Dispersed powder, aqueous dispersion, masterbatch composition, masterbatch, near-infrared shielding transparent resin molded body, near-infrared shielding transparent laminate, and method for producing masterbatch composition

Abstract

This dispersed powder comprises: a cationic surfactant; and composite tungsten oxide particles having a hexagonal crystal structure and represented by the general formula MxWOy (where the M element includes at least one element selected from among Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, and Ra, and 0.1≤x≤1.0 and 2.0≤y<4.0 are satisfied).

Description

Dispersed powder, aqueous dispersion, masterbatch composition, masterbatch, near-infrared shielding transparent resin molded body, near-infrared shielding transparent laminate, and method for producing masterbatch composition

[0001] The present invention relates to a dispersed powder, an aqueous dispersion, a masterbatch composition, a masterbatch, a near-infrared shielding transparent resin molded product, a near-infrared shielding transparent laminate, and a method for producing a masterbatch composition.

[0002] In the fields of agriculture and construction, resin films that can control the transmission and reflection properties of near-infrared and visible light have been studied.

[0003] For example, Patent Document 1 proposes a thermal insulation sheet made of a knitted or woven fabric in which a strip-shaped film having infrared reflectivity and a strip-shaped film having infrared absorbing properties are used as warp and weft threads, respectively.

[0004] Furthermore, Patent Document 2 proposes a film for cultivating agricultural crops, in which a film surface is whitened to a total light transmittance of 30% or more and a diffuse reflectance of 40% or more, and a black or blue pigment such as carbon black is printed on the film surface by dispersing it in a binder.

[0005] Patent Document 3 proposes an agricultural film made of a resin film containing hexaboride particles as an infrared absorbing filler.

[0006] Patent Document 4 proposes a method for producing a fine particle-dispersed resin composition, which includes kneading composite particles containing fine particles and a dispersant therefor, a compatibilizer, and polyethylene, wherein the dispersant for the composite particles contains a polar group-containing resin and the compatibilizer is a polar group-containing polyolefin. The fine particles include tungsten-based oxide particles, and it is said that dispersibility has a significant effect on the near-infrared absorption properties.

[0007] Japanese Patent Application Publication No. 9-107815 Japanese Patent Application Publication No. 55-127946 Japanese Patent Application Publication No. 2012-021056 Japanese Patent Application Publication No. 2020-083951

[0008] Composite tungsten oxide particles are known as a substance with excellent near-infrared absorption properties, and masterbatches and dispersions in which composite tungsten oxide particles are added to resins and the like have been investigated.

[0009] Masterbatches and the like containing composite tungsten oxide particles are produced, for example, by dispersing the composite tungsten oxide particles into a dispersion liquid, and then kneading the dispersion liquid with a resin, etc. Conventionally, when preparing a dispersion liquid of composite tungsten oxide particles, an organic solvent has mainly been used as a dispersion medium, and from the viewpoint of reducing the environmental load, a dispersion liquid that does not use an organic solvent as a dispersion medium has been desired.

[0010] Therefore, one aspect of the present invention aims to provide a dispersion powder that can be made into an aqueous dispersion using water as a dispersion medium by adding water, and that can be used to produce a masterbatch containing composite tungsten oxide particles or a near-infrared shielding transparent resin molded product.

[0011] The dispersed powder according to one embodiment of the present invention comprises a cationic surfactant and a compound having a hexagonal crystal structure represented by the general formula M ｘ WO ｙ (wherein the M element includes one or more elements selected from Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, and Ra, and 0.1≦x≦1.0, 2.0≦y<4.0 are satisfied).

[0012] According to the dispersion powder of one aspect of the present invention, by adding water, an aqueous dispersion liquid using water as a dispersion medium can be obtained, and a dispersion powder that can be used for producing a master batch containing composite tungsten oxide particles or a near-infrared shielding transparent resin molded product can be provided.

[0013] Fig. 1 is an explanatory diagram of an aqueous dispersion according to one embodiment of the present disclosure. Fig. 2 is an explanatory diagram of a masterbatch and a near-infrared shielding transparent resin molded product according to one embodiment of the present disclosure. Fig. 3 is an explanatory diagram of a near-infrared shielding transparent laminate according to one embodiment of the present disclosure. Fig. 4 is an explanatory diagram of a near-infrared shielding transparent laminate according to one embodiment of the present disclosure. Fig. 5 is a flow diagram of a method for producing a masterbatch composition according to one embodiment of the present disclosure.

[0014] Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the present invention is not limited to the following embodiments, and various modifications and substitutions can be made to the following embodiments without departing from the scope of the present invention. [Aqueous Dispersion] A dispersed powder according to one embodiment of the present disclosure (hereinafter referred to as "this embodiment") can be produced by reducing or removing water from the aqueous dispersion of this embodiment described below. Furthermore, the aqueous dispersion of this embodiment can be obtained by adding water to the dispersed powder according to one embodiment of the present disclosure. For this reason, the aqueous dispersion will be described first.

[0015] The aqueous dispersion of this embodiment can contain water and a dispersion powder according to one aspect of the present disclosure, which will be described later.

[0016] Therefore, the aqueous dispersion of this embodiment can contain a cationic surfactant, water, and composite tungsten oxide particles.

[0017] 1 , an aqueous dispersion 10 of this embodiment can contain composite tungsten oxide particles 11 and water 12. The composite tungsten oxide particles 11 are preferably dispersed in the water 12.

[0018] Although not shown in Fig. 1, the aqueous dispersion 10 of this embodiment further contains a cationic surfactant. The cationic surfactant can be disposed on the surface of the composite tungsten oxide particles 11, for example, to modify the surface of the composite tungsten oxide particles 11. Furthermore, a portion of the cationic surfactant may be dissolved in the water 12.

[0019] 1 is a schematic diagram, and the aqueous dispersion of this embodiment is not limited to this form. For example, in FIG. 1, the composite tungsten oxide particles 11 are represented by circles and depicted as spherical particles, but the shape of the composite tungsten oxide particles 11 is not limited to this form and can have any shape. The aqueous dispersion 10 can contain other additives as needed in addition to the composite tungsten oxide particles 11, water 12, and cationic surfactant.

[0020] The aqueous dispersion of the present embodiment can be composed only of a cationic surfactant, water, and composite tungsten oxide particles, but even in this case, it does not exclude the inclusion of unavoidable impurities that are mixed in during the manufacturing process.

[0021] The components contained in the aqueous dispersion of this embodiment will be described below. (1) Composite tungsten oxide particles (1-1) Composition The composite tungsten oxide particles are composed of a tungsten oxide having a general formula M ｘ WO ｙ The particles can be composite tungsten oxide particles that can be represented by the following formula:

[0022] The M element in the above general formula is H (hydrogen), He (helium), alkali metal element, alkaline earth metal element, rare earth element, Mg (magnesium), Zr (zirconium), Cr (chromium), Mn (manganese), Fe (iron), Ru (ruthenium), Co (cobalt), Rh (rhodium), Ir (iridium), Ni (nickel), Pd (palladium), Pt (platinum), Cu (copper), Ag (silver), Au (gold), Zn (zinc), Cd (cadmium), Al (aluminum), Ga (gallium), In (indium), The element may be one or more elements selected from the group consisting of Tl (thallium), Si (silicon), Ge (germanium), Sn (tin), Pb (lead), Sb (antimony), B (boron), F (fluorine), P (phosphorus), S (sulfur), Se (selenium), Br (bromine), Te (tellurium), Ti (titanium), Nb (niobium), V (vanadium), Mo (molybdenum), Ta (tantalum), Re (rhenium), Be (beryllium), Hf (hafnium), Os (osmium), Bi (bismuth), and I (iodine). W represents tungsten, O represents oxygen, and x may be 0.1≦x≦1.0 or 0.25≦x≦0.39. y may satisfy the relationship 2.0≦y<4.0.

[0023] Examples of alkali metal elements include Li (lithium), Na (sodium), K (potassium), Rb (rubidium), Cs (cesium), and Fr (francium). Examples of alkaline earth metal elements include Ca (calcium), Sr (strontium), Ba (barium), and Ra (radium). Examples of rare earth elements include Sc (scandium), Y (yttrium), La (lanthanum), Ce (cerium), Pr (praseodymium), Nd (neodymium), Pm (promethium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Tm (thulium), Yb (ytterbium), and Lu (lutetium).

[0024] The M element in the above general formula contained in the composite tungsten oxide particles preferably contains one or more elements selected from, for example, Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Tl, and In. This is because the M element contains one or more elements selected from Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Tl, and In, making the composite tungsten oxide particles more likely to have a hexagonal crystal structure, particularly improving the transmittance of light in the visible light range and improving the near-infrared shielding function. In particular, considering the ease of handling of raw materials, it is more preferable that the M element contains one or more elements selected from, for example, Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, and Ra. It is even more preferable that the M element contains one or more elements selected from, for example, Cs, Rb, K, and Ba.

[0025] Typical examples of composite tungsten oxide particle materials include Cs ０．３３ WO ３ , Rb ０．３３ WO ３ , K. ０．３３ WO ３ , Ba ０．３３ WO ３ As long as x and y fall within the above ranges, useful near-infrared shielding properties can be obtained.

[0026] The composite tungsten oxide can have one or more tungsten bronze-type crystal structures selected from, for example, tetragonal, cubic, and hexagonal crystal structures. The composite tungsten oxide contained in the composite tungsten oxide particles contained in the aqueous dispersion of this embodiment preferably has a hexagonal crystal structure.

[0027] When the composite tungsten oxide has a hexagonal crystal structure, the particles have improved transmittance in the visible light region and improved absorption of light in the near-infrared region.

[0028] Composite tungsten oxide also functions as a near-infrared shielding material when it has a tetragonal or cubic tungsten bronze-type crystal structure. However, the absorption position of light in the near-infrared region tends to change depending on the crystal structure of the composite tungsten oxide. The absorption position of light in the near-infrared region tends to shift toward longer wavelengths in the tetragonal crystal compared to the cubic crystal, and further shift toward longer wavelengths in the hexagonal crystal compared to the tetragonal crystal. In addition, accompanying this shift in absorption position, hexagonal crystals absorb light in the visible light region least, followed by tetragonal crystals, and among these, cubic crystals absorb light in the visible light region most. Therefore, for applications requiring more transmission of light in the visible light region and more shielding of light in the infrared region, it is preferable to use a composite tungsten oxide having a hexagonal tungsten bronze-type crystal structure. For this reason, the composite tungsten oxide particles contained in the aqueous dispersion of this embodiment can have, for example, a hexagonal crystal structure. (1-2) Dispersion Particle Diameter of Composite Tungsten Oxide Particles The dispersion particle diameter of the composite tungsten oxide particles used in the aqueous dispersion of this embodiment is not particularly limited, and can be selected depending on the intended use, etc.

[0029] The composite tungsten oxide particles used in the aqueous dispersion of this embodiment largely absorb light in the near-infrared region, particularly light with a wavelength around 1000 nm, and therefore the transmitted color tone is often blue.

[0030] When used in applications that require transparency, the composite tungsten oxide particles preferably have a dispersed particle diameter of 800 nm or less. This is because particles with a dispersed particle diameter of 800 nm or less do not completely block light in the visible light range due to scattering, and can maintain high visibility in the visible light range while efficiently maintaining transparency. In particular, when transparency in the visible light range is important, it is preferable to further consider scattering by the particles.

[0031] In this specification, the term "transparency" is used to mean "high transmittance with little scattering of light in the visible light range."

[0032] When emphasis is placed on reducing scattering by particles, the dispersed particle diameter of the composite tungsten oxide particles is more preferably 200 nm or less, and even more preferably 100 nm or less, because a smaller dispersed particle diameter of the composite tungsten oxide particles reduces scattering of light in the visible light range due to geometric scattering or Mie scattering.

[0033] By setting the dispersed particle diameter of the composite tungsten oxide particles to, for example, 200 nm or less, scattering of light in the visible light region is reduced, and as a result, the transparency of the near-infrared shielding film, which is a dispersion or molded body containing the composite tungsten oxide particles, can be improved. In other words, it is possible to reliably prevent the near-infrared shielding film from becoming like frosted glass and failing to achieve clear transparency.

[0034] When the dispersed particle diameter of the composite tungsten oxide particles is 200 nm or less, the geometric scattering or Mie scattering is reduced, and the region reaches the Rayleigh scattering region. In the Rayleigh scattering region, scattered light is reduced in proportion to the sixth power of the particle diameter, so scattering is reduced as the dispersed particle diameter decreases, and transparency is improved. Furthermore, when the dispersed particle diameter of the composite tungsten oxide particles is 100 nm or less, scattered light is significantly reduced, which is preferable. From the viewpoint of avoiding light scattering, a smaller dispersed particle diameter of the composite tungsten oxide particles is preferable.

[0035] There is no particular lower limit to the dispersed particle diameter of the composite tungsten oxide particles, but the dispersed particle diameter may be set to, for example, 1 nm or more, since this facilitates industrial production.

[0036] That is, the dispersed particle diameter of the composite tungsten oxide particles may be 1 nm or more and 800 nm or less, 1 nm or more and 200 nm or less, or 1 nm or more and 100 nm or less. (1-3) Color of composite tungsten oxide particles In order to achieve a desired color for the aqueous dispersion of this embodiment, a masterbatch using the aqueous dispersion, or a near-infrared shielding transparent resin molded product formed from the masterbatch, the color of the composite tungsten oxide particles can be set within a predetermined range. The powder color of the composite tungsten oxide particles is L ＊ is 25 or more and 80 or less, a ＊ is between -10 and 10, b ＊ The color parameter may be set to L, which is recommended by the International Commission on Illumination (CIE). ＊ a ＊ b ＊ It means the powder color in the color space (JIS Z 8729 (2004)).

[0037] The color of the composite tungsten oxide particles can be selected by the conditions of the heat treatment step in the method for producing composite tungsten oxide particles, which will be described later. (1-4) Method for producing composite tungsten oxide particles The method for producing the composite tungsten oxide particles contained in the aqueous dispersion of this embodiment is not particularly limited, and any method can be used as long as it can produce composite tungsten oxide particles that satisfy the general formula and crystal structure described above.

[0038] The method for producing composite tungsten oxide particles can include, for example, a heat treatment step in which the starting material is heat treated in an inert gas atmosphere or a reducing gas atmosphere.

[0039] The method for producing composite tungsten oxide particles may further include an oxidation treatment step of performing oxidation treatment after the heat treatment step.

[0040] Each step will be described below. (Heat Treatment Step) The starting material to be subjected to the heat treatment step can include a tungsten raw material containing tungsten, which serves as a supply source of tungsten.

[0041] The tungsten raw material may include one or more selected from, for example, tungsten acid, tungsten trioxide powder, tungsten dioxide powder, tungsten oxide hydrate, tungsten hexachloride powder, ammonium tungstate powder, tungsten oxide hydrate powder, tungsten compound powder, and metallic tungsten powder.

[0042] As the tungsten oxide hydrate, for example, a tungsten oxide hydrate powder obtained by dissolving tungsten hexachloride in alcohol and then drying the solution, or a tungsten oxide hydrate powder obtained by dissolving tungsten hexachloride in alcohol, adding water to cause precipitation, and then drying the precipitate, can be used.

[0043] The tungsten compound powder may be a powder obtained by drying an aqueous solution of ammonium tungstate.

[0044] The tungsten source may include a solution containing one or more selected from the above powder materials.

[0045] When producing composite tungsten oxide particles, if the starting material is a solution, the elements contained in the starting material can be easily and uniformly mixed. Therefore, it is more preferable to use a solution such as an ammonium tungstate aqueous solution or a tungsten hexachloride solution as the tungsten raw material.

[0046] The starting material may also include an element M raw material containing element M, which serves as a source of element M.

[0047] The element M raw material may contain one or more types selected from the element M itself and compounds containing the element M.

[0048] The starting material may be a mixture of a tungsten material and an element M material.

[0049] Here, in order to produce a starting material in which each component is uniformly mixed at the molecular level, it is preferable to mix each raw material in the form of a solution. Therefore, it is preferable that the element M raw material containing element M is soluble in a solvent such as water or an organic solvent. For example, the element M raw material may be one or more selected from tungstates, chlorides, nitrates, sulfates, oxalates, oxides, carbonates, hydroxides, etc. containing element M, but is not limited to these, and any raw material that can be formed into a solution can be suitably used.

[0050] In the heat treatment step, the heat treatment condition in the inert atmosphere is preferably 650°C or higher. The starting material heat-treated at 650°C or higher has sufficient near-infrared absorption ability and is efficient as heat ray shielding particles. The upper limit of the heat treatment temperature in the inert atmosphere is not particularly limited, but can be, for example, 1200°C or lower.

[0051] That is, the heat treatment conditions in the inert atmosphere can be set to 650° C. or higher and 1200° C. or lower.

[0052] The inert gas may be Ar or N ２ Inert gases such as the above can be used.

[0053] In the heat treatment step, when the heat treatment is performed in a reducing atmosphere, it is preferable to first heat treat the starting material in a reducing gas atmosphere at a temperature of 300°C or higher and 1000°C or lower, and then heat treat the starting material in an inert gas atmosphere at a temperature of 650°C or higher and 1200°C or lower.

[0054] The reducing gas used in the reducing atmosphere is not particularly limited, but may be H ２ The reducing gas is preferably H ２ When using the reducing atmosphere, the composition of the reducing atmosphere is, for example, Ar, N ２ Inert gas such as H ２ It is preferable that the volume ratio of H is 0.1% or more, and more preferably 0.2% or more. ２ If the volume ratio is 0.1% or more, the reduction can be efficiently carried out.

[0055] H in a reducing atmosphere ２The upper limit of the concentration is not particularly limited, but can be, for example, 100% or less in volume ratio. (Oxidation Treatment Step) In the oxidation treatment step, the composite tungsten oxide particles obtained in the heat treatment step can be oxidized in a mild environment.

[0056] The oxygen source gas used in the oxidation treatment step is not particularly limited, but is preferably one or more selected from oxygen, air, and water vapor. The concentration of the oxygen source may be selected appropriately depending on the heat treatment temperature and the amount of material to be heat-treated, and is not particularly limited. The heat treatment temperature may be selected appropriately depending on the amount of material to be heat-treated, and is not particularly limited, but is preferably 400°C or higher and 850°C or lower. (Other Steps) The method for producing composite tungsten oxide particles may also include a surface treatment step in which the surface is treated with at least one selected from silane compounds, titanium compounds, aluminum compounds, and zirconia compounds. Weather resistance can be improved by coating the surface of the composite tungsten oxide particles with a compound containing one or more selected from Si, Ti, Al, and Zr. (2) Cationic Surfactant: Because cationic surfactants are water-soluble, the composite tungsten oxide particles can be dispersed in water to form an aqueous dispersion.

[0057] The cationic surfactant may be a quaternary ammonium salt represented by the following formula (A):

[0058] R1 in the above formula (A) may be an alkyl group, and may be an alkyl group having 1 to 18 carbon atoms.

[0059] X1 in the above formula 1 － is not particularly limited as long as it is an anion, and may be, for example, one or more types selected from a hydroxyl group, a halogen group, and the like.

[0060] As the cationic surfactant, for example, one or more selected from ammonium chloride, ammonium hydroxide, ammonium fluoride, ammonium bromide, ammonium iodide, and the like can be used.

[0061] Examples of ammonium chloride include cetyltrimethylammonium chloride represented by the following formula (1), dodecyltrimethylammonium chloride represented by the formula (2), tetramethylammonium chloride represented by the formula (3), and decyltrimethylammonium chloride represented by the formula (4).

[0062]

[0063]

[0064]

[0065] Examples of ammonium hydroxide include tetramethylammonium hydroxide represented by the following formula (5) and cetyltrimethylammonium hydroxide represented by the following formula (6).

[0066]

[0067] Of these, the cationic surfactant is preferably ammonium chloride, and more preferably one or more selected from dodecyltrimethylammonium chloride and cetyltrimethylammonium chloride.

[0068] The amount of cationic surfactant added to the aqueous dispersion can be selected depending on the type of cationic surfactant and composite tungsten oxide particles, the specific surface area of ​​the composite tungsten oxide particles, and the like, and is not particularly limited. For example, the amount of cationic surfactant added can be 0.1 parts by mass or more and 100 parts by mass or less per 100 parts by mass of the composite tungsten oxide particles. That is, the aqueous dispersion of this embodiment can contain the cationic surfactant in a proportion of 0.1% by mass or more and 100% by mass or less, assuming that the content of the composite tungsten oxide particles is 100 parts by mass. By containing 0.1 parts by mass or more and 100 parts by mass or less of the cationic surfactant per 100 parts by mass of the composite tungsten oxide particles, the aqueous dispersion of this embodiment can achieve a particularly good dispersion state for the composite tungsten oxide particles.

[0069] According to the aqueous dispersion of this embodiment, the surfaces of the composite tungsten oxide particles are modified with a cationic surfactant, so that dispersibility can be improved even when water is used as a dispersion medium, and therefore the aqueous dispersion can be used to produce a masterbatch containing the composite tungsten oxide particles or a near-infrared shielding transparent resin molded product.

[0070] The aqueous dispersion of this embodiment does not require the addition of an organic solvent, so the content of the organic solvent can be reduced, for example, to 0.1 mass % or less, or even to 0 mass %. [Dispersed Powder] The dispersed powder of this embodiment can contain a cationic surfactant and composite tungsten oxide particles.

[0071] The dispersion powder of this embodiment can be prepared by evaporating water from the aqueous dispersion according to one aspect of the present disclosure. Therefore, the dispersion powder of this embodiment can be a dispersion powder of composite tungsten oxide particles whose particle surfaces have been modified with a cationic surfactant.

[0072] The cationic surfactant and the composite tungsten oxide particles have already been described in detail in relation to the aqueous dispersion, and therefore, a detailed description thereof will be omitted. As mentioned above, the composite tungsten oxide particles have a hexagonal crystal structure and are represented by the general formula M ｘ WO ｙ The element M in the general formula and the preferred ranges of x and y have already been explained, so further explanation will be omitted.

[0073] According to the dispersion powder of this embodiment, since it can be prepared using an aqueous dispersion using water as a solvent, it is possible to obtain a dispersion powder with a sufficiently reduced content of organic solvent. Furthermore, according to the dispersion powder of this embodiment, by adding water, it is possible to obtain an aqueous dispersion using water as a dispersion medium. That is, according to the dispersion powder of this embodiment, it is possible to obtain a dispersion in which composite tungsten oxide particles are dispersed in a dispersion medium without adding an organic solvent.

[0074] The dispersion powder of this embodiment can use the aqueous dispersion according to one aspect of the present disclosure as a raw material, and therefore the proportion of residual organic solvent can be reduced, for example, to 0.1 mass % or less, or even to 0 mass %.

[0075] The dispersed powder of this embodiment can be mixed with a solid medium to form a masterbatch composition or a near-infrared shielding transparent resin composition. Furthermore, a mixture of the dispersed powder of this embodiment and the solid medium can be kneaded and molded to form a masterbatch or a near-infrared shielding transparent resin. [Masterbatch Composition, Masterbatch] The masterbatch composition and masterbatch of this embodiment can contain the dispersed powder of this embodiment and a solid medium. That is, the masterbatch composition and masterbatch of this embodiment can contain a cationic surfactant, a solid medium, and composite tungsten oxide particles.

[0076] The masterbatch composition of this embodiment can be a mixture of a solid medium and composite tungsten oxide particles. In the masterbatch composition of this embodiment, the cationic surfactant can be disposed on the particle surface of the composite tungsten oxide particles, thereby modifying the particle surface of the composite tungsten oxide particles.

[0077] The masterbatch composition of this embodiment can be melt-kneaded and processed into, for example, pellets to produce a masterbatch. That is, the masterbatch of this embodiment is a molded product of the masterbatch composition of this embodiment. Therefore, like the masterbatch composition, the masterbatch of this embodiment can include the dispersed powder of this embodiment and a solid medium. In the masterbatch of this embodiment, the solid medium can be arranged so as to cover or contain the composite tungsten oxide particles, i.e., to encapsulate them. Furthermore, the acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic anhydride contained in the solid medium preferably covers, i.e., modifies, at least a portion of the surface of the composite tungsten oxide particles in the masterbatch of this embodiment. Therefore, the masterbatch composition of this embodiment can also contain an acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic anhydride as a surface-modifying resin.

[0078] A schematic diagram of the masterbatch of this embodiment is shown in Figure 2. As schematically shown in Figure 2, the masterbatch 20 of this embodiment can include, for example, composite tungsten oxide particles 21 and a solid medium 22, and the composite tungsten oxide particles 21 can be disposed in the solid medium 22. The composite tungsten oxide particles 21 are preferably dispersed in the solid medium 22.

[0079] Note that FIG. 2 is a schematic diagram, and the masterbatch of this embodiment is not limited to this form. For example, in FIG. 2, the composite tungsten oxide particles 21 are represented by circles and are depicted as spherical particles, but the shape of the composite tungsten oxide particles 21 is not limited to this form and can have any shape. The composite tungsten oxide particles 21 can have, for example, a surface coating. Furthermore, although not shown in FIG. 2, as already described, the masterbatch 20 of this embodiment further contains a cationic surfactant. The cationic surfactant can be disposed on the surface of the composite tungsten oxide particles 21 to modify the surface of the composite tungsten oxide particles 21. Furthermore, the masterbatch 20 of this embodiment can also contain other additives as necessary. (1) Regarding the masterbatch composition, the components contained in the masterbatch, the cationic surfactant, and the composite tungsten oxide particles, details and preferred properties have already been described in the aqueous dispersion, so description will be omitted here. Note that the composite tungsten oxide particles have a hexagonal crystal structure as already described and are represented by the general formula M ｘ WO ｙ The solid medium contained in the masterbatch composition and masterbatch of this embodiment will be described. (1-1) Solid Medium (1-1-1) Acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic acid anhydride In the masterbatch composition and masterbatch of this embodiment, the solid medium preferably contains an acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic acid anhydride. The solid medium may be composed of an acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic acid anhydride, and may further contain other resins as described below.

[0080] In the acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic anhydride, the polyolefin polymer or polyolefin copolymer constituting the backbone is acid-modified with maleic anhydride or carboxylic anhydride.

[0081] Examples of the polyolefin polymer constituting the backbone of the acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic anhydride include one or more types selected from polymers of one type of olefin, such as polyethylene, polypropylene, polybutene, and polyoctene, i.e., homopolymers.

[0082] In addition, the polyolefin copolymer constituting the skeleton of the acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic anhydride includes ethylene-propylene copolymer, ethylene-1-butene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-4-methyl-1-pentene copolymer, propylene-1-octene copolymer, propylene-1-decene copolymer, propylene-1,4-hexadiene copolymer, propylene-dicyclopentadiene copolymer, propylene-5-ethylidene-2-norbornene copolymer, propylene-2,5-norbornadiene copolymer, propylene-1,4-hexadiene ... The copolymer may be one or more selected from two-component copolymers such as 1-butene-5-ethylidene-2-norbornene copolymer, 1-octene-ethylene copolymer, 1-butene-propylene copolymer, 1-butene-1-hexene copolymer, 1-butene-4-methyl-1-pentene copolymer, 1-butene-1-octene copolymer, 1-butene-1-decene copolymer, 1-butene-1,4-hexadiene copolymer, 1-butene-dicyclopentadiene copolymer, 1-butene-5-ethylidene-2-norbornene copolymer, 1-butene-2,5-norbornadiene copolymer, and 1-butene-5-ethylidene-2-norbornene copolymer.

[0083] The polyolefin copolymer constituting the skeleton of the acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic anhydride is an ethylene-propylene-1-butene copolymer, an ethylene-propylene-1-hexene copolymer, an ethylene-propylene-1-octene copolymer, an ethylene-propylene-1-octene copolymer, an ethylene-propylene-1,4-hexadiene copolymer, an ethylene-propylene-1,4-hexadiene copolymer, an ethylene-propylene- Dicyclopentadiene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene-5-ethylidene-2-norbornene copolymer, ethylene-propylene-5-ethylidene-2-norbornene copolymer, ethylene-propylene-2,5-norbornadiene copolymer, ethylene-propylene-2,5-norbornadiene copolymer, ethylene-propylene-5-ethylidene-2-norbornene copolymer, ethylene-propylene-5-ethylidene-2 -norbornene copolymer, 1-butene / ethylene / propylene copolymer, 1-butene / ethylene / 1-hexene copolymer, 1-butene / ethylene / 1-octene copolymer, 1-butene / propylene / 1-octene copolymer, 1-butene / ethylene / 1,4-hexadiene copolymer, 1-butene / propylene / 1,4-hexadiene copolymer, 1-butene / ethylene / dicyclopentadiene copolymer, 1-butene / propylene / dicyclopentadiene copolymer, 1-butene / ethylene The copolymer may be one or more selected from multi-component copolymers such as ethylene / 5-ethylidene-2-norbornene copolymer, 1-butene / propylene / 5-ethylidene-2-norbornene copolymer, 1-butene / ethylene / 2,5-norbornadiene copolymer, 1-butene / propylene / 2,5-norbornadiene copolymer, 1-butene / ethylene / 5-ethylidene-2-norbornene copolymer, and 1-butene / propylene / 5-ethylidene-2-norbornene copolymer.

[0084] The polyolefin polymer or copolymer constituting the backbone of these acid-modified polyolefin polymers or copolymers with maleic anhydride or carboxylic anhydride is preferably one or more selected from polyethylene, polypropylene, polybutene, polyoctene, ethylene-propylene copolymer, ethylene-1-butene copolymer, 1-butene-propylene copolymer, ethylene-propylene-1-butene copolymer, and 1-octene-ethylene copolymer. (1-1-2) Polyethylene resin, polylactic acid resin, polypropylene resin. The masterbatch composition and masterbatch of this embodiment may also contain a resin other than the polyolefin polymer or copolymer acid-modified with maleic anhydride or carboxylic anhydride. When the masterbatch composition of this embodiment contains a resin other than the polyolefin polymer or copolymer acid-modified with maleic anhydride or carboxylic anhydride, it is preferable that composite tungsten oxide particles or the like are dispersed in the resin.

[0085] Considering workability during molding, resins other than the acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic anhydride are preferably thermoplastic resins. When the resin other than the acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic anhydride is a thermoplastic resin, one or more resins selected from polyethylene resin, polylactic acid resin, and polypropylene resin can be suitably used as the thermoplastic resin. Therefore, the masterbatch composition and the solid medium of the masterbatch of this embodiment can further contain one or more resins selected from polyethylene resin, polylactic acid resin, and polypropylene resin.

[0086] The polyethylene resin is not particularly limited, and examples thereof include one or more types selected from low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), and ethylene-vinyl acetate copolymer.

[0087] The polylactic acid resin is also not particularly limited, and examples thereof include polylactic acid resins whose constituent units are composed only of L-lactic acid, polylactic acid resins whose constituent units are composed only of D-lactic acid, and polylactic acid resins in which L-lactic acid and D-lactic acid are present in various ratios.

[0088] Furthermore, the polypropylene resin is not particularly limited. (1-2) Other Additives The masterbatch composition and masterbatch of this embodiment may further contain general additives.

[0089] For example, in order to adjust the color tone as needed, the masterbatch composition and masterbatch of the present embodiment may contain a dye or a pigment.

[0090] As the dye or pigment, a material generally used for coloring a thermoplastic resin can be used, and for example, one or more types selected from azo dyes, cyanine dyes, quinoline dyes, perylene dyes, carbon black, etc. can be used.

[0091] The masterbatch composition and masterbatch of the present embodiment may also contain one or more selected from the group consisting of hindered phenol-based, phosphorus-based, and other stabilizers, release agents, hydroxybenzophenone-based, salicylic acid-based, HALS-based, triazole-based, and triazine-based ultraviolet absorbers, coupling agents, surfactants, antistatic agents, and the like.

[0092] When the master batch composition or master batch of this embodiment contains additives such as dyes, pigments, stabilizers, or release agents, the amount of each additive is not particularly limited, and each additive can be added or contained in an amount that effectively exhibits a predetermined function. (2) Method for Producing Master Batch Composition The master batch composition of this embodiment can be produced according to flow 50 shown in Figure 5.

[0093] 5, the method for producing a masterbatch composition of this embodiment can include a dispersion preparation step S1, a surface modification step S2, a dispersed powder preparation step S3, and a masterbatch composition preparation step S4. Each step will be described below. (Dispersion Preparation Step) In the dispersion preparation step S1, composite tungsten oxide particles and water are mixed, and the composite tungsten oxide particles are pulverized and dispersed to prepare a dispersion.

[0094] As the composite tungsten oxide particles used in the dispersion preparation step, for example, the composite tungsten oxide particles described in the aqueous dispersion can be used, and therefore further description will be omitted. Note that, as already described, the composite tungsten oxide particles have a hexagonal crystal structure and are represented by the general formula M ｘ WO ｙ It can be expressed as:

[0095] The specific method for pulverizing and dispersing the composite tungsten oxide particles in the dispersion preparation step is not particularly limited, and for example, one or more methods selected from a bead mill, a ball mill, a sand mill, ultrasonic dispersion, etc. may be used. The dispersion preparation step may also be carried out in multiple stages, and the composite tungsten oxide particles may be pulverized and dispersed in multiple steps.

[0096] In the dispersion preparation step, the conditions for the pulverization and dispersion treatment can be selected so that the dispersed particle diameter of the composite tungsten oxide particles contained in, for example, the dispersed powder preparation step, the dispersed powder obtained after the masterbatch composition preparation step, or the masterbatch composition, is within a predetermined range. For example, as already explained, the dispersed particle diameter of the composite tungsten oxide particles is preferably 800 nm or less, more preferably 200 nm or less, and even more preferably 100 nm or less. Note that the dispersed particle diameter of the composite tungsten oxide particles may be, for example, 1 nm or more. (Surface Modification Step) In the surface modification step, a cationic surfactant is added to the dispersion obtained in the dispersion preparation step to modify the surfaces of the composite tungsten oxide particles.

[0097] The amount of cationic surfactant added is not particularly limited, but can be added in an amount of 0.1 parts by mass or more and 100 parts by mass or less per 100 parts by mass of the composite tungsten oxide particles.

[0098] In the surface modification step, after the cationic surfactant is added to the dispersion, the dispersion may be stirred as necessary.

[0099] By carrying out the surface modification step, it is possible to prepare an aqueous dispersion according to one embodiment of the present disclosure. (Dispersion Powder Preparation Step) In the dispersion powder preparation step, water is evaporated from the dispersion liquid after the surface modification step to prepare a dispersion powder.

[0100] The specific method for evaporating water from the dispersion in the dispersion powder preparation step is not particularly limited, and can be one or more methods selected from, for example, natural drying in which the dispersion is left in the atmosphere, heat drying using a dryer or the like, vacuum drying in a vacuum atmosphere, spray drying, etc. Note that, in the dispersion powder preparation step, a plurality of methods for evaporating water from the dispersion can be combined and carried out in multiple stages as necessary. (Masterbatch Composition Preparation Step) In the masterbatch composition preparation step, the masterbatch composition can be prepared by mixing the dispersion powder with a solid medium containing an acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic anhydride.

[0101] The solid medium may further contain one or more resins selected from polyethylene resin, polylactic acid resin, and polypropylene resin.

[0102] Examples of mixers that can be suitably used for mixing include one or more mixers selected from ribbon blenders, tumblers, Nauta mixers, Henschel mixers, super mixers, planetary mixers, and the like.

[0103] If an aqueous dispersion is prepared in advance, the method for producing a masterbatch can start with the dispersed powder preparation step. Alternatively, if a dispersed powder is prepared in advance, the method for producing a masterbatch can start with the masterbatch composition preparation step. (3) Masterbatch The masterbatch of this embodiment can be prepared by melt-kneading the masterbatch composition using a melt-kneader and processing it into pellets.

[0104] The temperature during melt-kneading is maintained at a temperature at which the solid medium used does not decompose.

[0105] Examples of kneaders that can be suitably used for melt-kneading include single-screw extruders and twin-screw extruders.

[0106] Masterbatch pellets can be obtained by the most common method of cutting melt-extruded strands. Therefore, the pellets can be cylindrical or prismatic in shape. Alternatively, a so-called hot-cut method can be used, in which the melt-extruded material is directly cut. In this case, the masterbatch generally has a shape close to spherical.

[0107] The masterbatch of the present embodiment can have any form or shape, although it is preferable that the masterbatch has the same or similar size and shape as the thermoplastic resin used to dilute the masterbatch when molding the near-infrared shielding transparent resin molded article.

[0108]

[0041] For the masterbatch composition or masterbatch of this embodiment, the aqueous dispersion or dispersed powder according to one aspect of the present disclosure can be used as a raw material, and therefore the content of the organic solvent can be reduced, and for example, the content of the residual organic solvent can be reduced to 0.1 mass % or less, or even 0 mass %. [Near-infrared shielding transparent resin molded product, near-infrared shielding transparent laminate] Next, the near-infrared shielding transparent resin molded product of this embodiment will be described.

[0109] The near-infrared shielding transparent resin molded article of the present embodiment is a molded article containing the masterbatch. Since the masterbatch is a molded article of the masterbatch composition according to one aspect of the present disclosure, the near-infrared shielding transparent resin molded article of the present embodiment can also be said to be a molded article containing the masterbatch composition.

[0110] The near-infrared shielding transparent resin molded product of the present embodiment can also be produced by molding the masterbatch according to one aspect of the present disclosure. That is, the near-infrared shielding transparent resin molded product of the present embodiment can also be a molded product made of the masterbatch.

[0111] The near-infrared shielding transparent resin molded product of this embodiment can also contain a masterbatch and a thermoplastic resin. The thermoplastic resin is a resin for diluting the masterbatch and adjusting the concentration of the composite tungsten oxide particles contained therein. Therefore, it is preferable that the thermoplastic resin is the same type of resin as the solid medium contained in the masterbatch, or a different type of resin that is compatible with the solid medium. In other words, it is preferable that the thermoplastic resin is a resin that can be mixed with the masterbatch without separation when kneaded.

[0112] The solid medium contained in the masterbatch may consist solely of an acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic anhydride, or may further contain a thermoplastic resin such as one or more resins selected from polyethylene resin, polylactic acid resin, and polypropylene resin. Therefore, the thermoplastic resin is preferably the same type of resin as, for example, either the acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic anhydride contained in the masterbatch or one or more resins selected from polyethylene resin, polylactic acid resin, and polypropylene resin, or a different type of resin that is compatible with the acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic anhydride contained in the masterbatch and one or more resins selected from polyethylene resin, polylactic acid resin, and polypropylene resin.

[0113] The near-infrared shielding transparent resin molded article of this embodiment can be obtained by molding the masterbatch or a mixture of the masterbatch and a thermoplastic resin into a predetermined shape.

[0114] In the near-infrared shielding transparent resin molding of this embodiment, the composite tungsten oxide particles, which are near-infrared shielding particles, may be sufficiently dispersed in the near-infrared shielding transparent resin molding, so that the near-infrared shielding transparent resin molding of this embodiment can ensure good visible light transmittance and exhibit excellent near-infrared shielding function.

[0115] The near-infrared shielding transparent resin molding of this embodiment can be molded into any shape as needed, for example, a flat shape or a curved shape.

[0116] The thickness of the near-infrared shielding transparent resin molding of this embodiment is not particularly limited and can be adjusted to any thickness as needed. Furthermore, a resin sheet formed into a flat shape can also be formed into any shape, such as a curved or spherical shape, by post-processing.

[0117] The near-infrared shielding transparent resin molded article of this embodiment can be molded by any method such as injection molding, extrusion molding, compression molding, rotational molding, etc. In particular, the near-infrared shielding transparent resin molded article of this embodiment can be molded by injection molding or extrusion molding.

[0118] Examples of methods for obtaining plate- or film-shaped molded products by extrusion include a method in which a molten thermoplastic resin is extruded using an extruder such as a T-die and taken up while being cooled by a cooling roll.

[0119] The near-infrared shielding transparent resin molding of this embodiment may be used by itself as a structural material for window glass, arcades, and the like.

[0120] Furthermore, the near-infrared shielding transparent resin molding of the present embodiment can be laminated by any method to another transparent molding such as inorganic glass, resin glass, or resin film to form an integrated near-infrared shielding transparent laminate, which can be used as a structural material.

[0121] That is, the near-infrared shielding transparent laminate of the present embodiment can have a transparent molded body and a near-infrared shielding transparent resin molded body according to one aspect of the present disclosure laminated on the transparent molded body.

[0122] 3, which is a cross-sectional schematic view along the lamination direction of the transparent molded body and the near-infrared shielding transparent resin molded body, a near-infrared shielding transparent laminate 30 can have a transparent molded body 31 and a near-infrared shielding transparent resin molded body 32. The near-infrared shielding transparent resin molded body 32 can be disposed on at least one surface 31A of the transparent molded body 31.

[0123] The near-infrared shielding transparent laminate of the present embodiment is not limited to the form shown in Fig. 3. For example, as shown in Fig. 4, which is a cross-sectional schematic view along the lamination direction of a transparent molded body and a near-infrared shielding transparent resin molded body, a near-infrared shielding transparent laminate 40 may have a plurality of transparent molded bodies 411, 412 and a near-infrared shielding transparent resin molded body 42. The near-infrared shielding transparent resin molded body 42, which is an intermediate film, can be disposed between the plurality of transparent molded bodies 411, 412. Although Fig. 4 shows an example in which two transparent molded bodies 411, 412 are provided, the present invention is not limited to this form.

[0124] The shape of the transparent molded body used in the near-infrared shielding transparent laminate is not particularly limited and can be selected depending on the shape required for the near-infrared shielding transparent laminate. The shape of the transparent molded body may be, for example, a board shape, a sheet shape, or a film shape, as shown in Figures 3 and 4. When the near-infrared shielding transparent laminate has a plurality of transparent molded bodies, the thicknesses and shapes of the transparent molded bodies may be different.

[0125] The material of the transparent molded body is not particularly limited, but it is preferable to use one or more types selected from glass, a resin sheet, a resin board, a resin film, etc. The transparent molded body is a material that transmits light in the visible light region, and the degree of transmittance of light in the visible light region can be selected as desired depending on the application of the near-infrared shielding transparent laminate, etc.

[0126] When the transparent molded body includes one or more types selected from a resin sheet, a resin board, a resin film, etc., the resin to be used is not particularly limited and can be selected depending on the required properties such as the surface condition and durability of the sheet, board, or film. Examples of the resin include one or more selected from polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, polycarbonate polymers, acrylic polymers such as polymethyl methacrylate, styrene polymers such as polystyrene and acrylonitrile-styrene copolymers, olefin polymers such as polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, and ethylene-propylene copolymers, vinyl chloride polymers, amide polymers such as aromatic polyamides, imide polymers, sulfone polymers, polyethersulfone polymers, polyetheretherketone polymers, polyphenylene sulfide polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers, arylate polymers, polyoxymethylene polymers, epoxy polymers, and transparent polymers such as various binary and ternary copolymers, graft copolymers, and blends thereof. In particular, polyester-based biaxially oriented films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene-2,6-naphthalate are preferred in terms of mechanical properties, optical properties, heat resistance, and cost efficiency. The polyester-based biaxially oriented film may be a copolymer polyester.

[0127] The transparent molded body may contain various additives, such as particles having an infrared absorbing function, as needed.

[0128] The method for producing the near-infrared shielding transparent laminate of the present embodiment is not particularly limited. For example, a near-infrared shielding transparent resin molded product previously formed into a film shape can be laminated and integrated with an inorganic glass transparent molded product by a thermal lamination method to obtain a near-infrared shielding transparent laminate having a near-infrared shielding function and a shatterproof function.

[0129] It is also possible to obtain a near-infrared shielding transparent laminate by laminating and integrating another transparent molded body simultaneously with molding of the near-infrared shielding transparent resin molded body by a thermal lamination method, a co-extrusion method, a press molding method, an injection molding method, etc. The near-infrared shielding transparent laminate can be used as a more useful structural material by effectively utilizing the advantages of each molded body while complementing each other's disadvantages.

[0130] The near-infrared shielding transparent resin molded article of the present embodiment and the near-infrared shielding transparent laminate of the present embodiment described above have a molded article containing the masterbatch according to one aspect of the present disclosure.

[0131] A masterbatch according to one aspect of the present disclosure includes a cationic surfactant, a solid medium containing a polyolefin polymer or copolymer modified with maleic anhydride or carboxylic anhydride, and composite tungsten oxide particles. Therefore, when molding the masterbatch, aggregation of the composite tungsten oxide particles can be prevented. As a result, the near-infrared shielding transparent resin molded product and the near-infrared shielding transparent laminate of this embodiment have good light transmittance in the visible light region and can exhibit excellent near-infrared shielding properties.

[0132] The near-infrared shielding transparent resin molded product of the present embodiment and the near-infrared shielding transparent laminate of the present embodiment can use the aqueous dispersion or dispersed powder according to one aspect of the present disclosure as a raw material, and therefore the content of organic solvent can be reduced. In the near-infrared shielding transparent resin molded product of the present embodiment and the near-infrared shielding transparent laminate of the present embodiment, the content of residual organic solvent can be reduced to, for example, 0.1 mass % or less, and can also be 0 mass %.

[0133] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. 1. Evaluation Method In the following examples and comparative examples, the visible light transmittance and solar radiation transmittance of the near-infrared shielding transparent laminate were measured using a spectrophotometer U-4000 manufactured by Hitachi, Ltd. The visible light transmittance and solar radiation transmittance were calculated from the measured spectral data in accordance with JIS R 3106 (2019). The solar radiation transmittance is an index indicating near-infrared shielding performance. The evaluation results are shown in the "Optical Properties" column in Table 1. 2. Description of Experimental Conditions and Procedures [Example 1] (1) Preparation of Composite Tungsten Oxide Particles (Heat Treatment Step) Starting materials to be subjected to the heat treatment step were prepared according to the following procedure.

[0134] 900 g of water was added to Cs, which is the raw material for element M. ２ CO ３ 591.8 g of tungsten was dissolved in the solution containing the element M raw material. ２ WO ４ 2470 g of the mixture was added and dried in a vacuum dryer with stirring to obtain a starting material in the form of a dry powder.

[0135] The resulting dry powder was first ２ 5% H by volume with gas as carrier ２ The mixture was heated while gas was fed, and fired in a reducing atmosphere at a temperature of 800° C. for 0.5 hours.

[0136] Next, N ２ The mixture was then fired at 800°C for 1 hour in an inert gas atmosphere to obtain particles A. Chemical analysis revealed that the composition of particles A, which are composite tungsten oxide particles, was Cs ０．３３ WO ２．４５ Furthermore, as a result of powder X-ray diffraction, it was confirmed that particle A was a hexagonal Cs ０．３ WO ３ The diffraction pattern of the masterbatch composition was confirmed to be hexagonal, as shown in Fig. 2. (2) Preparation of Masterbatch Composition (2-1) Dispersion Preparation Step Next, 12.5 mass% of particles A and 87.5 mass% of water were weighed out, and the particles were pulverized and dispersed for 2.5 hours using a media agitation mill containing 0.3 mm diameter ZrO beads to prepare a dispersion containing composite tungsten oxide particles.

[0137] The dispersed particle diameter of the composite tungsten oxide particles in the obtained dispersion was measured using a particle size analyzer (ELS-8000 manufactured by Otsuka Electronics Co., Ltd.) based on dynamic light scattering, and was found to be 20 nm. The dispersed particle diameter was also measured using the same device in other examples. (2-2) Surface Modification Step: Cetyltrimethylammonium chloride, a cationic surfactant, was added to the dispersion obtained in the dispersion preparation step in a ratio of 1.25 mass% relative to the composite tungsten oxide particles, and the mixture was held with stirring for 6 hours. By the above operation, an aqueous dispersion containing composite tungsten oxide particles surface-modified with a cationic surfactant was obtained (hereinafter also referred to as "Liquid A"). (2-3) Dispersed Powder Preparation Step: Water was removed from Liquid A, the aqueous dispersion obtained in the surface modification step, using a spray dryer to obtain a dispersed powder of composite tungsten oxide particles (hereinafter also referred to as "Dry Powder A").

[0138] It has been confirmed that the composite tungsten oxide particles of dry powder A, which is the dispersion powder prepared in this example, and the dispersion powders prepared and used in the other examples below, can be dispersed in water by adding water, and become an aqueous dispersion again. (2-4) Masterbatch Composition Preparation Step Dry powder A and a powder of maleic anhydride-modified ethylene-1-butene copolymer were uniformly mixed using a blender so that the composite tungsten oxide particles accounted for 10% by mass of the powder of maleic anhydride-modified ethylene-1-butene copolymer, thereby preparing a masterbatch composition.

[0139] The maleic anhydride-modified ethylene-1-butene copolymer is referred to as "ME-B copolymer" in the "Acid-modified polyolefin polymer (copolymer)" column in Table 1. (3) Production of masterbatch and near-infrared shielding transparent resin molded product The prepared masterbatch composition was melt-kneaded at 180°C using a twin-screw extruder, and the extruded strands were cut into pellets using a pelletizer to obtain a masterbatch for a near-infrared shielding transparent resin molded product (hereinafter also referred to as "masterbatch A").

[0140] The obtained masterbatch A was hot-pressed at 130° C. to obtain a near-infrared shielding transparent resin film A having a thickness of 43 μm, which was a near-infrared shielding transparent resin molded article.

[0141] In the column of "Near-infrared shielding transparent resin molding" in Table 1, the column "Concentration of composite tungsten oxide particle" indicates the concentration of the composite tungsten oxide particles contained in the near-infrared shielding transparent resin molding, and the column "Thickness" indicates the thickness of the near-infrared shielding transparent resin molding.

[0142] The optical properties of the near-infrared shielding transparent resin film A according to Example 1 were measured, and as shown in Table 1, the solar radiation transmittance was 18.5% when the visible light transmittance was 47.8%.

[0143] Example 2 In the surface modification step, cetyltrimethylammonium chloride, a cationic surfactant, was added in an amount of 3.75% by mass relative to the composite tungsten oxide particles. A water dispersion, a dispersed powder, a masterbatch composition, a masterbatch, and a near-infrared shielding transparent resin film B, which was a near-infrared shielding transparent resin molded product, were obtained under the same conditions and procedures as in Example 1, except for the above.

[0144] The optical properties of the near-infrared shielding transparent resin film B according to Example 2 were measured, and as shown in Table 1, the solar radiation transmittance was 18.2% when the visible light transmittance was 47.6%.

[0145] Example 3 In the surface modification step, cetyltrimethylammonium chloride, a cationic surfactant, was added in an amount of 6.25% by mass relative to the composite tungsten oxide particles. A water dispersion, a dispersed powder, a masterbatch composition, a masterbatch, and a near-infrared shielding transparent resin film C, which was a near-infrared shielding transparent resin molded product, were obtained under the same conditions and procedures as in Example 1, except for the above.

[0146] The optical properties of the near-infrared shielding transparent resin film C according to Example 3 were measured, and as shown in Table 1, the solar radiation transmittance was 17.1% when the visible light transmittance was 47.4%.

[0147] [Example 4] In the surface modification step, dodecyltrimethylammonium chloride was used as the cationic surfactant instead of cetyltrimethylammonium chloride. Except for the above, an aqueous dispersion, a dispersed powder, a masterbatch composition, a masterbatch, and a near-infrared shielding transparent resin film D, which is a near-infrared shielding transparent resin molded product, were obtained under the same conditions and procedures as in Example 1.

[0148] The optical properties of the near-infrared shielding transparent resin film D according to Example 4 were measured, and as shown in Table 1, the solar radiation transmittance was 18.7% when the visible light transmittance was 47.9%.

[0149] [Example 5] The masterbatch A obtained in Example 1 was diluted with LDPE (low-density polyethylene) resin, which is a thermoplastic resin, to set the composite tungsten oxide particle concentration to 1 mass %. When the masterbatch was diluted with a thermoplastic resin, the type of thermoplastic resin used for dilution is listed in the thermoplastic resin column in Table 1.

[0150] Then, under the same conditions and procedures as in Example 1, except that the diluted masterbatch was used instead of the masterbatch A, a near-infrared shielding transparent resin film E, which was a near-infrared shielding transparent resin molding, was obtained.

[0151] The optical properties of the near-infrared shielding transparent resin film E according to Example 5 were measured, and as shown in Table 1, the solar radiation transmittance was 55.3% when the visible light transmittance was 80.8%.

[0152] Example 6 The master batch A obtained in Example 1 was diluted with HDPE (high density polyethylene) resin, which is a thermoplastic resin, to make the concentration of composite tungsten oxide particles 1 mass %.

[0153] Then, under the same conditions and procedures as in Example 1, except that the diluted masterbatch was used instead of masterbatch A, a near-infrared shielding transparent resin film F, which was a near-infrared shielding transparent resin molding, was obtained.

[0154] When the optical properties of the near-infrared shielding transparent resin film F according to Example 6 were evaluated, as shown in Table 1, the solar radiation transmittance was 54.9% when the visible light transmittance was 80.3%.

[0155] Example 7 The master batch A obtained in Example 1 was diluted with LLDPE (linear low density polyethylene) resin, which is a thermoplastic resin, to make the concentration of composite tungsten oxide particles 1 mass %.

[0156] Then, under the same conditions and procedures as in Example 1, except that the diluted masterbatch was used instead of masterbatch A, a near-infrared shielding transparent resin film G, which was a near-infrared shielding transparent resin molding, was obtained.

[0157] When the optical properties of the near-infrared shielding transparent resin film G according to Example 7 were evaluated, as shown in Table 1, the solar radiation transmittance was 55.2% when the visible light transmittance was 80.7%.

[0158] [Example 8] In the dispersion liquid preparation step, 20 mass % of particles A and 80 mass % of water were weighed, and pulverization and dispersion treatment were carried out for 5 hours using a bead mill containing 0.3 mm diameter ZrO2 beads, thereby preparing a dispersion liquid containing composite tungsten oxide particles.

[0159] Here, the dispersed particle diameter of the composite tungsten oxide particles in the dispersion liquid was measured and found to be 20 nm.

[0160] In the surface modification step, a cationic surfactant, cetyltrimethylammonium chloride, was added to the dispersion obtained in the dispersion preparation step in an amount of 2.0 mass % relative to the composite tungsten oxide particles, and the mixture was maintained with stirring for 10 hours. This procedure yielded an aqueous dispersion containing composite tungsten oxide particles surface-modified with the cationic surfactant (hereinafter also referred to as "Liquid H").

[0161] In the dispersed powder preparation step, water was removed from Liquid H, which was the aqueous dispersion obtained in the surface modification step, using a spray dryer to obtain a dispersed powder of dry powder of composite tungsten oxide particles (hereinafter also referred to as "dry powder H").

[0162] In the masterbatch composition preparation step, the dry powder H and the maleic anhydride-modified ethylene-1-butene copolymer powder were uniformly mixed using a blender to prepare a masterbatch composition. In the masterbatch composition preparation step, the maleic anhydride-modified ethylene-1-butene copolymer powder was added and mixed so that the composite tungsten oxide particles accounted for 10 mass % of the maleic anhydride-modified ethylene-1-butene copolymer powder.

[0163] The prepared masterbatch composition was melt-kneaded at 180°C using a twin-screw extruder, and the extruded strands were cut into pellets using a pelletizer, thereby obtaining a masterbatch for a near-infrared shielding transparent resin molding (hereinafter also referred to as "masterbatch H").

[0164] The obtained masterbatch H was diluted with LDPE (low density polyethylene) resin, which is a thermoplastic resin, to make the concentration of composite tungsten oxide particles 1 mass %.

[0165] Then, under the same conditions and procedures as in Example 1, except that the diluted masterbatch was used instead of the masterbatch A, a near-infrared shielding transparent resin film H, which was a near-infrared shielding transparent resin molding, was obtained.

[0166] The optical properties of the near-infrared shielding transparent resin film H according to Example 8 were measured, and as shown in Table 1, the solar radiation transmittance was 56.0% when the visible light transmittance was 80.6%.

[0167] Example 9 In the masterbatch composition preparation step, a powder of maleic anhydride-modified ethylene-1-butene copolymer was added and mixed so that the composite tungsten oxide particles accounted for 15 mass % of the powder of maleic anhydride-modified ethylene-1-butene copolymer. A masterbatch for a near-infrared shielding transparent resin molding was obtained under the same conditions as in Example 8, except for the above points (hereinafter also referred to as "masterbatch I").

[0168] The obtained master batch I was diluted with LDPE (low density polyethylene) resin, which is a thermoplastic resin, to make the concentration of composite tungsten oxide particles 1% by mass.

[0169] Then, under the same conditions and procedures as in Example 1, except that the diluted masterbatch was used instead of masterbatch A, a near-infrared shielding transparent resin film I, which was a near-infrared shielding transparent resin molding, was obtained.

[0170] The optical properties of the near-infrared shielding transparent resin film I according to Example 9 were measured, and as shown in Table 1, the solar radiation transmittance was 57.9% when the visible light transmittance was 81.3%.

[0171] Example 10 In the masterbatch composition preparation step, a powder of maleic anhydride-modified ethylene-1-butene copolymer was added and mixed so that the composite tungsten oxide particles accounted for 20 mass % of the powder of maleic anhydride-modified ethylene-1-butene copolymer. A masterbatch for a near-infrared shielding transparent resin molding was obtained under the same conditions as in Example 8, except for the above points (hereinafter also referred to as "masterbatch J").

[0172] The obtained master batch J was diluted with LDPE (low density polyethylene) resin, which is a thermoplastic resin, to make the concentration of composite tungsten oxide particles 1 mass %.

[0173] Then, under the same conditions and procedures as in Example 1, except that the diluted masterbatch was used instead of the masterbatch A, a near-infrared shielding transparent resin film J, which was a near-infrared shielding transparent resin molding, was obtained.

[0174] The optical properties of the near-infrared shielding transparent resin film J according to Example 10 were measured, and as shown in Table 1, the solar radiation transmittance was 54.2% when the visible light transmittance was 80.3%.

[0175] Example 11 (1) Preparation of Composite Tungsten Oxide Particles (Heat Treatment Step) Starting materials to be subjected to the heat treatment step were prepared according to the following procedure.

[0176] 16.5 g of water was added to the raw material for element M, Cs ２ CO ３ 8.8 g of tungsten was dissolved in the solution containing the element M raw material. ２ WO ４ The mixture was added to 50 g of the starting material and dried in a vacuum dryer while stirring to obtain a dry powder of the starting material.

[0177] The resulting dry powder was first ２ 5% H by volume with gas as carrier ２ The mixture was fired in a gas atmosphere at a temperature of 570° C. for 1 hour.

[0178] Next, N ２ The mixture was fired at 800° C. for 1 hour in an air atmosphere with a volume ratio of 1% using gas as a carrier.

[0179] Furthermore, N ２ The mixture was fired in a gas atmosphere at 820° C. for 0.5 hours to obtain particles K.

[0180] Chemical analysis revealed that the composition of particle K, a composite tungsten oxide particle, was Cs ０．２７ WO ２．８６ Furthermore, as a result of powder X-ray diffraction, it was confirmed that particle K was a hexagonal Cs ０．３ WO ３ Since the diffraction pattern matches that of the sample shown in Fig. 1, it was confirmed that the sample has a hexagonal crystal structure.

[0181] Then, under the same conditions and procedures as in Example 1, except that particles K were used, the aqueous dispersion, the dispersed powder, the masterbatch composition, the masterbatch, and the near-infrared shielding transparent resin molded product, that is, near-infrared shielding transparent resin film K, were produced.

[0182] The optical properties of the near-infrared shielding transparent resin film K according to Example 11 were measured, and as shown in Table 1, the solar radiation transmittance was 18.9% when the visible light transmittance was 48.3%.

[0183] Example 12 (1) Preparation of Composite Tungsten Oxide Particles Composite tungsten oxide particles were produced by the following procedure.

[0184] A hybrid plasma reactor was used, in which DC plasma and high-frequency plasma were superimposed. The reaction system was evacuated to approximately 0.1 Pa (approximately 0.001 torr) using a vacuum exhaust device, and then completely replaced with argon gas to create a flow system at 1 atmosphere. Argon gas was then flowed through the plasma generation gas supply port at a rate of 8 L / min to generate DC plasma. The DC power input was 6 kW.

[0185] Furthermore, argon gas (40 L / min) and hydrogen gas (3 L / min) were spirally flowed along the inner wall of the water-cooled quartz tube from the sheath gas supply port to generate high-frequency plasma and protect the quartz tube, generating high-frequency plasma. The high-frequency power input was 45 kW. After generating the hybrid plasma in this manner, the starting material (the dry powder obtained in Example 1) was supplied into the plasma at a rate of 2 g / min from the raw material powder supply device using a mixed gas of argon gas (3 L / min) and oxygen gas (0.15 L / min) as a carrier gas.

[0186] As a result, the raw material was instantly vaporized, condensed in the plasma tail flame, and pulverized to obtain particles L.

[0187] Chemical analysis of particle L shows that its composition is Cs ０．３２ WO ３．１６ As a result of powder X-ray diffraction, it was found that the hexagonal Cs ０．３ WO ３ Since the diffraction pattern matches that of the sample shown in Fig. 1, it was confirmed that the sample has a hexagonal crystal structure.

[0188] Except for using particles L, the aqueous dispersion, the dispersed powder, the masterbatch composition, the masterbatch, and the near-infrared shielding transparent resin molded product, that is, near-infrared shielding transparent resin film L, were produced under the same conditions and procedures as in Example 1.

[0189] The optical properties of the near-infrared shielding transparent resin film L according to Example 12 were measured, and as shown in Table 1, the solar radiation transmittance was 25.5% when the visible light transmittance was 50.7%.

[0190] [Example 13] When preparing the starting material to be subjected to the heat treatment step in order to prepare composite tungsten oxide particles, K was used as the element M raw material. ２ CO ３ Using H as a tungsten raw material ２ WO ４ Then, K ２ CO ３ and H ２ WO ４ were weighed and mixed so that the K / W (molar ratio) was 0.33 to prepare a starting material.

[0191] Composite tungsten oxide particles, an aqueous dispersion, a dispersed powder, a masterbatch composition, a masterbatch, and a near-infrared shielding transparent resin molded product, that is, a near-infrared shielding transparent resin film M, were produced under the same conditions and procedures as in Example 1, except that the above starting materials were used.

[0192] The composition of the composite tungsten oxide particles M obtained in this example is K ０．３３ WO ２．４５ It was confirmed that the particles M were hexagonal K crystals. ０．３ WO ３ Since the diffraction pattern matches that of the sample shown in Fig. 1, it was confirmed that the sample has a hexagonal crystal structure.

[0193] When the optical properties of the near-infrared shielding transparent resin film M according to Example 13 were measured, the solar radiation transmittance was 22.0% when the visible light transmittance was 46.3%, as shown in Table 1. [Example 14] When preparing the starting material to be subjected to the heat treatment step for preparing the composite tungsten oxide particles, Rb was used as the element M raw material. ２ CO ３ Using H as a tungsten raw material ２ WO ４ Then, Rb ２ CO ３ and H ２ WO ４ These were weighed and mixed so that the molar ratio of Rb / W was 0.33 to prepare a starting material.

[0194] Composite tungsten oxide particles, an aqueous dispersion, a dispersed powder, a masterbatch composition, a masterbatch, and a near-infrared shielding transparent resin molded product, that is, a near-infrared shielding transparent resin film N, were produced under the same conditions and procedures as in Example 1, except that the above starting materials were used.

[0195] The composition of the composite tungsten oxide particles N obtained in this example is Rb ０．３３ WO ２．４５ Furthermore, as a result of powder X-ray diffraction, it was confirmed that the particles N were hexagonal Rb ０．３３ WO ３ Since the diffraction pattern matches that of the sample shown in Fig. 1, it was confirmed that the sample has a hexagonal crystal structure.

[0196] When the optical properties of the near-infrared shielding transparent resin film N according to Example 14 were measured, the solar radiation transmittance was 21.8% when the visible light transmittance was 46.3%, as shown in Table 1. [Example 15] When preparing starting materials to be subjected to a heat treatment step to prepare composite tungsten oxide particles, BaCO was used as the element M raw material. ３ Using H as a tungsten raw material ２ WO ４ Then, BaCO ３ and H ２ WO ４ The above were weighed and mixed so that the Ba / W (molar ratio) was 0.33 to prepare a starting material.

[0197] Composite tungsten oxide particles, an aqueous dispersion, a dispersed powder, a masterbatch composition, a masterbatch, and a near-infrared shielding transparent resin molded product, that is, a near-infrared shielding transparent resin film O, were produced under the same conditions and procedures as in Example 1, except that the above starting materials were used.

[0198] The composition of the composite tungsten oxide particles O obtained in this example is Ba. ０．３３ WO ２．４５ Furthermore, as a result of powder X-ray diffraction, it was confirmed that the particles O were hexagonal Ba. ０．２１ WO ３ Since the diffraction pattern matches that of the sample shown in Fig. 1, it was confirmed that the sample has a hexagonal crystal structure.

[0199] The optical properties of the near-infrared shielding transparent resin film O according to Example 15 were measured, and as shown in Table 1, the solar radiation transmittance was 29.2% when the visible light transmittance was 51.8%.

[0200] Example 16 In the masterbatch composition preparation step, maleic anhydride-modified polypropylene was used in place of the maleic anhydride-modified ethylene / 1-butene copolymer.

[0201] In the column of "acid-modified polyolefin polymer (copolymer)" in Table 1, the maleic anhydride-modified polypropylene is referred to as "MP polymer."

[0202] Except for the above points, the masterbatch composition, the masterbatch, and the near-infrared shielding transparent resin molded article, that is, the near-infrared shielding transparent resin film P, were produced under the same conditions and procedures as in Example 10.

[0203] The optical properties of the near-infrared shielding transparent resin film P according to Example 16 were measured, and as shown in Table 1, the solar radiation transmittance was 55.5% when the visible light transmittance was 80.9%.

[0204] [Example 17] The masterbatch J obtained in Example 10 was diluted with polylactic acid resin to a composite tungsten oxide particle concentration of 1 mass %. That is, a diluted masterbatch was prepared under the same conditions as in Example 10, except that polylactic acid resin was used instead of LDPE as the resin for diluting masterbatch J.

[0205] Then, under the same conditions and procedures as in Example 1, except that the diluted masterbatch was used instead of masterbatch A, a near-infrared shielding transparent resin film Q, which was a near-infrared shielding transparent resin molding, was obtained.

[0206] The optical properties of the near-infrared shielding transparent resin film Q according to Example 17 were measured, and as shown in Table 1, the solar radiation transmittance was 54.0% when the visible light transmittance was 79.8%.

[0207] [Example 18] The masterbatch J obtained in Example 10 was diluted with polypropylene resin to a composite tungsten oxide particle concentration of 1 mass %. That is, a diluted masterbatch was prepared under the same conditions as in Example 10, except that polypropylene resin was used instead of LDPE as the resin for diluting masterbatch J.

[0208] Then, under the same conditions and procedures as in Example 1, except that the diluted masterbatch was used instead of masterbatch A, a near-infrared shielding transparent resin film R, which was a near-infrared shielding transparent resin molding, was obtained.

[0209] The optical properties of the near-infrared shielding transparent resin film R according to Example 18 were measured, and the solar transmittance was 54.1% when the visible light transmittance was 80.1%, as shown in Table 1. [Example 19] In the masterbatch composition preparation step, a carboxylic acid anhydride-modified polypropylene was used in place of the maleic anhydride-modified ethylene / 1-butene copolymer.

[0210] In the column of "acid-modified polyolefin polymer (copolymer)" in Table 1, the carboxylic acid anhydride-modified polypropylene is referred to as "KP polymer."

[0211] Except for the above points, the masterbatch composition, the masterbatch, and the near-infrared shielding transparent resin molded article, that is, the near-infrared shielding transparent resin film S, were produced under the same conditions and procedures as in Example 10.

[0212] The optical properties of the near-infrared shielding transparent resin film S according to Example 19 were measured, and as shown in Table 1, the solar radiation transmittance was 54.3% when the visible light transmittance was 80.5%.

[0213] Comparative Example 1 An aqueous dispersion, a dispersed powder, a masterbatch composition, and a masterbatch were produced under the same conditions and procedures as in Example 1, except that cetyltrimethylammonium chloride was not added in the surface modification step.

[0214] The visual appearance of the master batch obtained in Comparative Example 1 showed significant color unevenness, and the dispersibility of the composite tungsten oxide particles was determined to be poor, so no near-infrared shielding transparent resin molded article was produced.

[0215] Comparative Example 2 In the surface modification step, a long-chain alkylbenzene sulfonic acid, an anionic surfactant, was used instead of cetyltrimethylammonium chloride. Except for the above, an aqueous dispersion, a dispersed powder, a masterbatch composition, and a masterbatch were produced under the same conditions and procedures as in Example 1.

[0216] The visual appearance of the master batch obtained in Comparative Example 2 was found to be significantly uneven in color, and the dispersibility of the composite tungsten oxide particles was determined to be poor, so no near-infrared shielding transparent resin molded article was produced.

[0217] As shown in Table 1, the near-infrared shielding transparent resin sheets, which were the near-infrared shielding transparent resin molded articles of Examples 1 to 19, had a visible light transmittance of 46% or more and a solar radiation transmittance of 65% or less. On the other hand, the masterbatches of Comparative Examples 1 and 2 had noticeable color unevenness in their visual appearance, and the dispersibility of the composite tungsten oxide particles was determined to be poor, so no near-infrared shielding transparent resin molded articles were produced.

[0218] This application claims priority based on Japanese Patent Application No. 2024-145981 filed with the Japan Patent Office on August 27, 2024, Japanese Patent Application No. 2024-205795 filed with the Japan Patent Office on November 26, 2024, and Japanese Patent Application No. 2025-082083 filed with the Japan Patent Office on May 15, 2025, and the entire contents of Japanese Patent Application Nos. 2024-145981, 2024-205795, and 2025-082083 are incorporated by reference into this international application.

[0219] REFERENCE SIGNS LIST 10 Aqueous dispersion 11 Composite tungsten oxide particles 12 Water 20 Masterbatch 21 Composite tungsten oxide particles 22 Solid medium 30 Near-infrared shielding transparent laminate 31 Transparent molded body 32 Near-infrared shielding transparent resin molded body 31A One surface 40 Near-infrared shielding transparent laminate 411 Transparent molded body 412 Transparent molded body 42 Near-infrared shielding transparent resin molded body

Claims

1. A cationic surfactant having a hexagonal crystal structure, represented by the general formula M ｘ WO ｙ (wherein the M element includes one or more elements selected from Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, and Ra, and 0.1≦x≦1.0, 2.0≦y<4.0 are satisfied).

2. An aqueous dispersion comprising the dispersed powder according to claim 1 and water.

3. A masterbatch composition comprising the dispersed powder of claim 1 and a solid medium containing an acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic anhydride.

4. The masterbatch composition of claim 3, wherein the solid medium further comprises one or more resins selected from polyethylene resin, polylactic acid resin, and polypropylene resin.

5. The cationic surfactant is a quaternary ammonium salt represented by formula (A), wherein R1 in formula (A) is an alkyl group, X1 － The masterbatch composition according to claim 3 or claim 4, wherein is an anion.

6. The masterbatch composition according to claim 5, wherein the cationic surfactant is one in which R1 contained in formula (A) is an alkyl group having 1 to 18 carbon atoms.

7. The masterbatch composition according to claim 3 or 4, wherein the M element contained in the composite tungsten oxide particles includes one or more elements selected from the group consisting of Cs, Rb, K, and Ba.

8. A masterbatch which is a molded product of the masterbatch composition according to claim 3 or 4.

9. A near-infrared shielding transparent resin molded article, which is a molded article containing the masterbatch composition according to claim 3 or 4.

10. A near-infrared shielding transparent laminate comprising: a transparent molded body; and the near-infrared shielding transparent resin molded body according to claim 9 laminated on the transparent molded body.

11. A compound of the general formula M having a hexagonal crystal structure ｘ WO ｙ a surface modification step of adding a cationic surfactant to the dispersion to modify the surfaces of the composite tungsten oxide particles; a dispersion preparation step of evaporating water from the dispersion after the surface modification step to prepare a dispersed powder; and a masterbatch composition preparation step of mixing the dispersed powder with a solid medium containing an acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic anhydride to prepare a masterbatch composition.

12. The method for producing a masterbatch composition according to claim 11, wherein the solid medium further comprises one or more resins selected from polyethylene resin, polylactic acid resin, and polypropylene resin.

13. The method for producing a masterbatch composition according to claim 11 or 12, wherein the dispersed particle diameter of the composite tungsten oxide particles is 200 nm or less.

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