Master batch, composition, near-infrared shielding transparent resin molded body, and near-infrared shielding transparent multilayer body

Abstract

Disclosed is a master batch which is used for the production of a near-infrared shielding transparent resin molded body, and which includes at least: a polymer dispersant having a functional group that is an amine group; a solid medium containing a maleic anhydride-modified polyolefin polymer or copolymer; and composite tungsten oxide particles which are disposed in the solid medium, and are represented by general formula MxWOy (where 0.1 ≤ x ≤ 1.0 and 2.0 ≤ y < 4.0), while having a hexagonal crystal structure.

Description

Masterbatch, composition, near-infrared shielding transparent resin molded body, and near-infrared shielding transparent laminate

[0001] The present invention relates to a masterbatch, a composition, a near-infrared shielding transparent resin molded article, and a near-infrared shielding transparent laminate.

[0002] It is generally known that materials containing free electrons exhibit a reflection / absorption response due to plasma oscillation to electromagnetic waves with wavelengths of 200 nm to 2600 nm, which are in the vicinity of the wavelength region of sunlight.

[0003] It is known that if the particles of the powder that make up the material containing free electrons are made into fine particles with a diameter smaller than the wavelength of light, the geometric scattering of the material containing free electrons in the visible light range (wavelengths of 380 nm to 780 nm) is reduced, and transparency in the visible light range is obtained.

[0004] The applicant of the present application has disclosed in Patent Document 1 an infrared-shielding material microparticle dispersion in which infrared-shielding material microparticles are dispersed in a medium, the infrared-shielding material microparticles containing tungsten oxide microparticles and / or composite tungsten oxide microparticles, and the infrared-shielding material microparticles have a particle diameter of 1 nm or more and 800 nm or less.

[0005] International Publication No. 2005 / 037932

[0006] However, when a masterbatch containing composite tungsten oxide particles is molded into a near-infrared shielding transparent resin molded article, the transmittance of light in the visible light region may be reduced, and the near-infrared shielding properties of the near-infrared shielding transparent resin molded article may be insufficient.

[0007] Therefore, one aspect of the present invention aims to provide a masterbatch that, when made into a near-infrared shielding transparent resin molded article, has good light transmittance in the visible light region and excellent near-infrared shielding function.

[0008] In one aspect of the present invention, there is provided a masterbatch for use in producing a near-infrared shielding transparent resin molding, the masterbatch comprising: a polymer dispersant having at least an amine functional group; a solid medium containing a maleic anhydride-modified polyolefin polymer or copolymer; and a polymer having a hexagonal crystal structure and general formula M ｘ WO ｙ (wherein the M element is one or more elements selected from H, He, alkali metal elements, alkaline earth metal elements, rare earth elements, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Hf, Os, Bi, and I, and satisfying 0.1≦x≦1.0 and 2.0≦y<4.0).

[0009] According to one aspect of the present invention, a masterbatch can be provided which, when made into a near-infrared shielding transparent resin molded article, has good light transmittance in the visible light region and an excellent near-infrared shielding function.

[0010] Fig. 1 is a schematic diagram of a masterbatch according to one embodiment of the present disclosure. Fig. 2 is a schematic diagram of a near-infrared shielding transparent laminate according to one embodiment of the present disclosure.

[0011] 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.

[0012] [Masterbatch] The inventors of the present invention have conducted extensive research into a masterbatch that, when made into a near-infrared shielding transparent resin molded article, has good light transmittance in the visible light region and excellent near-infrared shielding function. As a result, the inventors of the present invention have found that the above-mentioned problems can be solved by preparing a masterbatch containing a polymer dispersant having a specific functional group, a solid medium containing a maleic anhydride-modified polyolefin polymer or copolymer, and composite tungsten oxide particles.

[0013] This is thought to be because the masterbatch containing a polymer dispersant having a specific functional group, a solid medium containing a maleic anhydride-modified polyolefin polymer or copolymer, and composite tungsten oxide particles prevents the composite tungsten oxide particles from aggregating during molding, etc. Therefore, when a near-infrared shielding transparent resin molded article containing the masterbatch of this embodiment is made, it has good light transmittance in the visible light region and can exhibit excellent near-infrared shielding properties.

[0014] The masterbatch of this embodiment is a masterbatch used for producing a near-infrared shielding transparent resin molded article, and therefore can also be called a masterbatch for a near-infrared shielding transparent resin molded article.

[0015] The masterbatch of this embodiment contains a polymer dispersant, a solid medium, and composite tungsten oxide particles. (1) Components contained in the masterbatch The components (materials) contained in the masterbatch of this embodiment will be described below. (1-1) Composite tungsten oxide particles (Composition) The composite tungsten oxide particles have a hexagonal crystal structure and are represented by the general formula M ｘ WO ｙ It is expressed as:

[0016] However, it is preferable that x and y in the above general formula satisfy the conditions of 0.1≦x≦1.0 and 2.0≦y<4.0. Note that in the above general formula, M represents the element M described below, W represents tungsten, and O represents oxygen.

[0017] The amount x of the M element added is preferably 0.1 or more and 1.0 or less, more preferably around 0.33, and specifically, for example, 0.25 or more and 0.39 or less. This is because the value theoretically calculated from the hexagonal crystal structure is 0.33, and particularly preferable optical properties can be obtained with an amount added around this range.

[0018] The range of the oxygen content y is preferably 2.0≦y<4.0.

[0019] The element M represented by M in the above general formula contained in the composite tungsten oxide particles is not particularly limited, but may be H, He, an alkali metal element, an alkaline earth metal element, a rare earth element, 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), etc. It is preferable that the element is one or more elements selected from the group consisting of Cr (chromium), In (indium), 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), Hf (hafnium), Os (osmium), Bi (bismuth), and I (iodine).

[0020] 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 Be (beryllium), Mg (magnesium), 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).

[0021] The M element more preferably includes one or more elements selected from, for example, Cs, Rb, K, Tl, Ba, and In. Note that the M element may be composed of only one or more elements selected from Cs, Rb, K, Tl, Ba, and In.

[0022] This is because when the M element contains one or more elements selected from Cs, Rb, K, Tl, Ba, and In, the composite tungsten oxide particles are more likely to have a hexagonal crystal structure, thereby particularly increasing the transmittance of light in the visible light range and also improving the near-infrared shielding function.

[0023] Typical examples of the material for the composite tungsten oxide particles include Cs ０．３３ WO ３ , Rb ０．３３ WO ３ , K. ０．３３ WO ３ , Ba ０．３３ WO ３ Examples include, but as long as x and y fall within the above ranges, useful near-infrared shielding properties can be obtained. (Regarding dispersed particle size) The composite tungsten oxide particles used as a near-infrared shielding material in the masterbatch of this embodiment largely absorb light in the near-infrared region, particularly in the vicinity of a wavelength of 1000 nm. For this reason, many composite tungsten oxide particles have a blue-based transmitted color tone. The particle size of the composite tungsten oxide particles can be appropriately selected depending on the intended use.

[0024] First, when used in applications that require transparency to light in the visible light region, the composite tungsten oxide particles preferably have a dispersed particle diameter of 800 nm or less. Note that, in this specification, the term "transparency" is used to mean that there is little scattering of light in the visible light region and that light in the visible light region has high transmittance.

[0025] When the dispersed particle diameter of the composite tungsten oxide particles is 800 nm or less, the light is not completely blocked by scattering, and the visibility of light in the visible light region is maintained, and at the same time, the transparency of light in the visible light region can be efficiently maintained. In particular, when the transparency of light in the visible light region is important, it is preferable to further consider the scattering of light by the particles.

[0026] Furthermore, when particularly focusing on reducing light 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. This is because, if the dispersed particle diameter of the composite tungsten oxide particles is small, scattering of light in the visible light region due to geometric scattering or Mie scattering is reduced. As a result of reducing light scattering by the composite tungsten oxide particles, particularly clear transparency can be obtained for the masterbatch of this embodiment and the near-infrared shielding film obtained using the masterbatch of this embodiment.

[0027] That is, 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 Rayleigh scattering region is reached. In the Rayleigh scattering region, scattered light is reduced in proportion to the sixth power of the particle diameter, so scattering is reduced as the dispersed particle diameter decreases, and transparency is improved. Furthermore, when the dispersed particle diameter is 100 nm or less, scattered light is significantly reduced, which is preferable. From the viewpoint of avoiding light scattering, the dispersed particle diameter of the composite tungsten oxide particles is preferably small. Therefore, although the lower limit of the dispersed particle diameter is not particularly limited, since industrial production is easy if the dispersed particle diameter is 1 nm or more, the dispersed particle diameter can be, for example, 1 nm or more.

[0028] The dispersed particle size of the composite tungsten oxide particles can be measured using an instrument based on dynamic light scattering, such as an ELS-8000 manufactured by Otsuka Electronics Co., Ltd. (Method for Producing Composite Tungsten Oxide Particles) The method for producing the composite tungsten oxide particles contained in the master batch 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.

[0029] 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. The method for producing composite tungsten oxide particles can also include an oxidation treatment step in which oxidation treatment is performed in a mild environment after the heat treatment step.

[0030] The starting material may include a tungsten-containing tungsten source, which serves as a tungsten supply source. The tungsten source preferably includes one or more selected from the group consisting of tungsten acid, tungsten trioxide, tungsten dioxide, tungsten oxide hydrate, tungsten hexachloride, ammonium tungstate, a tungsten compound powder obtained by drying an aqueous solution of ammonium tungstate, and metallic tungsten. The tungsten source may be a powder of the above material, or may include a solution containing one or more selected from the above materials.

[0031] As the tungsten oxide hydrate, for example, a tungsten oxide hydrate powder obtained by dissolving tungsten hexachloride in alcohol and then drying, or a tungsten oxide hydrate powder obtained by dissolving tungsten hexachloride in alcohol, adding water to precipitate, and then drying the precipitate, can be used.

[0032] 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.

[0033] The starting material for the composite tungsten oxide particles may also include an M element raw material containing the M element, which serves as a supply source of the M element. The M element raw material preferably includes, for example, one or more types selected from a simple substance of the M element and an M element-containing compound.

[0034] Here, in order to produce a starting material in which each component is mixed uniformly at the molecular level, it is preferable to mix the respective raw materials in the form of a solution. Therefore, it is preferable that the M element raw material be soluble in a solvent such as water or an organic solvent. For this reason, examples of the M element raw material include, but are not limited to, tungstates, chlorides, nitrates, sulfates, oxalates, oxides, carbonates, hydroxides, etc. containing the M element, and any raw material that can be formed into a solution can be suitably used.

[0035] By using the above starting materials and subjecting them to a heat treatment step in an inert gas atmosphere or a reducing gas atmosphere, composite tungsten oxide particles having the above-mentioned dispersed particle size can be obtained.

[0036] In the heat treatment step, the heat treatment conditions in the inert gas atmosphere are preferably, for example, 650°C or higher. The starting material heat treated at 650°C or higher has sufficient near-infrared shielding function and is efficient as heat ray shielding fine particles. The upper limit of the heat treatment temperature in the inert gas atmosphere is not particularly limited, but can be, for example, 1200°C or lower. Examples of the inert gas include Ar, N ２ Inert gases such as the above can be used.

[0037] In the heat treatment step, the heat treatment conditions in a reducing gas atmosphere are preferably such that the starting material is first heat treated in a reducing gas atmosphere at a temperature of 300° C. to 1000° C., and then heat treated in an inert gas atmosphere at a temperature of 650° C. to 1200° C. The reducing gas used in the reducing gas atmosphere is not particularly limited, but may be H ２ The reducing gas is preferably H ２ When using the reducing gas atmosphere, the composition of the reducing gas atmosphere is, for example, Ar, N ２ Inert gas such as H ２ It is preferable that the amount of H be 0.1% or more by volume, and more preferably 0.2% or more. ２ By using a reducing gas atmosphere containing 0.1% or more by volume, reduction can be efficiently carried out.

[0038] H as a reducing gas ２ When using H, the upper limit of the proportion of the reducing gas in the reducing gas atmosphere is not particularly limited. ２ Therefore, the volume ratio of the reducing gas in the reducing gas atmosphere can be 100% or less.

[0039] The inert gas in the inert gas atmosphere that is carried out after the heat treatment in the reducing gas atmosphere is Ar, N ２ Inert gases such as the above can be used.

[0040] When oxidation treatment is performed in a mild environment after the heat treatment step, the oxygen source gas is not particularly limited, but is preferably at least one 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. For example, a temperature of 400°C or higher and 850°C or lower is preferred.

[0041] The composite tungsten oxide particles exhibiting the near-infrared shielding function of this embodiment may be surface-treated with at least one compound selected from the group consisting of silane compounds, titanium compounds, aluminum compounds, and zirconium compounds. The surface of the composite tungsten oxide particles is preferably coated with a compound containing at least one compound selected from the group consisting of Si, Ti, Al, and Zr, because this improves weather resistance.

[0042] In addition, from the viewpoint of molding the masterbatch of this embodiment to obtain a near-infrared shielding transparent resin molded product having a desired color, the powder color of the composite tungsten oxide particles is L ＊ is 25 or more and 80 or less, a ＊ is between -10 and 10, b ＊ It is desirable that the condition be met between -15 and 15. The above color parameters are the L recommended by the International Commission on Illumination (CIE). ＊ a ＊ b ＊ It means the powder color in the color space (JIS Z 8729 (2004)).

[0043] The color of the composite tungsten oxide particles can be selected by the conditions of the heat treatment process, etc. (1-2) Polymer Dispersant Polymer dispersants are used for the purpose of hydrophobizing the surfaces of the composite tungsten oxide particles. The polymer dispersant can be selected according to the dispersion system, which is a combination of composite tungsten oxide particles, a solid medium, etc.

[0044] The polymer dispersant is preferably a polymer dispersant having at least an amine functional group, for example.

[0045] The polymer dispersant is more preferably a copolymer having at least an amine functional group and further having one or more functional groups selected from a hydroxyl group, a carboxyl group, a carbonyl group, a sulfo group, a phospho group, and an epoxy group.

[0046] The amount of polymer dispersant added can be selected depending on the type of polymer dispersant and composite tungsten oxide particles, the specific surface area of ​​the composite tungsten oxide particles, and other factors, and is not particularly limited. For example, the amount of polymer dispersant added can be 10 parts by mass or more and 100 parts by mass or less per 100 parts by mass of composite tungsten oxide particles. That is, in the masterbatch of this embodiment, when the content of the composite tungsten oxide particles is 100 parts by mass, the content of the polymer dispersant is preferably 10 parts by mass or more and 100 parts by mass or less. The masterbatch of this embodiment preferably contains 10 parts by mass or more and 100 parts by mass or less of the polymer dispersant per 100 parts by mass of the composite tungsten oxide particles, because this facilitates the preparation of a dispersion or masterbatch with a particularly well-dispersed state of the composite tungsten oxide particles. (1-3) Solid Medium (1-3-1) Maleic Anhydride-Modified Polyolefin Polymer or Copolymer The masterbatch of this embodiment preferably contains a maleic anhydride-modified polyolefin polymer or copolymer as the solid medium. The solid medium may be comprised of a maleic anhydride modified polyolefin polymer or copolymer and may further contain other resins as described below.

[0047] The maleic anhydride-modified polyolefin polymer or copolymer contained in the solid medium preferably covers, in other words modifies, at least a portion of the surface of the composite tungsten oxide particles.

[0048] The solid medium can be arranged, for example, to surround and contain, i.e., enclose, the composite tungsten oxide particles.

[0049] 1 , the masterbatch 10 of the present embodiment can include, for example, composite tungsten oxide particles 11 and a solid medium 12, and the composite tungsten oxide particles 11 can be disposed in the solid medium 12. The composite tungsten oxide particles 11 are preferably dispersed in the solid medium 12.

[0050] Note that FIG. 1 is a schematic diagram, and the masterbatch of this embodiment is not limited to this form. For example, in FIG. 1, the composite tungsten oxide particles 11 are represented by circles and are depicted as spherical particles, but the shape of the composite tungsten oxide particles 11 is not limited to this form and can have any shape. The composite tungsten oxide particles 11 can also have, for example, a coating on their surfaces. Furthermore, although not shown in FIG. 1, as described above, the masterbatch 10 of this embodiment further contains a polymer dispersant. Furthermore, the masterbatch 10 of this embodiment can also contain other additives as necessary.

[0051] The polyolefin constituting the skeleton of the maleic anhydride modified polyolefin polymer or copolymer may be, for example, one or more types selected from homopolymers such as polyethylene, polypropylene, polybutene, and polyoctene.

[0052] The polyolefin polymer or copolymer constituting the skeleton of the maleic anhydride modified polyolefin polymer or copolymer is an ethylene-propylene copolymer, an ethylene-1-butene copolymer, a propylene-1-butene copolymer, a propylene-1-hexene copolymer, a propylene-4-methyl-1-pentene copolymer, a propylene-1-octene copolymer, a propylene-1-decene copolymer, a propylene-1,4-hexadiene copolymer, a propylene-dicyclopentadiene copolymer, a propylene-5-ethylidene-2-norbornene copolymer, a propylene-2,5-norbornadiene copolymer, a propylene-5- It may be one or more selected from two-component copolymers such as 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.

[0053] Furthermore, the polyolefin polymer or copolymer constituting the skeleton of the maleic anhydride modified polyolefin polymer or copolymer is an ethylene-propylene-1-butene copolymer, an ethylene-propylene-1-hexene copolymer, an ethylene-propylene-1-octene copolymer, an ethylene-propylene-1-octene copolymer, an ethylene-propylene-1,4-hexadiene copolymer, an ethylene-propylene-1,4-hexadiene copolymer, an ethylene-propylene-1,4-hexadiene copolymer, an ethylene-propylene-1,4-dimethylsilyl ... cyclopentadiene 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, ethylene-propylene-2,5-norbornadiene copolymer ethylene 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 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.

[0054] Of the polyolefin polymers or copolymers that constitute the backbone of these maleic anhydride-modified polyolefin polymers or copolymers, the polyolefin polymer or copolymer is preferably one or more selected from polyethylene, polypropylene, polybutene, polyoctene, ethylene-propylene copolymer, ethylene-1-butene copolymer, propylene-1-butene copolymer, ethylene-propylene-1-butene copolymer, and 1-octene-ethylene copolymer. (1-3-2) Polyethylene Resin The solid medium can also contain a resin other than the maleic anhydride-modified polyolefin polymer or copolymer.

[0055] Considering workability during molding, the resin other than the maleic anhydride-modified polyolefin polymer or copolymer is preferably a thermoplastic resin. When the resin contained in the solid medium other than the maleic anhydride-modified polyolefin polymer or copolymer is a thermoplastic resin, a polyethylene resin can be suitably used as the thermoplastic resin. Therefore, the solid medium can also contain a polyethylene resin.

[0056] The polyethylene resin is not particularly limited, and examples thereof include one or more selected from low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), and ethylene-vinyl acetate copolymer. (2) Masterbatch Manufacturing Method The masterbatch manufacturing method of this embodiment can include a hydrophobization / dispersion step in which the surfaces of the composite tungsten oxide particles are hydrophobized with a polymer dispersant and the composite tungsten oxide particles are dispersed in a solid medium. As the polymer dispersant, the above-mentioned polymer dispersant having at least an amine functional group can be used. As the solid medium, a maleic anhydride-modified polyolefin polymer or copolymer can be used, and a thermoplastic resin such as polyethylene resin can also be contained.

[0057] In the hydrophobization / dispersion step, the hydrophobization step of hydrophobizing the surfaces of the composite tungsten oxide particles with a polymer dispersant and the dispersion step of dispersing the composite tungsten oxide particles in a solid medium may be carried out simultaneously or as separate steps.

[0058] In the hydrophobization and dispersion step, the method for dispersing the composite tungsten oxide particles, which are particles having a near-infrared shielding function, in a solid medium can be selected arbitrarily as long as it is a method that can disperse the composite tungsten oxide particles in a solid medium.

[0059] For example, first, a dispersion liquid is prepared by dispersing the composite tungsten oxide particles in a solvent (dispersion medium) using a method such as a bead mill, a ball mill, a sand mill, ultrasonic dispersion, etc. Next, the dispersion liquid, a polymer dispersant, powder or pellets of a solid medium, and other additives, if necessary, are melt-mixed using a mixer or kneader while removing the solvent from the dispersion liquid.

[0060] By melt mixing, a mixture can be prepared in which composite tungsten oxide particles are uniformly dispersed in a solid medium. Furthermore, the surfaces of the composite tungsten oxide particles can be hydrophobized with a polymer dispersant. In other words, the hydrophobization process and the dispersion process can be carried out simultaneously.

[0061] The temperature during kneading is maintained at a temperature at which the solid medium used does not decompose.

[0062] Examples of mixers that can be suitably used for melt mixing include ribbon blenders, tumblers, Nauta mixers, Henschel mixers, super mixers, planetary mixers, etc. Examples of kneading machines that can be used include Banbury mixers, kneaders, rolls, kneader-ruders, single-screw extruders, twin-screw extruders, etc.

[0063] Furthermore, in the hydrophobizing and dispersing step, the surfaces of the composite tungsten oxide particles can be hydrophobized with a polymer dispersant, and the composite tungsten oxide particles can be dispersed in a solid medium using the following method.

[0064] First, a polymer dispersant is added to a dispersion of composite tungsten oxide particles having near-infrared shielding properties, and the solvent is removed by a known method. This results in composite tungsten oxide particles whose surfaces have been hydrophobized with the polymer dispersant (hydrophobization step). The powder of composite tungsten oxide particles whose surfaces have been hydrophobized with the polymer dispersant obtained in this hydrophobization step can also be called a dispersed powder.

[0065] Next, the powder obtained in the hydrophobization step, the solid medium powder or pellets, and, if necessary, other additives may be melt-mixed to prepare a mixture in which the composite tungsten oxide particles are uniformly dispersed in the solid medium (dispersion step).

[0066] In this case, the hydrophobizing step and the dispersion step are carried out as separate steps.

[0067] The composite tungsten oxide particles having their surfaces hydrophobized with a polymer dispersant obtained in the hydrophobizing step, powder or pellets of the solid medium, and other additives as needed, can be mixed to prepare a composition as described below. The composition can be dispersed, for example, by melting and kneading the contained solid medium, and then molded into a desired shape to produce a masterbatch or a near-infrared shielding transparent resin molded product.

[0068] As another method for the hydrophobization and dispersion step, a method can be used in which a powder of composite tungsten oxide particles that has not been subjected to dispersion treatment and a polymer dispersant are directly added to a solid medium and melt-mixed.

[0069] In this case, the hydrophobizing step and the dispersion step can be carried out in one step.

[0070] The hydrophobization / dispersion step is not limited to these methods as long as the surfaces of the composite tungsten oxide particles are hydrophobized with a polymer dispersant and the composite tungsten oxide particles are dispersed in a solid medium.

[0071] The method for producing a masterbatch of the present embodiment may further include a molding step of molding the mixture obtained in the hydrophobizing / dispersing step, which is a solid medium in which the composite tungsten oxide particles are dispersed, into pellets.

[0072] In the molding step, the mixture obtained in the hydrophobization / dispersion step can be kneaded in a vented single-screw or twin-screw extruder and processed into pellets. The masterbatch of this embodiment can be obtained by the molding step.

[0073] 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.

[0074] As described above, the masterbatch of the present embodiment can have any form or shape, although it is preferable that the masterbatch has the same or similar size and shape as the thermoplastic resin used to dilute the masterbatch when molding the near-infrared shielding transparent resin molded article.

[0075] The masterbatch of this embodiment may further contain common additives. For example, in order to impart a desired color tone as needed, the masterbatch of this embodiment may contain one or more dyes or pigments that are generally used to color thermoplastic resins, such as azo dyes, cyanine dyes, quinoline dyes, perylene dyes, and carbon black.

[0076] The masterbatch of the present embodiment may also contain one or more selected from the group consisting of hindered phenol-based, phosphorus-based, and other stabilizers, release agents, hydroxybenzophenone-based, salicylic acid-based, HALS-based, triazole-based, and triazine-based ultraviolet absorbers, coupling agents, surfactants, and antistatic agents.

[0077] When the masterbatch of this embodiment contains additives such as dyes, pigments, stabilizers, and release agents, the content thereof is not particularly limited, and for example, each additive can be added or contained in an amount that is effective for exhibiting a predetermined function. [Composition] Next, the composition of this embodiment will be described.

[0078] The composition of this embodiment is a composition used to produce a masterbatch according to one aspect of the present disclosure, and contains a polymer dispersant, a solid medium, and composite tungsten oxide particles. The composition of this embodiment can also be referred to as a masterbatch composition. Furthermore, since the composition of this embodiment is a mixture containing components (materials) such as a polymer dispersant, it can also be referred to as a mixed composition, mixed powder, or the like.

[0079] The polymer dispersant is preferably a polymer dispersant having at least an amine functional group.

[0080] The solid medium is preferably a solid medium containing a maleic anhydride modified polyolefin polymer or copolymer.

[0081] The composite tungsten oxide particles have a hexagonal crystal structure and are represented by the general formula M ｘ WO ｙ It is preferable that the composite tungsten oxide particles be represented by the formula: In addition, the same materials as those described for the masterbatch can be suitably used as the polymer dispersant, solid medium, and composite tungsten oxide particles, and the suitable content ratios of each component, such as the polymer dispersant, can also be the same as those for the masterbatch. Therefore, explanations of each material and their suitable content ratios will be omitted.

[0082] The composition of the present embodiment is only required to contain a polymer dispersant, a solid medium, and composite tungsten oxide particles, and the state and arrangement of each of these components are not particularly limited.

[0083] For example, as a material containing a polymer dispersant and composite tungsten oxide particles, a dispersed powder obtained by adding a polymer dispersant to a dispersion of composite tungsten oxide particles and then removing the solvent can be used. The dispersed powder can have a configuration in which the polymer dispersant is disposed on the surface of the composite tungsten oxide particles. A mixture of the dispersed powder and a solid medium can then be used as the composition of this embodiment. However, as mentioned above, the form of the composition of this embodiment is not limited to the above configuration. The composition of this embodiment may also be a mixture of, for example, a polymer dispersant, a solid medium, and composite tungsten oxide particles.

[0084] The composition of this embodiment can be made into the above-mentioned master batch or near-infrared shielding transparent resin molded article by melting, kneading, etc. the solid medium contained therein and further molding it into a desired shape. The bonding state, form, arrangement, etc. of each component contained in the composition of this embodiment may remain the same or may change and become different before and after melting, kneading, molding, etc. to make a master batch, etc. Note that when the composition of this embodiment is melted, kneaded, molded, etc., various additives can also be added as needed. [Near-infrared shielding transparent resin molded article, near-infrared shielding transparent laminate] Next, the near-infrared shielding transparent resin molded article of this embodiment will be described.

[0085] The near-infrared shielding transparent resin molded article of the present embodiment is a molded article containing the above-mentioned masterbatch.

[0086] 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.

[0087] 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 contained in the masterbatch. In other words, it is preferable that the thermoplastic resin is a resin that can be mixed with the masterbatch without separation when kneaded.

[0088] The solid medium contained in the masterbatch may be a maleic anhydride-modified polyolefin polymer or copolymer only, or may further contain a thermoplastic resin such as a polyethylene resin. For example, when the masterbatch contains a maleic anhydride-modified polyolefin polymer or copolymer and a polyethylene resin, the thermoplastic resin is preferably the same type of resin as either the maleic anhydride-modified polyolefin polymer or copolymer or the polyethylene resin, or a different type of resin that is compatible with them.

[0089] 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.

[0090] The near-infrared shielding transparent resin molded product of this embodiment is produced using the masterbatch according to one aspect of the present disclosure, and therefore suffers from very little thermal degradation during molding. Therefore, the composite tungsten oxide particles, which are near-infrared shielding particles, are sufficiently dispersed in the near-infrared shielding transparent resin molded product. As a result, the near-infrared shielding transparent resin molded product of this embodiment has a good visible light transmittance and exhibits excellent near-infrared shielding properties.

[0091] The near-infrared shielding transparent resin molding of this embodiment can be molded into any shape as needed, and can be molded into a flat or curved shape.

[0092] The thickness of the near-infrared shielding transparent resin molding of the present embodiment is not particularly limited and can be adjusted to any thickness as needed. Furthermore, a resin sheet molded into a flat shape can also be molded into any shape, such as a spherical shape, by post-processing.

[0093] The near-infrared shielding transparent resin molded article of the present 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 the present embodiment can be molded by a method of obtaining a molded article by injection molding or a method of obtaining a molded article by extrusion molding.

[0094] A method for obtaining a plate-shaped or film-shaped molded product by extrusion molding is to extrude a molten thermoplastic resin using an extruder such as a T-die, and take it up while cooling it with a cooling roll.

[0095] The near-infrared shielding transparent resin molding can be used by itself as a structural material for window glass, arcades, and the like.

[0096] 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.

[0097] 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.

[0098] 2 , which is a cross-sectional schematic view along the lamination direction of the transparent molded body 21 and the near-infrared shielding transparent resin molded body 22, the near-infrared shielding transparent laminate 20 can have the transparent molded body 21 and the near-infrared shielding transparent resin molded body 22. The near-infrared shielding transparent resin molded body 22 can be disposed on at least one surface 21A of the transparent molded body 21.

[0099] For example, a near-infrared shielding transparent resin molded body that has been previously formed into a film can be laminated and integrated onto a transparent molded body of inorganic glass by a thermal lamination method to obtain a near-infrared shielding transparent laminate having near-infrared shielding and shatterproof functions.

[0100] 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.

[0101] 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.

[0102] A masterbatch according to one embodiment of the present disclosure includes a polymer dispersant having a specific functional group, a solid medium containing a maleic anhydride-modified polyolefin polymer or copolymer, and composite tungsten oxide particles. Therefore, when molding the masterbatch, aggregation of the composite tungsten oxide particles can be prevented. As a result, the near-infrared shielding transparent resin molded product and the near-infrared shielding transparent laminate of this embodiment have good light transmittance in the visible light region and can exhibit excellent near-infrared shielding properties.

[0103] Up to this point, examples have been shown of the near-infrared shielding transparent resin molded product and near-infrared shielding transparent laminate of the present embodiment containing a masterbatch according to one aspect of the present disclosure and produced using the masterbatch according to one aspect of the present disclosure, but the present embodiment is not limited to such examples. The near-infrared shielding transparent resin molded product and near-infrared shielding transparent laminate of the present embodiment may contain a composition according to one aspect of the present disclosure and may be produced using a composition according to one aspect of the present disclosure.

[0104] Therefore, the near-infrared shielding transparent resin molding of the present embodiment can also be said to be a molding containing the composition according to one aspect of the present disclosure.

[0105] When the near-infrared shielding transparent resin molded article of the present embodiment is a molded article containing the composition according to one aspect of the present disclosure, the composition according to one aspect of the present disclosure can be used instead of the masterbatch as a raw material for the near-infrared shielding transparent resin molded article. Other than the above points, the explanation is the same as up to this point, except that the explanation is the same as the explanation except for replacing the masterbatch with the composition, and therefore further explanation will be omitted.

[0106] Examples of the present invention will be specifically described below together with comparative examples, but the present invention is not limited to the following examples.

[0107] In each example, the visible light transmittance and solar radiation transmittance of the near-infrared shielding transparent resin film 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.

[0108] [Example 1] (1) Preparation of composite tungsten oxide particles Cs ２ CO ３ 10.8 g was dissolved in H ２ WO ４ The mixture was added to 50 g of the sucrose solution and dried in a vacuum dryer while stirring to prepare a dry powder (raw material preparation). ２ 2% H by volume with gas as carrier ２ The mixture was heated while feeding gas, and calcined at a temperature of 800°C for 0.5 hours. ２ The mixture was fired in a gas atmosphere at 800° C. for 1 hour to obtain composite tungsten oxide particles, particles a.

[0109] Chemical analysis shows that particle a has a composition of Cs ０．３３ WO ２．４５ It was confirmed that the composition is shown in the "Composition" column of "Composite Tungsten Oxide Particles" in Table 1. Furthermore, as a result of powder X-ray diffraction, the peak position of the diffraction line of particle a is hexagonal Cs ０．３ WO ３ It was therefore confirmed that particle a has a hexagonal crystal structure.

[0110] (2) Preparation of Composition and Masterbatch Next, 20% by mass of particles a, 6% by mass of a polymer dispersant (MMA-DMAEMA polymer) which is a copolymer of methyl methacrylate (MMA) and dimethylaminoethyl methacrylate (DMAEMA) and has carbonyl and amine functional groups, and 74% by mass of toluene were weighed out. The weighed material was pulverized and dispersed for 24 hours in a paint shaker containing 0.3 mm diameter ZrO beads to prepare a composite tungsten oxide particle dispersion (Liquid A).

[0111] The dispersed particle diameter of the composite tungsten oxide particles in the composite tungsten oxide particle dispersion liquid (liquid A) was measured and found to be 20 nm. Note that when the content of the composite tungsten oxide particles in the composition or master batch is taken as 100 parts by mass, the content of the polymer dispersant is 30 parts by mass.

[0112] The dispersed particle size was measured using a particle size measuring device (ELS-8000 manufactured by Otsuka Electronics Co., Ltd.) based on the dynamic light scattering method.

[0113] Thereafter, the toluene, which corresponds to the solvent, was removed from Solution A using a spray dryer, to obtain a composite tungsten oxide particle dispersion powder (hereinafter abbreviated as dispersion powder A) (hydrophobization step).

[0114] The obtained dispersion powder A and the powder of maleic anhydride-modified ethylene / 1-butene copolymer were uniformly mixed using a blender so that the composite tungsten oxide particles accounted for 3.5% by mass relative to the powder of maleic anhydride-modified ethylene / 1-butene copolymer, thereby preparing a composition.

[0115] The obtained composition was melt-kneaded at 180°C using a twin-screw extruder (dispersion step), and the extruded strands were cut into pellets to obtain a masterbatch for a near-infrared shielding transparent resin molding (hereinafter, abbreviated as masterbatch A) (molding step).

[0116] In Table 1, the concentration of the composite tungsten oxide particles relative to the maleic anhydride-modified polyolefin polymer or copolymer contained in the masterbatch is shown in the "Concentration" column of "Composite Tungsten Oxide Particles." The maleic anhydride-modified polyolefin polymer or copolymer used in preparing the masterbatch is shown in the "Maleic Anhydride-Modified Polyolefin" column of Table 1. The maleic anhydride-modified ethylene-1-butene copolymer is referred to as "ME-E-B copolymer."

[0117] (3) Production of near-infrared shielding transparent resin molded body The obtained masterbatch A was hot-pressed at 130°C to obtain a near-infrared shielding transparent resin film a, which is a near-infrared shielding transparent resin molded body having a thickness of 20 µm. The concentration of the composite tungsten oxide particles relative to the solid medium in the near-infrared shielding transparent resin molded body is shown in the "Particle concentration" column of "Near-infrared shielding transparent resin molded body" in Table 1. The thickness of the near-infrared shielding transparent resin film, which is a near-infrared shielding transparent resin molded body, is shown in the "Thickness" column of "Near-infrared shielding transparent resin molded body" in Table 1.

[0118] 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 41.6% when the visible light transmittance was 76.0%.

[0119] [Example 2] In the hydrophobization step, a polymer dispersant (MMA-DMAEMA-HEMA polymer) was used, which was a copolymer of methyl methacrylate (MMA), dimethylaminoethyl methacrylate (DMAEMA), and 2-hydroxyethyl methacrylate (HEMA), and had carbonyl, amine, and hydroxyl groups as functional groups. Except for the above points, a composition, a masterbatch, and a 20 μm-thick near-infrared shielding transparent resin film b according to Example 2 were obtained in the same manner as in Example 1.

[0120] 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 42.1% when the visible light transmittance was 76.3%.

[0121] Example 3 In the hydrophobization step, toluene was removed from the dispersion liquid (liquid A) using a vacuum dryer to obtain hydrophobized composite tungsten oxide particles.

[0122] Except for the above points, the composition of Example 3, the master batch, and the near-infrared shielding transparent resin film c having a thickness of 20 μm were obtained in the same manner as in Example 1.

[0123] When the optical properties of the near-infrared shielding transparent resin film c according to Example 3 were measured, as shown in Table 1, the solar radiation transmittance was 43.9% when the visible light transmittance was 76.6%.

[0124] [Example 4] When preparing raw materials for composite tungsten oxide particles, Cs ２ CO ３ Replace with K ２ CO ３ Using K ２ CO ３ and H ２ WO ４ and were weighed out so that the molar ratio of potassium to tungsten, K / W, was 0.33, to obtain particles d, which are composite tungsten oxide particles.

[0125] A composition, a master batch, and a near-infrared shielding transparent resin film d having a thickness of 20 μm according to Example 4 were obtained in the same manner as in Example 1, except that particles d were used instead of particles a.

[0126] In addition, particle d has a composition of K by chemical analysis. ０．３３ WO ２．４５ It was confirmed that the peak position of the diffraction line of particle d is hexagonal K. ０．３ WO ３ It was confirmed that the peak position of particle d coincided with that of particle d. Therefore, it was confirmed that particle d had a hexagonal crystal structure. The dispersed particle diameter of particle d in the composite tungsten oxide particle dispersion liquid was 20 nm.

[0127] When the optical properties of the near-infrared shielding transparent resin film d according to Example 4 were measured, the solar radiation transmittance was 45.7% when the visible light transmittance was 74.1%, as shown in Table 1. [Example 5] When preparing the raw material for the composite tungsten oxide particles, Cs ２CO ３ Instead of Rb ２ CO ３ Using Rb ２ CO ３ and H ２ WO ４ and were weighed out so that the molar ratio of rubidium to tungsten, Rb / W, was 0.33, to obtain particles e, which are composite tungsten oxide particles.

[0128] A composition, a master batch, and a near-infrared shielding transparent resin film e having a thickness of 20 μm according to Example 5 were obtained in the same manner as in Example 1, except that particles e were used instead of particles a.

[0129] Chemical analysis of particle e revealed that the composition was Rb ０．３３ WO ２．４５ It was confirmed that the peak position of the diffraction line of particle e was hexagonal Rb ０．３３ WO ３ It was confirmed that the peak position of particle e coincided with that of particle e. Therefore, it was confirmed that particle e had a hexagonal crystal structure. The dispersed particle diameter of particle e in the composite tungsten oxide particle dispersion was 20 nm.

[0130] The optical properties of the near-infrared shielding transparent resin film e according to Example 5 were measured, and the solar radiation transmittance was 49.3% when the visible light transmittance was 80.9%, as shown in Table 1. [Example 6] When preparing the raw material for the composite tungsten oxide particles, Cs ２ CO ３ Instead of BaCO ３ Using BaCO ３ and H ２ WO ４ and were weighed out so that the molar ratio of barium to tungsten, Ba / W, was 0.33, to obtain particles f, which were composite tungsten oxide particles.

[0131] A composition, a master batch, and a near-infrared shielding transparent resin film f having a thickness of 20 μm according to Example 6 were obtained in the same manner as in Example 1, except that particles f were used instead of particles a.

[0132] Chemical analysis of particle f reveals that its composition is Ba. ０．３３ WO ２．４５It was confirmed that the diffraction peak position of particle f was hexagonal Ba. ０．２１ WO ３ It was confirmed that the peak position of the particle f coincided with that of the particle f. Therefore, it was confirmed that the particle f had a hexagonal crystal structure. The dispersed particle diameter of the particle f in the composite tungsten oxide particle dispersion liquid was 20 nm.

[0133] When the optical properties of the near-infrared shielding transparent resin film f according to Example 6 were measured, the solar radiation transmittance was 55.8% when the visible light transmittance was 80.1%, as shown in Table 1. [Example 7] When preparing the raw material for the composite tungsten oxide particles, Cs ２ CO ３ Instead of Tl(NO ３ ) ３ 3H ２ O, and Tl(NO ３ ) ３ 3H ２ O and H ２ WO ４ and were weighed out so that the molar ratio of thallium to tungsten, Tl / W, was 0.33, to obtain particles g that were composite tungsten oxide particles.

[0134] A composition, a master batch, and a near-infrared shielding transparent resin film g having a thickness of 20 μm according to Example 7 were obtained in the same manner as in Example 1, except that particles g were used instead of particles a.

[0135] The composition of particle g is Tl ０．３３ WO ２．４５ It was confirmed that the peak position of the diffraction line of particle g was hexagonal Tl ０．３ WO ３ It was confirmed that the peak position of the particle g coincided with that of the particle g. Therefore, it was confirmed that the particle g had a hexagonal crystal structure. The dispersed particle diameter of the particle g in the composite tungsten oxide particle dispersion was 20 nm.

[0136] When the optical properties of the near-infrared shielding transparent resin film g according to Example 7 were measured, the solar radiation transmittance was 44.8% when the visible light transmittance was 76.3%, as shown in Table 1. [Example 8] As the material to be mixed with the dispersion powder A when forming the composition of Example 1, a maleic anhydride-modified polyethylene polymer was used instead of the maleic anhydride-modified ethylene-1-butene copolymer. Except for the above points, the composition, masterbatch, and near-infrared shielding transparent resin film h according to Example 8 having a thickness of 20 μm were obtained in the same manner as in Example 1.

[0137] In Table 1, the maleic anhydride modified polyethylene polymer is referred to as "ME polymer."

[0138] The optical properties of the near-infrared shielding transparent resin film h of Example 8 were measured, and as shown in Table 1, the solar radiation transmittance was 45.1% when the visible light transmittance was 76.1%. [Examples 9 to 11] The masterbatches obtained in Examples 1 to 3 were diluted with low-density polyethylene resin, a thermoplastic resin, to set the concentration of the composite tungsten oxide particles relative to the solid medium to 1.0 mass%. The low-density polyethylene, a thermoplastic resin, is shown as "LDPE" in the thermoplastic resin column of "Masterbatch composition" in Table 1.

[0139] The masterbatch of Example 1 was used in Example 9, the masterbatch of Example 2 in Example 10, and the masterbatch of Example 3 in Example 11.

[0140] Except for the above points, a near-infrared shielding transparent resin film i having a thickness of 20 μm according to Example 9, a near-infrared shielding transparent resin film j having a thickness of 20 μm according to Example 10, and a near-infrared shielding transparent resin film k having a thickness of 20 μm according to Example 11 were obtained in the same manner as in Example 1.

[0141] The optical properties of the near-infrared shielding transparent resin film i according to Example 9, the near-infrared shielding transparent resin film j according to Example 10, and the near-infrared shielding transparent resin film k according to Example 11 were evaluated. As a result, it was confirmed that the optical properties shown in Table 1 were exhibited. [Example 12] The masterbatch obtained in Example 1 was diluted with high-density polyethylene resin, which is a thermoplastic resin, so that the concentration of the composite tungsten oxide particles relative to the solid medium was 1.0 mass%. The high-density polyethylene, which is a thermoplastic resin, is shown as "HDPE" in the thermoplastic resin column of "Masterbatch composition" in Table 1.

[0142] A near-infrared shielding transparent resin film 1 of Example 12 having a thickness of 20 μm was obtained in the same manner as in Example 1 except for the above points.

[0143] The optical properties of the near-infrared shielding transparent resin film 1 according to Example 12 were evaluated. As a result, it was confirmed that the film had the optical properties shown in Table 1.

[0144] [Example 13] The masterbatch obtained in Example 1 was diluted with a linear low-density polyethylene resin, which is a thermoplastic resin, to set the concentration of the composite tungsten oxide particles to 1.0 mass% relative to the solid medium. The linear low-density polyethylene resin, which is a thermoplastic resin, is shown as "LLDPE" in the thermoplastic resin column of "Masterbatch composition" in Table 1.

[0145] A near-infrared shielding transparent resin film m according to Example 13 having a thickness of 20 μm was obtained in the same manner as in Example 1 except for the above points.

[0146] The optical properties of the near-infrared shielding transparent resin film m according to Example 13 were evaluated. As a result, it was confirmed that the optical properties shown in Table 1 were exhibited.

[0147] [Example 14] When preparing a composite tungsten oxide particle dispersion, the particles a of Example 1 were weighed out to 20 mass%, a polymer dispersant having a carbonyl group and an amine group as functional groups to 20 mass%, and methyl isobutyl ketone to 60 mass%. Except for the above, in the same manner as in Example 1, the composite tungsten oxide particle dispersion (Liquid N) was prepared by dispersing and pulverizing the composite tungsten oxide particles in the composite tungsten oxide particle dispersion until the dispersed particle diameter of the composite tungsten oxide particles in the composite tungsten oxide particle dispersion was 20 nm.

[0148] Thereafter, the solvent, methyl isobutyl ketone, was removed from the N solution using a vacuum crusher to obtain a composite tungsten oxide particle dispersion powder (hereinafter referred to as dispersion powder N) (hydrophobization step).

[0149] The obtained dispersion powder N and the powder of maleic anhydride-modified ethylene / 1-butene copolymer were uniformly mixed using a blender so that the composite tungsten oxide particles accounted for 10 mass % of the powder of maleic anhydride-modified ethylene / 1-butene copolymer, thereby preparing a composition.

[0150] The obtained composition was melt-kneaded at 180°C using a twin-screw extruder (dispersion step), and the extruded strands were cut into pellets to obtain a masterbatch for a near-infrared shielding transparent resin molding (hereinafter, abbreviated as Masterbatch N) (molding step).

[0151] The obtained Masterbatch N was diluted with a low-density polyethylene resin, which is a thermoplastic resin, so that the concentration of the composite tungsten oxide particles relative to the solid medium was 1.0 mass %.

[0152] A near-infrared shielding transparent resin film n having a thickness of 20 μm according to Example 14 was obtained in the same manner as in Example 1 except for the above points.

[0153] The optical properties of the near-infrared shielding transparent resin film n according to Example 14 were evaluated. As a result, it was confirmed that the optical properties shown in Table 1 were exhibited.

[0154] Comparative Example 1 A composition and masterbatch according to Comparative Example 1 were obtained in the same manner as in Example 1, except that a low-density polyethylene resin powder was used instead of the maleic anhydride-modified ethylene-1-butene copolymer powder as the material to be mixed with the dispersion powder A when forming the composition of Example 1. Visual inspection of the masterbatch revealed significant color unevenness, and the dispersibility of the composite tungsten oxide particles was determined to be poor, so further sheet production was not performed. Comparative Example 2 Polymethyl methacrylate (MMA polymer) (an acrylic dispersant with an amine value of 48 mg KOH / g and a decomposition temperature of 250°C) was used as the polymer dispersant. A composition, masterbatch, and a 20 μm-thick near-infrared shielding transparent resin film o according to Comparative Example 2 were obtained in the same manner as in Example 1, except for the above points.

[0155] The optical properties of the near-infrared shielding transparent resin film o according to Comparative Example 2 were measured, and as shown in Table 1, the solar radiation transmittance was 62.1% when the visible light transmittance was 82.1%. [Comparative Example 3] Polymethyl methacrylate (MMA polymer) (an acrylic dispersant with an amine value of 48 mg KOH / g and a decomposition temperature of 250°C) was used as the polymer dispersant. Except for the above points, the composition and masterbatch according to Comparative Example 3 were obtained in the same manner as in Example 1. The masterbatch was then formed into a film so as to have a visible light transmittance of 75%, thereby obtaining a near-infrared shielding transparent resin film p. The near-infrared shielding transparent resin film p had a thickness of 117 μm and a solar radiation transmittance of 50.7%. [Comparative Example 4] A copolymer of methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) (MMA-HEMA polymer) was used as the polymer dispersant.

[0156] Except for the above points, the composition and masterbatch according to Comparative Example 4, and a near-infrared shielding transparent resin film q having a thickness of 20 μm using the masterbatch were obtained in the same manner as in Example 1.

[0157] When the optical properties of the near-infrared shielding transparent resin film q according to Comparative Example 4 were measured, the solar radiation transmittance was 64.2% when the visible light transmittance was 81.8%, as shown in Table 1. [Comparative Examples 5 and 6] The masterbatches obtained in Comparative Examples 2 and 4 were diluted with a low-density polyethylene resin, which is a thermoplastic resin, so that the concentration of the composite tungsten oxide particles relative to the solid medium was 1.0 mass%.

[0158] Except for the above points, a near-infrared shielding transparent resin film r having a thickness of 20 μm according to Comparative Example 5 and a near-infrared shielding transparent resin film s having a thickness of 20 μm according to Comparative Example 6 were obtained in the same manner as in Comparative Example 2 and Comparative Example 4.

[0159] The optical properties were evaluated for the near-infrared shielding transparent resin film r according to Comparative Example 5 and the near-infrared shielding transparent resin film s according to Comparative Example 6. As a result, it was confirmed that the optical properties shown in Table 1 were exhibited.

[0160] As shown in Table 1 above, the near-infrared shielding transparent resin films of Examples 1 to 14 had a visible light transmittance of 74% or more and a solar radiation transmittance of 56% or less.

[0161] On the other hand, the visual appearance of the master batch of Comparative Example 1 showed significant color unevenness, and the dispersibility of the composite tungsten oxide particles was determined to be poor, so no further sheet production was carried out.

[0162] Furthermore, the near-infrared shielding transparent resin films of Comparative Examples 2 and 4 to 6 had a visible light transmittance of 74% or more, but a solar radiation transmittance of 62% or more, and it was confirmed that they had poor solar radiation shielding properties.

[0163] Although the near-infrared shielding transparent resin film of Comparative Example 3 had a visible light transmittance of 74% or more and a solar radiation transmittance of 56% or less, it was confirmed that the near-infrared shielding transparent resin film of Comparative Example 3 had inferior solar radiation shielding properties compared to the near-infrared shielding transparent resin films of Examples 1 to 8, which had the same particle concentration.

[0164] This application claims priority based on Japanese Patent Application No. 2023-147506, filed with the Japan Patent Office on September 12, 2023, the entire contents of which are incorporated herein by reference.

[0165] REFERENCE SIGNS LIST 10 Masterbatch 11 Composite tungsten oxide particles 12 Solid medium 20 Near-infrared shielding transparent laminate 21 Transparent molded body 21A One surface 22 Near-infrared shielding transparent resin molded body

Claims

1. A master batch used for producing a near-infrared shielding transparent resin molding, comprising: a polymer dispersant having at least an amine functional group; a solid medium containing a maleic anhydride-modified polyolefin polymer or copolymer; and a hexagonal crystal structure of general formula M ｘ WO ｙ (wherein M element is one or more elements selected from H, He, an alkali metal element, an alkaline earth metal element, a rare earth element, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Hf, Os, Bi, and I, and satisfies 0.1≦x≦1.0, 2.0≦y<4.0).

2. The masterbatch of claim 1, wherein said solid medium comprises a polyethylene resin.

3. The masterbatch according to claim 1 or 2, wherein the polymer dispersant is a copolymer further having one or more functional groups selected from a hydroxyl group, a carboxyl group, a carbonyl group, a sulfo group, a phospho group and an epoxy group.

4. A master batch according to claim 1 or 2, wherein the content of the polymer dispersant is 10 parts by mass or more and 100 parts by mass or less when the content of the composite tungsten oxide particles is 100 parts by mass.

5. The master batch according to claim 1 or 2, 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, Tl, Ba and In.

6. The master batch according to claim 1 or 2, wherein the dispersed particle diameter of the composite tungsten oxide particles is 200 nm or less.

7. A composition for use in producing the masterbatch according to claim 1 or 2, comprising: a polymeric dispersant having at least an amine functional group; a solid medium containing a maleic anhydride modified polyolefin polymer or copolymer; and a hexagonal crystal structure represented by the general formula M ｘ WO ｙ (wherein M element is one or more elements selected from H, He, an alkali metal element, an alkaline earth metal element, a rare earth element, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Hf, Os, Bi, and I, and satisfies 0.1≦x≦1.0, 2.0≦y<4.0).

8. A near-infrared shielding transparent resin molded article, which is a molded article containing the masterbatch according to claim 1 or 2.

9. A near-infrared shielding transparent laminate comprising: a transparent molded body; and the near-infrared shielding transparent resin molded body according to claim 8 laminated on the transparent molded body.

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