及び比較例１３のポリエステル樹脂組成物を選択し、以下の方法でペレットの断面のＳＥＭ像を取得し、解析した。 (Image analysis using SEM images)
Among the examples and comparative examples of the pelletized polyester resin composition described in Tables 3 to 5 above, the polyester resin compositions of Example 3, Example 8, Example 19, Examples 25 to 27, Example 31, Comparative Example 2, Comparative Example 6, and Comparative Example 13 were selected, and SEM images of the cross sections of the pellets were obtained and analyzed by the following method.

－ＳＥＭ像－
　ポリエステル樹脂組成物のペレットを、ドライアイス、もしくは液体窒素を用いて十分に冷却した。片刃トリミング用カミソリ（日新ＥＭ社製）を用いて、冷却したペレットの流れ方向（Ｍａｃｈｉｎｅ　Ｄｉｒｅｃｔｉｏｎ、ＭＤ）に対して、垂直に切断することで、ＳＥＭ測定面であるペレット断面を作製した。切断したペレットを試料台へ挟み、ペレット断面をＳＥＭで観察できるように試料台へ固定した。測定面へのチャージアップ防止を目的として測定面の両端と試料台が接触するようにＳＥＭ用カーボン両面テープ（日新ＥＭ社製）を貼り付けた。
　ＳＥＭ観察用貴金属薄膜コーティング専用装置「ＭＳＰ－１Ｓ」（真空デバイス社製）を用い、ペレットの断面への白金蒸着を実施した。
　走査型電子顕微鏡（ＳＥＭ）「ＪＳＭ－７９００Ｆ」（日本電子社製）を用い、ペレット断面を３００倍の倍率で撮影し、ＳＥＭ像を得た。ＳＥＭ像は１５，０００～２５，０００倍の倍率でピントを合わせ、徐々に３００倍の倍率へ変更することで、ペレット断面の測定面の品質とＳＥＭ像の品質を確認しながら測定し、満足できる品質が得られない場合はペレット断面の作製からやり直した。ＳＥＭ像は、異なる領域で５箇所以上を撮影し、最も平均的と考えられる１枚を目視で選定した。
　ペレット断面の状態不良が原因でＳＥＭ像の品質が悪い場合、ミクロトーム、クライオミクロトーム、イオンミリングを用いて断面の品質を向上させてもよい。
　ＳＥＭ：日本電子社製ショットキー電界放出形走査電子顕微鏡「ＪＳＭ－７９００Ｆ」
　真空モード：低真空
　真空度設定：３０Ｐａ
　観察モード：ＳＥＭ
　加速電圧：５．０ｋＶ
　照射電流：１４
　検出器：低真空用反射電子検出器（ＬＶＢＥＤ－Ｃ）
　倍率：×３００（有効視野角０．４ｍｍ（４００μｍ）×０．３ｍｍ（３００μｍ） -SEM image-
The pellets of the polyester resin composition were sufficiently cooled using dry ice or liquid nitrogen. The pellets were cut perpendicular to the flow direction (machine direction, MD) of the cooled pellets using a single-edged trimming razor (manufactured by Nisshin EM Co., Ltd.) to prepare a pellet cross section as a SEM measurement surface. The cut pellets were sandwiched between a sample stage and fixed to the sample stage so that the pellet cross section could be observed with an SEM. In order to prevent charging up on the measurement surface, SEM carbon double-sided tape (manufactured by Nisshin EM Co., Ltd.) was attached so that both ends of the measurement surface and the sample stage were in contact.
Platinum was evaporated onto the cross section of the pellet using a precious metal thin film coating device "MSP-1S" (manufactured by Vacuum Device Co., Ltd.) for SEM observation.
Using a scanning electron microscope (SEM) "JSM-7900F" (manufactured by JEOL Ltd.), the cross section of the pellet was photographed at a magnification of 300 times to obtain an SEM image. The SEM image was focused at a magnification of 15,000 to 25,000 times, and gradually changed to a magnification of 300 times, so that the quality of the measurement surface of the pellet cross section and the quality of the SEM image were confirmed while measuring, and if satisfactory quality was not obtained, the preparation of the pellet cross section was started over. SEM images were photographed at five or more different locations in different regions, and the one that was considered to be the most average was selected by visual inspection.
If the quality of the SEM image is poor due to poor condition of the pellet cross section, microtome, cryomicrotome or ion milling may be used to improve the quality of the cross section.
SEM: JEOL Schottky field emission scanning electron microscope "JSM-7900F"
Vacuum mode: Low vacuum Vacuum setting: 30 Pa
Observation mode: SEM
Acceleration voltage: 5.0 kV
Irradiation current: 14
Detector: Low vacuum backscattered electron detector (LVBED-C)
Magnification: x300 (effective viewing angle 0.4mm (400μm) x 0.3mm (300μm)

　また、白金蒸着を実施していないペレット断面を、エネルギー分散型Ｘ線分光装置（ＥＤＸ、オックスフォードインスツルメンツ社製「ＵＬＴＩＭ１００型エネルギー分散Ｘ線マイクロアナライザー」）を用いて元素分析と組成分析を行い、撮影したＳＥＭ像において、周囲よりも顕著に明度が高い箇所がリン酸ジルコニウム粒子であることを確認した。 In addition, elemental and compositional analysis was performed on the cross-section of the pellets that had not been subjected to platinum deposition using an energy dispersive X-ray spectrometer (EDX, Oxford Instruments' ULTIM100 Energy Dispersive X-ray Microanalyzer), and it was confirmed in the SEM images that the areas that were significantly brighter than the surrounding areas were zirconium phosphate particles.

－画像解析－
　選定したＳＥＭ像の視野角０．４ｍｍ（４００μｍ）×０．３ｍｍ（３００μｍ）、視野サイズ：０．１２ｍｍ２の範囲を、画像解析ソフト「Ｉｍａｇｅ　Ｊ　Ｆｉｊｉ」を用いて二値化し、検出された粒子のサイズ（面積）を各々計測した。
　選定したＳＥＭ像を画像解析ソフトで読み込み、ＳＥＭ像に記載された換算スケールバーから画像解析ソフトの換算スケールを設定した。
　ＳＥＭ像撮影時の情報が記載された不要箇所を削除して、有効視野角０．４ｍｍ（４００μｍ）×０．３ｍｍ（３００μｍ）、視野サイズ：０．１２ｍｍ２の画像とした。画像解析ソフトに組み込まれたＩｓｏＤａｔａアルゴリズムを用い、粒子が白色となるように二値化を実施した。二値化の閾値は粒子の数やサイズが妥当となるように、画像解析前のＳＥＭ像と二値化した画像とを目視で比較しながら実施した。画像解析ソフトに組み込まれた粒子計測アルゴリズムを用いて二値化後の粒子を全て検出し、その粒子のサイズ（面積）を各々計測し、粒子サイズの計算結果を得た。 - Image analysis -
The selected SEM image was binarized using the image analysis software "Image J Fiji" within a viewing angle of 0.4 mm (400 μm) × 0.3 mm (300 μm) and a viewing size of 0.12 mm2 , and the size (area) of each detected particle was measured.
The selected SEM image was read into image analysis software, and the conversion scale of the image analysis software was set based on the conversion scale bar written on the SEM image.
Unnecessary parts containing information on the time of SEM image capture were deleted to obtain an image with an effective viewing angle of 0.4 mm (400 μm) × 0.3 mm (300 μm) and a viewing size of 0.12 mm2 . Using the IsoData algorithm built into the image analysis software, binarization was performed so that the particles were white. The threshold value of binarization was performed while visually comparing the SEM image before image analysis with the binarized image so that the number and size of the particles were appropriate. All particles after binarization were detected using a particle measurement algorithm built into the image analysis software, and the size (area) of each particle was measured, and the calculation result of the particle size was obtained.

　ＳＥＭ像内のコントラスト差が原因で、ＳＥＭ像と二値化時の画像とを対応させた場合の粒子の数及び粒子サイズの少なくともいずれかが、よく一致しない場合には、画像解析ソフトに組み込まれたフーリエ変換やフィルター処理を実施せず、画像解析前のＳＥＭ像を分割し、上記画像解析を実施して、それぞれの分割領域においてＳＥＭ像と二値化画像とを対比し、粒子の数及びサイズがよく一致するまで画像解析前のＳＥＭ像の画像を分割する対応をとった。粒子の数及びサイズがよく一致するまで分割したＳＥＭ像に対して、それぞれの分割領域で画像解析を実施し、得られた各々の計測結果を全て加算することで、有効視野角内の画像解析結果として、粒子サイズの計算結果を得た。 If at least one of the number of particles and the particle size does not match well when the SEM image and the binarized image are matched due to contrast differences within the SEM image, the Fourier transform and filter processing built into the image analysis software are not performed, but the SEM image before image analysis is divided, the above image analysis is performed, and the SEM image and the binarized image are compared in each divided area, and the image of the SEM image before image analysis is divided until the number and size of particles match well. Image analysis is performed in each divided area for the SEM image that has been divided until the number and size of particles match well, and the calculation result of the particle size is obtained as the result of image analysis within the effective field of view by adding up all the respective measurement results obtained.

　画像解析で得られた粒子サイズの計算結果を表計算ソフト「Ｍｉｃｒｏｓｏｆｔ　Ｅｘｃｅｌ　２０１６」を用いて粒子サイズ別に分類し、粒子サイズ追加の粒子数を算出した。
　画像解析ソフト：ＩｍａｇｅＪ　Ｆｉｊｉ
　バージョン：ＩｍａｇｅＪ　１．５４ｆ
　処理方法：二値化
　二値化アルゴリズム：ＩｓｏＤａｔａ
　表計算ソフト：マイクロソフト社製「Ｍｉｃｒｏｓｏｆｔ　Ｅｘｃｅｌ　２０１６」 The particle size calculation results obtained by image analysis were classified by particle size using the spreadsheet software "Microsoft Excel 2016," and the number of particles added for each particle size was calculated.
Image analysis software: ImageJ Fiji
Version: ImageJ 1.54f
Processing method: Binarization Binarization algorithm: IsoData
Spreadsheet software: Microsoft Excel 2016

　図１は、実施例２７のポリエステル樹脂組成物ペレットの断面を３００倍で撮影したＳＥＭ像である。図１に示すＳＥＭ像を５つに画像分割して、上記ソフトウェアを用い二値化し得られた画像を図２に示す。図２は、実施例２７のポリエステル樹脂組成物ペレットの断面を画像解析し、二値化した画像である。図２では、一つ一つのリン酸ジルコニウムの粒子が鮮明な白色像として確認できた。
　図３は、比較例６のポリエステル樹脂組成物ペレットの断面を３００倍で撮影したＳＥＭ像である。図３のＳＥＭ像を、前記実施例２８と同様にしてペレットの断面を３つに画像分割して、上記ソフトウェアを用い画像解析し、二値化した画像を図４に示す。図４によれば、図２に対し、リン酸ジルコニウムの粗大粒子がより多く存在することが分かる。
　このように、ＳＥＭ像を画像解析し、二値化することで、ポリエステル樹脂組成物に含まれる微細なリン酸ジルコニウムの粒子が確認しやすくなる。 Fig. 1 is an SEM image of the cross section of the polyester resin composition pellet of Example 27 taken at 300x magnification. The SEM image shown in Fig. 1 was divided into five images and binarized using the above software, and the resulting images are shown in Fig. 2. Fig. 2 is an image of the cross section of the polyester resin composition pellet of Example 27 that was subjected to image analysis and binarized. In Fig. 2, each zirconium phosphate particle could be confirmed as a clear white image.
Fig. 3 is an SEM image of the cross section of the polyester resin composition pellet of Comparative Example 6 taken at 300x magnification. The SEM image of Fig. 3 was divided into three images of the cross section of the pellet in the same manner as in Example 28, and the images were analyzed using the above software to obtain a binarized image, which is shown in Fig. 4. Fig. 4 shows that there are more coarse particles of zirconium phosphate than in Fig. 2.
By performing image analysis and binarization of the SEM image in this manner, the fine zirconium phosphate particles contained in the polyester resin composition can be easily identified.

　二値化により得られた画像における粒子サイズを測定した。計測された粒子サイズにおいて、視野サイズ中でのリン酸ジルコニウムの粒子サイズが２０μｍ２以上となる粒子数、粒子サイズが１０μｍ２以上となる粒子数、粒子サイズが２μｍ２以上となる粒子数、粒子サイズが１μｍ２以上となる粒子数及び粒子サイズが０．５μｍ２以上となる粒子数の数を計測した。
　結果を下記表６に示す。
　さらに、ポリエステル樹脂組成物の流動性及び粒子分散性の目安として、上記実施例及び比較例で測定したポリエステル樹脂組成物を流す前と後の高密度ポリエチレン（ＨＤＰＥ）の樹脂圧力の差圧（ΔＰ）を表に併記した。 The particle size in the image obtained by binarization was measured. In the measured particle size, the number of zirconium phosphate particles having a particle size of 20 μm2 or more, the number of particles having a particle size of 10 μm2 or more, the number of particles having a particle size of 2 μm2 or more, the number of particles having a particle size of 1 μm2 or more, and the number of particles having a particle size of 0.5 μm2 or more in the field of view were counted.
The results are shown in Table 6 below.
Furthermore, as a measure of the fluidity and particle dispersibility of the polyester resin composition, the differential pressure (ΔP) of the resin pressure of high density polyethylene (HDPE) before and after pouring the polyester resin composition, measured in the above examples and comparative examples, is also shown in the table.

　表６に明らかなように、各実施例のポリエステル樹脂組成物はいずれも、２０μｍ２以上のリン酸ジルコニウム粒子を含まないことが分かる。また、実施例８のポリエステル樹脂においても、２０μｍ２以上のリン酸チタン粒子を含まないことが分かる。他方、各比較例のポリエステル樹脂組成物は、いずれも２０μｍ２以上のリン酸ジルコニウム粒子を１個以上含んでいた。
　また、各実施例の差圧（ΔＰ）の値は、各比較例の差圧（ΔＰ）より小さく、リン酸ジルコニウム又はリン酸チタンの粒子の分散性が良好であることが分かる。また、分散性が良好であることから、メッシュで捕捉されるリン酸ジルコニウム又はリン酸チタン粒子の粗大粒子が少なく、メッシュが閉塞しづらい。
　これらの対比より、画像解析による粒子の数、特に２０μｍ２以上のリン酸ジルコニウム粒子又はリン酸チタン粒子の有無の測定結果は、ポリエステル樹脂組成物における４価金属リン酸塩化合物の分散性とよく相関しており、各実施例のポリエステル樹脂組成物は、溶融紡糸時の紡糸性が良好であることが期待される。また、各実施例のポリエステル樹脂組成物により消臭性に優れる成形体が得られることが確認された。 As is clear from Table 6, none of the polyester resin compositions of the Examples contain zirconium phosphate particles of 20 μm2 or more. Also, the polyester resin of Example 8 does not contain titanium phosphate particles of 20 μm2 or more. On the other hand, each of the polyester resin compositions of the Comparative Examples contained one or more zirconium phosphate particles of 20 μm2 or more.
The pressure difference (ΔP) in each Example was smaller than that in each Comparative Example, indicating that the zirconium phosphate or titanium phosphate particles had good dispersibility. Since the dispersibility was good, fewer coarse particles of zirconium phosphate or titanium phosphate were captured by the mesh, and the mesh was less likely to become clogged.
From these comparisons, the number of particles by image analysis, particularly the measurement results of the presence or absence of zirconium phosphate particles or titanium phosphate particles of 20 μm2 or more, correlates well with the dispersibility of the tetravalent metal phosphate compound in the polyester resin composition, and the polyester resin composition of each Example is expected to have good spinnability during melt spinning. It was also confirmed that the polyester resin composition of each Example can produce a molded product with excellent deodorizing properties.

　２０２３年１２月５日に出願された日本国特許出願第２０２３－２０５２２７号の開示、及び、２０２４年８月９日に出願された日本国特許出願第２０２４－１３４５４６号の開示は、その全体が参照により本明細書に取り込まれる。
　本明細書に記載された全ての文献、特許出願、及び、技術規格は、個々の文献、特許出願、及び、技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。 The disclosures of Japanese Patent Application No. 2023-205227 filed on December 5, 2023 and Japanese Patent Application No. 2024-134546 filed on August 9, 2024 are incorporated herein by reference in their entirety.
All publications, patent applications, and technical standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, or technical standard was specifically and individually indicated to be incorporated by reference.

Claims (20)

　（成分Ａ）下記（ａ－１）及び（ａ－２）を満たす４価金属リン酸塩化合物、
　（成分Ｂ）下記（ｂ－１）及び（ｂ－２）を満たすポリエステル樹脂、並びに、
　（成分Ｃ）分散剤を含有し、
　成分Ａの含有量が、組成物の全質量に対し、４０質量％～７２質量％であり、
　成分Ｂの含有量が、組成物の全質量に対し、２５質量％～５０質量％であり、
　成分Ｃの含有量が、組成物の全質量に対し、３質量％～２５質量％である
　ポリエステル樹脂組成物。
（ａ－１）下記式（１）で表される化合物である
　ＭＨａ（ＰＯ４）ｂ・ｎＨ２Ｏ　（１）
　式（１）中、Ｍは１種以上の４価金属を表し、ａ及びｂは３ｂ－ａ＝４を満たす正数であり、ｂは２＜ｂ≦２．１であり、ｎは０≦ｎ≦２である。
（ａ－２）メジアン径（Ｄ５０）が１．５μｍ以下である
（ｂ－１）結晶性である
（ｂ－２）テレフタル酸及びエチレングリコール以外のモノマーが１種類以上共重合されている (Component A) a tetravalent metal phosphate compound that satisfies the following (a-1) and (a-2):
(Component B) a polyester resin satisfying the following (b-1) and (b-2), and
(Component C) contains a dispersant,
The content of component A is 40% by mass to 72% by mass based on the total mass of the composition,
The content of component B is 25% by mass to 50% by mass based on the total mass of the composition,
A polyester resin composition, wherein the content of component C is 3% by mass to 25% by mass based on the total mass of the composition.
(a-1) A compound represented by the following formula (1): MH a (PO 4 ) b ·nH 2 O (1)
In formula (1), M represents one or more tetravalent metals, a and b are positive numbers satisfying 3b-a=4, b is 2<b≦2.1, and n is 0≦n≦2.
(a-2) The median diameter (D 50 ) is 1.5 μm or less. (b-1) It is crystalline. (b-2) At least one monomer other than terephthalic acid and ethylene glycol is copolymerized. 　（成分Ａ）下記（ａ－１）及び（ａ－２）を満たす４価金属リン酸塩化合物、
　（成分Ｂ）下記（ｂ－１）及び（ｂ－２）を満たすポリエステル樹脂、
　（成分Ｃ）分散剤、並びに、
　（成分Ｄ）下記（ｄ－１）を満たすポリエステル樹脂を含有し、
　成分Ａの含有量が、組成物の全質量に対し、０．４質量％～３０質量％であり、
　成分Ｂの含有量が、組成物の全質量に対し、７質量％～３５質量％であり、
　成分Ｃの含有量が、組成物の全質量に対し、０．１質量％～１１質量％であり、
　成分Ｄの含有量が、組成物の全質量に対し、３７質量％～８３．６質量％である
　ポリエステル樹脂組成物。
（ａ－１）下記式（１）で表される化合物である
　ＭＨａ（ＰＯ４）ｂ・ｎＨ２Ｏ　（１）
　式（１）中、Ｍは１種以上の４価金属を表し、ａ及びｂは３ｂ－ａ＝４を満たす正数であり、ｂは２＜ｂ≦２．１であり、ｎは０≦ｎ≦２である。
（ａ－２）メジアン径（Ｄ５０）が１．５μｍ以下である
（ｂ－１）結晶性である
（ｂ－２）テレフタル酸及びエチレングリコール以外のモノマーが１種類以上共重合されている
（ｄ－１）示差走査熱量計で測定した融点が２４０℃以上である (Component A) a tetravalent metal phosphate compound that satisfies the following (a-1) and (a-2):
(Component B) a polyester resin that satisfies the following (b-1) and (b-2):
(Component C) a dispersant, and
(Component D) A polyester resin that satisfies the following (d-1):
The content of component A is 0.4% by mass to 30% by mass based on the total mass of the composition,
The content of component B is 7% by mass to 35% by mass based on the total mass of the composition,
The content of component C is 0.1% by mass to 11% by mass based on the total mass of the composition;
A polyester resin composition, wherein the content of component D is 37% by mass to 83.6% by mass relative to the total mass of the composition.
(a-1) A compound represented by the following formula (1): MH a (PO 4 ) b ·nH 2 O (1)
In formula (1), M represents one or more tetravalent metals, a and b are positive numbers satisfying 3b-a=4, b is 2<b≦2.1, and n is 0≦n≦2.
(a-2) The median diameter (D 50 ) is 1.5 μm or less. (b-1) It is crystalline. (b-2) At least one monomer other than terephthalic acid and ethylene glycol is copolymerized. (d-1) It has a melting point of 240° C. or more as measured by a differential scanning calorimeter. 　成分Ｃが、分子構造中に極性基を有する分散剤である請求項１又は請求項２に記載のポリエステル樹脂組成物。 The polyester resin composition according to claim 1 or 2, wherein component C is a dispersant having a polar group in its molecular structure. 　前記極性基が、エステル、エーテル、水酸基及びイミノ基よりなる群から選ばれた少なくとも１種の基である請求項３に記載のポリエステル樹脂組成物。 The polyester resin composition according to claim 3, wherein the polar group is at least one group selected from the group consisting of an ester, an ether, a hydroxyl group, and an imino group. 　成分Ｄが、下記（ｄ－２）を満たす請求項２に記載のポリエステル樹脂組成物。
（ｄ－２）固有粘度（ＩＶ）が０．６ｄＬ／ｇ以上である The polyester resin composition according to claim 2, wherein component D satisfies the following (d-2):
(d-2) Intrinsic viscosity (IV) is 0.6 dL/g or more 　前記Ｍが、ジルコニウム、チタン及びハフニウムよりなる群から選ばれた１種以上の４価金属である請求項１又は請求項２に記載のポリエステル樹脂組成物。 The polyester resin composition according to claim 1 or 2, wherein M is one or more tetravalent metals selected from the group consisting of zirconium, titanium, and hafnium. 　成分Ｂが、下記（ｂ－３）を満たすポリエステル樹脂を含む請求項１又は請求項２に記載のポリエステル樹脂組成物。
（ｂ－３）示差走査熱量計で測定した融点が２００℃以下である The polyester resin composition according to claim 1 or 2, wherein component B contains a polyester resin that satisfies the following (b-3):
(b-3) The melting point measured by a differential scanning calorimeter is 200° C. or less. 　成分Ｂが、下記（ｂ－４）を満たすポリエステル樹脂を含む請求項１又は請求項２に記載のポリエステル樹脂組成物。
（ｂ－４）固有粘度（ＩＶ）が１ｄＬ／ｇ以上である The polyester resin composition according to claim 1 or 2, wherein component B contains a polyester resin that satisfies the following (b-4):
(b-4) Intrinsic viscosity (IV) is 1 dL/g or more 　４価金属リン酸塩化合物及びポリエステル樹脂を含み、
　視野サイズが０．４ｍｍ×０．３ｍｍのポリエステル樹脂組成物の断面ＳＥＭ像において、前記４価金属リン酸塩化合物の粒子サイズが２０μｍ２以上となる粒子数が１個未満である
　ポリエステル樹脂組成物。 Contains a tetravalent metal phosphate compound and a polyester resin,
A polyester resin composition, wherein in a cross-sectional SEM image of the polyester resin composition having a field of view size of 0.4 mm x 0.3 mm, the number of particles of the tetravalent metal phosphate compound having a particle size of 20 μm2 or more is less than 1. 　前記４価金属リン酸塩化合物の粒子サイズが１０μｍ２以上となる粒子数が１個以下である請求項９に記載のポリエステル樹脂組成物。 The polyester resin composition according to claim 9, wherein the number of particles of the tetravalent metal phosphate compound having a particle size of 10 μm 2 or more is 1 or less. 　前記４価金属リン酸塩化合物の粒子サイズが２μｍ２以上となる粒子数が１０個以下である請求項９に記載のポリエステル樹脂組成物。 The polyester resin composition according to claim 9, wherein the number of particles of the tetravalent metal phosphate compound having a particle size of 2 μm 2 or more is 10 or less. 　前記ポリエステル樹脂に加え、前記ポリエステル樹脂とは異なる追加のポリエステル樹脂を更に含む請求項１、請求項２又は請求項９に記載のポリエステル樹脂組成物。 The polyester resin composition according to claim 1, claim 2 or claim 9, further comprising, in addition to the polyester resin, an additional polyester resin different from the polyester resin. 　請求項１２に記載のポリエステル樹脂組成物を成形加工してなる成形体。 A molded article obtained by molding the polyester resin composition according to claim 12. 　前記成形加工が、溶融紡糸である請求項１３に記載の成形体。 The molded article according to claim 13, wherein the molding process is melt spinning. 　請求項１３に記載の成形体を高次加工してなる成形体。 A molded product obtained by advanced processing of the molded product according to claim 13. 　織布又は不織布である請求項１５に記載の成形体。 The molded article according to claim 15, which is a woven or nonwoven fabric. 　（成分Ａ）下記（ａ－１）及び（ａ－２）を満たす４価金属リン酸塩化合物、（成分Ｂ）下記（ｂ－１）及び（ｂ－２）を満たすポリエステル樹脂、並びに、（成分Ｃ）分散剤をバッチ式混練手段により混練し、成分Ａの含有量が、組成物の全質量に対し、４０質量％～７２質量％であり、成分Ｂの含有量が、組成物の全質量に対し、２５質量％～５０質量％であり、成分Ｃの含有量が、組成物の全質量に対し、３質量％～２５質量％であるポリエステル樹脂組成物αを得る工程を含む
　ポリエステル樹脂組成物の製造方法。
（ａ－１）下記式（１）で表される化合物である
　ＭＨａ（ＰＯ４）ｂ・ｎＨ２Ｏ　（１）
　式（１）中、Ｍは１種以上の４価金属を表し、ａ及びｂは３ｂ－ａ＝４を満たす正数であり、ｂは２＜ｂ≦２．１であり、ｎは０≦ｎ≦２である。
（ａ－２）メジアン径（Ｄ５０）が１．５μｍ以下である
（ｂ－１）結晶性である
（ｂ－２）テレフタル酸及びエチレングリコール以外のモノマーが１種類以上共重合されている A method for producing a polyester resin composition, comprising: kneading (component A) a tetravalent metal phosphate compound that satisfies the following (a-1) and (a-2), (component B) a polyester resin that satisfies the following (b-1) and (b-2), and (component C) a dispersant by batch kneading means to obtain a polyester resin composition α, in which the content of component A is 40% by mass to 72% by mass, the content of component B is 25% by mass to 50% by mass, and the content of component C is 3% by mass to 25% by mass, relative to the total mass of the composition.
(a-1) A compound represented by the following formula (1): MH a (PO 4 ) b ·nH 2 O (1)
In formula (1), M represents one or more tetravalent metals, a and b are positive numbers satisfying 3b-a=4, b is 2<b≦2.1, and n is 0≦n≦2.
(a-2) The median diameter (D 50 ) is 1.5 μm or less. (b-1) It is crystalline. (b-2) At least one monomer other than terephthalic acid and ethylene glycol is copolymerized. 　（成分Ａ）下記（ａ－１）及び（ａ－２）を満たす４価金属リン酸塩化合物、（成分Ｂ）下記（ｂ－１）及び（ｂ－２）を満たすポリエステル樹脂、並びに、（成分Ｃ）分散剤を含有し、成分Ａの含有量が、組成物の全質量に対し、４０質量％～７２質量％であり、成分Ｂの含有量が、組成物の全質量に対し、２５質量％～５０質量％であり、成分Ｃの含有量が、組成物の全質量に対し、３質量％～２５質量％であるポリエステル樹脂組成物αに、（成分Ｄ）下記（ｄ－１）を満たすポリエステル樹脂と、成分Ｂとして、下記（ｂ－３）及び（ｂ－４）を満たすポリエステル樹脂とを添加して混練する工程を含む
　ポリエステル樹脂組成物の製造方法。
（ａ－１）下記式（１）で表される化合物である
　ＭＨａ（ＰＯ４）ｂ・ｎＨ２Ｏ　（１）
　式（１）中、Ｍは１種以上の４価金属を表し、ａ及びｂは３ｂ－ａ＝４を満たす正数であり、ｂは２＜ｂ≦２．１であり、ｎは０≦ｎ≦２である。
（ａ－２）メジアン径（Ｄ５０）が１．５μｍ以下である
（ｂ－１）結晶性である
（ｂ－２）テレフタル酸及びエチレングリコール以外のモノマーが１種類以上共重合されている
（ｂ－３）示差走査熱量計で測定した融点が２００℃以下である
（ｂ－４）固有粘度（ＩＶ）が１ｄＬ／ｇ以上である
（ｄ－１）示差走査熱量計で測定した融点が２４０℃以上である A method for producing a polyester resin composition, comprising: adding (component D) a polyester resin that satisfies the following (d-1) and (b-4) as component B to a polyester resin composition α, the polyester resin composition α comprising (component A) a tetravalent metal phosphate compound that satisfies the following (a-1) and (a-2); (component B) a polyester resin that satisfies the following (b-1) and (b-2); and (component C) a dispersant, the content of component A being 40% by mass to 72% by mass, the content of component B being 25% by mass to 50% by mass, and the content of component C being 3% by mass to 25% by mass, relative to the total mass of the composition; and kneading the resulting polyester resin composition.
(a-1) A compound represented by the following formula (1): MH a (PO 4 ) b ·nH 2 O (1)
In formula (1), M represents one or more tetravalent metals, a and b are positive numbers satisfying 3b-a=4, b is 2<b≦2.1, and n is 0≦n≦2.
(a-2) The median diameter (D 50 ) is 1.5 μm or less. (b-1) It is crystalline. (b-2) At least one monomer other than terephthalic acid and ethylene glycol is copolymerized. (b-3) It has a melting point of 200° C. or less as measured by a differential scanning calorimeter. (b-4) It has an intrinsic viscosity (IV) of 1 dL/g or more. (d-1) It has a melting point of 240° C. or more as measured by a differential scanning calorimeter. 　成分Ｄが、下記（ｄ－２）を満たす請求項１８に記載のポリエステル樹脂組成物の製造方法。
（ｄ－２）固有粘度（ＩＶ）が０．６ｄＬ／ｇ以上である The method for producing a polyester resin composition according to claim 18, wherein component D satisfies the following (d-2):
(d-2) Intrinsic viscosity (IV) is 0.6 dL/g or more 　前記混練する工程が、連続式混練手段により混練する工程である請求項１８に記載のポリエステル樹脂組成物の製造方法。 The method for producing a polyester resin composition according to claim 18, wherein the kneading step is a step of kneading by a continuous kneading means.
PCT/JP2024/042735 2023-12-05 2024-12-03 Polyester resin composition, method for producing same, and molded body Pending WO2025121326A1 (en)

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JPS63295711A (en) * 1987-05-25 1988-12-02 Kuraray Co Ltd Deodorizing polyester fiber
JPH0551816A (en) * 1991-08-20 1993-03-02 Kuraray Co Ltd Antibacterial fiber and manufacturing method thereof
JPH1046135A (en) * 1996-08-07 1998-02-17 Toagosei Co Ltd UV shielding agent
JP2004169216A (en) * 2002-11-20 2004-06-17 Kuraray Co Ltd Deodorant fiber
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JP2008503436A (en) * 2004-06-22 2008-02-07 ロディア・シミ High form factor crystalline zirconium phosphate, process for its production and its use in polymeric materials
US20190345640A1 (en) * 2017-01-05 2019-11-14 Hyosung TNC Corporation Deodorizing spandex and manufacturing method therefor
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63295711A (en) * 1987-05-25 1988-12-02 Kuraray Co Ltd Deodorizing polyester fiber
JPH0551816A (en) * 1991-08-20 1993-03-02 Kuraray Co Ltd Antibacterial fiber and manufacturing method thereof
JPH1046135A (en) * 1996-08-07 1998-02-17 Toagosei Co Ltd UV shielding agent
JP2005517786A (en) * 2002-02-22 2005-06-16 ロディアニル Thermoplastic material with high shielding properties
JP2004169216A (en) * 2002-11-20 2004-06-17 Kuraray Co Ltd Deodorant fiber
JP2008503436A (en) * 2004-06-22 2008-02-07 ロディア・シミ High form factor crystalline zirconium phosphate, process for its production and its use in polymeric materials
US20190345640A1 (en) * 2017-01-05 2019-11-14 Hyosung TNC Corporation Deodorizing spandex and manufacturing method therefor
CN116288792A (en) * 2023-03-28 2023-06-23 浙江康东新材料科技有限公司 Flame-retardant multifunctional fiber and preparation method thereof

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