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

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

Polyester resin composition, its manufacturing method, and molded article

[0001] The present disclosure relates to a polyester resin composition, a method for producing the same, and a molded article.

[0002] Synthetic fibers such as polyester, nylon, and acrylic have excellent properties such as heat resistance and chemical resistance, and are therefore widely used in applications such as clothing, industrial materials, and bedding. In recent years, fibers with deodorizing functions against sweat odor, aging odor, fatigue odor, and the like have been distributed for these fiber applications. Examples include 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 melt-spun using this resin composition. Various proposals have been made to impart functionality and improve the properties of these resin compositions and deodorizing fibers.

[0003] For example, Patent Document 1 discloses a method for producing functional yarn using a masterbatch prepared from a blend amount of zirconium phosphate and a polyester having an intrinsic viscosity of 0.70 to 0.95 dL / g.

[0004] Furthermore, Patent Document 2 discloses an eccentric sheath-core type antibacterial composite polyester fiber and a method for preparing the same, including a process for producing a nano-antibacterial masterbatch, in which a resin composition is prepared in advance by kneading a predetermined blend of an antibacterial agent containing silver-supported 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.

[0005] WO 2016 / 076572 Chinese Patent Application Publication No. 103343398

[0006] The present disclosure aims to provide a polyester resin composition having excellent dispersibility of a tetravalent metal phosphate compound, and a method for producing the same. Another aim of the present disclosure is to provide a molded article using the polyester resin composition.

[0007] Specific means for solving the above problems include the following aspects. <1> 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, 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, relative to the total mass of the composition. (a-1) A compound represented by the following formula (1): MH ａ (P.O. ４ ) ｂ ・nH ２ 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) Median diameter (D ５０ ) is 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 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), 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, relative to the total mass of the composition; 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) is a compound represented by the following formula (1): MH ａ (P.O. ４ ) ｂ ・nH ２ 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) Median diameter (D ５０(b-1) The polyester resin composition is crystalline. (b-2) At least one monomer other than terephthalic acid and ethylene glycol is copolymerized therein. (d-1) The polyester resin composition has a melting point of 240°C or higher 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 ester, ether, hydroxyl, and imino groups. <5> The polyester resin composition according to <2>, wherein component D satisfies the following (d-2): (d-2) The polyester resin composition has an intrinsic viscosity (IV) of 0.6 dL / g or higher. <6> The polyester resin composition according to any one of <1> to <5>, wherein M is at least one tetravalent metal 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) The melting point measured with 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) The intrinsic viscosity (IV) is 1 dL / g or more.

[0008] <9> In a cross-sectional SEM image of a polyester resin composition containing a tetravalent metal phosphate compound and a polyester resin, the particle size of the tetravalent metal phosphate compound is 20 μm or less in a field of view of 0.4 mm × 0.3 mm. ２ <10> A polyester resin composition in which the number of particles of the tetravalent metal phosphate compound having a particle size of 10 μm or more is less than 1. ２ <11> The polyester resin composition according to <9>, wherein the number of particles having a particle size of 2 μm or more is 1 or less. ２<12> The polyester resin composition according to any one of <1> to <11>, further comprising, in addition to the polyester resin, an additional polyester resin different from 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 is melt spinning. <15> A molded article obtained by advanced processing of the molded article according to <13>. <16> The molded article according to <15>, which is a woven fabric or a nonwoven fabric.

[0009] <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 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) is a compound represented by the following formula (1): MH ａ (P.O. ４ ) ｂ ・nH ２ 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) Median diameter (D ５０) is 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. <18> A method for producing 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, 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, relative to the total mass of the composition; (Component D) a polyester resin satisfying the following (d-1); and, as Component B, a polyester resin satisfying the following (b-3) and (b-4), and kneading the resulting polyester resin composition. (a-1) is a compound represented by the following formula (1): MH ａ (P.O. ４ ) ｂ ・nH ２ 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) Median diameter (D ５０ (b-1) The polyester resin composition is crystalline. (b-2) At least one monomer other than terephthalic acid and ethylene glycol is 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): (d-2) The intrinsic viscosity (IV) is 0.6 dL / g or more. <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.

[0010] The present disclosure provides a polyester resin composition having excellent dispersibility of a tetravalent metal phosphate compound, a method for producing the same, and a molded article using the polyester resin composition.

[0011] 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 image analysis and binarization of the comparative SEM image of Fig. 1. Fig. 3 is an SEM image of a cross section of a polyester resin composition pellet of Comparative Example 6 taken at 300x magnification. Fig. 4 is an image obtained by image analysis and binarization of the SEM image of Fig. 3.

[0012] In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. In the present disclosure, when multiple substances corresponding to each component are present in the composition, the amount of each component in the composition means the total amount of the multiple substances present in the composition, unless otherwise specified. In the numerical ranges described in stages in the present disclosure, the upper or lower limit described in one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. In the numerical ranges described in the present disclosure, the upper or lower limit of that numerical range may be replaced with a value shown in the examples. In the present disclosure, combinations of preferred embodiments are more preferred embodiments. In the description of groups (atomic groups) in the present disclosure, a description that does not specify whether they are substituted or unsubstituted includes both unsubstituted and substituted groups. In the present disclosure, unless otherwise specified, each component may be used alone or in combination of two or more types.

[0013] In the present disclosure, the term "dispersibility" of a tetravalent metal phosphate compound 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 refers to the property that individual tetravalent metal phosphate compound particles (primary particles) do not aggregate to form coarse particles (secondary particles) but tend to be monodispersed, and distribution refers to the property that tetravalent metal phosphate particles tend to be uniformly present throughout the substrate of the polyester resin composition. In this specification, when simply referring to a "polyester resin composition according to the present disclosure" without any particular specification, it refers to all of the first embodiment, second embodiment, and third embodiment described below.

[0014] (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, relative to the total mass of the composition. (a-1) is a compound represented by the following formula (1): MH ａ (P.O. ４ ) ｂ ・nH ２ 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) Median diameter (D ５０ (b-1) It is crystalline. (b-2) It is copolymerized with one or more monomers other than terephthalic acid and ethylene glycol.

[0015] A second 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), (component C) a dispersant, and (component D) a polyester resin satisfying the following (d-1), wherein the content of component A is 0.4% by mass to 30% by mass, the content of component B is 7% by mass to 35% by mass, 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) is a compound represented by the following formula (1): MH ａ (P.O. ４ ) ｂ ・nH ２ 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) Median diameter (D ５０(b-1) It is crystalline. (b-2) It is copolymerized with one or more monomers other than terephthalic acid and ethylene glycol. (d-1) It has a melting point of 240°C or higher as measured by a differential scanning calorimeter.

[0016] A third embodiment of the polyester resin composition according to the present disclosure comprises a tetravalent metal phosphate compound and a polyester resin, and 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 particle size of the tetravalent metal phosphate compound represented by zirconium phosphate is 20 μm ２ The polyester resin composition has less than one particle having the above particle size.

[0017] 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 the dispersibility of the tetravalent metal phosphate compound. In the present disclosure, when simply referring to "component A" or the like without any particular specification, all of the first, second, and third embodiments are described.

[0018] According to the results of investigations conducted by the present inventors, it has been found that when melt spinning is carried out using a polyester resin composition described in the prior art, if the dispersibility of a tetravalent metal phosphate compound in the polyester resin composition is poor, coarse particles (secondary particles) formed by aggregation of primary particles are trapped by a mesh installed at the tip of the extruder used for melt spinning, causing the mesh to become clogged, and the resin pressure increases, resulting in an insufficient discharge rate of the resin composition and reduced productivity due to thread breakage caused by coarse particles that pass through the mesh, as well as reduced performance due to an insufficient blending amount of the tetravalent metal phosphate compound trapped 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 the tetravalent metal phosphate compound, are pulverized by shear and elongation energy during kneading, and the primary particles of the tetravalent metal phosphate compound are uniformly dispersed. By satisfying the above-mentioned blending ratio, the surface of the tetravalent metal phosphate compound is thoroughly wetted and coated with the polyester resin, which is an organic substance, and the 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 tetravalent metal phosphate compounds, which is thought to occur mechanochemically due to shear and elongation energy during kneading, and results in excellent dispersibility of the tetravalent metal phosphate compound.

[0019] In addition, in the third embodiment of the polyester resin composition according to the present disclosure, the amount of coarse particles (secondary particles) that are aggregates of 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, typified 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 aggregation of the particles of the tetravalent metal phosphate compound is suppressed, resulting in excellent dispersibility of the tetravalent metal phosphate compound. The particles of the tetravalent metal phosphate compound, typified by zirconium phosphate, exhibit a deodorizing function in the polyester resin composition. In the polyester resin composition, the particles of the tetravalent metal phosphate compound do not aggregate, and the particle size at the above viewing angle of the cross-sectional SEM image is 20 μm or less. ２ The number of particles having the above properties is less than one, and more preferably, the particle size of all particles in a cross-sectional SEM image is 20 μm or less. ２ When the polyester resin composition is spun using the tetravalent metal phosphate compound, the surface area of ​​the particles is increased and the deodorizing effect is improved when particles of the tetravalent metal phosphate compound are used at the same content. Furthermore, particles of a tetravalent metal phosphate compound, such as zirconium phosphate, have ion adsorptive, antibacterial, antiviral, and antiallergenic properties, and the same functions are also exhibited in polyester resin compositions containing the tetravalent metal phosphate compound.

[0020] <(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). The 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 (P.O. ４ ) ｂ ・nH ２O (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 not greater than 2.1, and n represents an integer of 0 to 2. (a-2) Median diameter (D ５０ ) is 1.5 μm or less

[0021] 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 Zr １－ｘ Hf ｘ It is particularly preferable that x is a number of 0 or more and 0.2 or less.

[0022] In formula (1), b satisfies 2<b≦2.1, preferably 2.0≦b≦2.1, and more preferably 2.01≦b≦2.06. The larger b is, i.e., 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 be eluted are reduced.

[0023] In formula (1), n ​​satisfies 0≦n≦2, and n is preferably less than 1, more preferably 0.01 to 0.5, and even more preferably 0.03 to 0.3. If n exceeds 2, the absolute amount of water contained in the tetravalent metal phosphate compound is large, which may cause foaming, hydrolysis, etc. during processing.

[0024] The compound represented by the formula (1) is preferably a compound represented by the following formula (2) or (3), and more preferably a compound represented by the following formula (2): Zr １－Ｘ Hf Ｘ H ａ (P.O. ４ ) ｂ ・nH ２ O (2) Ti １－Ｘ Hf Ｘ H ａ (P.O. ４ ) ｂ ・nH ２ O (3) In the formulas (2) and (3), X is 0≦n<1, a and b are positive numbers that satisfy 3b−a=4, b is 2<b≦2.1, and n is 0≦n≦2.

[0025] 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 because hafnium contains radioactive isotopes, excessive hafnium content may have adverse effects when used in electronic components.

[0026] The analytical method for the composition formula of Component A in the present disclosure is not particularly limited, but can be measured, for example, by the following method: Elemental analysis using fluorescent X-rays and hydration water analysis using thermogravimetric differential thermal analysis (TG-DTA).

[0027] - X-ray fluorescence analysis - X-ray fluorescence analysis is measured under the following conditions. <Measurement conditions> Measurement equipment: ZSX Primus II manufactured by Rigaku Corporation Measurement elements: C to U (fixed angle measurement for F, Cl, Br, I, BG 4 sec, peak 8 sec) Analysis diameter: 20 mm Number of measurements: n = 2 Sample treatment: Using a tablet press, the sample is press-molded into pellets and then subjected to measurement. <Analysis> Software: ZSX version 7.49 Model: Bulk

[0028] Thermogravimetric Differential Thermal Analysis (TG-DTA) Thermogravimetric Differential Thermal Analysis (TG-DTA) is measured under the following conditions: Measuring instrument: TG / DTA 6300 manufactured by Hitachi High-Tech Science Corporation Measuring method: 7 to 8 mg of sample is placed in an Al pan and set therein, the temperature is raised to 600°C at 20°C / min, and the weight loss from room temperature to 100°C is estimated as the amount of water (adherent water), and the weight loss from 100°C to 250°C is estimated as water of crystallization (water of hydration).

[0029] Among the tetravalent metal phosphate compounds, preferred specific examples of zirconium phosphate include the following: Zr ０．９９ Hf ０．０１ H ２．０３ (P.O. ４ ) ２．０１ ・0.05H ２ OZr ０．９９ Hf ０．０１ H ２．０６ (P.O. ４ ) ２．０２ ・0.05H２ Oo Oo ０．９９ Hf ０．０１ H ２．１２ (PO ４ ) ２．０４ ・0.05H ２ Oo Oo ０．９９ Hf ０．０１ H ２．２４ (PO ４ ) ２．０８ ・0.05H ２ Oo Oo ０．９８ Hf ０．０２ H ２．０３ (PO ４ ) ２．０１ ・0.05H ２ Oo Oo ０．９８ Hf ０．０２ H ２．０６ (PO ４ ) ２．０２ ・0.05H ２ Oo Oo ０．９８ Hf ０．０２ H ２．１２ (PO ４ ) ２．０４ ・0.05H ２ Oo Oo ０．９８ Hf ０．０２ H ２．２４ (PO ４ ) ２．０８ ・0.05H ２ Oo Oo ０．９７ Hf ０．０３ H ２．０３ (PO ４ ) ２．０１ ・0.05H ２ Oo Oo ０．９４ Hf ０．０６ H ２．０３ (PO ４ ) ２．０１ ・0.05H ２ Oo Oo ０．９ Hf ０．１ H ２．０３ (PO ４ ) ２．０１ ・0.05H ２ O

[0030] There are no particular restrictions on the crystal structure of the tetravalent metal phosphate compound, but from the viewpoint of deodorizing properties, tetravalent metal phosphate compounds obtained by contacting an α-, β-, γ- or amorphous tetravalent metal phosphate compound having basic gas adsorption ability with a basic liquid of pH 9 or higher and then contacting it with an acidic liquid of pH 6 or lower are preferred, with α-type tetravalent metal phosphate compounds being more preferred. Furthermore, it is preferable that the compound represented by formula (1) is a compound represented by formula (2), and that the crystal structure of the compound represented by formula (2) is α-type.

[0031] The method for measuring the crystalline structure of Component A in the present disclosure is not particularly limited, but it can be evaluated, for example, by powder X-ray diffraction. The X-ray diffractometer used is a D8 ADVANCE manufactured by BRUKER. An X-ray diffraction pattern is obtained using a Cu sealed X-ray source and CuKα generated at an applied voltage of 40 kV and a current value of 40 mA. Detailed measurement conditions are as follows: X-ray source: sealed X-ray source (Cu source), 0.4 x 12 mm ２ , Long Fine Focus Rating: 2.2 kW Output power: 40 kV-40 mA (1.6 kW) Goniometer radius: 280 mm Sample stage: FlipStick_Twin_Twin-XE Measurement range 2θ: 5° to 55° Step width: 0.02° Step time: 0.05 seconds / step Entrance side Soller slit: 2.5° Anti-scatter slit: 10.5 mm Curvature: 1.00 Detector: LYNXEYE XE Detector slit width: 5.758 mm Detector window width: 2.9°

[0032] The median diameter of component A (D ５０ ) 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.

[0033] The method for measuring the median diameter (also simply referred to as "particle diameter") 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 dispersion is measured using a laser diffraction particle size distribution analyzer "Mastersizer 2000" (manufactured by Malvern Instruments), and the results are analyzed on a volume basis. Dispersion medium: water Particle concentration: 1 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

[0034] Furthermore, from the viewpoints of dispersibility and suppressing 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.

[0035] The method for measuring the loss on drying is not particularly limited, but can be, for example, measured by 4.1.1(1) Method 1 of JIS K0067:1992 (Testing methods for weight loss and residue of chemical products). A tetravalent metal phosphate compound is left to stand in a room at a temperature of 25°C and a humidity of 50% for 24 hours, and then heated at 250°C under normal pressure for 2 hours. The masses before and after heating are measured, and the loss on drying Y of the tetravalent metal phosphate compound is calculated from the following formula (4): Loss on drying Y (mass%) = {(B ０ -B １ ) / B ０} x 100 (4) B ０ B: Mass of tetravalent metal phosphate compound before heating １ : Mass of tetravalent metal phosphate compound after heating

[0036] 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. From the viewpoints of dispersibility, deodorizing properties, and moldability, it is preferably 40% by mass to 63% by mass, and more preferably 45% by mass to 63% by mass.

[0037] 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. From the viewpoints of dispersibility, deodorizing properties, and moldability, it 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.

[0038] 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, relative to the total mass of the composition, from the viewpoints of dispersibility, deodorizing properties, and moldability.

[0039] The method for identifying the type of resin from an unknown resin composition is not particularly limited, but examples 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. Apparatus name: "Nicolet iS50 FT-IR" manufactured by Thermo Fisher Scientific Measurement method: ATR method (DuraScope unit, diamond disc) Accessories: μ-ATR Conditions: Resolution 4 cm －１ , 32 times of accumulation

[0040] When confirming the type of resin using NMR, １ H-NMR, １３ It can be determined from the peak intensity of each component by measuring C-NMR. Apparatus name: "AVANCE III 400" manufactured by Bruker. Measured nuclides: １ H. １３ C Resonance frequency: 400MHz ( １ H), 100.6MHz ( １３ C) Measurement solvent: CDCl ３

[0041] Methods for confirming the presence and content of a tetravalent metal phosphate compound from an unknown resin composition include scanning electron microscope-energy dispersive X-ray spectroscopy (SEM-EDX) and ash measurement. Examples of measurement methods using SEM-EDX include, for example, SEM ("JSM-7900F" manufactured by JEOL Ltd.) and EDX (EDS, "ULTIM100 type energy dispersive X-ray microanalyzer" manufactured by Oxford Instruments), performing elemental analysis and composition analysis to confirm whether the particles are a tetravalent metal phosphate compound. The ash content can be calculated from the following formula: Ash content (wt%) = (mass of residue ÷ mass of resin composition) × 100. The resin composition is placed in a crucible and heated in air at 750°C for 4 hours to thermally decompose and remove the resin component. The residue derived from the tetravalent metal phosphate compound is then weighed.

[0042] <(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 (Component B) a polyester resin that satisfies the following (b-1) and (b-2). A third embodiment of the polyester resin composition according to the present disclosure preferably contains, as the polyester resin, (Component B) a polyester resin that satisfies the following (b-1) and (b-2). (b-1) It is crystalline. (b-2) One or more monomers other than terephthalic acid and ethylene glycol are copolymerized.

[0043] Component B is a crystalline polyester resin having a melting point. The melting point of Component B 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 suppressing thermal degradation and hydrolysis of the polyester resin. The melting point in the present disclosure is measured using a differential scanning calorimeter (DSC), and the endothermic peak on the higher temperature side of the second run (second temperature rise) is taken as the melting point.

[0044] The differential scanning calorimeter (DSC) is not particularly limited, but can be measured, for example, in accordance with JIS K7121. The endothermic peak on the high temperature side of the second run (second temperature rise) is taken as the melting point. DSC: "DSC 214 Polymer" 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 Heating 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

[0045] Polyester resins are polycondensates primarily composed of polycarboxylic 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). These may be used alone or in combination.

[0046] Examples of polycarboxylic acid components include alicyclic dicarboxylic acids such as terephthalic acid and substituted derivatives thereof. While not particularly limited, 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 (e.g., carbon number 1 to 5) alkyl esters thereof, and polycarboxylic acids having a sodium sulfonate group. These polycarboxylic acid components can be used alone or in combination of two or more.

[0047] Examples of the polyhydric alcohol component include aliphatic diols such as ethylene glycol and diethylene glycol, and alicyclic diols such as 1,4-cyclohexanedimethanol. Examples of the polyhydric alcohol component include, but are not limited to, 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.

[0048] Copolymerized polyester resins are polycondensates of either the polycarboxylic acid component or the polyhydric alcohol component of polyester resins, or a combination of two or more of both components. Commercially available copolymerized polyester resins include glycol-modified polyethylene terephthalate (PETG) and thermoplastic polyester elastomers (TPEE, TPC), and can be used alone or in a blend of two or more.

[0049] The polyester resin and copolymer polyester resin may be end-capped such that the terminal hydroxyl groups or carboxylic acid groups are blocked with an epoxy compound, a carbodiimide compound, an isocyanate compound, or the like.

[0050] The method for measuring the copolymerization monomer components of the polyester resin is not particularly limited, but for example, nuclear magnetic resonance spectroscopy (hereinafter abbreviated as NMR) can be used. １ H-NMR, １３ C-NMR is measured and the value can be calculated from the peak intensity of each component. Apparatus name: "AVANCE III 400" manufactured by Bruker. Measured nuclides: １ H. １３ C Resonance frequency: 400MHz (１ H), 100.6MHz ( １３ C) Measurement solvent: CDCl ３

[0051] Component B may be any 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.

[0052] The copolymerization amount of the monomer 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.

[0053] As will be 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, and (b-4) The intrinsic viscosity (IV) is 1 dL / g or more.

[0054] 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.

[0055] 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. 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 in resin component) Temperature: 30°C

[0056] 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. From the viewpoints of dispersibility, deodorizing properties, and moldability, it is preferably 25% by mass to 45% by mass, and more preferably 27% by mass to 40% by mass.

[0057] 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. From the viewpoints of dispersibility, deodorizing properties, and moldability, it is preferably 10% by mass to 32% by mass, and more preferably 12% by mass to 30% by mass.

[0058] 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, deodorizing properties, and moldability.

[0059] <(Component C) Dispersant> The first and second embodiments of the polyester resin composition according to the present disclosure contain a dispersant (component C). A 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 known dispersants can be used. However, from the viewpoint of dispersibility, it is preferable that the component C has a polar group containing an atom 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 an ester or hydroxyl group. Furthermore, from the viewpoint of dispersibility, component C is preferably an ester-based dispersant, and more preferably an aliphatic ester-based dispersant. Furthermore, from the viewpoint of dispersibility, component C is particularly preferably a bulky molecular structure having a branched structure, a cyclic structure, or the like, which causes greater steric hindrance than a linear structure. Commercially available products can also be suitably used as Component C, and examples thereof include Rikemal TG-12 manufactured by Riken Vitamin Co., Ltd., Unistar H-476 manufactured by NOF Corporation, Zinc Stearate manufactured by NOF Corporation, 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 two or more dispersants as Component C, more preferably contains two or more aliphatic ester-based dispersants, and particularly preferably contains two aliphatic ester-based dispersants.

[0060] The method for measuring the polar group of the dispersant is not particularly limited, but for example, nuclear magnetic resonance spectroscopy (hereinafter abbreviated as NMR) can be used. １ H-NMR, １３ It can be determined from the peak intensity of each component by measuring C-NMR. Apparatus name: "AVANCE III 400" manufactured by Bruker. Measured nuclides: １ H. １３ C Resonance frequency: 400MHz ( １ H), 100.6MHz ( １３ C) Measurement solvent: CDCl ３Alternatively, the peak intensity of each component can be determined by measuring the infrared spectrum using a Fourier transform infrared spectrometer (FT-IR). Apparatus 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 4 cm －１ , 32 times of accumulation

[0061] 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, and from the viewpoints of dispersibility, deodorizing properties, and molding processability, is preferably 3% by mass to 19% by mass, and more preferably 7% by mass to 16% by mass, relative to the total mass of the composition.

[0062] 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. From the viewpoints of dispersibility, deodorizing properties, and moldability, it 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.

[0063] 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, deodorizing properties, and moldability.

[0064] <(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). A third embodiment of the polyester resin composition according to the present disclosure preferably contains, as the polyester resin, (Component D) a polyester resin that satisfies the following (d-1): (d-1) The melting point measured with a differential scanning calorimeter is 240°C or higher. Furthermore, from the viewpoint of dispersibility, Component D preferably satisfies the following (d-2): (d-2) The intrinsic viscosity (IV) is 0.6 dL / g or higher.

[0065] From the viewpoint of heat resistance, the melting point of Component D measured with a differential scanning calorimeter is preferably 240° C. to 260° C. 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.

[0066] Furthermore, from the viewpoint of heat resistance and dispersibility, component D is preferably polyethylene terephthalate (PET) composed of terephthalic acid and ethylene glycol. The 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 copolymerized by partially converting it to diethylene glycol during polymerization. The diethylene glycol structural units contained in the ethylene glycol-derived structural units are often about 2 mol %, and the polyethylene terephthalate may contain 3 mol % or less of diethylene glycol-derived structural units. Furthermore, component D is preferably a polyester resin other than component B.

[0067] 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. From the viewpoints of dispersibility, deodorizing properties, and moldability, it 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.

[0068] 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, deodorizing properties, and moldability.

[0069] <Other Components> 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 incorporated into 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, deodorizers, antibacterial agents, antifungal agents, antiviral processing agents, and antiallergens.

[0070] The deodorizer is not particularly limited, and known deodorizers can be used, such as acidic gas deodorizers, basic gas deodorizers, sulfur-based gas deodorizers, aldehyde-based gas deodorizers, ketone-based gas deodorizers, and aromatics. Compounds that cause malodors 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-based gases such as hydrogen sulfide and methyl mercaptan. Other deodorizers that have deodorizing properties against these compounds can be contained. Deodorizers for basic gases include zeolite, Al, and the like. ２ O ３ , SiO ２ , MgO, CaO, SrO, BaO, ZrO ２ , TiO ２ , W.O. ２ , CeO ２ , Li ２ O, Na ２ O.K. ２Examples of deodorizers for acidic gases include hydrotalcite compounds such as zirconium hydroxide, zirconium oxide, and 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 deodorizers for sulfur gases include copper silicate, copper zirconium phosphate hydrate, zinc oxide, aluminum zinc oxide, zinc silicate, aluminum zinc silicate, and layered zinc aluminosilicate.

[0071] In the second and third embodiments of the polyester resin composition according to the present disclosure, the resin pressure difference (ΔP) of high-density polyethylene (HDPE) before and after flowing 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.

[0072] The method for measuring the differential pressure (ΔP) in the present disclosure is not particularly limited, and can be measured, for example, by the following method. Using a φ20 mm single-screw extruder "Labo Plastomill" (manufactured by Toyo Seiki Seisakusho, Ltd., basic device model "10S100" connected to single-screw extruder unit model "D2025"), P9210 (high-density polyethylene (HDPE)) manufactured by Keiyo Polyethylene Co., Ltd. is fed through a 40 / 730 / 40 mesh at an extrusion temperature of 287°C and a rotation speed of 50 rpm 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. After that, P9210 (HDPE) manufactured by Keiyo Polyethylene Co., Ltd. is again fed until the resin pressure stabilizes, and the HDPE resin pressure before and after feeding the tetravalent metal phosphate compound-containing polyester resin composition (masterbatch) is measured as the 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 better dispersibility of the tetravalent metal phosphate compound in the polyester resin composition.

[0073] 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.

[0074] 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 field of view size of 0.4 mm x 0.3 mm, the particle size of a tetravalent metal phosphate compound represented by zirconium phosphate is 20 μm ２ The number of particles having the above value is less than 1, preferably less than 0.5, more preferably less than 0.1, and even more preferably 0, i.e., none.

[0075] In a third embodiment of the polyester resin composition, in a cross-sectional SEM image of the polyester resin composition, the particle size of the zirconium phosphate is 20 μm ２The number of particles exceeding this limit can be confirmed by taking a photograph of the cross section of a pellet of the polyester resin composition using a scanning electron microscope (SEM) to obtain an SEM image, and then analyzing the obtained SEM image to determine whether the particle size within the viewing angle is 20 μm or less. ２ The number of particles with a particle size of 20 μm or more is counted. ２ When the number of particles is less than 1, the dispersibility of the zirconium phosphate particles is considered to be good. ２ When the number of particles observed is not greater than this, the dispersibility of the zirconium phosphate particles is evaluated to be excellent.

[0076] Observation by image analysis of the obtained SEM image showed that the particle size of zirconium phosphate was 10 μm ２ It is preferable that the number of particles having a particle size of 2 μm or more is 1 or less. ２ It is more preferable that the number of particles having a particle size of 1 μm or more is 10 or less. ２ It is more preferable that the number of particles having a particle size of 0.5 μm or less is 30 or less. ２ It is particularly preferable that the number of particles having the above value is 50 or less.

[0077] More specifically, a SEM image can be obtained at 300x magnification using an SEM of a cross section obtained by cutting a polyester resin composition pellet obtained by the method described in the Examples below perpendicularly to the machine direction (MD) of the pellet. The pellets can be obtained by mixing the polyester resin composition according to the present disclosure to be measured, heating it using a twin-screw extruder, melt-extruding it, and pelletizing it by a strand-cutting method. That is, the machine direction (MD) of the pellets coincides with the machine direction (MD) of the strands, and the longitudinal direction of the pellets is usually the MD. The method for producing pellets will be described later in the Examples. When evaluating already produced pellets, i.e., pellets whose machine direction and pellet direction are unknown, the pellets can be cut in any direction to prepare a cross section, and the obtained cross section can be evaluated by the above method.

[0078] The field of view of the obtained SEM image was 0.4 mm (400 μm) × 0.3 mm (300 μm), and the field of view size was 0.12 mm. ２ The range is binarized using the image analysis software "Image J Fiji" and the particles are measured. In the particle size measured by binarization, the particle size of zirconium phosphate in the field of view size is 20 μm. ２ The number of particles with a particle size of 10 μm or more is 0. ２ It is preferable that the number of particles having a particle size of 2 μm or less is 1 or less. ２ It is more preferable that the number of particles having a particle size of 1 μm or less is 10 or less. ２ It is more preferable that the number of particles having a particle size of 0.5 μm or less is 30 or less. ２ It is particularly preferable that the number of particles having the above value is 50 or less.

[0079] The polyester resin composition of the present disclosure may further contain, 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.

[0080] 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. As the additional polyester resin, a commercially available product may be used, and examples of commercially available products include, but are not limited to, the following: Examples of suitable copolymer polyester resins include crystalline copolymer polyester resins (Vylon GM-913 manufactured by Toyobo Co., Ltd.), amorphous copolymer polyester resins (GN001 manufactured by Eastman Chemical Japan Co., Ltd.), polyethylene terephthalate (MA-2101M manufactured by Unitika Ltd.), crystalline copolymer polyester resins (SB654 manufactured by Toray Celanese Co., Ltd.), and crystalline copolymer polyester resins (Vylon GA-6300 manufactured by Toyobo Co., Ltd.).

[0081] <Method for producing polyester resin composition> There are no particular limitations on the method for producing a polyester resin composition according to the present disclosure, but it preferably includes 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 α in which the content of Component A is 40% by mass to 72% by mass, relative to 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, relative to the total mass of the composition. Furthermore, a method for producing a polyester resin composition according to the present disclosure preferably comprises a step of adding (component D) a polyester resin that satisfies the following (d-1) and (b-3) as component B, and a polyester resin that satisfies the following (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. ａ (P.O. ４ ) ｂ ・nH ２ 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) Median diameter (D ５０(b-1) is crystalline; (b-2) is copolymerized with one or more monomers other than terephthalic acid and ethylene glycol; (b-3) has a melting point of 200°C or less as measured by a differential scanning calorimeter; (b-4) has an intrinsic viscosity (IV) of 1 dL / g or more; (d-1) has a melting point of 240°C or more as measured by a differential scanning calorimeter. Note that 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. Furthermore, the polyester resin composition obtained after the kneading step by the method for producing 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 the same as those described above.

[0082] From the viewpoint of dispersibility, the kneading step is preferably a step of kneading by a continuous kneading means. Also, from the viewpoint of dispersibility, it is more preferable to include a step of obtaining the polyester resin composition α before the kneading step.

[0083] <<Step of Obtaining the Polyester Resin Composition α by Kneading Using a Batch-Type Kneading Means>> Examples of 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 rotor mixer, and a thin-film rotary mixer. 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-type kneading means is not particularly limited, and they may be added all at once, or each component may be added sequentially or continuously. The heating temperature in the step of kneading using a batch-type kneading means may be selected depending on the components used. From the viewpoints of dispersibility and decomposability, the heating temperature is preferably 100°C to 200°C, more preferably 130°C to 190°C, and even more preferably 140°C to 180°C. Furthermore, from the viewpoints of dispersibility and decomposability, 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 batch kneading means is not particularly limited, but is preferably, for example, 0.1 to 12 hours, more preferably 0.3 to 6 hours, and even more preferably 0.5 to 2 hours.

[0084] <<Step of Kneading by Continuous Kneading Means>> Examples of 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 by 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 by the step of kneading by batch kneading means with component D and a polyester resin satisfying (b-3) and (b-4) above. In the step of kneading by continuous kneading means, the amount of the polyester resin composition obtained by the step of kneading by batch kneading means added 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, relative to the total mass of the resulting 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 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 resulting composition, from the viewpoints of dispersibility, deodorizing properties, and moldability. Furthermore, the amount of polyester resin satisfying the above (b-3) and (b-4) added in the step of kneading by 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, relative to the total mass of the resulting composition, from the viewpoints of dispersibility, deodorizing properties, and moldability.

[0085] In the step of kneading by continuous kneading means, the components are preferably mixed in advance and then charged into the continuous kneading means. The heating temperature in the step of kneading by 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. In addition, 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 continuous kneading means is not particularly limited, and the discharge rate and the like may be appropriately selected depending on the continuous kneading means to be used, etc.

[0086] The method for producing a polyester resin composition according to the present disclosure may include other steps, such as a step of pelletizing the obtained polyester resin composition, as needed.

[0087] (Molded Article) 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 a polyester resin composition according to the present disclosure, or a molded article obtained by mixing and molding the polyester resin composition according to the present disclosure with the additional polyester resin. In particular, the molded article according to the present disclosure is preferably a molded article obtained by mixing and molding the second or third embodiment of the polyester resin composition according to the present disclosure with the additional polyester resin. The molding method for 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, and melt spinning. These molding methods 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. Also preferred are molded articles obtained by advanced processing of the molded article according to the present disclosure. Examples of molded articles obtained by advanced processing include yarns and textile products obtained by further processing the fibers that are molded articles. 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 stretch ratio of the fibers and yarns in the molded article may be appropriately selected as desired. The fibers and yarns 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 yarns (UDY: Undrawn Yarn), fully oriented yarns (FOY: Fully Oriented Yarn) in which UDY is drawn and twisted in a separate process to produce a highly oriented yarn, direct spin-draw (DSD: Direct Spin Draw) in which spinning and drawing are directly combined to produce a drawn yarn in one process, partially oriented yarns (POY: Partially Oriented Yarn), drawn textured yarns (DTY: Draw Textured Yarn), or drawn textured yarns (DTY: Draw 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 polyester resin composition according to the present disclosure may be a polyester yarn (Filament Twisted Yarn) or a covered yarn (FTY: Filament Twisted Yarn). The yarn formed using 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.

[0088] The additional polyester resin to be mixed with the first, second, or 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 product to be produced, etc. From the viewpoint of spinnability, 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.

[0089] The molded article according to the present disclosure can be used, for example, as a deodorizing molded article, an ion-adsorbing molded article, an antibacterial molded article, an antiviral molded article, an antiallergenic molded article, etc. Examples of the molded article include fibers, threads, textile products, films, plates, and three-dimensional structures (for example, bags, containers, housings, building materials, automobile parts, etc.). Among these, preferred examples of the molded article include fibers, threads, and textile products, and more preferred examples include woven fabrics and nonwoven fabrics.

[0090] Examples of textile products include woven fabrics, nonwoven fabrics, and clothing and bedding made from these. Examples of clothing 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, undergarments, wigs, T-shirts, dress shirts, suits, formal wear, neckties, masks, belly warmers, obi belts, kimonos, tabi socks, 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. These products may be dyed, primarily for coloring purposes, or finished, primarily to maintain the properties and enhance functionality of the textile material, as needed.

[0091] The present disclosure will be described 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.

[0092] (Tetravalent Metal Phosphate Compound) Synthesis Example 1 (Preparation of Tetravalent Metal Phosphate Compound) Kesmon NS-10 manufactured by Toagosei Co., Ltd. was used as zirconium phosphate particles having a median diameter of 0.8 μm.

[0093] Synthesis Example 2 (Preparation of Tetravalent Metal Phosphate Compound) Kesmon NS-10TZ manufactured by Toagosei Co., Ltd. was used as zirconium phosphate particles having a median diameter of 1.5 μm.

[0094] Synthesis Example 3 Zirconium phosphate particles having a median diameter of 0.51 μm were prepared by the following method. ３ A 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 thoroughly stirring this solution, 403 kg of 75% phosphoric acid was added. The temperature was raised to 98°C over 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 precipitate was then crushed in a grinder and sieved. The resulting zirconium phosphate particles were analyzed using a powder X-ray diffractometer and confirmed to be α-zirconium phosphate particles.

[0095] Synthesis Example 4 Zirconium phosphate particles having a median diameter of 0.22 μm were prepared by the following method. ３ A 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. Then, 328 kg of oxalic acid dihydrate was dissolved. While thoroughly stirring this solution, 482 kg of 75% phosphoric acid was added. The temperature was raised to 98°C over 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 precipitate was then crushed in a grinder. The resulting particles were then sieved. The resulting zirconium phosphate particles were analyzed using a powder X-ray diffractometer and confirmed to be α-zirconium phosphate particles.

[0096] Synthesis Example 5 Titanium phosphate particles having a median diameter of 0.56 μm were prepared by the following method. ３A reactor was charged with 2,745 kg of deionized water, and 2,432 kg of 75% phosphoric acid was added. While thoroughly stirring this solution, 823 kg of titanyl sulfate was added, and stirring was continued for 10 minutes. The temperature was then raised to 100°C over 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 then crushed in a grinder. The resulting titanium phosphate particles were then sieved. Measurement of the resulting titanium phosphate particles using a powder X-ray diffractometer confirmed that they were α-titanium phosphate particles.

[0097] Synthesis Example 6 Zirconium phosphate particles having a median diameter of 0.11 μm were prepared by the following method. ３ A reactor was charged with 228 kg of deionized water, and 4,320 kg of 75% phosphoric acid was added. While thoroughly stirring this solution, 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 over 1 hour, 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 then crushed in a grinder and sieved. The resulting zirconium phosphate particles were analyzed using a powder X-ray diffractometer, and were confirmed to be α-zirconium phosphate particles.

[0098] Synthesis Example 7 Zirconium phosphate particles having a median diameter of 1.0 μm were prepared by the following method. ３ A 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. While thoroughly stirring this solution, 274 kg of 75% phosphoric acid was added. The temperature was raised to 98°C over 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 precipitate was then crushed in a grinder and sieved. The resulting zirconium phosphate particles were analyzed using a powder X-ray diffractometer and confirmed to be α-zirconium phosphate particles.

[0099] The composition formula of the particles identified by X-ray fluorescence analysis and thermogravimetric differential thermal analysis is shown in Table 1.

[0100]

[0101] (Examples 1 to 48 and Comparative Examples 1 to 15) <Preparation of Intermediate: Blending Examples> The tetravalent metal phosphate compound, polyester resin, dispersant, and other components shown in Table 2 were placed in a 3 L pressure kneader (batch kneader, "DS-3-10MWB-E" model, 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 3 mm thick sheet using two 10-inch rolls at a roll temperature of 110°C, which was then shredded and pelletized to obtain a tetravalent metal phosphate compound-containing polyester resin composition (intermediate).

[0102] <Preparation of Masterbatch> A tetravalent metal phosphate compound-containing polyester resin composition (intermediate) shown in Table 3 or Table 4 and a polyester resin were mixed in the blending ratios shown in Table 3 or Table 4, 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, thereby obtaining a tetravalent metal phosphate compound-containing polyester resin composition (masterbatch). In addition, a tetravalent metal phosphate compound and a polyester resin shown in Table 5 were mixed in the blending 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 polyester resin composition (masterbatch) containing a tetravalent metal phosphate compound.

[0103] <Production of Fibers> A tetravalent metal phosphate compound-containing polyester resin composition (masterbatch) and a polyester resin shown in Table 3 or Table 4 were mixed in the blending ratios shown in Table 3 or Table 4. Using a φ20 mm melt spinning facility ("ALM-S3500-T1" manufactured by AIKI LIOTECH Co., Ltd.) equipped with a 30 / 325 / 30 mesh spinneret for 48 filaments, 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 a stretching section at a godet roller temperature of 120°C and a speed of 2,970 m / min to an apparent draw ratio of 4.0. The fiber was then heat-set in a 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 tetravalent metal phosphate compound-containing polyester fiber having a fineness of 75 denier and 48 filaments.

[0104] <Evaluation> - Median diameter - The dispersion liquid containing the tetravalent metal phosphate compound was dispersed using an ultrasonic generator, and the dispersion was measured using a laser diffraction particle size distribution analyzer "Mastersizer 2000" (manufactured by Malvern Instruments), and the results were analyzed on a volume basis. Dispersion medium: water Particle concentration: 1 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 repeated

[0105] - Crystal structure analysis - Evaluation was performed by powder X-ray diffraction. The X-ray diffractometer used was a D8 ADVANCE manufactured by BRUKER. An X-ray diffraction pattern was obtained using a Cu sealed X-ray source and CuKα generated at an applied voltage of 40 kV and a current value of 40 mA. Detailed measurement conditions are as follows: X-ray source: sealed X-ray source (Cu source), 0.4 x 12 mm ２, Long Fine Focus Rating: 2.2 kW Output power: 40 kV-40 mA (1.6 kW) Goniometer radius: 280 mm Sample stage: FlipStick_Twin_Twin-XE Measurement range 2θ: 5° to 55° Step width: 0.02° Step time: 0.05 seconds / step Entrance side Soller slit: 2.5° Anti-scatter slit: 10.5 mm Curvature: 1.00 Detector: LYNXEYE XE Detector slit width: 5.758 mm Detector window width: 2.9°

[0106] The composition formula was determined by elemental analysis using fluorescent X-rays and hydration water analysis using thermogravimetric differential thermal analysis (TG-DTA).

[0107] - X-ray fluorescence analysis - X-ray fluorescence analysis was measured under the following conditions. <Measurement conditions> Measurement equipment: ZSX Primus II manufactured by Rigaku Corporation Measurement elements: C to U (fixed angle measurement for F, Cl, Br, I, BG 4 sec, peak 8 sec) Analysis diameter: 20 mm Number of measurements: n = 2 Sample treatment: Using a tablet press, the sample was press-molded into pellets and subjected to measurement. <Analysis> Software: ZSX version 7.49 Model: Bulk

[0108] Thermogravimetric Differential Thermal Analysis (TG-DTA) Thermogravimetric Differential Thermal Analysis (TG-DTA) was measured under the following conditions: Measuring instrument: TG / DTA 6300 manufactured by Hitachi High-Tech Science Corporation Measuring method: 7 mg to 8 mg of a sample was placed in an Al pan and set therein, and the temperature was raised to 600°C at 20°C / min, and the weight loss from room temperature to 100°C was estimated as the water content (adherent water), and the weight loss from 100°C to 250°C was estimated as water of crystallization (water of hydration).

[0109] - Melting point - Measured using a differential scanning calorimeter (DSC). Measurement was performed in accordance with JIS K7121 under the following measurement conditions, and the endothermic peak on the higher temperature side in the second run (second temperature rise) was taken as the melting point. DSC: "DSC 214 Polymer" manufactured by NETZSCH - 1st run - Heating rate: 10°C / min Measurement temperature: 30°C to 300°C Measurement atmosphere: nitrogen Hold: 5 minutes after reaching 300°C Heating 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

[0110] - Intrinsic Viscosity (IV) - Measured 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°C

[0111] - Differential Pressure (ΔP): Dispersibility - Using a φ20 mm single-screw extruder "Labo Plastomill" (manufactured by Toyo Seiki Seisaku-sho, Ltd., basic device model "10S100" connected to single-screw extruder unit model "D2025"), P9210 (high-density polyethylene (HDPE)) manufactured by Keiyo Polyethylene Co., Ltd. was fed through a 40 / 730 / 40 mesh at an extrusion temperature of 287°C and a rotation speed of 50 rpm until the resin pressure stabilized. After confirming that the resin pressure had stabilized, the extruder was switched to a polyester resin composition weighed out so that the tetravalent metal phosphate compound content was 200 g, and the entire amount was fed. After that, P9210 (HDPE) manufactured by Keiyo Polyethylene Co., Ltd. was again fed until the resin pressure stabilized, and the HDPE resin pressure before and after the tetravalent metal phosphate compound-containing polyester resin composition (masterbatch) was fed was measured as the 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 better dispersibility of the tetravalent metal phosphate compound in the polyester resin composition.

[0112] - Deodorizing rate - Measurements were made 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, which was then sealed with a heat sealer. A predetermined amount of test gas adjusted to an initial ammonia concentration of 100 ppm was injected, and the residual gas concentration (ppm) after 2 hours and 24 hours was measured using a component-specific detector tube (manufactured by Gastec Corporation). The rate of decrease in the residual gas concentration was calculated and expressed as the deodorizing rate. Measurements were made using an average value of n = 3. The gas filling volume was 3 L, and dry air was used as the dilution gas.

[0113] - Tensile strength - Measured using a Tensilon universal testing machine "RTE-1210" (manufactured by A&D Co., Ltd.) in accordance with JIS L1013: 2010. Measurement was performed by pulling at an initial chuck distance of 200 mm, a pulling speed of 200 mm / min, and an environment of 23°C, and the average of three tests was taken as the measured value.

[0114] The evaluation results are summarized in Tables 3 to 5.

[0115]

[0116]

[0117]

[0118]

[0119] As shown in Tables 3 to 5, the polyester resin compositions of Examples 1 to 48 had low differential pressure (ΔP) and excellent dispersibility of the tetravalent metal phosphate compound. Furthermore, the polyester resin compositions of Examples 1 to 48 exhibited good spinnability during melt spinning, and the tensile strength was at a level that was practically acceptable. Furthermore, the polyester resin compositions of Examples 1 to 6, 9, 10, 12 to 32, and 34 to 48 were spun into fibers that had high deodorizing rates. On the other hand, the polyester resin compositions of Comparative Examples 1, 2, and 5 to 11 were capable of melt spinning, but exhibited higher differential pressure (ΔP) and poorer dispersibility of the tetravalent metal phosphate compound compared to the Examples. As shown in Tables 3 and 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.

[0120] 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 (Sunwax 171-P manufactured by Sanyo Chemical Industries, Ltd.) H-476: Pentaerythritol tetrastearate (Unistar H-476 manufactured by NOF Corporation) Zinc stearate: Zinc stearate manufactured by NOF Corporation 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: Polymer dispersant (manufactured by Lubrizol) Solplus L400: Polymer 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.)

[0121] As shown in Tables 3 to 5, the polyester resin compositions of Examples 1 to 48 are superior in dispersibility of tetravalent metal phosphate compounds compared to 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 also superior in tensile strength and spinnability.

[0122] From the Examples and Comparative Examples 1 and 2, it was found that when the content of component C in the intermediate was less than 0.1% by mass, the dispersibility of the tetravalent metal phosphate compound was insufficient, resulting in a high differential pressure ΔP. From the Examples and Comparative Example 3, it was found that when the content of component A in the intermediate was 75% by mass or more, the amount of tetravalent metal phosphate became excessive, making it difficult to fill the polyester resin, making it impossible to pelletize the intermediate, and making it impossible to subsequently mold it into a masterbatch or fiber.

[0123] From the examples and comparative example 4, it was found that when the content of component B in the intermediate was 55% by mass or more, the polyester resin became excessive, adhered to the pressure kneader, and was difficult to recover, making it impossible to pelletize the intermediate and subsequent molding processing into a masterbatch or fibers impossible.

[0124] 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 reduced.

[0125] From Example and Comparative Example 6, it was found that if component B was not crystalline, the differential pressure ΔP increased.

[0126] From the examples and comparative example 7, when component B was not copolymerized with one or more monomers other than terephthalic acid and ethylene glycol, that is, when component B was polyethylene terephthalate (homoPET) composed of terephthalic acid and ethylene glycol, the differential pressure ΔP was high and the deodorizing rate was reduced.

[0127] From Examples and Comparative Example 8, when the content of component C in the intermediate was 30% by mass or more, slippage occurred on the screw of the single-screw extruder during measurement of the differential pressure ΔP, preventing the sample from being fed to the extruder and making it impossible to measure the differential pressure ΔP. This is thought to be due to the possibility of poor fiber quality caused by separation of the masterbatch and base resin during processing into fibers.

[0128] From Example and Comparative Example 9, it was found that when component C was not contained in the intermediate and masterbatch, the differential pressure ΔP increased.

[0129] From the results of Example and Comparative Example 10, when the content of component A in the masterbatch exceeded 30 mass %, the differential pressure ΔP increased.

[0130] From the results of Example and Comparative Example 11, when the content of component D in the masterbatch was less than 37 mass %, the differential pressure ΔP increased.

[0131] From Examples and Comparative Examples 12 to 15, it was found that when Component B and Component C were not blended, the differential pressure ΔP was high, making it difficult to process the mixture into fibers, and the fibers could not be evaluated.

[0132] (Image analysis using SEM images) Among the examples and comparative examples of pelletized polyester resin compositions listed in Tables 3 to 5 above, 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.

[0133] -SEM Image- Pellets of the polyester resin composition were thoroughly cooled using dry ice or liquid nitrogen. Using a single-edged trimming razor (manufactured by Nisshin EM Co., Ltd.), the cooled pellets were cut perpendicular to the flow direction (machine direction, MD) to prepare pellet cross sections, which served as SEM measurement surfaces. The cut pellets were clamped between sample stages and fixed to the sample stage so that the pellet cross sections could be observed with the SEM. To prevent charge buildup 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 deposition was performed on the pellet cross sections using a precious metal thin film coating device "MSP-1S" (manufactured by Vacuum Device Co., Ltd.) for SEM observation. The pellet cross sections were photographed at 300x magnification using a scanning electron microscope (SEM) "JSM-7900F" (manufactured by JEOL Ltd.) to obtain SEM images. The SEM image was focused at a magnification of 15,000 to 25,000x, and gradually changed to 300x magnification, allowing the quality of the measurement surface of the pellet cross section and the quality of the SEM image to be checked while measurement was performed. If satisfactory quality was not obtained, the pellet cross section was prepared again. SEM images were taken at five or more locations in different areas, and the one that was considered to be the most average was selected by visual inspection. If the quality of the SEM image was poor due to poor condition of the pellet cross section, the quality of the cross section may be improved using a microtome, cryomicrotome, or ion milling. 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: ×300 (effective field of view angle 0.4 mm (400 μm) × 0.3 mm (300 μm)

[0134] Furthermore, elemental analysis and composition analysis were performed on the cross section of the pellet that had not been subjected to platinum deposition using an energy dispersive X-ray spectrometer (EDX, "ULTIM100 Energy Dispersive X-ray Microanalyzer" manufactured by Oxford Instruments), and it was confirmed that areas in the SEM image that were significantly brighter than the surrounding area were zirconium phosphate particles.

[0135] -Image analysis- Selected SEM image field angle: 0.4 mm (400 μm) × 0.3 mm (300 μm), field size: 0.12 mm ２ The range was binarized using the image analysis software "Image J Fiji," and the size (area) of each detected particle was measured. The selected SEM image was read into the image analysis software, and the conversion scale of the image analysis software was set from the conversion scale bar written on the SEM image. Unnecessary parts containing information written at the time of SEM image capture were deleted, and the effective field of view angle was set to 0.4 mm (400 μm) × 0.3 mm (300 μm), field of view size: 0.12 mm. ２ The image was binarized using the IsoData algorithm incorporated in the image analysis software so that the particles were white. The threshold for binarization was determined by 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 incorporated in the image analysis software, and the size (area) of each particle was measured, and the particle size calculation results were obtained.

[0136] 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 a contrast difference within the SEM image, the Fourier transform or filter processing incorporated in the image analysis software is not performed, but the SEM image before image analysis is divided, the above-mentioned image analysis is performed, and the SEM image and the binarized image are compared in each divided region, 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 region for the SEM image divided until the number and size of particles match well, and the calculation result of the particle size is obtained as the image analysis result within the effective field of view by adding up all the obtained measurement results.

[0137] 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" manufactured by Microsoft Corporation

[0138] FIG. 1 is an SEM image of the cross section of a polyester resin composition pellet of Example 27, taken at 300x magnification. The SEM image shown in FIG. 1 was divided into five parts and binarized using the above software. The resulting image is shown in FIG. 2. FIG. 2 is a binarized image of the cross section of the polyester resin composition pellet of Example 27, obtained by image analysis. Individual zirconium phosphate particles are clearly visible in FIG. 2. FIG. 3 is an SEM image of the cross section of a polyester resin composition pellet of Comparative Example 6, taken at 300x magnification. The SEM image of FIG. 3 was divided into three parts in the same manner as in Example 28, and the binarized image was obtained by image analysis using the above software. FIG. 4 shows the binarized image. It can be seen from FIG. 4 that there are more coarse zirconium phosphate particles than in FIG. 2. By performing image analysis and binarization on the SEM image, it is possible to easily identify the fine zirconium phosphate particles contained in the polyester resin composition.

[0139] The particle size in the image obtained by binarization was measured. The particle size measured was 20 μm for zirconium phosphate in the field of view. ２ The number of particles and particle size are 10 μm or more. ２ The number of particles and particle size are 2 μm or more. ２ The number of particles and particle size are 1 μm or more. ２ The number of particles and particle size are 0.5 μm or more. ２ The number of particles exceeding this value was counted. The results are shown in Table 6 below. Furthermore, as a measure of the flowability and particle dispersibility of the polyester resin composition, the differential pressure (ΔP) of the resin pressure of the high-density polyethylene (HDPE) before and after the polyester resin composition was poured, measured in the above Examples and Comparative Examples, is also shown in the table.

[0140]

[0141] As is clear from Table 6, the polyester resin compositions of each Example had a viscosity of 20 μm. ２ It can be seen that the polyester resin of Example 8 does not contain zirconium phosphate particles of 20 μm or more. ２ On the other hand, the polyester resin compositions of the comparative examples all contained 20 μm titanium phosphate particles. ２ The mesh contained one or more zirconium phosphate particles of the above size. Furthermore, the differential pressure (ΔP) value of each example was smaller than the differential pressure (ΔP) of each comparative example, which indicates that the zirconium phosphate or titanium phosphate particles had good dispersibility. Furthermore, because the dispersibility was good, few coarse particles of zirconium phosphate or titanium phosphate particles were captured by the mesh, and the mesh was less likely to clog. From these comparisons, it can be seen that the number of particles by image analysis, particularly those of 20 μm ２ The results of the measurement of the presence or absence of zirconium phosphate particles or titanium phosphate particles correlate well with the dispersibility of the tetravalent metal phosphate compound in the polyester resin composition, and it is expected that the polyester resin compositions of each Example will have good spinnability during melt spinning. It was also confirmed that the polyester resin compositions of each Example can produce molded articles with excellent deodorizing properties.

[0142] 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 documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

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, wherein the content of Component A is 40% by mass to 72% by mass relative to the total mass of the composition, the content of Component B is 25% by mass to 50% by mass relative to the total mass of the composition, and the content of Component C is 3% by mass to 25% by mass relative to the total mass of the composition. (a-1) MH ａ (P.O. ４ ) ｂ ・nH ２ 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) Median diameter (D ５０ (b-1) It is crystalline. (b-2) At least one monomer other than terephthalic acid and ethylene glycol is copolymerized.

2. 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); (Component C) a dispersant; and (Component D) a polyester resin satisfying 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 relative to the total mass of the composition, 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 (P.O. ４ ) ｂ ・nH ２ 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) Median diameter (D ５０ (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 higher as measured by a differential scanning calorimeter.

3. A polyester resin composition according to claim 1 or 2, wherein component C is a dispersant having a polar group in its molecular structure.

4. The polyester resin composition according to claim 3, wherein said polar group is at least one group selected from the group consisting of ester, ether, hydroxyl and imino groups.

5. The polyester resin composition according to claim 2, wherein component D satisfies the following (d-2): (d-2) the intrinsic viscosity (IV) is 0.6 dL / g or more.

6. The polyester resin composition according to claim 1 or 2, wherein M is at least one tetravalent metal selected from the group consisting of zirconium, titanium and hafnium.

7. 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 lower.

8. 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) the intrinsic viscosity (IV) is 1 dL / g or more.

9. A polyester resin composition containing a tetravalent metal phosphate compound and a polyester resin, wherein in a cross-sectional SEM image of a polyester resin composition having a field of view size of 0.4 mm x 0.3 mm, the particle size of the tetravalent metal phosphate compound is 20 μm or less. ２ The number of particles having the above-mentioned properties is less than one.

10. The particle size of the tetravalent metal phosphate compound is 10 μm. ２ The polyester resin composition according to claim 9, wherein the number of particles having the above particle size is 1 or less.

11. The particle size of the tetravalent metal phosphate compound is 2 μm. ２ The polyester resin composition according to claim 9, wherein the number of particles having the above particle size is 10 or less.

12. 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.

13. A molded article obtained by molding the polyester resin composition according to claim 12.

14. The molded article according to claim 13, wherein the molding process is melt spinning.

15. A molded product obtained by subjecting the molded product according to claim 13 to advanced processing.

16. The molded article according to claim 15, which is a woven or nonwoven fabric.

17. A method for producing a polyester resin composition, comprising 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. (a-1) MH is a compound represented by the following formula (1): ａ (P.O. ４ ) ｂ ・nH ２ 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) Median diameter (D ５０ (b-1) It is crystalline. (b-2) At least one monomer other than terephthalic acid and ethylene glycol is copolymerized.

18. A method for producing a polyester resin composition, comprising a step of adding (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) 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) MH ａ (P.O. ４ ) ｂ ・nH ２ 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) Median diameter (D ５０ (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.

19. The method for producing a polyester resin composition according to claim 18, wherein component D satisfies the following (d-2): (d-2) the intrinsic viscosity (IV) is 0.6 dL / g or more.

20. 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.

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