Dispersed powder, aqueous dispersion, masterbatch composition, masterbatch, near-infrared shielding transparent resin molded body, near-infrared shielding transparent laminate, method for manufacturing 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 article, 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 for some time.

[0003] For example, Patent Document 1 proposes a heat-retaining sheet for covering the ground, in which a strip-shaped film having infrared reflectivity and a strip-shaped film having infrared absorption are knitted together as warp or weft threads, respectively.

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

[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 dispersion resin composition, which includes kneading fine particles, composite particles containing a dispersant thereof, a compatibilizer, and polyethylene, wherein the dispersant of the composite particles contains a polar group-containing resin, and the compatibilizer is a polar group-containing polyolefin, and tungsten oxide particles are given as fine particles, and it is stated that the dispersibility greatly affects the infrared absorption properties. [Prior art documents] [Patent Documents]

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

[0008] Composite tungsten oxide particles are known as substances having excellent near-infrared absorption characteristics, and masterbatches obtained by adding composite tungsten oxide particles to resins and the like, and dispersions have been conventionally studied.

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

[0010] Therefore, in one aspect of the present invention, by adding water, it is possible to obtain an aqueous dispersion liquid using water as the dispersion medium, and it is an object to provide a dispersion powder that can be used in the production of a masterbatch containing composite tungsten oxide particles and a near-infrared shielding transparent resin molded body. [Means for Solving the Problems]

[0011] The dispersion powder according to one aspect of the present invention includes a cationic surfactant and Composite tungsten oxide particles having a hexagonal crystal structure and represented by the general formula M x WO y (However, the M element includes one or more elements selected from Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, and satisfies 0.1 ≦ x ≦ [Advantages of the Invention]

[0012] According to the dispersion powder according to one aspect of the present invention, by adding water, an aqueous dispersion using water as a dispersion medium can be obtained, and a masterbatch containing composite tungstate oxide particles or a near-infrared blocking transparent resin molded body can be obtained. A dispersion powder that can be used in the production of the body can be provided. [Brief Description of the Drawings]

[0013] [Figure 1] FIG. 1 is an explanatory diagram of an aqueous dispersion according to one aspect of the present disclosure. [Figure 2] FIG. 2 is an explanatory diagram of a masterbatch and a near-infrared blocking transparent resin molded body according to one aspect of the present disclosure. [Figure 3] FIG. 3 is an explanatory diagram of a near-infrared blocking transparent laminate according to one aspect of the present disclosure. [Figure 4] FIG. 4 is an explanatory diagram of a near-infrared blocking transparent laminate according to one aspect of the present disclosure. [Figure 5] FIG. 5 is a flowchart of a method for producing a masterbatch composition according to one aspect of the present disclosure. [Modes for Carrying Out the Invention] <00001!7>

[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. Further, by adding water to the dispersion powder according to one embodiment of the present disclosure, the aqueous dispersion of the present embodiment can be obtained. Therefore, the aqueous dispersion will be described first

[0015] The aqueous dispersion of the present embodiment can contain the dispersion powder according to one aspect of the present disclosure described below and water.

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

[0017] For example, as shown in Figure 1, the aqueous dispersion 10 of this embodiment may contain composite tungsten oxide particles 11 and water 12. Preferably, the composite tungsten oxide particles 11 are dispersed in the water 12.

[0018] Although not shown in Figure 1, the aqueous dispersion 10 of this embodiment further contains a cationic surfactant. The cationic surfactant can be, for example, placed on the surface of the composite tungsten oxide particles 11, and can modify the surface of the composite tungsten oxide particles 11. In addition, some of the cationic surfactant may be dissolved in the water 12.

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

[0020] The aqueous dispersion of this embodiment may consist only of a cationic surfactant, water, and composite tungsten oxide particles; however, even in this case, the presence of unavoidable impurities introduced during the manufacturing process is not excluded.

[0021] The components contained in the aqueous dispersion of this embodiment are described below. (1) Composite tungsten oxide particles (1-1) About the composition Composite tungsten oxide particles are of the general formula M x WO yThese can be represented as particles of a composite tungsten oxide.

[0022] In the general formula above, element M is H (hydrogen), He (helium), alkali metals, alkaline earth metals, 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). It can be one or more elements selected from 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). Also, W represents tungsten and O represents oxygen, and x may be 0.1 ≤ x ≤ 1.0 or 0.25 ≤ x ≤ 0.39. y may satisfy 2.0 ≤ y < 4.0.

[0023] Alkali metal elements include Li (lithium), Na (sodium), K (potassium), Rb (rubidium), Cs (cesium), and Fr (francium). Alkaline earth metal elements include Ca (calcium), Sr (strontium), Ba (barium), and Ra (radium). 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 element M 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 inclusion of one or more elements selected from Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Tl, and In as the element M makes it easier for the composite tungsten oxide particles to adopt a hexagonal crystal structure, particularly enhancing the transmittance of light in the visible light region and improving the near-infrared shielding function. In particular, considering the ease of handling of the raw materials, it is more preferable that the element M 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 element M contains one or more elements selected from, for example, Cs, Rb, K, and Ba.

[0025] A typical example of a composite tungsten oxide particle material is Cs 0.33 WO3, Rb 0.33 WO3, K 0.33 WO3, Ba 0.33 While WO3 is one example, useful near-infrared shielding properties can be obtained as long as x and y fall within the above range.

[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. In this embodiment, it is preferable that the composite tungsten oxide contained in the composite tungsten oxide particles has a hexagonal crystal structure.

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

[0028] Composite tungsten oxides function as near-infrared shielding materials even when they adopt a tetragonal or cubic tungsten bronze 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. This absorption position of near-infrared light tends to shift to longer wavelengths when the crystal structure is tetragonal compared to cubic, and further to longer wavelengths when the crystal structure is hexagonal. In addition, in conjunction with this variation in absorption position, the absorption of visible light is least in the hexagonal crystal, followed by the tetragonal crystal, and among these, the absorption of visible light is greatest in the cubic crystal. Therefore, for applications that transmit more visible light and shield more infrared light, it is preferable to use a composite tungsten oxide having a hexagonal tungsten bronze crystal structure. For this reason, the composite tungsten oxide particles contained in the aqueous dispersion of this embodiment can, for example, have a hexagonal crystal structure. (1-2) Dispersion particle size of composite tungsten oxide particles The particle size of the composite tungsten oxide particles used in the aqueous dispersion of this embodiment is not particularly limited and can be selected according to the intended use, etc.

[0029] The composite tungsten oxide particles used in the aqueous dispersion of this embodiment absorb a large amount of light in the near-infrared region, especially around 1000 nm in wavelength, so their transmitted color tone is often blue.

[0030] When used in applications where transparency must be maintained, it is preferable that the composite tungsten oxide particles 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 region due to scattering, thus maintaining high visibility in the visible light region while efficiently maintaining transparency. When transparency in the visible light region is particularly important, it is preferable to further consider scattering by the particles.

[0031] In this specification, "transparency" is used to mean "having low scattering and high transmittance to light in the visible light range."

[0032] When prioritizing the reduction of scattering by particles, the dispersed particle size of the composite tungsten oxide particles is more preferably 200 nm or less, and even more preferably 100 nm or less. This is because a smaller dispersed particle size of the composite tungsten oxide particles reduces the scattering of light in the visible light region due to geometric scattering or Mie scattering.

[0033] By setting the particle size of the composite tungsten oxide particles to, for example, 200 nm or less, the scattering of light in the visible light region is reduced, resulting in improved transparency of the near-infrared shielding film, which is a dispersion or molded product containing the composite tungsten oxide particles. In other words, it is possible to reliably avoid the near-infrared shielding film becoming cloudy 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 described above is reduced, and the region becomes Rayleigh scattering. In this 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 becomes very small, which is preferable. From the viewpoint of avoiding light scattering, it is preferable for the dispersed particle diameter of the composite tungsten oxide particles to be small.

[0035] The lower limit of the dispersed particle size of the composite tungsten oxide particles is not particularly limited, but for ease of industrial production, the dispersed particle size may be, for example, 1 nm or larger.

[0036] In other words, the dispersed particle size of the composite tungsten oxide particles may be between 1 nm and 800 nm, between 1 nm and 200 nm, or between 1 nm and 100 nm. (1-3) Color of composite tungsten oxide particles For the aqueous dispersion of the present embodiment, the masterbatch using the aqueous dispersion, and the near-infrared shielding transparent resin molded body obtained by molding the masterbatch, in order to obtain a desired color tone, the color tone of the composite tungsten oxide particles can also be 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 -10 or more and 10 or less, b * may satisfy the condition of being -15 or more and 15 or less. The above color tone parameters are L * a * b * in the powder color in the color system (JIS Z 8729 (2004)) recommended by the International Commission on Illumination (CIE).

[0037] The color tone of the composite tungsten oxide particles can be selected according to the conditions of the heat treatment step and the like in the method for producing the composite tungsten oxide particles 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 the present embodiment is not particularly limited, and any production method can be used as long as it can produce composite tungsten oxide particles that satisfy the above general formula and crystal structure.

[0038] The method for producing the composite tungsten oxide particles can have, for example, a heat treatment step of heat-treating the starting material in an inert gas atmosphere or a reducing gas atmosphere.

[0039] The method for producing the composite tungsten oxide particles can also have an oxidation treatment step of performing an oxidation treatment after the heat treatment step.

[0040] Hereinafter, each step will be described. (Heat treatment step) The starting material to be subjected to the heat treatment step may include a tungsten raw material containing tungsten, which serves as a source of tungsten.

[0041] The tungsten raw material may include one or more selected from, for example, tungstic 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 hydrated tungsten oxide, for example, hydrated tungsten oxide powder obtained by dissolving tungsten hexachloride in alcohol and then drying it, or hydrated tungsten oxide powder obtained by dissolving tungsten hexachloride in alcohol, adding water to precipitate it, and then drying it can be used.

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

[0044] The tungsten raw material may include a solution containing one or more of the above-mentioned powder materials.

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

[0046] The starting materials may also include element M raw materials containing element M, which serve as a source of element M.

[0047] The element M raw material may include one or more selected elements, such as element M in its elemental form or compounds containing element M.

[0048] The starting material may be a mixture of tungsten raw material and element M raw 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 can be one or more selected from tungstates, chlorides, nitrates, sulfates, oxalates, oxides, carbonates, hydroxides, etc., that contain element M, but is not limited to these, and any material that can be dissolved in solution can be suitably used.

[0050] In the heat treatment process, a heat treatment temperature of 650°C or higher is preferred in an inert atmosphere. Starting materials heat-treated at 650°C or higher have sufficient near-infrared absorption capacity and are efficient as heat-shielding particles. The upper limit of the heat treatment temperature in an inert atmosphere is not particularly limited, but it can be, for example, 1200°C or lower.

[0051] In other words, the heat treatment conditions in an inert atmosphere can be set to a temperature between 650°C and 1200°C.

[0052] Inert gases such as Ar and N2 can be used.

[0053] In the heat treatment process, 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 to 1000°C, and then heat-treat it in an inert gas atmosphere at a temperature of 650°C to 1200°C.

[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, and more preferably 0.2% or more. If H2 is at a volume ratio of 0.1% or more, reduction can be carried out efficiently.

[0055] There is no particular upper limit to the H2 concentration in a reducing atmosphere, but it can be set to, for example, 100% or less by volume. (Oxidation process) In the oxidation treatment process, the composite tungsten oxide particles obtained in the heat treatment process can be oxidized under mild conditions.

[0056] The oxygen source gas used in the oxidation process is not particularly limited, but one or more selected from oxygen, air, and water vapor is preferred. The concentration of the oxygen source can be appropriately selected according to the heat treatment temperature and the amount of material to be heat treated, and is not particularly limited. The heat treatment temperature can also be appropriately selected according to the amount of material to be heat treated, and is not particularly limited, but for example, it is preferably between 400°C and 850°C. (Other processes) A method for producing composite tungsten oxide particles may also include a surface treatment step in which the surface is treated with at least one compound selected from silane compounds, titanium compounds, aluminum compounds, and zirconia compounds. By coating the surface of the composite tungsten oxide particles with a compound containing one or more elements selected from Si, Ti, Al, and Zr, the weather resistance can be improved. (2) Cationic surfactants Since cationic surfactants are water-soluble, they can be used to disperse complex tungsten oxide particles 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] In the above formula (A), R1 may be an alkyl group, and may also be an alkyl group having 1 to 18 carbon atoms.

[0059] X1 in the above formula 1 - The anion can be any anion and is not particularly limited, but may be one or more selected from, for example, a hydroxyl group or a halogen group.

[0060] As cationic surfactants, one or more selected from, for example, ammonium chloride, ammonium hydroxide, ammonium fluoride, ammonium bromide, ammonium iodide, etc., can be used.

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

[0062] [ka]

[0063] [ka]

[0064] [ka]

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

[0066] [ka]

[0067] [ka] Among cationic surfactants, ammonium chloride is preferred, and one or more selected from dodecyltrimethylammonium chloride and cetyltrimethylammonium chloride are more preferred.

[0068] The amount of cationic surfactant added to the aqueous dispersion can be selected according to the type of cationic surfactant and composite tungsten oxide particles, as well as the specific surface area of ​​the composite tungsten oxide particles, 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 cationic surfactant in a ratio of 0.1% by mass or more and 100% by mass or less when the content of 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 cationic surfactant per 100 parts by mass of composite tungsten oxide particles, the aqueous dispersion of this embodiment can achieve a particularly good dispersion state for the composite tungsten oxide particles.

[0069] In this embodiment, the aqueous dispersion is modified with a cationic surfactant on the surface of the composite tungsten oxide particles, thus improving dispersibility even when water is used as the dispersion medium. Therefore, it can be used in the production of masterbatches containing composite tungsten oxide particles and near-infrared shielding transparent resin molded articles.

[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% by mass or less, or even 0% by mass. [Dispersed powder] The dispersed powder of this embodiment may contain a cationic surfactant and composite tungsten oxide particles.

[0071] The dispersion powder of this embodiment can be prepared by evaporating water from an 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 surface is modified with a cationic surfactant.

[0072] Details of the cationic surfactant and composite tungsten oxide particles, as well as their preferred properties, have already been explained in the section on aqueous dispersions, so this explanation will be omitted here. The composite tungsten oxide particles, as previously described, have a hexagonal crystal structure and are represented by the general formula M x WO y It can be expressed as follows. The elements M in the general formula and the suitable ranges for x and y have already been explained, so we will omit further explanation.

[0073] The dispersion powder of this embodiment can be prepared using an aqueous dispersion with water as the solvent, thus allowing for a dispersion powder with a sufficiently reduced organic solvent content. Furthermore, the dispersion powder of this embodiment can be prepared by adding water to create an aqueous dispersion with water as the dispersion medium. In other words, the dispersion powder of this embodiment can be prepared by preparing a dispersion in which composite tungsten oxide particles are dispersed in the dispersion medium without adding an organic solvent.

[0074] Since the dispersed powder of this embodiment can use an aqueous dispersion according to one aspect of the present disclosure as a raw material, the proportion of residual organic solvent can be reduced, for example to 0.1% by mass or less, or even 0% by 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 a 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 may include the dispersed powder and solid medium of this embodiment. That is, the masterbatch composition and masterbatch of this embodiment may 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, a cationic surfactant can be placed on the particle surface of the composite tungsten oxide particles and can modify the particle surface of the composite tungsten oxide particles.

[0077] The masterbatch composition of this embodiment can be melt-kneaded and processed, for example, into pellets to form a masterbatch. That is, the masterbatch of this embodiment is a molded body of the masterbatch composition of this embodiment. For this reason, the masterbatch of this embodiment, like the masterbatch composition, can contain the dispersed powder and solid medium of this embodiment. In the masterbatch of this embodiment, the solid medium can be arranged to cover and enclose, i.e., encapsulate, the composite tungsten oxide particles, for example. Furthermore, it is preferable that the acid-modified polyolefin polymer or copolymer, containing maleic anhydride or carboxylic acid anhydride, contained in the solid medium, covers, i.e., modifies, at least a portion of the surface of the composite tungsten oxide particles in the masterbatch of this embodiment. Accordingly, the masterbatch composition and masterbatch of this embodiment may also contain an acid-modified polyolefin polymer or copolymer, containing maleic anhydride or carboxylic acid anhydride, as a surface modification resin.

[0078] Figure 2 shows a schematic diagram of the masterbatch of this embodiment. As schematically shown in Figure 2, the masterbatch 20 of this embodiment may include, for example, composite tungsten oxide particles 21 and a solid medium 22, and the composite tungsten oxide particles 21 may be arranged in the solid medium 22. It is preferable that the composite tungsten oxide particles 21 are dispersed in the solid medium 22.

[0079] Figure 2 is a schematic diagram, and the masterbatch of this embodiment is not limited to this form. For example, in Figure 2, the composite tungsten oxide particles 21 are represented by circles and described 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 may also have a coating on their surface, for example. Although not shown in Figure 2, as previously described, the masterbatch 20 of this embodiment further contains a cationic surfactant. The cationic surfactant can be placed 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 may also contain other additives as needed. (1) Regarding the masterbatch composition and the components contained in the masterbatch Details of the cationic surfactant and composite tungsten oxide particles, as well as their preferred properties, have already been explained in the section on aqueous dispersions, so this explanation will be omitted here. The composite tungsten oxide particles, as previously described, have a hexagonal crystal structure and are represented by the general formula M x WO y This can be expressed as follows. The masterbatch composition of this embodiment and the solid medium contained in the masterbatch will be described below. (1-1) Solid medium (1-1-1) Acid-modified polyolefin polymers or copolymers with maleic anhydride or carboxylic acid anhydride In the masterbatch composition and masterbatch of this embodiment, it is preferable that the solid medium contains an acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic acid anhydride. The solid medium may consist of an acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic acid anhydride, and may also contain other resins as described later.

[0080] Acid-modified polyolefin polymers or copolymers with maleic anhydride or carboxylic anhydride are those in which the polyolefin polymer or polyolefin copolymer constituting the backbone is acid-modified with maleic anhydride or carboxylic anhydride.

[0081] Examples of polyolefin polymers that constitute the backbone of acid-modified polyolefin polymers or copolymers with maleic anhydride or carboxylic acid anhydride include one or more selected from polymers of a single olefin, i.e., homopolymers, such as polyethylene, polypropylene, polybutene, and polyoctene.

[0082] Furthermore, polyolefin copolymers that constitute the backbone of acid-modified polyolefin polymers or copolymers with maleic anhydride or carboxylic acid anhydride include 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, and propylene It can be one or more types selected from two-component copolymers such as n·5-ethlylidene-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-ethlylidene-2-norbornene copolymer, 1-butene-2,5-norbornadiene copolymer, and 1-butene-5-ethlylidene-2-norbornene copolymer.

[0083] Polyolefin copolymers that constitute the backbone of acid-modified polyolefin polymers or copolymers with maleic anhydride or carboxylic acid 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, and 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-norbornne 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-ethylene It can also be one or more types 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 acid 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 In the masterbatch composition and masterbatch of this embodiment, a resin may be further included in addition to the acid-modified polyolefin polymer or copolymer, provided by maleic anhydride or carboxylic acid anhydride. When the masterbatch composition of this embodiment contains a resin other than the acid-modified polyolefin polymer or copolymer, provided by maleic anhydride or carboxylic acid anhydride, it is preferable that composite tungsten oxide particles or the like are dispersed in the resin.

[0085] Resins other than acid-modified polyolefin polymers or copolymers using maleic anhydride or carboxylic acid anhydride are preferably thermoplastic resins, considering workability during molding. When the resin other than acid-modified polyolefin polymers or copolymers using maleic anhydride or carboxylic acid 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 in this embodiment may 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 may include one or more selected from low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), and ethylene-vinyl acetate copolymer.

[0087] Furthermore, the polylactic acid resin is not particularly limited and includes polys composed solely of L-lactic acid, polys composed solely of D-lactic acid, and polys in which L-lactic acid and D-lactic acid are present in various proportions.

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

[0089] For example, the masterbatch composition and masterbatch of this embodiment may contain dyes or pigments in order to adjust the color tone as needed.

[0090] As dyes and pigments, materials commonly used for coloring thermoplastic resins can be used, such as one or more selected from azo dyes, cyanine dyes, quinoline dyes, perylene dyes, carbon black, etc.

[0091] Furthermore, the masterbatch composition and masterbatch of this embodiment may also contain one or more stabilizers such as hindered phenols and phosphorus-based agents, release agents, ultraviolet absorbers such as hydroxybenzophenones, salicylic acids, HALS, triazoles, and triazines, coupling agents, surfactants, antistatic agents, etc.

[0092] The masterbatch composition and masterbatch of this embodiment contain additives such as dyes, pigments, stabilizers, and release agents. However, the amount of these additives is not particularly limited, and for example, each additive can be added and included in an amount that is effective in exhibiting a predetermined function. (2) Method for producing a masterbatch composition The master batch composition of this embodiment can be manufactured according to the flow chart 50 shown in Figure 5.

[0093] As shown in the flowchart 50 of Figure 5, the method for producing the masterbatch composition of this embodiment may include a dispersion preparation step S1, a surface modification step S2, a dispersion powder preparation step S3, and a masterbatch composition preparation step S4. Each step will be described below. (Dispersion liquid preparation process) In the dispersion preparation step S1, the composite tungsten oxide particles and water are mixed, and the composite tungsten oxide particles are crushed and dispersed to prepare the dispersion.

[0094] As the composite tungsten oxide particles used in the dispersion preparation step, for example, the composite tungsten oxide particles described for the aqueous dispersion can be used, so the explanation is omitted. The composite tungsten oxide particles have a hexagonal crystal structure as previously described, and their general formula is M x WO y It can be expressed as follows.

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

[0096] In the dispersion preparation process, for example, in the dispersion powder preparation process or the masterbatch composition preparation process, the conditions for grinding and dispersion processing can be selected so that the particle size of the composite tungsten oxide particles contained in the dispersion powder or masterbatch composition obtained afterward are within a predetermined range. For example, as already explained, the particle size 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. The particle size of the composite tungsten oxide particles may also 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 surface of the composite tungsten oxide particles.

[0097] The amount of cationic surfactant added is not particularly limited, but it 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 composite tungsten oxide particles.

[0098] In the surface modification step, a cationic surfactant may be added to the dispersion, and the dispersion may be stirred as needed.

[0099] By performing a surface modification step, an aqueous dispersion according to one aspect of this disclosure can be prepared. (Dispersed powder preparation process) In the dispersion powder preparation process, the dispersion powder can be prepared by evaporating water from the dispersion liquid after the surface modification process.

[0100] The specific method for evaporating water from the dispersion in the dispersion powder preparation process is not particularly limited. For example, one or more methods selected from natural drying in the atmosphere, heat drying using a dryer, vacuum drying in a vacuum atmosphere, spray drying, etc., can be used. In addition, multiple methods for evaporating water from the dispersion in the dispersion powder preparation process can be combined and carried out in multiple stages as needed. (Masterbatch composition preparation process) In the masterbatch composition preparation process, a masterbatch composition can be prepared by mixing a dispersed powder with a solid medium containing an acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic acid anhydride.

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

[0102] Suitable mixers for mixing include one or more types selected from ribbon blenders, tumblers, Nauter mixers, Henschel mixers, Super mixers, planetary mixers, and the like.

[0103] Furthermore, if an aqueous dispersion has been prepared in advance, the masterbatch manufacturing method can begin from the dispersion powder preparation step. Also, if a dispersion powder has been prepared in advance, the masterbatch manufacturing method can begin from the masterbatch composition preparation step. (3) Masterbatch The masterbatch of this embodiment can be prepared by melting and kneading the masterbatch composition using a melting kneader and processing it into pellets.

[0104] The temperature during melt-mixing is maintained at a temperature that prevents the solid medium being used from decomposing.

[0105] Suitable kneaders for melt-kneading include single-screw extruders and twin-screw extruders.

[0106] Masterbatch pellets can be obtained by cutting the most common molten extruded strands. Therefore, their shapes can be cylindrical or prismatic. Alternatively, a so-called hot-cut method, where the molten extruded material is cut directly, is also possible. In this case, the masterbatch is generally nearly spherical.

[0107] The masterbatch of this embodiment may take any form or shape. However, 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 body.

[0108] The masterbatch composition and masterbatch of this embodiment can use an aqueous dispersion or dispersion powder according to one aspect of the present disclosure as raw materials, thereby reducing the content of organic solvents. For example, the percentage of residual organic solvents can be reduced to 0.1% by mass or less, or even 0% by mass. [Near-infrared shielding transparent resin molded body, near-infrared shielding transparent laminate] Next, the near-infrared shielding transparent resin molded body of this embodiment will be described.

[0109] The near-infrared shielding transparent resin molded article of this embodiment is a molded article containing the above-mentioned masterbatch.

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

[0111] Furthermore, the near-infrared shielding transparent resin molded article of this embodiment may also contain a masterbatch and a thermoplastic resin. The thermoplastic resin is used to dilute the masterbatch and adjust the concentration of the composite tungsten oxide particles contained therein. For this reason, the thermoplastic resin is preferably the same type of resin as the solid medium contained in the masterbatch, or a different type of resin that is compatible with it. In other words, the thermoplastic resin is preferably a resin that can be mixed with the masterbatch without separating when kneaded together.

[0112] The solid medium contained in the masterbatch may consist solely of an acid-modified polyolefin polymer or copolymer due to maleic anhydride or carboxylic acid anhydride, or it may also contain a thermoplastic resin such as one or more resins selected from polyethylene resin, polylactic acid resin, and polypropylene resin. For this reason, it is preferable that the thermoplastic resin is either the same type of resin as the acid-modified polyolefin polymer or copolymer due to maleic anhydride or carboxylic acid anhydride contained in the masterbatch, or one or more resins selected from polyethylene resin, polylactic acid resin, and polypropylene resin, or a different resin that is compatible with it.

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

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

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

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

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

[0118] One method for obtaining plate-shaped or film-shaped molded products by extrusion molding is to manufacture them by extruding molten thermoplastic resin using an extruder such as a T-die and then taking it down while cooling it with a cooling roll.

[0119] The near-infrared shielding transparent resin molded body of this embodiment may be used as a structural material for windows, arcades, etc., by itself.

[0120] Furthermore, the near-infrared shielding transparent resin molded body of this embodiment can be laminated in any way onto other transparent molded bodies such as inorganic glass, resin glass, or resin film, and used as a structural material as an integrated near-infrared shielding transparent laminate.

[0121] In other words, the near-infrared shielding transparent laminate of this embodiment may have a transparent molded body and a near-infrared shielding transparent resin molded body according to one aspect of the present disclosure, laminated onto the transparent molded body.

[0122] Specifically, as shown in Figure 3, a schematic cross-sectional view along the lamination direction of the transparent molded body and the near-infrared shielding transparent resin molded body, the near-infrared shielding transparent laminate 30 may 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 placed on at least one surface 31A of the transparent molded body 31.

[0123] The near-infrared shielding transparent laminate of this embodiment is not limited to the form shown in Figure 3. For example, as shown in Figure 4, a schematic cross-sectional view along the lamination direction of a transparent molded body and a near-infrared shielding transparent resin molded body, the 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 interlayer, can be placed between the plurality of transparent molded bodies 411, 412. In Figure 4, an example having two transparent molded bodies 411, 412 is shown, but the embodiment 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 according to 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, as shown in Figures 3 and 4, for example. If the near-infrared shielding transparent laminate has multiple transparent molded bodies, their thickness and shape may differ.

[0125] The material of the transparent molded body is not particularly limited, but one or more materials selected from glass, resin sheets, resin boards, resin films, etc., can preferably be used. A transparent molded body is a material that transmits light in the visible light region, and the degree of light transmission in the visible light region can be arbitrarily selected depending on the application of the near-infrared shielding transparent laminate.

[0126] When a transparent molded product includes one or more types selected from resin sheets, resin boards, resin films, etc., the resin used is not particularly limited and can be selected according to the required characteristics such as the surface condition and durability of the sheet, board, or film. Examples of the above-mentioned resins include polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetylcellulose and triacetylcellulose, 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, or polyethylene-2,6-naphthalate are preferred in terms of mechanical properties, optical properties, heat resistance, and cost-effectiveness. The polyester-based biaxially oriented film may also be a copolymerized polyester.

[0127] The transparent molded body may also contain various additives, such as particles with infrared absorption properties, as needed.

[0128] The method for manufacturing the near-infrared shielding transparent laminate of this embodiment is not particularly limited. For example, a near-infrared shielding transparent laminate having near-infrared shielding and shatterproof functions can be obtained by laminating a pre-formed near-infrared shielding transparent resin molded body, which is a transparent molded body made of inorganic glass, with a thermal lamination method.

[0129] Furthermore, by using methods such as thermal lamination, co-extrusion, press molding, and injection molding, it is possible to obtain near-infrared shielding transparent laminates by laminating and integrating near-infrared shielding transparent resin molded bodies with other transparent molded bodies simultaneously during the molding process. These near-infrared shielding transparent laminates can be used as more useful structural materials by effectively utilizing the advantages of each molded body while compensating for their respective disadvantages.

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

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

[0132] The near-infrared shielding transparent resin molded article and the near-infrared shielding transparent laminate of this embodiment can use an aqueous dispersion or dispersion powder according to one aspect of the present disclosure as raw materials, thereby reducing the content of organic solvents. The near-infrared shielding transparent resin molded article and the near-infrared shielding transparent laminate of this embodiment can have a residual organic solvent content of, for example, 0.1% by mass or less, or even 0% by mass. [Examples]

[0133] The present invention will be described more specifically 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 transmittance of the near-infrared shielding transparent laminate were measured using a Hitachi U-4000 spectrophotometer. Solar transmittance is an indicator of 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 for the heat treatment process were prepared according to the following procedure.

[0134] 1.8 g of Cs2CO359, the raw material for element M, was dissolved in 900 g of water to prepare a solution containing element M. 70 g of H2WO424, the raw material for tungsten, was added to the solution containing element M, and the mixture was dried in a vacuum dryer while stirring to obtain the starting material as a dry powder.

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

[0136] Next, particle A was obtained by calcining at 800°C for 1 hour under an N2 gas atmosphere, i.e., an inert gas atmosphere. Chemical analysis revealed that the composition of particle A, which is a composite tungsten oxide particle, is Cs 0.33 WO 2.45 It was confirmed that particle A is hexagonal Cs as a result of powder X-ray diffraction. 0.3 The diffraction pattern matched that of WO3, confirming that it has a hexagonal crystal structure. (2) Preparation of the masterbatch composition (2-1) Dispersion liquid preparation process Next, a dispersion containing composite tungsten oxide particles was prepared by weighing 12.5% ​​by mass of particle A and 87.5% by mass of water, and then grinding and dispersing them for 2.5 hours in a medium-stirring mill containing a 0.3 mmφ ZrO2 bead.

[0137] The particle size of the composite tungsten oxide particles dispersed in the resulting dispersion was measured to be 20 nm. (2-2) Surface modification process To the dispersion obtained in the dispersion preparation step, cetyltrimethylammonium chloride, a cationic surfactant, was added at a ratio of 1.25% by mass relative to the composite tungsten oxide particles, and the mixture was held for 6 hours while stirring. Through the above procedure, an aqueous dispersion containing composite tungsten oxide particles surface-modified with a cationic surfactant was obtained (hereinafter also referred to as "Solution A"). (2-3) Dispersed powder preparation process From solution A, an aqueous dispersion obtained in the surface modification process, water was removed using a spray dryer to obtain a dry composite tungsten oxide particle dispersion (hereinafter also referred to as "dry powder A").

[0138] It has been confirmed that the dry powder A, which is the dispersed powder prepared in this embodiment, and the dispersed powders prepared and used in the following other embodiments, disperse the composite tungsten oxide particles in water and become an aqueous dispersion again when water is added. (2-4) Masterbatch composition preparation process A masterbatch composition was prepared by uniformly mixing dry powder A and maleic anhydride-modified ethylene-1-butene copolymer powder using a blender so that the composite tungsten oxide particles made up 10% by mass relative to the maleic anhydride-modified ethylene-1-butene copolymer powder.

[0139] In the "Acid-Modified Polyolefin Polymers (Copolymers)" column of Table 1, maleic anhydride-modified ethylene-1-butene copolymer is referred to as "MEB copolymer". (3) Manufacturing of masterbatches and near-infrared shielding transparent resin molded products 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 near-infrared shielding transparent resin molded articles (hereinafter also referred to as "Masterbatch A").

[0140] The obtained masterbatch A was heated and pressed at 130°C to obtain a near-infrared shielding transparent resin film A with a thickness of 43 μm, which is a near-infrared shielding transparent resin molded body.

[0141] In Table 1, under the "Near-Infrared Shielding Transparent Resin Molded Body" column, the "Composite Tungsten Oxide Particle Concentration" column indicates the concentration of composite tungsten oxide particles contained in the near-infrared shielding transparent resin molded body, and the "Thickness" column indicates the thickness of the near-infrared shielding transparent resin molded body.

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

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

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

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

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

[0147] [Example 4] In the surface modification step, dodecyltrimethylammonium chloride was used as the cationic surfactant instead of cetyltrimethylammonium chloride. Except for the above, a near-infrared shielding transparent resin film D was obtained using the same conditions and procedures as in Example 1.

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

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

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

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

[0152] [Example 6] The masterbatch A obtained in Example 1 was diluted with HDPE (high-density polyethylene) resin, a thermoplastic resin, to obtain a composite tungsten oxide particle concentration of 1% by mass.

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

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

[0155] [Example 7] The masterbatch A obtained in Example 1 was diluted with LLDPE (linear low-density polyethylene) resin, a thermoplastic resin, to a composite tungsten oxide particle concentration of 1% by mass.

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

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

[0158] [Example 8] In the dispersion preparation process, 20% by mass of particle A and 80% by mass of water were weighed out, and a dispersion containing composite tungsten oxide particles was prepared by grinding and dispersing them in a bead mill containing 0.3 mmφ ZrO2 beads for 5 hours.

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

[0160] In the surface modification step, cetyltrimethylammonium chloride, a cationic surfactant, was added to the dispersion obtained in the dispersion preparation step at a ratio of 2.0% by mass relative to the composite tungsten oxide particles, and the mixture was held for 10 hours while stirring. Through this operation, an aqueous dispersion containing composite tungsten oxide particles surface-modified with a cationic surfactant was obtained (hereinafter also referred to as "Solution H").

[0161] In the dispersion powder preparation process, water was removed from the aqueous dispersion liquid H obtained in the surface modification process using a spray dryer to obtain a dry composite tungsten oxide particle dispersion 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 uniformly mixed 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 constituted 10% by 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 near-infrared shielding transparent resin molded articles (hereinafter also referred to as "masterbatch H").

[0164] The obtained masterbatch H was diluted with LDPE (low-density polyethylene) resin, a thermoplastic resin, to obtain a composite tungsten oxide particle concentration of 1% by mass.

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

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

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

[0168] The obtained masterbatch I was diluted with LDPE (low-density polyethylene) resin, a thermoplastic resin, to a composite tungsten oxide particle concentration of 1% by mass.

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

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

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

[0172] The obtained masterbatch J was diluted with LDPE (low-density polyethylene) resin, a thermoplastic resin, to achieve a composite tungsten oxide particle concentration of 1% by mass.

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

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

[0175] [Example 11] (1) Preparation of composite tungsten oxide particles (Heat treatment process) The starting materials for the heat treatment process were prepared according to the following procedure.

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

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

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

[0179] Furthermore, particle K was obtained by calcining at 820°C for 0.5 hours under an N2 gas atmosphere.

[0180] Chemical analysis revealed that the composition of particle K, which is a composite tungsten oxide particle, is Cs 0.27 WO 2.86 This was confirmed. Furthermore, the particle K was found to be hexagonal Cs as a result of powder X-ray diffraction. 0.3 The diffraction pattern matched that of WO3, confirming that it has a hexagonal crystal structure.

[0181] Then, under the same conditions and procedures as in Example 1, except for the use of particle K, a near-infrared shielding transparent resin film K was manufactured, comprising an aqueous dispersion, a dispersion powder, a masterbatch composition, a masterbatch, and a near-infrared shielding transparent resin molded article.

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

[0183] [Example 12] (1) Preparation of composite tungsten oxide particles Composite tungsten oxide particles were manufactured using the following procedure.

[0184] A hybrid plasma reactor combining DC plasma and high-frequency plasma was used. 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. Subsequently, argon gas was supplied from the plasma generation gas supply port at a rate of 8 L / min to generate DC plasma. The DC power input at this time was 6 kW.

[0185] Furthermore, 40 L / min of argon gas and 3 L / min of hydrogen gas were flowed spirally from the sheath gas supply port along the inner wall of the water-cooled quartz tube as gases for generating high-frequency plasma and protecting the quartz tube, thereby generating high-frequency plasma. The high-frequency power input at this time was 45 kW. After generating the hybrid plasma in this way, a mixed gas of 3 L / min of argon gas and 0.15 L / min of oxygen gas was used as a carrier gas, and the starting material, which was the dried powder obtained in Example 1, was supplied into the plasma at a rate of 2 g / min from the raw material powder supply device.

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

[0187] Particle L, according to chemical analysis, has a composition of Cs 0.32 WO 3.16Therefore, powder X-ray diffraction results showed that hexagonal Cs 0.3 The diffraction pattern matched that of WO3, confirming that it has a hexagonal crystal structure.

[0188] Except for using particles L, a near-infrared shielding transparent resin film L was manufactured under the same conditions and procedures as in Example 1, comprising an aqueous dispersion, a dispersion powder, a masterbatch composition, a masterbatch, and a near-infrared shielding transparent resin molded article.

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

[0190] [Example 13] To prepare composite tungsten oxide particles, K2CO3 was used as the element M raw material and H2WO4 as the tungsten raw material when preparing the starting materials for the heat treatment process. The K2CO3 and H2WO4 were weighed and mixed so that the K / W molar ratio was 0.33 to obtain the starting materials.

[0191] Except for using the above-mentioned starting materials, a near-infrared shielding transparent resin film M was manufactured under the same conditions and procedures as in Example 1, comprising composite tungsten oxide particles, an aqueous dispersion, a dispersion powder, a masterbatch composition, a masterbatch, and a near-infrared shielding transparent resin molded article.

[0192] The composition of particle M, which is a composite tungsten oxide particle obtained in this embodiment, is K 0.33 WO 2.45 This was confirmed. Furthermore, the particle M was found to be hexagonal K based on powder X-ray diffraction results. 0.3 The diffraction pattern matched that of WO3, confirming that it 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] To prepare composite tungsten oxide particles, Rb2CO3 was used as the element M raw material and H2WO4 as the tungsten raw material when preparing the starting materials for the heat treatment process. Then, Rb2CO3 and H2WO4 were weighed and mixed so that the Rb / W molar ratio was 0.33 to obtain the starting materials.

[0194] Except for using the above-mentioned starting materials, a near-infrared shielding transparent resin film N was manufactured under the same conditions and procedures as in Example 1, comprising composite tungsten oxide particles, an aqueous dispersion, a dispersion powder, a masterbatch composition, a masterbatch, and a near-infrared shielding transparent resin molded article.

[0195] The composition of particle N, which is a composite tungsten oxide particle obtained in this embodiment, is Rb 0.33 WO 2.45 This was confirmed. Furthermore, the particle N was found to be hexagonal Rb as a result of powder X-ray diffraction. 0.33 The diffraction pattern matched that of WO3, confirming that it 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] To prepare composite tungsten oxide particles, BaCO3 was used as the element M raw material and H2WO4 as the tungsten raw material when preparing the starting materials for the heat treatment process. BaCO3 and H2WO4 were weighed and mixed so that the Ba / W molar ratio was 0.33 to obtain the starting materials.

[0197] Except for using the above-mentioned starting materials, a near-infrared shielding transparent resin film O was manufactured under the same conditions and procedures as in Example 1, comprising composite tungsten oxide particles, an aqueous dispersion, a dispersion powder, a masterbatch composition, a masterbatch, and a near-infrared shielding transparent resin molded article.

[0198] The composition of particle O, which is a composite tungsten oxide particle obtained in this example, is Ba 0.33 WO 2.45This was confirmed. Furthermore, the particle O was found to be hexagonal Ba as a result of powder X-ray diffraction. 0.21 The diffraction pattern matched that of WO3, confirming that it has a hexagonal crystal structure.

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

[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 "Acid-Modified Polyolefin Polymers (Copolymers)" column of Table 1, maleic anhydride-modified polypropylene is referred to as "MP polymer."

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

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

[0204] [Example 17] The masterbatch J obtained in Example 10 was diluted with polylactic acid resin to achieve a composite tungsten oxide particle concentration of 1% by mass. In other words, a 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, using the same conditions and procedure as in Example 1, except that a diluted masterbatch was used instead of masterbatch A, a near-infrared shielding transparent resin film Q, which is a near-infrared shielding transparent resin molded body, was obtained.

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

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

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

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

[0210] In the "Acid-Modified Polyolefin Polymers (Copolymers)" column of Table 1, carboxylic acid anhydride-modified polypropylene is referred to as "KP Polymer".

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

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

[0213] [Comparative Example 1] Except for the absence of cetyltrimethylammonium chloride in the surface modification step, an aqueous dispersion, a dispersion powder, a masterbatch composition, and a masterbatch were prepared under the same conditions and procedures as in Example 1.

[0214] Visual inspection of the masterbatch obtained in Comparative Example 1 revealed significant color unevenness, leading to the conclusion that the dispersibility of the composite tungsten oxide particles was poor. Therefore, the near-infrared shielding transparent resin molded product was not produced.

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

[0216] The masterbatch obtained in Comparative Example 2 showed significant color unevenness in its visual appearance, and it was determined that the dispersibility of the composite tungsten oxide particles was poor. Therefore, the near-infrared shielding transparent resin molded product was not manufactured.

[0217] [Table 1] As shown in Table 1, the near-infrared shielding transparent resin molded articles of Examples 1 to 19, the near-infrared shielding transparent resin sheets, 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 showed significant color unevenness in their visual appearance, and it was determined that the dispersibility of the composite tungsten oxide particles was poor, so the near-infrared shielding transparent resin molded articles were not 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 molded body 32 Near-infrared shielding transparent resin molding 31A One side 40 Near-infrared shielding transparent laminate 411 Transparent molded body 412 Transparent molded body 42 Near-infrared shielding transparent resin molding

Claims

1. Cationic surfactants and A crystal with a hexagonal crystal structure, general formula M ｘ WO ｙ (However, element M includes one or more elements selected from Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, and satisfies 0.1 ≤ x ≤ 1.0 and 2.0 ≤ y < 4.0) and comprises composite tungsten oxide particles, The cationic surfactant is a quaternary ammonium salt represented by formula (A), wherein R1 in formula (A) is an alkyl group having 1 to 18 carbon atoms, and X1- is an anion, and is a dispersed powder. 【Chemistry 1】

2. The dispersed powder according to claim 1, A water dispersion containing water.

3. The dispersed powder according to claim 1, A masterbatch composition comprising a solid medium containing an acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic acid anhydride.

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

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

6. A masterbatch, which is a molded article of the masterbatch composition according to claim 3 or claim 4.

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

8. A transparent molded body and A near-infrared shielding transparent laminate comprising a near-infrared shielding transparent resin molded body according to claim 7 laminated onto the transparent molded body.

9. A crystal with a hexagonal crystal structure, general formula M ｘ WO ｙ A dispersion preparation step involves mixing composite tungsten oxide particles (wherein element M is one or more elements selected from Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, and satisfies 0.1 ≤ x ≤ 1.0 and 2.0 ≤ y < 4.0) with water, and then grinding and dispersing the composite tungsten oxide particles to prepare a dispersion. A surface modification step is performed by adding a cationic surfactant to the dispersion to modify the surface of the composite tungsten oxide particles. A dispersion powder preparation step is performed in which water is evaporated from the dispersion liquid after the surface modification step to prepare a dispersion powder, The process includes a masterbatch composition preparation step of mixing the aforementioned dispersed powder with a solid medium containing an acid-modified polyolefin polymer or copolymer with maleic anhydride or carboxylic acid anhydride to prepare a masterbatch composition. A method for producing a masterbatch composition, wherein the cationic surfactant is a quaternary ammonium salt represented by formula (A), where R1 in formula (A) is an alkyl group having 1 to 18 carbon atoms, and X1- is an anion. 【Chemistry 2】

10. The method for producing a masterbatch composition according to claim 9, wherein the solid medium further comprises one or more resins selected from polyethylene resin, polylactic acid resin, and polypropylene resin.

11. A method for producing the masterbatch composition according to claim 9 or claim 10, wherein the dispersed particle size of the composite tungsten oxide particles is 200 nm or less.

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