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

The present invention provides a dispersion powder that can be converted 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. A cationic surfactant and It has a hexagonal crystal structure and 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 satisfies 0.1≦x≦1.0 and 2.0≦y<4.0).

Description

[Technical Field]

[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. [Background technology]

[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 for covering the ground, which is made of a woven fabric having a strip-shaped film with infrared reflectivity and a strip-shaped film with infrared absorbing properties as the warp and weft, respectively.

[0004] In addition, Patent Document 2 proposes a film for growing agricultural crops, in which the surface of the film has been whitened to a total light transmittance of 30% or more and a diffuse reflectance of 40% or more, and black or blue pigments such as carbon black are printed on the surface by dispersing them 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 infrared absorption properties. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 9-107815 [Patent Document 2] Japanese Unexamined Patent Publication No. 55-127946 [Patent Document 3] Japanese Patent Application Laid-Open No. 2012-021056 [Patent Document 4] Japanese Patent Application Publication No. 2020-083951 Summary of the Invention [Problem to be solved by the invention]

[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. [Means for solving the problem]

[0011] The dispersion powder according to one aspect of the present invention comprises a cationic surfactant and A compound having a hexagonal crystal structure and 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 satisfies 0.1≦x≦1.0 and 2.0≦y<4.0). [Effects of the Invention]

[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 masterbatch containing composite tungsten oxide particles or a near-infrared shielding transparent resin molded product can be provided. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 is an explanatory diagram of an aqueous dispersion according to one embodiment of the present disclosure. [Figure 2] 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. [Figure 3] FIG. 3 is an explanatory diagram of a near-infrared shielding transparent laminate according to one embodiment of the present disclosure. [Figure 4] FIG. 4 is an explanatory diagram of a near-infrared shielding transparent laminate according to one embodiment of the present disclosure. [Figure 5] FIG. 5 is a flow diagram of a method for producing a masterbatch composition according to one embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0014] Hereinafter, embodiments for carrying out 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] The dispersion powder according to one embodiment of the present disclosure (hereinafter referred to as "the present embodiment") can be produced by reducing or removing water from the aqueous dispersion of the present embodiment described below. Alternatively, the aqueous dispersion of the present embodiment can be obtained by adding water to the dispersion powder according to one embodiment of the present disclosure. Therefore, 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, composite tungsten oxide particles 11 are represented by circles and depicted as spherical particles, but the shape of composite tungsten oxide particles 11 is not limited to this form and can have any shape. Aqueous dispersion 10 can contain other additives as needed in addition to composite tungsten oxide particles 11, water 12, and a cationic surfactant.

[0020] The aqueous dispersion of this 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 represented by the general formula M x WO yThe 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 elements, alkaline earth metal elements, rare earth elements, 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, and O represents oxygen. 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 includes one or more elements selected from Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Tl, and In. This is because the M element includes one or more elements selected from Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Tl, and In, which makes the composite tungsten oxide particles more likely to have a hexagonal crystal structure, thereby particularly improving light transmittance in the visible light range and enhancing near-infrared blocking function. In particular, considering ease of handling of raw materials, it is more preferable that the M element includes one or more elements selected from Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, and Ra. It is even more preferable that the M element includes one or more elements selected from Cs, Rb, K, and Ba.

[0025] Typical examples of composite tungsten oxide particle materials include Cs 0.33 WO3, Rb 0.33 WO3, K 0.33 WO3, Ba 0.33 WO3, etc., and useful near-infrared shielding properties can be obtained as long as x and y fall within the above ranges.

[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 size of composite tungsten oxide particles The dispersed particle size 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 losing its 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 decreases in proportion to the sixth power of the particle diameter, so scattering decreases as the dispersed particle diameter decreases, improving transparency. 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, and a near-infrared shielding transparent resin molded product from the masterbatch, the color of the composite tungsten oxide particles can be adjusted to a predetermined range. * is between 25 and 80, a * is between -10 and 10, b * The above color parameters are based on the L * a * b * This refers to 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 process) 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 is a source of element M.

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

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

[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 650°C or higher and 1200°C or lower.

[0052] As the inert gas, an inert gas such as Ar or N2 can be used.

[0053] In the heat treatment step, when 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 it 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 H2 is preferred. When H2 is used as the reducing gas, the composition of the reducing atmosphere is preferably a mixture of an inert gas such as Ar or N2 with H2 at a volume ratio of 0.1% or more, more preferably 0.2% or more. If the volume ratio of H2 is 0.1% or more, reduction can proceed efficiently.

[0055] The upper limit of the H2 concentration in the reducing atmosphere is not particularly limited, but can be set to, for example, 100% or less by volume. (Oxidation treatment process) 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 appropriately selected 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 appropriately selected depending on the amount of material to be heat treated, and is not particularly limited, but is preferably, for example, 400°C or higher and 850°C or lower. (Other processes) The method for producing composite tungsten oxide particles can also include a surface treatment step of treating the surface with at least one compound selected from the group consisting of silane compounds, titanium compounds, aluminum compounds, and zirconia compounds. By coating the surfaces of the composite tungsten oxide particles with a compound containing at least one compound selected from the group consisting of Si, Ti, Al, and Zr, weather resistance can be improved. (2) Cationic surfactants The cationic surfactant is water-soluble, and therefore 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] [ka] R1 in the above formula (A) may be an alkyl group, and may be an alkyl group having 1 or more and 18 or less 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] [ka]

[0063] [ka]

[0064] [ka]

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

[0066] [ka]

[0067] [ka] 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 composite tungsten oxide particles. That is, the aqueous dispersion of this embodiment can contain 0.1% by mass or more and 100% by mass or less of the cationic surfactant, assuming that the content of the composite tungsten oxide particles is 100 parts by mass. By including 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 in the aqueous dispersion of this embodiment, the composite tungsten oxide particles can be in a particularly good dispersed state.

[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] Since the aqueous dispersion of this embodiment does not require the addition of an organic solvent, 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 the present 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 with respect to the aqueous dispersion, and therefore, a detailed description thereof will be omitted. As described 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 0 mass %.

[0075] The dispersion powder of the present embodiment can be mixed with a solid medium to form a masterbatch composition or a near-infrared shielding transparent resin composition. Furthermore, the mixture of the dispersion powder of the present 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 include the dispersion powder of this embodiment and a solid medium, that is, the masterbatch composition and masterbatch of this embodiment can include 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 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 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 also have, for example, a coating on their surfaces. Although not shown in FIG. 2, as described above, 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 and can modify the surface of the composite tungsten oxide particles 21. The masterbatch 20 of this embodiment can also contain other additives as necessary. (1) Masterbatch composition and ingredients contained in the masterbatch The cationic surfactant and the composite tungsten oxide particles have already been described in detail with respect to the aqueous dispersion, and therefore, a detailed description thereof will be omitted. As described above, the composite tungsten oxide particles have a hexagonal crystal structure and are represented by the general formula M x WO y The masterbatch composition of this embodiment and the solid medium contained in the masterbatch will now be described. (1-1) Solid medium (1-1-1) Acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic anhydride In the masterbatch composition or masterbatch of this embodiment, the solid medium preferably contains an acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic anhydride. The solid medium may be composed of an acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic 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 backbone 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-norbornadi ... and 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 copolymers constituting the backbone of the acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic anhydride include ethylene-propylene-1-butene copolymer, ethylene-propylene-1-hexene copolymer, ethylene-propylene-1-octene copolymer, ethylene-propylene-1-octene copolymer, ethylene-propylene-1,4-hexadiene copolymer, ethylene-propylene-1,4-hexadiene copolymer, 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 -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 the acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic anhydride is preferably at least one 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 or masterbatch of this embodiment may further contain a resin other than the acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic anhydride. When the masterbatch composition of this embodiment contains a resin other than the acid-modified polyolefin polymer or copolymer 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 masterbatch solid medium 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 polys whose constituent units are composed only of L-lactic acid, polys whose constituent units are composed only of D-lactic acid, and polys in which L-lactic acid and D-lactic acid exist in various ratios.

[0088] Furthermore, the polypropylene resin is not particularly limited. (1-2) Other additives The masterbatch composition and masterbatch of the present 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, materials generally used for coloring thermoplastic resins 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, mold release agents, hydroxybenzophenone-based, salicylic acid-based, HALS-based, triazole-based, and triazine-based ultraviolet absorbers, coupling agents, surfactants, and antistatic agents.

[0092] When the masterbatch composition or masterbatch of the present embodiment contains additives such as dyes, pigments, stabilizers, or release agents, the contents thereof are not particularly limited, and for example, each additive can be added or contained in an amount that is effective for exhibiting a predetermined function. (2) Method for producing the master batch composition The method for producing the master batch composition of this embodiment can be carried out in accordance with a flow chart 50 shown in FIG.

[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 liquid preparation process) In the dispersion liquid preparation step S1, composite tungsten oxide particles are mixed with water, and the composite tungsten oxide particles are subjected to pulverization and dispersion treatment to prepare a dispersion liquid.

[0094] The composite tungsten oxide particles used in the dispersion preparation step can be, for example, the composite tungsten oxide particles described in the aqueous dispersion, and therefore further description will be omitted. As described above, 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 the dispersed powder preparation step, the dispersed powder obtained after the masterbatch composition preparation step, the masterbatch composition, etc., falls 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 process) In the surface modification step, a cationic surfactant can be 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 to 100 parts by mass per 100 parts by mass of 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, an aqueous dispersion according to one embodiment of the present disclosure can be prepared. (Dispersed powder preparation process) In the dispersed powder preparation step, the dispersed powder can be prepared by evaporating water from the dispersion liquid after the surface modification step.

[0100] The specific method for evaporating water from the dispersion liquid in the dispersed powder preparation step is not particularly limited, and for example, one or more methods selected from natural drying in which the dispersion liquid 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 dispersed powder preparation step, multiple methods for evaporating water from the dispersion liquid can be combined and carried out in multiple stages as necessary. (Masterbatch composition preparation step) In the masterbatch composition preparation step, the dispersed powder is mixed with a solid medium containing an acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic anhydride to prepare the masterbatch composition.

[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] When an aqueous dispersion is prepared in advance, the method for producing a masterbatch can start from the dispersed powder preparation step. When a dispersed powder is prepared in advance, the method for producing a masterbatch can start from 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 product.

[0108] The masterbatch composition and masterbatch 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; for example, the content of residual organic solvent can be reduced to 0.1 mass % or less, or even 0 mass %. [Near-infrared shielding transparent resin molded body, near-infrared shielding transparent laminate] Next, the near-infrared shielding transparent resin molding 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 above-mentioned masterbatch.

[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 of a transparent molded body and a near-infrared shielding transparent resin molded body along the lamination direction, 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 configuration shown in Fig. 3. For example, as shown in Fig. 4, which is a cross-sectional schematic view taken 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 serves as 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 configuration.

[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 a board shape, a sheet shape, or a film shape, for example, 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 range, and the degree of transmittance of light in the visible light range 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 according to 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, biaxially oriented polyester 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 biaxially oriented polyester film may be a copolymer polyester film.

[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 the near-infrared shielding transparent resin molded article with another transparent molded article at the same time as molding the same 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 article 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 article 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 %. [Example]

[0133] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. 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 solar radiation transmittance is an index showing the near-infrared shielding performance. The evaluation results are shown in the "Optical Properties" column of Table 1. 2. Explanation of experimental conditions and procedures [Example 1] (1) Preparation of composite tungsten oxide particles (Heat treatment process) The starting materials to be subjected to the heat treatment step were prepared according to the following procedure.

[0134] 591.8 g of Cs2CO3, a raw material for element M, was dissolved in 900 g of water to prepare a solution containing the raw material for element M. 470 g of H2WO42, a tungsten raw material, was added to the solution containing the raw material for element M, and the mixture was dried in a vacuum dryer while stirring to obtain a starting material in the form of a dry powder.

[0135] The obtained dry powder was heated while feeding 5% by volume of H2 gas with N2 gas as a carrier, and then calcined at 800°C for 0.5 hours in a reducing atmosphere.

[0136] Next, the mixture was sintered at 800°C for 1 hour under an N2 gas atmosphere, i.e., 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, the results of powder X-ray diffraction showed that particle A was composed of hexagonal Cs 0.3 The diffraction pattern matches that of WO3, confirming that it has a hexagonal crystal structure. (2) Preparation of Masterbatch Composition (2-1) Dispersion liquid preparation process Next, 12.5% ​​by mass of particles A and 87.5% by mass of water were weighed out, and the mixture was ground and dispersed for 2.5 hours in a media stirring mill containing 0.3 mm diameter ZrO2 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 and found to be 20 nm. (2-2) Surface modification process To the dispersion obtained in the dispersion preparation step, a cationic surfactant, cetyltrimethylammonium chloride, was added in a proportion of 1.25 mass% relative to the composite tungsten oxide particles, and the mixture was stirred for 6 hours. This procedure yielded an aqueous dispersion containing composite tungsten oxide particles surface-modified with the cationic surfactant (hereinafter also referred to as "Liquid A"). (2-3) Dispersed powder preparation process Water was removed from Liquid A, 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 A").

[0138] It has been confirmed that when water is added to the dry powder A, which is the dispersion powder prepared in this example, and the dispersion powders prepared and used in the other examples described below, the composite tungsten oxide particles are dispersed in water and become an aqueous dispersion again. (2-4) Masterbatch composition preparation process Dry powder A and the maleic anhydride-modified ethylene-1-butene copolymer powder were uniformly mixed using a blender so that the composite tungsten oxide particles accounted for 10 mass% of the maleic anhydride-modified ethylene-1-butene copolymer powder, to prepare a masterbatch composition.

[0139] In the "Acid-modified polyolefin polymer (copolymer)" column of Table 1, maleic anhydride-modified ethylene-1-butene copolymer is referred to as "MEB copolymer." (3) Manufacturing of master batches and near-infrared shielding transparent resin moldings 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 molding (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 "Near-infrared shielding transparent resin molding" column of Table 1, the "Concentration of composite tungsten oxide particles" column shows the concentration of the composite tungsten oxide particles contained in the near-infrared shielding transparent resin molding, and the "Thickness" column shows 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, a cationic surfactant, cetyltrimethylammonium chloride, 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 is 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, a cationic surfactant, cetyltrimethylammonium chloride, 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% by mass.

[0153] 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 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% by mass.

[0156] 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 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 out, and the mixture was ground and dispersed for 5 hours in a bead mill containing 0.3 mm diameter ZrO2 beads to prepare 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 a proportion of 2.0 mass% relative to the composite tungsten oxide particles, and the mixture was stirred for 10 hours to obtain 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 the H liquid, which was the aqueous dispersion obtained in the surface modification step, using a spray dryer to obtain a dispersed powder of composite tungsten oxide particle dry powder (hereinafter also referred to as "dry powder H").

[0162] In the masterbatch composition preparation process, the dry powder H and the maleic anhydride-modified ethylene-1-butene copolymer powder were mixed uniformly using a blender to prepare the masterbatch composition. In the masterbatch composition preparation process, the maleic anhydride-modified ethylene-1-butene copolymer powder was added and mixed so that the composite tungsten oxide particles were 10 mass% relative to 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 to obtain 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% by 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 molded product, 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, the maleic anhydride-modified ethylene-1-butene copolymer powder was added and mixed so that the composite tungsten oxide particles accounted for 15 mass% of the maleic anhydride-modified ethylene-1-butene copolymer powder. A masterbatch for near-infrared shielding transparent resin moldings was obtained under the same conditions as in Example 8 (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, the maleic anhydride-modified ethylene-1-butene copolymer powder was added and mixed so that the composite tungsten oxide particles accounted for 20 mass % of the maleic anhydride-modified ethylene-1-butene copolymer powder. A masterbatch for near-infrared shielding transparent resin moldings (hereinafter also referred to as "masterbatch J") was obtained under the same conditions as in Example 8, except for the above points.

[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% by mass.

[0173] 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 J, which was a near-infrared shielding transparent resin molded product, 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 process) The starting materials to be subjected to the heat treatment step were prepared according to the following procedure.

[0176] 8.8 g of Cs2CO3, a raw material for element M, was dissolved in 16.5 g of water to prepare a solution containing the raw material for element M. 450 g of H2WO, a raw material for tungsten, was added to the solution containing the raw material for element M, and the mixture was dried in a vacuum dryer while stirring to obtain the starting material in the form of a dry powder.

[0177] The obtained dried powder was first calcined at 570°C for 1 hour in an atmosphere of 5% H2 gas by volume with N2 gas as a carrier.

[0178] Next, the mixture was fired at 800°C for 1 hour in an air atmosphere with a volume ratio of 1% using N2 gas as a carrier.

[0179] Further, the mixture was calcined at 820°C for 0.5 hours in an N2 gas atmosphere to obtain particles K.

[0180] Chemical analysis showed that the composition of particle K, a composite tungsten oxide particle, was Cs 0.27 WO 2.86 Furthermore, the results of powder X-ray diffraction showed that particle K was composed of hexagonal Cs 0.3 The diffraction pattern matches that of WO3, confirming that it has a hexagonal crystal structure.

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

[0182] The optical properties of the near-infrared shielding transparent resin film K of 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, which combined DC plasma and high-frequency plasma. The reaction system was evacuated to approximately 0.1 Pa (approximately 0.001 torr) using a vacuum pump, 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 through the sheath gas supply port to generate high-frequency plasma and protect the quartz tube. 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 fed into the plasma at a rate of 2 g / min from the raw material powder feeder 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 3.16The powder X-ray diffraction results showed that the hexagonal Cs 0.3 The diffraction pattern matches that of WO3, confirming that it has a hexagonal crystal structure.

[0188] Except for using particles L, the aqueous dispersion, dispersed powder, masterbatch composition, masterbatch, and 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] To prepare the composite tungsten oxide particles, starting materials were prepared for the heat treatment step using K2CO3 as the element M material and H2WO4 as the tungsten material. K2CO3 and H2WO4 were weighed and mixed so that the K / W molar ratio was 0.33 to prepare the starting materials.

[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 particle M was a hexagonal K crystal as a result of powder X-ray diffraction. 0.3 The diffraction pattern matches that of WO3, confirming that it has a hexagonal crystal structure.

[0193] The optical properties of the near-infrared shielding transparent resin film M according to Example 13 were measured, and as shown in Table 1, the solar radiation transmittance was 22.0% when the visible light transmittance was 46.3%. [Example 14] To prepare the composite tungsten oxide particles, starting materials were prepared for the heat treatment step using Rb2CO3 as the element M material and H2WO4 as the tungsten material. Rb2CO3 and H2WO4 were weighed and mixed so that the Rb / W molar ratio was 0.33 to prepare the 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, i.e., 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, the results of powder X-ray diffraction showed that particle N was composed of hexagonal Rb 0.33 The diffraction pattern matches that of WO3, confirming that it has a hexagonal crystal structure.

[0196] The optical properties of the near-infrared shielding transparent resin film N according to Example 14 were measured, and as shown in Table 1, the solar radiation transmittance was 21.8% when the visible light transmittance was 46.3%. [Example 15] To prepare the composite tungsten oxide particles, starting materials were prepared for the heat treatment step using BaCO3 as the element M material and H2WO4 as the tungsten material. BaCO3 and H2WO4 were then weighed and mixed to give a Ba / W molar ratio of 0.33 to prepare the 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 obtained in this example is Ba. 0.33 WO 2.45In addition, the results of powder X-ray diffraction showed that particle O was composed of hexagonal Ba 0.21 The diffraction pattern matches that of WO3, confirming that it 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 process, maleic anhydride-modified polypropylene was used instead of maleic anhydride-modified ethylene-1-butene copolymer.

[0201] In the column of "acid-modified polyolefin polymer (copolymer)" in Table 1, 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 of 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 the 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 of 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 the 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 as shown in Table 1, the solar radiation transmittance was 54.1% when the visible light transmittance was 80.1%. [Example 19] In the masterbatch composition preparation process, carboxylic acid anhydride-modified polypropylene was used instead of maleic anhydride-modified ethylene-1-butene copolymer.

[0210] In the column of "acid-modified polyolefin polymer (copolymer)" in Table 1, 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 product, 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, dispersed powder, masterbatch composition, and 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 a near-infrared shielding transparent resin molded article was not 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 masterbatch 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] [Table 1] 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. [Explanation of symbols]

[0218] 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 molding 32 Near-infrared shielding transparent resin molding 31A One side 40 Near-infrared shielding transparent laminate 411 Transparent molding 412 Transparent molding 42 Near-infrared shielding transparent resin molding

Claims

1. a cationic surfactant; A compound having a hexagonal crystal structure and 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. The dispersion powder according to claim 1; and water.

3. The dispersion powder according to claim 1; a solid medium comprising a polyolefin polymer or copolymer acid-modified with maleic anhydride or carboxylic anhydride.

4. 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), in which R1 is an alkyl group, X1 － The masterbatch composition according to claim 3 or claim 4, wherein is an anion. 【Chemistry 1】

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

7. 5. The masterbatch composition according to claim 3, 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 transparent molded body; A near-infrared shielding transparent laminate comprising: the near-infrared shielding transparent resin molding according to claim 9 laminated on the transparent molding.

11. A compound having a hexagonal crystal structure and the general formula M ｘ WO ｙ a dispersion liquid preparation step of mixing composite tungsten oxide particles represented by the formula (wherein M element includes one or more elements selected from Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, and Ra, and satisfies 0.1≦x≦1.0, 2.0≦y<4.0) with water, and subjecting the composite tungsten oxide particles to pulverization and dispersion treatment to prepare a dispersion liquid; a surface modification step of adding a cationic surfactant to the dispersion liquid to modify the surfaces of the composite tungsten oxide particles; a dispersion powder preparation step of evaporating water from the dispersion liquid after the surface modification step to prepare a dispersion 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 a polyethylene resin, a polylactic acid resin, and a 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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