Master batch, composition, near-infrared shielding transparent resin molded article, and near-infrared shielding transparent laminate

Abstract

Provided is a master batch for producing a near-infrared shielding transparent resin molded article, the master batch containing a polymeric dispersant having a functional group having at least an amine group, a solid medium containing a maleic anhydride-modified polyolefin polymer or a co-polymer, and a filler, and composite tungsten oxide particles that are arranged in the solid medium, have a hexagonal crystal structure, and are represented by general formula MxWOy (wherein 0.1 < = x < = 1.0, and 2.0 < = y < 4.0).

Description

Technical Field

[0001] This invention relates to masterbatches, compositions, near-infrared shielding transparent resin molded articles, and near-infrared shielding transparent laminates. Background Technology

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

[0003] Furthermore, it is known that if the particles constituting the powder containing free electrons are made into microparticles with a diameter smaller than the wavelength of light, the geometric scattering in the visible light region (wavelength 380 nm to 780 nm) of the material containing free electrons is reduced, and transparency in the visible light region is obtained.

[0004] In Patent Document 1, the applicant of this application disclosed an infrared shielding material microparticle dispersion, characterized in that it is an infrared shielding material microparticle dispersion formed by dispersing infrared shielding material microparticles in a medium, wherein the infrared shielding material microparticles contain tungsten oxide microparticles or / and composite tungsten oxide microparticles, and the particle diameter of the infrared shielding material microparticles is more than 1 nm and less than 800 nm.

[0005] Existing technical documents Patent documents Patent Document 1: International Publication No. 2005 / 037932 Summary of the Invention The problem that the invention aims to solve However, when molding a near-infrared shielding transparent resin molded body from a masterbatch containing composite tungsten oxide particles, the transmittance of light in the visible light region sometimes decreases. Furthermore, the near-infrared shielding properties of this molded body are sometimes insufficient.

[0006] Therefore, in one aspect of the present invention, the object is to provide a masterbatch that has good light transmittance in the visible light region and excellent near-infrared shielding function when used to make a near-infrared shielding transparent resin molded body.

[0007] Methods for solving problems One aspect of the present invention provides a masterbatch for manufacturing near-infrared shielding transparent resin molded bodies, comprising: Polymer dispersants with at least an amine functional group, Solid media containing maleic anhydride-modified polyolefin polymers or copolymers, and The general formula M, which has a hexagonal crystal structure disposed in the above-mentioned solid medium, x WOy The composite tungsten oxide particles shown (wherein, element M is selected from one or more elements chosen from H, He, alkali metals, alkaline earth metals, 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, I, and satisfying 0.1≤x≤1.0, 2.0≤y<4.0).

[0008] The effects of the invention One aspect of the present invention can provide a masterbatch that has good light transmittance in the visible light region and excellent near-infrared shielding function when used to make a near-infrared shielding transparent resin molded body. Attached Figure Description

[0009] Figure 1 This is a schematic diagram of the masterbatch involved in one aspect of this disclosure.

[0010] Figure 2 This is a schematic diagram of a near-infrared shielding transparent laminate according to one aspect of the present disclosure. Detailed Implementation

[0011] Hereinafter, specific embodiments will be described with reference to the accompanying drawings. The present invention is not limited to the following embodiments, and various modifications and substitutions can be applied to the following embodiments without departing from the scope of the present invention.

[0012] [Masterbatch] The inventors of this invention have conducted in-depth research on masterbatches that exhibit good light transmittance in the visible light region and excellent near-infrared shielding function when used to manufacture near-infrared shielding transparent resin molded articles. As a result, the inventors of this invention discovered that the aforementioned problems can be solved by manufacturing a masterbatch containing a polymeric dispersant with specific functional groups, a solid medium comprising maleic anhydride-modified polyolefin polymers or copolymers, and composite tungsten oxide particles.

[0013] This is believed to be because by preparing a masterbatch containing a polymeric dispersant with specific functional groups, a solid medium comprising maleic anhydride-modified polyolefin polymers or copolymers, and composite tungsten oxide particles, aggregation of the composite tungsten oxide particles during molding can be prevented. Therefore, when a near-infrared shielding transparent resin molded body containing the masterbatch of this embodiment is prepared, light transmittance in the visible light region is good, and excellent near-infrared shielding function can be performed.

[0014] The masterbatch used in this embodiment is a masterbatch for manufacturing near-infrared shielding transparent resin molded bodies. Therefore, the masterbatch used in this embodiment can also be called a masterbatch for near-infrared shielding transparent resin molded bodies.

[0015] Furthermore, the masterbatch in this embodiment includes a polymeric dispersant, a solid medium, and composite tungsten oxide particles.

[0016] (1) Regarding the components contained in the masterbatch The following describes the components (materials) contained in the masterbatch of this embodiment.

[0017] (1-1) Composite tungsten oxide particles (Regarding composition) The composite tungsten oxide particles have a hexagonal crystal structure, with the general formula M x WO y express.

[0018] In the above general formula, x and y preferably satisfy 0.1≤x≤1.0 and 2.0≤y<4.0. Furthermore, M in the above general formula represents the element M as described below, W represents tungsten, and O represents oxygen.

[0019] The amount of element M added, x, is preferably 0.1 to 1.0, more preferably around 0.33, and specifically, for example, 0.25 to 0.39. This is because the theoretically calculated value based on the hexagonal crystal structure is 0.33, and particularly preferred optical properties are obtained with the addition amounts around this value.

[0020] Furthermore, regarding the range of y as the oxygen content, it is preferred to be 2.0 ≤ y < 4.0.

[0021] The element M represented by the general formula above in the composite tungsten oxide particles is not particularly limited, but is preferably selected from one or more elements selected from H, He, alkali metal elements, alkaline earth metal elements, rare earth elements, 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), 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).

[0022] In addition, 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 (diulonium).

[0023] The M element is more preferably composed of one or more selected from Cs, Rb, K, Tl, Ba, and In. Alternatively, the M element may consist of only one or more selected from Cs, Rb, K, Tl, Ba, and In.

[0024] This is because by including one or more of the elements selected from Cs, Rb, K, Tl, Ba, and In in the M element, the composite tungsten oxide particles can easily obtain a hexagonal crystal structure, which in particular improves the transmittance of light in the visible light region and also enhances the near-infrared shielding function.

[0025] A typical example of a material composed of composite tungsten oxide particles is Cs. 0.33 WO3, Rb 0.33 WO3, K 0.33 WO3, Ba 0.33 WO3, etc., if x and y fall within the above range, useful near-infrared shielding characteristics can be obtained.

[0026] (Regarding particle size) In this embodiment, the composite tungsten oxide particles used as a near-infrared shielding material in the masterbatch significantly absorb light in the near-infrared region, particularly light with wavelengths around 1000 nm. Therefore, the transmittance of the composite tungsten oxide particles is mostly in the blue hue. Furthermore, the particle size of the composite tungsten oxide particles can be appropriately selected according to their intended use.

[0027] First, in applications where transparency in the visible light region is maintained, the composite tungsten oxide particles preferably have a dispersion particle size of 800 nm or less. Furthermore, in this specification, "transparency" is used to mean that there is less scattering relative to light in the visible light region, and that light transmittance in the visible light region is high.

[0028] This is because by dispersing the composite tungsten oxide particles to a particle size of less than 800 nm, light is not completely blocked through scattering, thus maintaining the visibility of light in the visible light region while efficiently preserving the transparency of light in the visible light region. Especially when the transparency of light in the visible light region is of paramount importance, it is preferable to further consider the light scattering caused by the particles.

[0029] Furthermore, when particularly emphasizing the reduction of light scattering caused 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 if the dispersed particle size of the composite tungsten oxide particles is small, the scattering of light in the visible light region due to geometric scattering or Mie scattering is reduced. Since the light scattering caused by the composite tungsten oxide particles is reduced, the near-infrared shielding film obtained using the masterbatch of this embodiment exhibits particularly excellent transparency.

[0030] That is, if the dispersed particle size of the composite tungsten oxide particles is 200 nm or less, the aforementioned geometric scattering or Mie scattering decreases, entering the Rayleigh scattering region. Moreover, this is because in the Rayleigh scattering region, the scattered light decreases proportionally to the sixth power of the particle size, thereby reducing scattering and increasing transparency with a smaller dispersed particle size. Furthermore, if the dispersed particle size is 100 nm or less, the scattered light becomes very little, which is preferable. From the viewpoint of avoiding light scattering, a small dispersed particle size of the composite tungsten oxide particles is preferred. Therefore, there is no particular limitation on the lower limit of the dispersed particle size; if the dispersed particle size is 1 nm or more, industrial manufacturing is easy, and thus, for example, the dispersed particle size can be 1 nm or more.

[0031] The dispersed particle size of composite tungsten oxide particles can be determined using an ELS-8000 manufactured by Otsuka Electronics Co., Ltd., which is based on the principle of dynamic light scattering.

[0032] (Method for manufacturing composite tungsten oxide particles) The method for manufacturing the composite tungsten oxide particles contained in the masterbatch of this embodiment is not particularly limited, as long as it is a method that can manufacture composite tungsten oxide particles that satisfy the general formula and crystal structure described above.

[0033] The method for manufacturing composite tungsten oxide particles can include a heat treatment step, for example, heat-treating the starting material in an inert gas atmosphere or a reducing gas atmosphere. The method can also further include an oxidation treatment step, following the heat treatment step, where the material is oxidized in a mild environment.

[0034] The starting material may include a tungsten-containing raw material as a tungsten supply source. The tungsten raw material preferably includes one or more selected from tungstic acid, tungsten trioxide, tungsten dioxide, tungsten oxide hydrate, tungsten hexachloride, ammonium tungstate, tungsten compound powder obtained by drying an aqueous solution of ammonium tungstate, and metallic tungsten. The tungsten raw material may be a powder of the above materials or a solution containing one or more of the above materials.

[0035] As a hydrate of tungsten oxide, for example, tungsten oxide hydrate powder obtained by dissolving tungsten hexachloride in alcohol and then drying it, or tungsten oxide hydrate powder obtained by dissolving tungsten hexachloride in alcohol, adding water to precipitate it, and then drying it, can also be used.

[0036] When manufacturing composite tungsten oxide particles, if the starting material is a solution, the various elements contained in the starting material can be easily and uniformly mixed. Therefore, solutions such as ammonium tungstate aqueous solution and tungsten hexachloride solution are more preferably used as tungsten raw materials.

[0037] The starting material for the composite tungsten oxide particles may also include an M-element raw material containing the M-element as a supply source of the M-element. As an M-element raw material, it is preferable to include, for example, one or more selected from element monomers and compounds containing the M-element.

[0038] Here, in order to produce a starting material in which each component is uniformly mixed at the molecular level, it is preferable to mix the raw materials in solution form. Therefore, the raw material containing element M is preferably soluble in solvents such as water or organic solvents. Therefore, examples of raw materials containing element M include, for example, tungstates, chloride salts, nitrates, sulfates, oxalates, oxides, carbonates, hydroxides, etc., and are not limited thereto; if in solution form, they can be used appropriately.

[0039] By using the above-mentioned starting materials, a heat treatment process is performed to heat-treat the starting materials in an inactive gas atmosphere or a reducing gas atmosphere, thereby obtaining composite tungsten oxide particles with the above-mentioned dispersed particle size.

[0040] The heat treatment conditions in an inert gas atmosphere, used in the heat treatment process, are preferably, for example, 650°C or higher. Starting materials heat-treated at 650°C or higher have sufficient near-infrared shielding capabilities and are highly efficient at shielding heat-emitting particles. There is no particular upper limit to the heat treatment temperature in the inert gas atmosphere; for example, it can be 1200°C or lower. Inert gases such as Ar and N2 can be used as the inert gas.

[0041] As a heat treatment process, the heat treatment conditions in a reducing gas atmosphere are preferably as follows: first, the starting material is heat-treated in a reducing gas atmosphere at a temperature of 300°C to 1000°C, followed by heat treatment 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 H2 is preferred. Furthermore, when H2 is used as the reducing gas, the composition of the reducing gas atmosphere is preferably, for example, a mixture of at least 0.1% H2 by volume in an inert gas such as Ar or N2, and more preferably a mixture of at least 0.2% H2. By using a reducing gas atmosphere containing at least 0.1% H2 by volume, reduction can be performed efficiently.

[0042] When H2 is used as a reducing gas, there is no particular upper limit to the proportion of reducing gas in the reducing gas atmosphere, and it can be only H2. Therefore, the proportion of reducing gas in the reducing gas atmosphere can be less than 100% by volume.

[0043] In addition, as the inactive gas in the inactive gas atmosphere used for heat treatment in a reducing gas atmosphere, inactive gases such as Ar and N2 can be used.

[0044] After the heat treatment process, when performing oxidation treatment in a mild environment, the oxygen source gas is not particularly limited, but preferably selected from one or more of oxygen, air, and water vapor. The concentration of the oxygen source is not particularly limited, as long as it is appropriately selected based on the heat treatment temperature and the amount of material being heat-treated. Furthermore, the heat treatment temperature is not particularly limited, as long as it is appropriately selected based on the amount of material being heat-treated. For example, 400°C to 850°C is preferred.

[0045] The composite tungsten oxide particles that perform the aforementioned near-infrared shielding function in this embodiment can be surface-treated using at least one 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 one or more of Si, Ti, Al, and Zr, thereby improving weather resistance.

[0046] Furthermore, from the viewpoint of molding the masterbatch of this embodiment to obtain a near-infrared shielding transparent resin molded article with a desired color, it is desirable that the powder color of the composite tungsten oxide particles satisfies L ＊ For those aged 25 to 80, a ＊ For values ​​between -10 and 10, b ＊ This applies to conditions between -15 and 15. The color parameters mentioned above refer to the L recommended by the International Commission on Illumination (CIE). ＊ a ＊ b＊ Powder color in the color system (JISZ8729(2004)).

[0047] The color of the composite tungsten oxide particles can be selected according to the conditions of the heat treatment process.

[0048] (1-2) Polymer dispersants Polymer dispersants are used to hydrophobize the surface of composite tungsten oxide particles. The polymer dispersant can be selected based on the dispersion system of the composite tungsten oxide particles, solid media, etc.

[0049] The polymeric dispersant is preferably a polymeric dispersant having at least an amine functional group.

[0050] The polymeric dispersant is more preferably a copolymer having at least an amine functional group, and more preferably a copolymer having one or more functional groups selected from hydroxyl, carboxyl, carbonyl, sulfonyl, phosphonyl and epoxy groups.

[0051] The amount of polymeric dispersant added can be selected based on the type of polymeric dispersant, the type of composite tungsten oxide particles, and the specific surface area of ​​the composite tungsten oxide particles, and is not particularly limited. For example, the amount of polymeric dispersant added can be 10 to 100 parts by mass relative to 100 parts by mass of composite tungsten oxide particles. That is, in the case where the content of composite tungsten oxide particles in the masterbatch of this embodiment is 10 to 100 parts by mass, the content of polymeric dispersant is preferably 10 to 100 parts by mass. The masterbatch of this embodiment contains 10 to 100 parts by mass of polymeric dispersant relative to 100 parts by mass of composite tungsten oxide particles, thereby making it particularly easy to prepare a dispersion, masterbatch, etc., with a well-dispersed state for the composite tungsten oxide particles, and is therefore preferred.

[0052] (1-3) Solid media (1-3-1) Maleic anhydride modified polyolefin polymers or copolymers In this embodiment, the masterbatch is preferably used as a solid medium, comprising maleic anhydride-modified polyolefin polymers or copolymers. The solid medium may also be composed of maleic anhydride-modified polyolefin polymers or copolymers, and as described later, may further contain other resins.

[0053] In addition, the maleic anhydride-modified polyolefin polymer or copolymer contained in the solid medium preferably covers at least a portion of the surface of the composite tungsten oxide particles, i.e., it is modified.

[0054] Solid media, for example, can be used to cover composite tungsten oxide particles, containing such particles internally, i.e., encapsulated configuration.

[0055] Figure 1As illustrated, the masterbatch 10 of this embodiment may, for example, include composite tungsten oxide particles 11 and a solid medium 12, wherein the composite tungsten oxide particles 11 may be disposed in the solid medium 12. Preferably, the composite tungsten oxide particles 11 are dispersed in the solid medium 12.

[0056] in addition, Figure 1 The diagram is for illustrative purposes only; the masterbatch in this embodiment is not limited to this form. For example... Figure 1 In this text, the composite tungsten oxide particles 11 are represented by circles, described as spherical particles. However, the shape of the composite tungsten oxide particles 11 is not limited to this form and can have any shape. For example, the composite tungsten oxide particles 11 may also have a surface coating. Furthermore, Figure 1 As omitted in the text, the masterbatch 10 of this embodiment further includes a polymeric dispersant. Furthermore, the masterbatch 10 of this embodiment may also include other additives as needed.

[0057] The polyolefin that forms the backbone of the maleic anhydride-modified polyolefin polymer or copolymer may be, for example, one or more selected from individual polymers such as polyethylene, polypropylene, polybutene, and polyoctene.

[0058] Furthermore, the polyolefin polymer or copolymer constituting the backbone of the maleic anhydride-modified polyolefin polymer or copolymer can be selected from ethylene-propylene copolymer, ethylene-1-butene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-4-methyl-1-pentene copolymer, propylene-1-octene copolymer, propylene-1-decene copolymer, propylene-1,4-hexadiene copolymer, propylene-dicyclopentadiene copolymer, propylene-5-ethylidene-2-norbornene copolymer, propylene-2,5-norbornadiene copolymer, propylene-5-ethylidene-2- -One or more copolymers of two components, such as 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-ethylene-2-norbornene copolymer, 1-butene-2,5-norbornadiene copolymer, and 1-butene-5-ethylene-2-norbornene copolymer.

[0059] Furthermore, the polyolefin polymer or copolymer constituting the backbone of the maleic anhydride-modified polyolefin polymer or copolymer can also be selected from ethylene-propylene-1-butene copolymer, ethylene-propylene-1-hexene copolymer, ethylene-propylene-1-octene copolymer, ethylene-propylene-1-octene copolymer, ethylene-propylene-1,4-hexadiene copolymer, ethylene-propylene-1,4-hexadiene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene-5-ethylene-2-norbornene copolymer, ethylene-propylene-5-ethylene-2-norbornene copolymer, ethylene-propylene-2,5-norbornadiene copolymer, ethylene-propylene-5-ethylene-2-norbornene copolymer, ethylene-propylene-5-ethylene-2-norbornene copolymer, ethylene-propylene-5-ethylene-2-norbornene copolymer, 1-Butene-ethylene-propylene copolymer, 1-Butene-ethylene-1-hexene copolymer, 1-Butene-ethylene-1-octene copolymer, 1-Butene-propylene-1-octene copolymer, 1-Butene-ethylene-1,4-hexadiene copolymer, 1-Butene-propylene-1,4-hexadiene copolymer, 1-Butene-ethylene-dicyclopentadiene copolymer, 1-Butene-propylene-dicyclopentadiene copolymer, 1-Butene-ethylene- One or more of the following multi-component copolymers: 5-ethylene-2-norbornene copolymer, 1-butene-propylene-5-ethylene-2-norbornene copolymer, 1-butene-ethylene-2,5-norbornediene copolymer, 1-butene-propylene-2,5-norbornediene copolymer, 1-butene-ethylene-5-ethylene-2-norbornene copolymer, and 1-butene-propylene-5-ethylene-2-norbornene copolymer.

[0060] In these polyolefin polymers or copolymers that constitute the backbone of maleic anhydride-modified polyolefin polymers or copolymers, the polyolefin polymer or copolymer is preferably selected from one or more of 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.

[0061] (1-3-2) Polyethylene resin The solid medium may further contain resin in addition to maleic anhydride-modified polyolefin polymers or copolymers.

[0062] Resins other than maleic anhydride-modified polyolefin polymers or copolymers are preferably thermoplastic resins, taking into account factors such as workability during molding. When the solid medium contains a thermoplastic resin other than a maleic anhydride-modified polyolefin polymer or copolymer, polyethylene resin can be appropriately used as the thermoplastic resin. Therefore, the solid medium can also contain polyethylene resin.

[0063] The polyethylene resin is not particularly limited, but may be selected from one or more of low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE), and ethylene-vinyl acetate copolymer.

[0064] (2) Method for manufacturing masterbatch The method for manufacturing the masterbatch according to this embodiment can include: hydrophobicating treatment of the surface of composite tungsten oxide particles with a polymeric dispersant, and hydrophobicating and dispersing the composite tungsten oxide particles in a solid medium. As the polymeric dispersant, polymeric dispersants with at least amine functional groups as described above can be used. As the solid medium, maleic anhydride-modified polyolefin polymers or copolymers can be used, and further may include thermoplastic resins such as polyethylene resin.

[0065] In the hydrophobication and dispersion process, the hydrophobication process of using a polymeric dispersant to hydrophobize the surface of the composite tungsten oxide particles and the dispersion process of dispersing the composite tungsten oxide particles in a solid medium can be carried out simultaneously or as other processes.

[0066] In the hydrophobication and dispersion process, the method for dispersing composite tungsten oxide particles, which are particles with near-infrared shielding function, into a solid medium can be arbitrarily selected as long as it can disperse the composite tungsten oxide particles in the solid medium.

[0067] For example, firstly, a dispersion is prepared by dispersing the above-mentioned composite tungsten oxide particles in any solvent (dispersion medium) using methods such as bead milling, ball milling, sand milling, and ultrasonic dispersion. Next, the dispersion, polymeric dispersant, powder or granules of solid medium, and other additives as needed are melt-mixed using a mixer or kneader while removing the solvent from the dispersion.

[0068] By performing melt mixing, it is possible to prepare a mixture in which composite tungsten oxide particles are uniformly dispersed in a solid medium. Furthermore, the surface of the composite tungsten oxide particles can be hydrophobized using a polymeric dispersant. That is, the hydrophobication and dispersion processes can be performed simultaneously.

[0069] The temperature during mixing is maintained at a temperature at which the solid medium used will not decompose.

[0070] For melt mixing, suitable mixers include belt mixers, rotary drum mixers, Nottingham mixers, Henschel mixers, high-speed mixers, and planetary mixers. For compounding machines, examples include Banbury mixers, kneaders, roller mixers, and Kneader mixers. RUDER, single-shaft extruder, twin-shaft extruder, etc.

[0071] In addition, in the hydrophobication and dispersion process, as a method for dispersing the composite tungsten oxide particles in a solid medium by hydrophobizing the surface of the composite tungsten oxide particles with a polymeric dispersant, the following method can also be used.

[0072] First, a polymeric dispersant is added to a dispersion of composite tungsten oxide particles with near-infrared shielding function, and the solvent is removed using a known method. This yields composite tungsten oxide particles whose surface has been hydrophobically treated with the polymeric dispersant (hydrophobication process). Furthermore, the powder of composite tungsten oxide particles obtained by this hydrophobication process, whose surface has been hydrophobically treated with the polymeric dispersant, can also be referred to as a dispersing powder, etc.

[0073] Next, the powder, solid medium powder or particles obtained from the above hydrophobication process can be melt-mixed with other additives as needed to prepare a mixture in which composite tungsten oxide particles are uniformly dispersed in the solid medium (dispersion process).

[0074] In this case, the hydrophobication process and the dispersion process are performed as other processes.

[0075] Furthermore, it is possible to mix powdered composite tungsten oxide particles obtained from a hydrophobication process, whose surfaces have been hydrophobized with a polymeric dispersant, solid media powder or granules, and other additives as needed, to prepare the composition described later. The composition can be further shaped into a desired form by melting, mixing, or other processes involving the solid media it contains, thereby producing a masterbatch or a near-infrared shielding transparent resin molded body.

[0076] In addition, as another method for hydrophobication and dispersion, it is also possible to use a method of directly adding undispersed composite tungsten oxide particle powder and polymeric dispersant to a solid medium for melt mixing.

[0077] In this case, the hydrophobication process and the dispersion process can be carried out in one process.

[0078] The hydrophobication and dispersion process only requires hydrophobizing the surface of the composite tungsten oxide particles with a polymeric dispersant and dispersing the composite tungsten oxide particles in a solid medium; it is not limited to these methods.

[0079] The method for manufacturing the masterbatch in this embodiment can also include a molding process that further shapes a mixture of a solid medium in which composite tungsten oxide particles obtained by the hydrophobication and dispersion process are dispersed into granules.

[0080] In the molding process, the mixture obtained from the hydrophobication and dispersion processes can be kneaded using a vented single-shaft or twin-shaft extruder and processed into granules. The masterbatch of this embodiment can be obtained through the molding process.

[0081] Masterbatch particles can be obtained by cutting the most common melt extrusion strands. Therefore, cylindrical and prismatic particles can be used as examples of their shapes. Furthermore, a so-called thermal cutting method, in which the melt extrudate is directly cut, can also be employed. In such cases, the masterbatch is typically taken in a near-spherical shape.

[0082] Thus, the masterbatch in this embodiment can take any form or shape. Most preferably, the masterbatch, when used to mold a near-infrared shielding transparent resin molded body, has the same or similar size and shape as the thermoplastic resin used for diluting the masterbatch.

[0083] The masterbatch of this embodiment may further contain general additives. For example, in order to impart any desired hue, the masterbatch of this embodiment may also contain dyes or pigments used for coloring general thermoplastic resins selected from azo dyes, cyanine dyes, quinoline dyes, perylene dyes, carbon black, etc.

[0084] In addition, the masterbatch of this embodiment may contain one or more of the following: stabilizers selected from hindered phenolic and phosphorus-based stabilizers, mold release agents, hydroxybenzophenone-based stabilizers, salicylic acid-based stabilizers, HALS-based stabilizers, triazole-based stabilizers, triazine-based stabilizers, coupling agents, surfactants, antistatic agents, etc.

[0085] In this embodiment, the masterbatch contains additives such as dyes, pigments, stabilizers, and release agents, and their content is not particularly limited. For example, each additive can be added or contained in an effective amount to achieve the intended function.

[0086] [Composition] Next, the composition of this embodiment will be described.

[0087] The composition of this embodiment is a composition for manufacturing the masterbatch according to one aspect of this disclosure, containing a polymeric dispersant, a solid medium, and composite tungsten oxide particles. Furthermore, the composition of this embodiment can also be referred to as a masterbatch composition, etc. In addition, the composition of this embodiment is a mixture of components (materials) containing polymeric dispersants, etc., and therefore can also be referred to as a mixed composition, mixed powder, etc.

[0088] As a polymeric dispersant, a polymeric dispersant having at least an amine functional group is preferred.

[0089] As a solid medium, it is preferably a solid medium containing maleic anhydride-modified polyolefin polymer or copolymer.

[0090] The composite tungsten oxide particles are preferably of the general formula M with a hexagonal crystal structure. x WO y The composite tungsten oxide particles are shown. Furthermore, the same materials described in the masterbatch can be used as polymeric dispersants, solid media, and composite tungsten oxide particles. Moreover, the suitable proportions of each component, such as the polymeric dispersant, can be the same as in the masterbatch. Therefore, descriptions of each material and their suitable proportions are omitted.

[0091] The composition of this embodiment only needs to contain a polymeric dispersant, a solid medium, and composite tungsten oxide particles; their respective states and configurations are not particularly limited.

[0092] For example, as a material comprising a polymeric dispersant and composite tungsten oxide particles, a dispersion powder obtained by adding a polymeric dispersant to a dispersion of composite tungsten oxide particles and removing the solvent can also be used. The dispersion powder can have a structure in which a polymeric dispersant is disposed on the surface of the composite tungsten oxide particles. Furthermore, a mixture of the above-mentioned dispersion powder and a solid medium can be referred to as the composition of this embodiment. However, as described above, the form of the composition of this embodiment is not limited to the above-described structure. The composition of this embodiment can, for example, be a mixture containing a polymeric dispersant, a solid medium, and composite tungsten oxide particles.

[0093] The composition of this embodiment can be further molded into a desired shape by melting, mixing, etc., the contained solid medium, thereby producing the described masterbatch and near-infrared shielding transparent resin molded body. In order to produce the masterbatch, the state, morphology, and configuration of each component contained in the composition of this embodiment may remain unchanged or may change before and after melting, mixing, molding, etc. Furthermore, various additives as needed can be added during the melting, mixing, molding, etc., of the composition of this embodiment.

[0094] [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.

[0095] The near-infrared shielding transparent resin molded body of this embodiment is a molded body containing the above-mentioned masterbatch.

[0096] The near-infrared shielding transparent resin molded body of this embodiment can also be manufactured by molding the masterbatch involved in one aspect of this disclosure. That is, the near-infrared shielding transparent resin molded body of this embodiment can also be a molded body formed from the masterbatch.

[0097] Furthermore, the near-infrared shielding transparent resin molded body of this embodiment may also contain a masterbatch and a thermoplastic resin. The thermoplastic resin is a resin obtained by diluting the masterbatch to adjust the concentration of the contained composite tungsten oxide particles. Therefore, the thermoplastic resin is preferably a resin contained in the masterbatch that is the same as the solid medium, or a dissimilar resin that is compatible with the solid medium contained in the masterbatch. That is, when the thermoplastic resin is mixed with the masterbatch, it is preferably a resin that can be mixed without separation.

[0098] When the solid medium contained in the masterbatch is only maleic anhydride-modified polyolefin polymer or copolymer, it may further contain thermoplastic resins such as polyethylene resin. For example, when the masterbatch contains maleic anhydride-modified polyolefin polymer or copolymer and polyethylene resin, the thermoplastic resin is preferably a resin of the same kind as either the maleic anhydride-modified polyolefin polymer or copolymer or the polyethylene resin, or a compatible dissimilar resin.

[0099] The near-infrared shielding transparent resin molded body of this embodiment is obtained by molding a masterbatch, or a mixture of masterbatch and thermoplastic resin, into a predetermined shape.

[0100] The near-infrared shielding transparent resin molded body of this embodiment is manufactured using the masterbatch disclosed in one aspect, thus exhibiting very little thermal degradation during molding. Therefore, the composite tungsten oxide particles, serving as near-infrared shielding particles, are sufficiently dispersed within the near-infrared shielding transparent resin molded body. As a result, the near-infrared shielding transparent resin molded body of this embodiment ensures good visible light transmittance and exhibits excellent near-infrared shielding function.

[0101] The near-infrared shielding transparent resin molded body of this embodiment can be molded into any shape as needed, including planar and curved shapes.

[0102] 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. The resin sheet, further planarly molded, can also be post-processed into any shape such as a spherical shape.

[0103] As a molding method for the near-infrared shielding transparent resin molded body of this embodiment, any method such as injection molding, extrusion molding, compression molding, rotational molding, etc., can be cited. In particular, as a molding method for the near-infrared shielding transparent resin molded body of this embodiment, a method for obtaining a molded article by injection molding or a method for obtaining a molded article by extrusion molding is appropriately adopted.

[0104] As a method for obtaining sheet-like or film-like molded articles by extrusion molding, it is manufactured by traction of molten thermoplastic resin extruded from an extruder using a T-die or the like while being cooled by cooling rollers.

[0105] The aforementioned near-infrared shielding transparent resin molded body can be used solely for structural materials such as window glass and archways.

[0106] Furthermore, the near-infrared shielding transparent resin molded body of this embodiment can also be laminated with other transparent molded bodies such as inorganic glass, resin glass, and resin film using any method, and used as an integrated near-infrared shielding transparent laminate for structural materials.

[0107] That is, the near-infrared shielding transparent laminate of this embodiment can have a transparent molded body and a near-infrared shielding transparent resin molded body according to one aspect of this disclosure, which is laminated on the transparent molded body.

[0108] Specifically, this is a schematic cross-sectional view along the stacking direction of the transparent molded body 21 and the near-infrared shielding transparent resin molded body 22. Figure 2 As shown, the near-infrared shielding transparent laminate 20 can have a transparent molded body 21 and a 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.

[0109] For example, a near-infrared shielding transparent resin molded in a pre-formed film can be laminated onto an inorganic glass, which is a transparent molded body, by a hot lamination method to obtain a near-infrared shielding transparent laminate with near-infrared shielding function and scattering prevention function.

[0110] Furthermore, near-infrared shielding transparent resin molded bodies can be laminated and integrated onto other transparent molded bodies simultaneously through hot lamination, co-extrusion, compression molding, and injection molding to obtain near-infrared shielding transparent laminates. These near-infrared shielding transparent laminates effectively leverage the advantages of each molded body while compensating for their respective disadvantages, thus serving as more useful structural materials.

[0111] The near-infrared shielding transparent resin molded body and the near-infrared shielding transparent laminate of this embodiment described above have molded bodies containing the masterbatch involved in one aspect of this disclosure.

[0112] One aspect of this disclosure involves a masterbatch comprising a polymeric dispersant having specific functional groups, a solid medium comprising a maleic anhydride-modified polyolefin polymer or copolymer, and composite tungsten oxide particles. Therefore, when molding this masterbatch, agglomeration of the composite tungsten oxide particles can be prevented. As a result, the near-infrared shielding transparent resin molded body and the near-infrared shielding transparent laminate of this embodiment exhibit good light transmittance in the visible light region and can perform excellent near-infrared shielding function.

[0113] Thus, this embodiment of the near-infrared shielding transparent resin molded article and near-infrared shielding transparent laminate shows an example of manufacturing using a masterbatch according to one aspect of this disclosure, but it is not limited to this form. The near-infrared shielding transparent resin molded article and near-infrared shielding transparent laminate of this embodiment may also contain a composition according to one aspect of this disclosure, and may also be manufactured using a composition according to one aspect of this disclosure.

[0114] Therefore, the near-infrared shielding transparent resin molded body of this embodiment can also be referred to as a molded body containing the composition involved in one aspect of this disclosure.

[0115] In this embodiment, when the near-infrared shielding transparent resin molded body is a molded body containing a composition according to one aspect of the present disclosure, the composition according to one aspect of the present disclosure can be used as a raw material for the near-infrared shielding transparent resin molded body, in addition to the masterbatch. Except for the above points, the description is the same as the description of reading the masterbatch as the composition, so the description is omitted.

[0116] Example Hereinafter, embodiments and comparative examples of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

[0117] In each embodiment, the visible light transmittance and solar transmittance of the near-infrared shielding transparent resin film 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.

[0118] [Example 1] (1) Manufacturing of composite tungsten oxide particles 10.8 g of Cs₂CO₃ was dissolved in 16.5 g of water and added to 50 g of H₂WO₄. The mixture was dried using a vacuum dryer while stirring to prepare the dried powder (raw material preparation). The resulting dried powder was then heated with 2% H₂ gas (by volume) as N₂ gas as the charge carrier at 800 °C for 0.5 hours, followed by further calcination at 800 °C for 1 hour under an N₂ atmosphere to obtain particle a, which is a composite tungsten oxide particle.

[0119] Chemical analysis confirms that particle a has a composition of Cs. 0.33 WO 2.45 The composition is shown in the "Composition" column of "Composite Tungsten Oxide Particles" in Table 1. Furthermore, powder X-ray diffraction results confirmed that the peak positions of the diffraction lines of particle a corresponded to those of hexagonal Cs. 0.3 The peak positions of WO3 are consistent. Therefore, it can be confirmed that particle a has a hexagonal crystal structure.

[0120] (2) Manufacturing of compositions and masterbatches Next, 20% by mass of particles a, 6% by mass of the copolymer of methyl methacrylate (MMA) and dimethylaminoethyl methacrylate (DMAEMA), 6% by mass of the polymeric dispersant (MMA-DMAEMA polymer) with carbonyl and amine functional groups, and 74% by mass of toluene were weighed. The weighed material was crushed and dispersed for 24 hours using a paint shaker with 0.3 mm φ ZrO2 beads added, thereby preparing a composite tungsten oxide particle dispersion (liquid A).

[0121] The particle size of the composite tungsten oxide particles in the composite tungsten oxide particle dispersion (solution A) was measured and found to be 20 nm. Furthermore, the content of the polymeric dispersant in the composition and masterbatch was 30 parts by mass, assuming the content of composite tungsten oxide particles was 100 parts by mass.

[0122] The dispersed particle size was determined using a particle size measuring device based on dynamic light scattering (ELS-8000 manufactured by Otsuka Electronics Co., Ltd.).

[0123] Then, toluene, which is the solvent, is removed from liquid A using a spray dryer to obtain composite tungsten oxide particle dispersion powder (hereinafter referred to as dispersion powder A) (hydrophobication process).

[0124] The obtained dispersion powder A and the maleic anhydride modified ethylene-1-butene copolymer powder are mixed uniformly using a stirrer to prepare a composition, such that the composite tungsten oxide particles are 3.5% by mass relative to the maleic anhydride modified ethylene-1-butene copolymer powder.

[0125] The obtained composition was melt-blended at 180°C using a biaxial extruder (dispersion process), and the extruded strands were cut into granular form to obtain a masterbatch for near-infrared shielding transparent resin molding bodies (hereinafter referred to as masterbatch A) (molding process).

[0126] In Table 1, the concentration of composite tungsten oxide particles contained in the masterbatch relative to the maleic anhydride-modified polyolefin polymer or copolymer is shown in the "Concentration" column of "Composite Tungsten Oxide Particles". Furthermore, the maleic anhydride-to-polyolefin polymer or copolymer used in preparing the masterbatch is shown in the "Maleic Anhydride to Polyolefin" column of Table 1. The maleic anhydride-modified ethylene-1-butene copolymer is described as "MEB copolymer".

[0127] (3) Manufacturing of near-infrared shielding transparent resin molded body 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 20 μm, which serves as a near-infrared shielding transparent resin molded body. The concentration of 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. Furthermore, the thickness of the near-infrared shielding transparent resin film serving as the near-infrared shielding transparent resin molded body is shown in the "Thickness" column of "Near-infrared Shielding Transparent Resin Molded Body" in Table 1.

[0128] The optical properties of the near-infrared shielding transparent resin film a involved in Example 1 were measured, and the results are shown in Table 1. The solar transmittance at a visible light transmittance of 76.0% was 41.6%.

[0129] [Example 2] In the hydrophobication process, methyl methacrylate (MMA), dimethylaminoethyl methacrylate (DMAEMA), and a copolymer of 2-hydroxyethyl methacrylate (HEMA) with carbonyl, amino, and hydroxyl functional groups (MMA-DMAEMA-HEMA polymer) were used as polymeric dispersants. Except for the points mentioned above, the same procedure as in Example 1 was followed to obtain the composition, masterbatch, and near-infrared shielding transparent resin film b with a thickness of 20 μm involved in Example 2.

[0130] The optical properties of the near-infrared shielding transparent resin film b involved in Example 2 were measured, and the results are shown in Table 1. The solar transmittance was 42.1% when the visible light transmittance was 76.3%.

[0131] [Example 3] In the hydrophobication process, a vacuum dryer is used to remove toluene from the dispersion (liquid A) to obtain hydrophobicated composite tungsten oxide particles.

[0132] Apart from the points mentioned above, the same procedure as in Example 1 was followed to obtain the composition, masterbatch, and near-infrared shielding transparent resin film c with a thickness of 20 μm involved in Example 3.

[0133] The optical properties of the near-infrared shielding transparent resin film c involved in Example 3 were measured, and the results are shown in Table 1. The solar transmittance was 43.9% when the visible light transmittance was 76.6%.

[0134] [Example 4] When preparing the raw materials for composite tungsten oxide particles, K2CO3 was used instead of Cs2CO3. K2CO3 and H2WO4 were weighed so that the K / W molar ratio, which is the molar ratio of potassium to tungsten, was 0.33, and particles d as composite tungsten oxide particles were obtained.

[0135] Particle d was used instead of particle a, and otherwise operated in the same manner as in Example 1, to obtain the composition, masterbatch, and near-infrared shielding transparent resin film d with a thickness of 20 μm involved in Example 4.

[0136] Furthermore, chemical analysis confirmed that particle d is composed of K. 0.33 WO 2.45 Furthermore, it was confirmed that the peak positions of the diffraction lines of particle d were consistent with those of the hexagonal K crystal. 0.3 The peak positions of WO3 are consistent. Therefore, it can be confirmed that particle d has a hexagonal crystal structure. The dispersed particle size of particle d in the composite tungsten oxide particle dispersion is 20 nm.

[0137] The optical properties of the near-infrared shielding transparent resin film d involved in Example 4 were measured, and the results are shown in Table 1. The solar transmittance was 45.7% when the visible light transmittance was 74.1%.

[0138] [Example 5] When preparing the raw materials for composite tungsten oxide particles, Rb2CO3 is used instead of Cs2CO3. Rb2CO3 and H2WO4 are weighed so that the Rb / W molar ratio, which is the molar ratio of rubidium to tungsten, is 0.33, and particles e, which are composite tungsten oxide particles, are obtained.

[0139] Particle e was used instead of particle a, and otherwise the same procedure was followed as in Example 1 to obtain the composition, masterbatch, and near-infrared shielding transparent resin film e with a thickness of 20 μm involved in Example 5.

[0140] Furthermore, chemical analysis confirmed that particle e has the composition of Rb. 0.33 WO 2.45 Furthermore, it was confirmed that the peak positions of the diffraction lines of particle e corresponded to those of hexagonal Rb crystal. 0.33The peak positions of WO3 are consistent. Therefore, it can be confirmed that particle e has a hexagonal crystal structure. The dispersed particle size of particle e in the composite tungsten oxide particle dispersion is 20 nm.

[0141] The optical properties of the near-infrared shielding transparent resin film e involved in Example 5 were measured, and the results are shown in Table 1. The solar transmittance at a visible light transmittance of 80.9% was 49.3%.

[0142] [Example 6] When preparing the raw materials for composite tungsten oxide particles, BaCO3 was used instead of Cs2CO3. BaCO3 and H2WO4 were weighed so that the Ba / W molar ratio, which is the molar ratio of barium to tungsten, was 0.33, and particles f, which are composite tungsten oxide particles, were obtained.

[0143] Particle f was used instead of particle a, and otherwise operated in the same manner as in Example 1, to obtain the composition, masterbatch, and near-infrared shielding transparent resin film f with a thickness of 20 μm involved in Example 6.

[0144] Furthermore, chemical analysis confirmed that particle f has a composition of Ba. 0.33 WO 2.45 Furthermore, it was confirmed that the peak positions of the diffraction lines of particle f corresponded to those of hexagonal Ba. 0.21 The peak positions of WO3 are consistent. Therefore, it can be confirmed that particle f has a hexagonal crystal structure. The dispersed particle size of particle f in the composite tungsten oxide particle dispersion is 20 nm.

[0145] The optical properties of the near-infrared shielding transparent resin film f involved in Example 6 were measured, and the results are shown in Table 1. The solar transmittance was 55.8% when the visible light transmittance was 80.1%.

[0146] [Example 7] When preparing the raw materials for composite tungsten oxide particles, Tl(NO3)33H2O was used instead of Cs2CO3. Tl(NO3)33H2O and H2WO4 were weighed so that the Tl / W molar ratio, which is the molar ratio of thallium to tungsten, was 0.33, and g of particles as composite tungsten oxide particles were obtained.

[0147] Particle g was used instead of particle a, and otherwise operated in the same manner as in Example 1, to obtain the composition, masterbatch, and near-infrared shielding transparent resin film g with a thickness of 20 μm involved in Example 7.

[0148] Furthermore, chemical analysis confirmed that particle g's composition is Tl. 0.33 WO 2.45 Furthermore, it was confirmed that the peak positions of the diffraction lines of particle g corresponded to those of the hexagonal Tl crystal. 0.3The peak positions of WO3 are consistent. Therefore, it can be confirmed that particle g has a hexagonal crystal structure. The dispersed particle size of particle g in the composite tungsten oxide particle dispersion is 20 nm.

[0149] The optical properties of the near-infrared shielding transparent resin film g involved in Example 7 were measured, and the results are shown in Table 1. The solar transmittance was 44.8% when the visible light transmittance was 76.3%.

[0150] [Example 8] As the material mixed with dispersant powder A when forming the composition of Example 1, maleic anhydride-modified polyethylene polymer was used instead of maleic anhydride-modified ethylene-1-butene copolymer. Except for the points mentioned above, the same procedure as in Example 1 was followed to obtain the composition, masterbatch, and near-infrared shielding transparent resin film h with a thickness of 20 μm involved in Example 8.

[0151] In Table 1, maleic anhydride-modified polyethylene polymers are described as "ME polymers".

[0152] The optical properties of the near-infrared shielding transparent resin film h involved in Example 8 were measured, and the results are shown in Table 1. The solar transmittance was 45.1% when the visible light transmittance was 76.1%.

[0153] [Examples 9 to 11] The masterbatches obtained from Examples 1 to 3 were diluted with low-density polyethylene resin as a thermoplastic resin to make the concentration of composite tungsten oxide particles relative to the solid medium 1.0% by mass. The low-density polyethylene as a thermoplastic resin is described as "LDPE" in the thermoplastic resin column of "Masterbatch Composition" in Table 1.

[0154] In addition, Example 9 uses the masterbatch from Example 1, Example 10 uses the masterbatch from Example 2, and Example 11 uses the masterbatch from Example 3.

[0155] Apart from the points mentioned above, the same procedure as in Example 1 was followed to obtain the near-infrared shielding transparent resin film i with a thickness of 20 μm involved in Example 9, the near-infrared shielding transparent resin film j with a thickness of 20 μm involved in Example 10, and the near-infrared shielding transparent resin film k with a thickness of 20 μm involved in Example 11.

[0156] The optical properties of the near-infrared shielding transparent resin film i of Example 9, the near-infrared shielding transparent resin film j of Example 10, and the near-infrared shielding transparent resin film k of Example 11 were evaluated. The results confirmed the optical properties shown in Table 1.

[0157] [Example 12] The masterbatch obtained from Example 1 was diluted with high-density polyethylene resin, which is a thermoplastic resin, to make the concentration of composite tungsten oxide particles relative to the solid medium 1.0% by mass. High-density polyethylene, which is a thermoplastic resin, is described as "HDPE" in the thermoplastic resin column of "Masterbatch Composition" in Table 1.

[0158] Apart from the points mentioned above, the same procedure as in Example 1 was followed to obtain the near-infrared shielding transparent resin film l with a thickness of 20 μm involved in Example 12.

[0159] The optical properties of the near-infrared shielding transparent resin film l involved in Example 12 were evaluated. The results confirmed the optical properties shown in Table 1.

[0160] [Example 13] The masterbatch obtained in Example 1 was diluted with linear low-density polyethylene resin, a thermoplastic resin, to achieve a composite tungsten oxide particle concentration of 1.0% by mass relative to the solid medium. The linear low-density polyethylene resin, a thermoplastic resin, is described as "LLDPE" in the thermoplastic resin column of "Masterbatch Composition" in Table 1.

[0161] Apart from the points mentioned above, the same procedure as in Example 1 was followed to obtain the near-infrared shielding transparent resin film m with a thickness of 20 μm involved in Example 13.

[0162] The optical properties of the near-infrared shielding transparent resin film m involved in Example 13 were evaluated. The results confirmed the optical properties shown in Table 1.

[0163] [Example 14] When preparing the composite tungsten oxide particle dispersion, particles a from Example 1, comprising 20% ​​by mass, were weighed as a polymeric dispersant with carbonyl and amine functional groups, and methyl isobutyl ketone, comprising 60% by mass. Except as described above, the process was the same as in Example 1, involving dispersion and pulverization until the particle size of the composite tungsten oxide particles in the dispersion reached 20 nm, thereby preparing the composite tungsten oxide particle dispersion (N-liquid).

[0164] Then, using a vacuum crusher, the methyl isobutyl ketone, which is equivalent to the solvent, is removed from the N liquid to obtain composite tungsten oxide particle dispersion powder (hereinafter referred to as dispersion powder N) (hydrophobication process).

[0165] The obtained dispersed powder N and the maleic anhydride-modified ethylene-1-butene copolymer powder are mixed uniformly using a stirrer to prepare a composition, such that the composite tungsten oxide particles are 10% by mass relative to the maleic anhydride-modified ethylene-1-butene copolymer powder.

[0166] The obtained composition was melt-blended at 180°C using a biaxial extruder (dispersion process), and the extruded strands were cut into granular form to obtain a masterbatch for near-infrared shielding transparent resin molding bodies (hereinafter referred to as masterbatch N) (molding process).

[0167] The obtained masterbatch N was diluted with low-density polyethylene resin, which is used as a thermoplastic resin, to make the concentration of composite tungsten oxide particles relative to the solid medium 1.0 by mass.

[0168] Apart from the points mentioned above, the same procedure as in Example 1 was followed to obtain the near-infrared shielding transparent resin film n with a thickness of 20 μm involved in Example 14.

[0169] The optical properties of the near-infrared shielding transparent resin film n involved in Example 14 were evaluated. The results confirmed the optical properties shown in Table 1.

[0170] [Comparative Example 1] As the material mixed with dispersing powder A when forming the composition of Example 1, low-density polyethylene resin powder was used instead of maleic anhydride-modified ethylene-1-butene copolymer powder. Otherwise, the same procedure as in Example 1 was followed to obtain the composition involved in Comparative Example 1, the masterbatch. When visually inspecting the masterbatch, the color was significantly uneven, which was judged to be due to poor dispersibility of the composite tungsten oxide particles, and conventional sheet production was not carried out.

[0171] [Comparative Example 2] As a polymeric dispersant, 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. Apart from the points mentioned above, the same procedure as in Example 1 was followed to obtain the composition, masterbatch, and near-infrared shielding transparent resin film with a thickness of 20 μm involved in Comparative Example 2.

[0172] The optical properties of the near-infrared shielding transparent resin film o involved in Comparative Example 2 were measured, and the results are shown in Table 1. The solar transmittance was 62.1% when the visible light transmittance was 82.1%.

[0173] [Comparative Example 3] As a polymeric dispersant, 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. Except for the points mentioned above, the composition and masterbatch of Comparative Example 3 were obtained by operating in the same manner as in Example 1. Furthermore, by using a film-forming masterbatch with a visible light transmittance of 75%, a near-infrared shielding transparent resin film p was obtained. At this time, the thickness of the near-infrared shielding transparent resin film p was 117 μm, and the solar transmittance was 50.7%.

[0174] [Comparative Example 4] As a polymeric dispersant, a copolymer of methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) (MMA-HEMA polymer) was used.

[0175] Apart from the points mentioned above, the same procedure as in Example 1 was followed to obtain the composition, masterbatch, and near-infrared shielding transparent resin film q with a thickness of 20 μm that involved in Comparative Example 4.

[0176] The optical properties of the near-infrared shielding transparent resin film q involved in Comparative Example 4 were measured, and the results are shown in Table 1. The solar transmittance was 64.2% when the visible light transmittance was 81.8%.

[0177] [Comparative Example 5, Comparative Example 6] The masterbatches obtained from Comparative Examples 2 and 4 were diluted with low-density polyethylene resin, a thermoplastic resin, to make the concentration of composite tungsten oxide particles relative to the solid medium 1.0 by mass.

[0178] In addition to the points mentioned above, the same procedures were followed as in Comparative Examples 2 and 4 to obtain the near-infrared shielding transparent resin film r with a thickness of 20 μm involved in Comparative Example 5 and the near-infrared shielding transparent resin film s with a thickness of 20 μm involved in Comparative Example 6.

[0179] The optical properties of the near-infrared shielding transparent resin film r involved in Comparative Example 5 and the near-infrared shielding transparent resin film s involved in Comparative Example 6 were evaluated. The results confirmed the optical properties shown in Table 1.

[0180] [Table 1] As shown in Table 1 above, the near-infrared shielding transparent resin films of Examples 1 to 14 have a visible light transmittance of 74% or more and a solar transmittance of 56% or less.

[0181] On the other hand, when visually inspecting the masterbatch of Comparative Example 1, the color was significantly uneven, and the dispersion of the composite tungsten oxide particles was judged to be poor, so the previous sheet production was not carried out.

[0182] Furthermore, it can be confirmed that the near-infrared shielding transparent resin films of Comparative Examples 2, 4 to 6 have a visible light transmittance of 74% or more, but a solar transmittance of 62% or more, indicating poor solar shielding characteristics.

[0183] It can be confirmed that the near-infrared shielding transparent resin film of Comparative Example 3 has a visible light transmittance of 74% or more and a solar transmittance of 56% or less. However, compared with the near-infrared shielding transparent resin films of Examples 1 to 8 with the same particle concentration, its solar shielding characteristics are poor.

[0184] This application claims priority based on Japanese Patent Application No. 2023-147506 filed with the Japanese Patent Office on September 12, 2023, and incorporates the entire contents of Japanese Patent Application No. 2023-147506 into this international application.

[0185] Explanation of symbols 10 Masterbatch 11 Composite tungsten oxide particles 12 Solid media 20 Near-infrared shielding transparent laminate 21 Transparent Molded Body 21A One side 22 Near-infrared shielding transparent resin molded body

Claims

1. A masterbatch for manufacturing near-infrared shielding transparent resin molded bodies, comprising: Polymer dispersants with at least an amine functional group, Solid media containing maleic anhydride-modified polyolefin polymers or copolymers, and General formula M, which has a hexagonal crystal structure disposed in the solid medium. x WO y The composite tungsten oxide particles shown, wherein, Element M is selected from one or more elements chosen from H, He, alkali metals, alkaline earth metals, 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 satisfies 0.1≤x≤1.0 and 2.0≤y<4.

0.

2. The masterbatch according to claim 1, The solid medium comprises polyethylene resin.

3. The masterbatch according to claim 1 or 2, The polymeric dispersant is a copolymer having one or more functional groups selected from hydroxyl, carboxyl, carbonyl, sulfonyl, phosphonyl and epoxy groups.

4. The masterbatch according to claim 1 or 2, When the content of the composite tungsten oxide particles is set to 100 parts by mass, the content of the polymeric dispersant is more than 10 parts by mass and less than 100 parts by mass.

5. The masterbatch according to claim 1 or 2, The M element contained in the composite tungsten oxide particles includes one or more selected from Cs, Rb, K, Tl, Ba, and In.

6. The masterbatch according to claim 1 or 2, The dispersed particle size of the composite tungsten oxide particles is below 200 nm.

7. A composition for manufacturing the masterbatch of claim 1 or 2, comprising: Polymer dispersants with at least an amine functional group, Solid media containing maleic anhydride-modified polyolefin polymers or copolymers, and The general formula M with a hexagonal crystal structure x WO y The composite tungsten oxide particles shown, wherein, Element M is selected from one or more elements chosen from H, He, alkali metals, alkaline earth metals, 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 satisfies 0.1≤x≤1.0 and 2.0≤y<4.

0.

8. A near-infrared shielding transparent resin molded body, which is a molded body containing the masterbatch described in claim 1 or 2.

9. A near-infrared shielding transparent laminate, comprising: Transparent molded bodies, and The near-infrared shielding transparent resin molded body of claim 8, which is laminated on the transparent molded body.

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